coatings

Review
Laser-Sustained Plasma (LSP) Nitriding of Titanium:
A Review
Amar M. Kamat 1, * , Stephen M. Copley 2,3 , Albert E. Segall 2 and Judith A. Todd 2
1 Advanced Production Engineering Group, University of Groningen, Nijenborgh 4, 9747AG Groningen,
The Netherlands
2 Department of Engineering Science and Mechanics, Pennsylvania State University, 212 EES Bldg,
University Park, PA 16802, USA; Stephen_Copley@comcast.net (S.M.C.); axs18@psu.edu (A.E.S.);
jat20@psu.edu (J.A.T.)
3 Applied Research Laboratory, P.O. Box 30, N. Atherton St, State College, PA 16804-0030, USA
* Correspondence: amar.kamat@outlook.com; Tel.: +31-64-149-0186




Received: 23 March 2019; Accepted: 24 April 2019; Published: 26 April 2019


Abstract: Titanium and its alloys possess several attractive properties that include a high
strength-to-weight ratio, biocompatibility, and good corrosion resistance. However, due to their
poor wear resistance, titanium components need to undergo surface hardening treatments before
being used in applications involving high contact stresses. Laser nitriding is a thermochemical
method of enhancing the surface hardness and wear resistance of titanium. This technique entails
scanning the titanium substrate under a laser beam near its focal plane in the presence of nitrogen
gas flow. At processing conditions characterized by low scan speeds, high laser powers, and small
off-focal distances, a nitrogen plasma can be struck near the surface of the titanium substrate. When
the substrate is removed, this plasma can be sustained indefinitely and away from any potentially
interacting surfaces, by the laser power and a cascade ionization process. This paper presents a critical
review of the literature pertaining to the laser nitriding of titanium in the presence of a laser-sustained
plasma, with the ultimate objective of forming wide-area, deep, crack-free, wear-resistant nitrided
cases on commercially pure titanium substrates.

Keywords: laser-sustained plasma; titanium; wear resistance; laser nitriding; case hardening

1. Titanium: Benefits and Drawbacks

Titanium and its alloys have been widely studied in the past few decades, mainly as potential
replacements for steel, aluminum, and superalloys. Titanium possesses a high strength-to-weight
ratio, is 40% less dense than steel and nickel-base superalloys, has a tensile strength higher than
aluminum and comparable to martensitic stainless steel [1], and can withstand higher operating
temperatures than aluminum [2]. Due to the formation of a thin, passive oxide on the surface, titanium
has excellent corrosion resistance, making it a suitable candidate for harsh reactive environments [3]
including the human body [4]. These properties have led to titanium being referred to as a “wonder
metal” [5], with current and future applications in the aerospace, chemical, automotive, and biomedical
industries, spurring recent research into titanium alloy development to achieve desired functionalities
and properties [6–8]. However, the widespread use of titanium in the industry has been hampered by
the high costs incurred during extraction, processing, and machining, making titanium more expensive
than steel or aluminum [9]. Apart from this economic disadvantage, titanium suffers from a serious
engineering drawback, namely, its poor tribological properties. Indeed, titanium is notorious for
exhibiting high coefficients of friction and wear rates, as well as poor abrasion and fretting resistance
when sliding against itself or other materials [10–13].

Coatings 2019, 9, 283; doi:10.3390/coatings9050283 www.mdpi.com/journal/coatings

Coatings 2019, 9, 283 2 of 22

At room temperature, titanium has a hexagonal close-packed (hcp) crystal structure (known
as α-Ti) with a c/a ratio of 1.587 that is less than the ideal value of 1.633 [14]. This makes titanium
prone to slip along the prismatic {1010} rather than the base plane {0001}, leading to an increase
in friction coefficient [15] and galling tendency [14]. Titanium’s metallic bond has a lower d-bond
character compared to other transition metals, enhancing its surface chemical activity and increasing
its tendency to form strong interfacial bonds with other mating surfaces. Buckley et al. [16] observed
a relation between this low d-bond character of titanium and high coefficients of friction with itself
and other materials. Miyoshi et al. [17] correlated the low theoretical tensile and shear strengths
of titanium to high tendencies of material transfer and the resulting high friction coefficients; they
reported friction coefficient values as high as 60 for titanium sliding against itself in a vacuum, making
titanium especially vulnerable to galling and seizing [11]. Molinari et al. [18] provided a metallurgical
basis for the low wear resistance of Ti-6Al-4V (henceforth Ti64) alloys. The researchers also recognized
two distinct speed-dependent wear regimes: at high sliding speeds, the titanium alloy was found to
wear by delamination attributed to the low plastic shear strength and low work hardening behavior
of titanium; at low sliding speeds, surface oxides formed and were easily worn by spalling and
microfragmentation, thus leading to oxidative wear [18]. The preceding discussion makes it clear that
the surfaces of titanium components need to be modified to improve their wear resistance before they
can be used in tribo-applications such as precision gears, orthopedic implants, bolts and fasteners,
among others. This paper reviews the laser-sustained plasma (LSP) nitriding process and its potential
to achieve deep-case hardening of titanium and is structured as follows: Section 2 discusses various
surface hardening treatments that are commonly employed to enhance the tribological properties of
titanium surfaces; Section 3 presents a detailed review of the laser nitriding process including the
role of near-surface plasma as discussed in the literature spanning the past three decades; finally,
Section 4 describes recent research conducted at the Pennsylvania State University to study the unique
properties of a LSP and its effects on the laser nitriding process, followed by the development of a
novel two-step “LSP nitriding-remelting” method to form homogenous, wide-area, deep, crack-free,
and wear-resistant nitrided cases on commercially-pure titanium (CP-Ti) substrates.

2. Surface Hardening of Titanium

Surface engineering in tribology can be achieved using either surface coating or other modification
techniques [19]. In surface coating methods, thin-film coatings of harder materials (such as TiN)
are deposited on titanium to improve its wear resistance using techniques such as physical vapor
deposition (PVD) and chemical vapor deposition (CVD) [20,21]. PVD processes further include
ion plating, plasma spray, thermal evaporation, and sputtering [22]. Surface coating methods can
achieve high hardness at the surface, but are characterized by low deposition rates, poor adhesion
to the substrate (especially in evaporation processes), complex equipment, and low film thicknesses
(1–10 µm) [23]; as such, PVD and CVD are incapable of producing a deep and hard case that is required
in high contact stress tribosystems such as gears and bearings [20,24]. The surface hardness of titanium
and its alloys can also be improved by forming thick-film coatings using laser cladding, wherein the
desired coating in powder form (either preplaced on the substrate or made to flow through a nozzle)
is melted and fused with the titanium substrate using a high-power laser [25–27], producing much
thicker coatings than possible with PVD or CVD processes.
Surface modification of titanium can be implemented by thermochemical processes such as
boronizing [28–30], carburizing [20], nitriding [24,31–40], and oxidizing [41–45]. Since the neutral
atomic radii of the oxygen (0.6 Å), nitrogen (0.71 Å), and carbon (0.77 Å) atoms are about half or less
than titanium (1.5 Å), O, N, and C atoms readily diffuse through the titanium lattice and can occupy the
interstitial octahedral sites (0.61 Å radius) in the HCP structure of α-Ti [46]. The N and O atoms exhibit
high interstitial solid solubility in the α-Ti phase, as seen in the phase diagrams of Figure 1 [47,48],
causing a significant solid solution hardening effect [49]. Further, the interstitial O, N, and C atoms
also increase the c/a ratio of the α-Ti HCP structure, which changes the slip plane from the prismatic
Coatings 2019, 9, 283 3 of 22

{1010}
Coatingsto the9,basal
2019, x FOR{0001} plane, increasing the galling resistance of titanium [15]. In addition, B,3C,
PEER REVIEW of N,
22
and O atoms also strengthen the titanium matrix by precipitation hardening, forming the hard ceramic
titanium
phases matrix.
TiB/TiB As nitrogen
2 , TiC, TiN/Ti2 N,has
andthe
TiO 2 /TiO respectively
highest hardening effect
withinofthe
alltitanium
these interstitial
matrix. As atoms [49],
nitrogen
nitriding
has is a widely
the highest usedeffect
hardening and well-investigated thermochemical
of all these interstitial atoms [49], method
nitridingofis hardening
a widely usedtitanium
and
surfaces.
well-investigated thermochemical method of hardening titanium surfaces.

(a) (b)

Figure 1.
Figure 1. (a)
(a) N-Ti
N-Tiand
and(b)
(b)O-Ti
O-Tiphase
phase diagrams.
diagrams. Figure
Figure 1a 1a reprinted
reprinted with
with permission
permission fromfrom
Ref. Ref. [47]
[47] and
and Figure
Figure 1b with1b with permission
permission reprinted
reprinted fromfrom Ref. [48].
Ref. [48]. Copyright
Copyright 1987 1987 Springer
Springer Nature.
Nature.

Nitriding of titanium may be effected effected by by ionion implantation,

implantation, diffusion,
diffusion, or or laser/electron
laser/electron beam beam
processes
processes [20], each method differing in the mechanism of impregnating the titanium substrate with
[20], each method differing in the mechanism of impregnating the titanium substrate with
nitrogen.
nitrogen. In In ion implantation,
implantation, nitrogen
nitrogen ions ions are accelerated into the titanium substrate through aa
voltage
voltage difference
difference [20];[20]; however,
however, this this method
method can can only
only produce
produce aa compound
compound nitride nitride layer
layer having
having aa
thickness
thickness of of about
about 25–250
25–250 atomic
atomic layers
layers [50].
[50]. As the name suggests, the diffusion method relies upon upon
the
the diffusion
diffusion of of nitrogen
nitrogen atoms
atoms into
into the
the titanium
titanium surface
surface at elevated temperatures.
temperatures. Nitrogen diffusion diffusion
into
into the
the titanium
titanium substrate
substrate cancan be brought
brought aboutabout either
either by by heating
heating the substrate
substrate to a high temperature
in
in aa nitrogen
nitrogen or or ammonia
ammonia gas gas atmosphere
atmosphere (gas (gas nitriding)
nitriding) [31,33,34],
[31,33,34], oror by
by exposing
exposing the the substrate
substrate to to a
nitrogen
nitrogenplasma
plasma(plasma
(plasmanitriding)
nitriding)thatthatsimultaneously
simultaneouslyheats heats the
thesurface
surface andandprovides
provides nitrogen
nitrogen ions to
ions
it [36–39,51]. Plasma nitriding has the added advantage of an inherent
to it [36–39,51]. Plasma nitriding has the added advantage of an inherent sputtering phenomenon sputtering phenomenon that
also
that cleans the substrate
also cleans and reduces
the substrate and reducesimpurities in the nitrided
impurities samplesample
in the nitrided [51]. Both theBoth
[51]. gas the
andgas plasma
and
nitriding processes
plasma nitriding are capable
processes of forming
are capable functionally
of forming gradedgraded
functionally cases comprising
cases comprising a compound
a compound layer
(TiN,
layer Ti 2 N) at
(TiN, Ti2the
N) top and
at the topa diffusion zone containing
and a diffusion zone containinga solid solution of nitrogen
a solid solution in titanium,
of nitrogen α-Ti(N),
in titanium,
deeper
α-Ti(N),indeeper
the titanium substratesubstrate
in the titanium [21]. The[21]. hardness and depth
The hardness andof depth
the resulting nitride cases
of the resulting nitride depend
cases
upon the temperature and duration of the process; compound
depend upon the temperature and duration of the process; compound layer depths up to 50 µm layer depths up to 50 µm (plasma
nitriding) and 15 µm
(plasma nitriding) (gas
and 15 nitriding) have beenhave
µm (gas nitriding) recorded, with totalwith
been recorded, depths (including
total the diffusion
depths (including the
layer)
diffusion achieved
layer) up to 200–300
achieved up toµm [31]. However,
200–300 since diffusion
µm [31]. However, since takes placetakes
diffusion in the solid
place instate, gas
the solid
and
state,plasma
gas and nitriding are slow processes,
plasma nitriding typicallytypically
are slow processes, requiringrequiring
1–100 h 1–100
[21]. Further, since the
h [21]. Further, whole
since the
substrate experiences a high temperature (400–950 ◦ C for plasma nitriding and 650–1000 ◦ C for gas
whole substrate experiences a high temperature (400–950 °C for plasma nitriding and 650–1000 °C
nitriding [21]) for[21])
for gas nitriding longfor
durations during the
long durations process,
during the bulk the
the process, microstructure is affected
bulk microstructure is along
affected with the
along
surface;
with thethus,surface;gas thus,
and plasma
gas andnitriding are not true
plasma nitriding are “surface
not true engineering” methods.methods.
“surface engineering” Plasma and gas
Plasma
nitriding methods have
and gas nitriding methodsalso have
been found
also been to reduce
foundthe to fatigue
reduce strength
the fatigueof titanium
strength alloys, especially
of titanium at
alloys,
high processing temperatures [24]. Nitriding titanium using high energy
especially at high processing temperatures [24]. Nitriding titanium using high energy density sources density sources such as a
laser
such circumvents these shortcomings
as a laser circumvents while introducing
these shortcomings new ones, as
while introducing explained
new ones, asin Section 3.inFigure
explained Section 2
presents
3. Figurean overviewan
2 presents of overview
the various oftechniques
the variousused for surface
techniques usedhardening
for surface of titanium
hardening and ofits alloys,
titanium
with
and itsa special
alloys, focus
with aon the nitriding
special focus onofthe titanium,
nitriding summarizing the discussionthe
of titanium, summarizing of Section
discussion 2. of Section
2.
Coatings 2019, 9, 283 4 of 22
Coatings 2019, 9, x FOR PEER REVIEW 4 of 22

Figure 2. An overview of surface hardening methods for titanium and its alloys.
Figure 2. An overview of surface hardening methods for titanium and its alloys.
3. Laser Nitriding of Titanium
3. Laser Nitriding of Titanium
3.1. Background
3.1. Background
Lasers are characterized by their monochromatic, coherent, polarized, narrow, and low-divergence
beams. Focused
Lasers laser beams can
are characterized bytherefore deliver large quantities
their monochromatic, coherent, of energy (kilowatts)
polarized, narrow,toand a narrow
low-
spot (usuallybeams.
divergence a fraction of a millimeter)
Focused laser beams on can
the surface of the
therefore substrate,
deliver large leading to high
quantities energy(kilowatts)
of energy intensities
of athe orderspot 10 –1012 W/m2 during welding (compared to 106 –108 W/m2 for flux-shielded or
of 10(usually
to narrow a fraction of a millimeter) on the surface of the substrate, leading to high
gas-shielded
energy arcs [52]).
intensities of theFurthermore,
order of 1010–10 this
12 energy is absorbed
W/m2 during weldingwithin the firstto
(compared few
106atomic
–108 W/mlayers
2 forof the
flux-
substrate,ormaking
shielded the laser
gas-shielded ideally
arcs and uniquely this
[52]). Furthermore, suited to surface
energy engineering
is absorbed withinapplications
the first few such
atomicas
nitriding
layers of ofthe
titanium.
substrate,Given these benefits,
making the laser laser nitriding
ideally andofuniquely
titanium has beentoextensively
suited researched
surface engineering
for more thansuch
applications threeasdecades.
nitridingAoftypical
titanium.laserGiven
nitriding
theseprocess canlaser
benefits, be described
nitridingasof follows:
titanium has been
extensively
• researched for more than three decades. A typical laser nitriding
The titanium substrate, usually in the form of a test coupon, is scanned under a laser process can be described
beam in the
as follows:
presence of pure or diluted nitrogen gas flow (Figure 3a), where the distance of the focal plane
• fromtitanium
The the substrate is dictated
substrate, usually byinthethedesired
form of beam spot
a test size (and
coupon, hence incident
is scanned under aenergy density)
laser beam in
on the substrate. The laser beam can be operated in the pulsed
the presence of pure or diluted nitrogen gas flow (Figure 3a), where the distance of the focalor continuous-wave (CW) mode.
The nitrogen
plane from the gassubstrate
issues through a nozzle
is dictated thatdesired
by the is eitherbeamcoaxial spot(coaxial nozzle)
size (and or atincident
hence an angleenergy
to the
laser beam
density) on(side
the nozzle).
substrate. TheThe process
laser is usually
beam canconducted
be operated in aincontrolled
the pulsed environment containing
or continuous-wave
pure or diluted nitrogen to avoid oxidation of the titanium substrate.
(CW) mode. The nitrogen gas issues through a nozzle that is either coaxial (coaxial nozzle) or at
• Dueangle
an to thetohigh energy
the laser beamdensity(sideofnozzle).
the laserThe beam at or is
process near focus,conducted
usually the irradiated in a area of the
controlled
titanium substrate melts to a depth of hundreds of microns and incorporates
environment containing pure or diluted nitrogen to avoid oxidation of the titanium substrate. nitrogen at its molten
• surface.
Due Thehigh
to the nitrogen-rich
energy density titanium of melt is transported
the laser beam at ordeeper into the
near focus, themelt pool by area
irradiated convection
of the
currents. The
titanium main driving
substrate melts tomechanism
a depth offor convection
hundreds of ismicrons
the so-called Marangoni force
and incorporates arising
nitrogen at out
its
of surface tension gradients; since the surface tension for liquid
molten surface. The nitrogen-rich titanium melt is transported deeper into the melt pool by titanium decreases with increasing
temperature,
convection the center
currents. The region
mainofdriving
the freemechanism
surface of the formelt pool hasislower
convection surface tension
the so-called Marangoni than
at the arising
force edges, driving
out of fluid
surface flowtension
from the center to since
gradients; the edges (Figure 3b).
the surface Sincefor
tension nitrogen
liquid transport
titanium
by diffusion
decreases with in increasing
the liquid phase is enhanced
temperature, by convection,
the center region of the thefree
laser nitriding
surface process
of the melt poolis much
has
faster than
lower surfacesolid-state
tension diffusion
than at the processes such asfluid
edges, driving gas nitriding
flow from and theplasma
center nitriding.
to the edges (Figure
• 3b).
When Since
the nitrogen
laser beam transport
moves away by diffusion
from theinarea
the liquid
under phase is enhanced
consideration (e.g.,byY-Yconvection,
in Figure 3b) theaslaser
the
nitriding
substrate process
is scanned, is much faster than melt
the nitrogen-rich solid-state diffusion
experiences rapidprocesses such as gas nitriding
and non-equilibrium solidificationand
plasma
due to anitriding.
“self-quenching” effect whereby the surface rapidly loses heat to the bulk via conduction.
• When the laser
This results in thebeam moves away
precipitation from such
of phases the area under consideration
as stoichiometric (e.g., Y-Y in Figure
or near-stoichiometric TiN, a3b) as
solid
the substrate
solution is scanned,
of nitrogen in titanium,the nitrogen-rich
α-Ti(N), and melt experiences
martensitic titanium,rapid and The
α’-Ti. non-equilibrium
TiN phase is
solidification
gold-colored and duehence
to a “self-quenching”
easily identified on effect
thewhereby
surface ofthe thesurface
treatedrapidly
sample.loses heatand
The TiN to the bulk
α-Ti(N)
via conduction.
phases form a strong This metallurgical
results in thebond precipitation
with the of phases thereby
substrate, such as enhancing
stoichiometric or near-
the hardness
stoichiometric
and wear resistance TiN, aofsolid solutionsubstrate.
the treated of nitrogen Theinmicrostructure
titanium, α-Ti(N), and
of the martensitic
resulting titanium,
nitrided layer
α’-Ti.
can beThe TiN phase
controlled is gold-colored
by varying processingand parameters
hence easilysuch identified
as laser onpower,
the surface
spot of the
size treated
(off-focal
sample.
distance),The scan TiN and and
speed, α-Ti(N) phases form
the nitrogen a strong
gas flow rate. metallurgical
On the other hand, bond withrapidthe substrate,
solidification
thereby enhancing the hardness and wear resistance of the treated substrate. The microstructure
 Coatings 2019, 9, x FOR PEER REVIEW 5 of 22
Coatings 2019, 9, 283 5 of 22

of the resulting nitrided layer can be controlled by varying processing parameters such as laser
power,the
makes spot size nitrided
brittle (off-focallayer
distance), scan speed,
susceptible and the
to cracking andnitrogen
porosity,gas
andflow rate.anOn
causes the other
increase in
hand, rapid
surface solidification
roughness. Studiesmakes
in thethe brittle
laser nitrided
nitriding layer susceptible
literature to cracking
usually focus and porosity,
on overcoming these
and causes an increase
disadvantages in surface
(especially surface roughness.
cracking) asStudies
detailedin in
theSection
laser nitriding
3.2. literature usually focus
on overcoming these disadvantages (especially surface cracking) as detailed in Section 3.2.

(a) (b)
Figure3.3. (a)
Figure (a) Schematic
Schematic of
of the
the laser
laser nitriding
nitriding process
process with
with coaxial
coaxial nitrogen
nitrogengas
gas flow,
flow,and
and(b)
(b)convective
convective
transportof
transport ofnitrogen
nitrogenin
inthe
themelt
meltpool
poolat
at the
the transverse
transverse cross-section
cross-sectionY-Y.
Y-Y.TTand
andσσindicate
indicatetemperature
temperature
andsurface
and surfacetension
tensionrespectively.
respectively.CP-Ti
CP-Tidenotes
denotescommercially-pure
commercially-puretitanium.
titanium.

3.2.
3.2. Literature
Literature Review
Review
3.2.1. Chronological Development of the Laser Nitriding Process
3.2.1. Chronological Development of the Laser Nitriding Process
The use of lasers to nitride titanium and its alloys was first demonstrated in 1984 by Katayama et al. [53],
The use of lasers to nitride titanium and its alloys was first demonstrated in 1984 by Katayama
who used pulsed and continuous-wave (CW) CO2 and Nd:YAG lasers to harden the surface of
et al. [53], who used pulsed and continuous-wave (CW) CO2 and Nd:YAG lasers to harden the surface
titanium up to 700 HV (the Vickers hardness values of untreated CP-Ti and Ti64 alloys are 140–200 HV
of titanium up to 700 HV (the Vickers hardness values of untreated CP-Ti and Ti64 alloys are 140–
and 327–370 HV, respectively [1]). In the 1980’s and 1990’s, research focused on understanding and
200 HV and 327–370 HV, respectively [1]). In the 1980’s and 1990’s, research focused on
characterizing the laser nitriding process and finding optimal processing conditions to produce
understanding and characterizing the laser nitriding process and finding optimal processing
crack-free nitrided surfaces on CP-Ti and Ti64 substrates. Bell et al. [24] used the laser nitriding
conditions to produce crack-free nitrided surfaces on CP-Ti and Ti64 substrates. Bell et al. [24] used
technique to improve the wear resistance and load bearing capacity of titanium for applications
the laser nitriding technique to improve the wear resistance and load bearing capacity of titanium for
such as gears and bearings. Using a CO2 laser in both the pulsed and CW modes, they were able
applications such as gears and bearings. Using a CO2 laser in both the pulsed and CW modes, they
to produce 500 µm deep nitrided cases on CP-Ti substrates. Two types of dendrites were observed
were able to produce 500 µm deep nitrided cases on CP-Ti substrates. Two types of dendrites were
in the microstructure: large dendrites near the surface, exhibiting cubic symmetry and hardness
observed in the microstructure: large dendrites near the surface, exhibiting cubic symmetry and
values close to 1500 HV and dendrites near the melted-unmelted region interface showing hexagonal
hardness values close to 1500 HV and dendrites near the melted-unmelted region interface showing
symmetry and having a hardness of 600 HV. The cubic dendrites were identified as the compound TiN,
hexagonal symmetry and having a hardness of 600 HV. The cubic dendrites were identified as the
while the hexagonal dendrites (which appeared to be hollow after deep etching) were identified as
compound TiN, while the hexagonal dendrites (which appeared to be hollow after deep etching)
a solid solution of nitrogen in α-titanium, α-Ti(N). Morton et al. [54] reported an improvement in
were identified as a solid solution of nitrogen in α-titanium, α-Ti(N). Morton et al. [54] reported an
the wear behavior of laser-nitrided titanium during lubricated rolling and sliding at high Hertzian
improvement in the wear behavior of laser-nitrided titanium during lubricated rolling and sliding at
contact stresses; they used a CO2 laser to nitride the Ti64 alloy using a side nozzle arrangement.
high Hertzian contact stresses; they used a CO2 laser to nitride the Ti64 alloy using a side nozzle
Morton et al. [54] found that the angle of the nozzle needed to be at least 30◦ and that the nitrogen flow
arrangement. Morton et al. [54] found that the angle of the nozzle needed to be at least 30° and that
had to cover at least thrice the melt pool width to avoid oxygen contamination. They also reported
the nitrogen flow had to cover at least thrice the melt pool width to avoid oxygen contamination.
that low scan speeds (less than 16 mm/s) led to embrittlement and high surface roughness, while
They also reported that low scan speeds (less than 16 mm/s) led to embrittlement and high surface
high speeds (more than 48 mm/s) made the nitrided layer inhomogeneous. Diluting the nitrogen gas
roughness, while high speeds (more than 48 mm/s) made the nitrided layer inhomogeneous. Diluting
flow with argon (up to 60% dilution) and preheating the substrate up to 300 ◦ C was found to reduce
the nitrogen gas flow with argon (up to 60% dilution) and preheating the substrate up to 300 °C was
crack formation. No cracks were observed at surface hardness values of 600 HV or lower, although
found to reduce crack formation. No cracks were observed at surface hardness values of 600 HV or
elsewhere [55] the threshold surface hardness value for crack formation was reported as 650 HV by the
lower, although elsewhere [55] the threshold surface hardness value for crack formation was reported
same authors. Roughness of the nitrided layer was attributed to the high viscosity of the TiN-rich
as 650 HV by the same authors. Roughness of the nitrided layer was attributed to the high viscosity
melt, whereas the waviness was due to convective flow. Jianglong et al. [56] nitrided Ti64 using a
of the TiN-rich melt, whereas the waviness was due to convective flow. Jianglong et al. [56] nitrided
Coatings 2019, 9, 283 6 of 22

CO2 laser and studied the general characteristics of the nitriding process. The authors noted that
TiN formation depended upon a threshold energy density of 5 × 108 W/m2 , below which no nitride
formation was observed irrespective of the scan speed. Given these observations, it was proposed that
the mechanism listed below could help explain the laser nitriding process, where the [] refers to a melt
and (N) represents the nitogen in the titanium structure [56]:

• Surface absorption [Ti] + N2 → [Ti] + [N2 ]

• Nitrogen decomposition [N2 ] → [2N]
• Nitrogen transfer [N]surface → [N]inside
• TiN precipitation [Ti(N)] → TiN + [Ti(N)]
• Melt solidification [Ti(N)] → TiN + α-Ti(N)

According to Kloosterman et al. [57] who nitrided CP-Ti using a CO2 laser in the presence of
pure N2 flow, the threshold laser energy density to form TiN was 2.5 × 109 W/m2 or higher. They
noted that apart from the mechanism proposed by Jianglong et al. [56], TiN could also form by the
exothermic reaction Ti + 0.5N2 → TiN. Kloosterman et al. [57] further differentiated between two types
of cracks in the nitrided layer: microcracks that were confined to the top 2–10 µm, and macrocracks
that penetrated deeper into the solidified layer. The microstructure near the surface of the nitrided
layer comprised a thin TiN layer (1–3 µm) and TiN dendrites that grew from the thin layer and were
surrounded by nitrogen-rich Ti. Needle-like particles (560 HV hardness), coarse structures (300 HV
hardness), and groups of TiN dendrites (swept away by convection currents) were observed by them
deeper in the melt pool. Mridha and Baker [58] used a 1.35 kW CO2 laser to nitride CP-Ti in a
controlled pure-N2 environment, and reported rippling, cracking, and pores at the surface; the cracks
were seen to originate at the pores. The melt pool was inhomogeneous due to capillary flow of the
melt. In a subsequent publication in which a parametric study of the process was conducted, Mridha
and Baker [59] found that low gas flow rates and high speeds were essential to reduce surface crack
formation on CP-Ti substrates in a pure-N2 gas flow. Moreover, they reported that crack-free nitrided
surfaces formed when the N2 gas flow was diluted with either Ar or He gases. Although nitrogen
dilution eliminated crack formation, the TiN dendrites produced by the pure N2 flow were absent
when the N2 flow was diluted. The crack-free nitrided layers had depths up to 550 µm. Weerasinghe
et al. [60] also found that diluting the nitrogen gas flow resulted in crack-free nitrided surfaces in CP-Ti
substrates; however, the TiN dendrites were found to be confined to the top 25 µm of the solidified layer.
Weerasinghe et al. [60] also explored the effects of a post-nitriding laser-remelting run in argon gas
flow, and found that it increased the homogeneity and reduced the surface roughness of the nitrided
layer. Hu and Baker [61] reported that the laser-nitrided Ti64 sample had a lower tendency to crack
when preheated to about 300 ◦ C (agreeing with Morton et al.’s [54] result) using a laser glazing run in
argon gas flow. Xue et al. [62] found that preheating reduced the macrocracking tendency, while N2
flow dilution eliminated microcracks on the surface of a pulsed Nd:YAG laser-nitrided Ti64 sample.
Further, Xue et al. [63] measured residual stresses in the nitrided layer to be tensile (950 MPa in the scan
direction and 800 MPa perpendicular to the scan direction); preheating reduced these tensile stresses
and hence the tendency to form macrocracks. Xue et al. [63] also detected minor oxygen contamination
on the nitrided surface (but none deeper in the nitrided layer), and concluded that oxidation did not
contribute towards cracking.
Hu et al. [64] identified the “thick needle” phase (also referred to as “laths with rounded ends” [65],
“plates” [66], or simply “dendrites” [67] in the laser nitriding literature) in laser-nitrided CP-Ti and
Ti64 specimens as being hexagonal TiN0.3 . Xin et al. [65] analyzed the microstructure of Ti64 specimens
nitrided using a CO2 laser in an 80% N2 flow and identified two distinct zones: zone I, about 50 µm
from the surface, consisted of cubic TiN0.8 dendrites, metastable hexagonal TiN0.3 , and martensitic
α’-Ti; whereas zone II consisted primarily of nitrogen-rich martensitic α’-Ti. The atomic percentage of
the nitrogen solute in the α’-Ti phase was found to be 3%–4% at the boundary of zones I and II, while it
was less than 1% at the bottom of zone II. Nwobu et al. [67] used quantitative microanalysis to identify
Coatings 2019, 9, 283 7 of 22

two types of dendrites in the microstructure of nitrided CP-Ti: δ-TiN dendrites with nitrogen content
greater than 30 at.%; and α-TiN0.3 dendrites containing 18 at.%–22 at.% nitrogen, produced by the
peritectic reaction L + δ-TiN → α (Figure 1a). Because of the measured composition of 18 at.%–22 at.%,
they referred to this phase as α-TiN0.25 instead of α-TiN0.3 . The effect of laser nitriding on the wear
properties of titanium was studied by Yerramareddy and Bahadur [68], Xin et al. [69], Man et al. [70],
and Ettaqi et al. [71], who reported an improvement in erosion and dry sliding wear resistance, abrasive
resistance, cavitation erosion resistance, and a reduction in the coefficient of friction respectively.
In the 2000’s, the process development of laser nitriding continued with a focus on reducing
oxidation on the laser-nitrided surface and conducting wear resistance tests on the laser-nitrided
titanium samples. Chen et al. [72] used a specially designed nozzle to avoid oxidation during pulsed
Nd:YAG laser nitriding of Ti64 in an uncontrolled atmosphere. They concluded that oxygen-free
nitriding was possible when the nitrogen gas flow was sufficiently low to maintain laminar flow
conditions; high flow rates promoted oxygen contamination of the flow through turbulent mixing and
led to oxide formation at the surface. Work by Abboud et al. [73] (who used a gas-shielding device to
avoid oxidation during CO2 laser nitriding of Ti64) and Chan et al. [74] (who investigated the extent of
oxidation of CP-Ti and Ti64 during fiber laser nitriding in open atmosphere) agreed with Chen et al. [72]
that turbulent gas flows should be avoided to ensure oxide-free nitrided layers. Raaif et al. [75] and
Kaspar et al. [66] used a bell-shaped inert gas cover to maintain an oxygen-free atmosphere during CO2
laser nitriding of CP-Ti and Ti64 respectively. More recently, Katahira et al. [76] successfully conducted
pulsed laser nitriding on Ti64 in open atmosphere using a specially designed jig to prevent oxidation.
Several researchers also discussed the effect of the laser nitriding treatment on the wear and
corrosion properties of titanium, the latter being especially important in biomedical applications where
good corrosion fatigue resistance is required [77]. Geetha et al. [78], who nitrided the biomedical
Ti-13Nb-13Zr alloy using a pulsed Nd:YAG laser and reported improved corrosion resistance compared
to the base alloy, argued that the surface roughness inherent to the laser nitriding process (especially
when carried out in a pure-N2 environment) can be advantageous for osseointegration. Vadiraj et al. [79]
nitrided a biomedical Ti alloy with a pulsed CO2 laser and found a reduction in fretting wear
rate. Sathish et al. [80], Zhang et al. [81], Majumdar [82], Dahotre et al. [83], Chan et al. [84], and
Hussein et al. [85] also reported an improvement in the wear and corrosion resistance, as well as
osseointegration of laser-nitrided biomedical titanium alloys. Kaspar et al. [66] used a CO2 laser to
nitride Ti64 in dilute N2 environments and found that increasing the hardness to a value of 550 HV
was enough to significantly increase the cavitation erosion wear resistance, which is important in
applications such as pumps, impellers, and steam turbine blades. Recently, the use of Ti64 in automotive
applications was explored by Duraiselvam et al. [86]. They used a CW diode laser with a rectangular
beam profile to produce a 120 µm-thick nitrided layer with a hardness of 760 HV on Ti64 specimens;
the nitrided sample performed better than grey cast iron at the same wear testing conditions, prompting
the authors to patent their technique as a viable process of producing wear-resistant Ti64 specimens
that can replace grey cast iron in disk brake rotor applications. Finally, Briguente et al. [87] also recently
demonstrated an improvement in the creep resistance of Ti64 after a laser nitriding treatment, the first
creep resistance test of its kind for laser-nitrided titanium alloys.
Apart from CO2 and Nd:YAG lasers, researchers in recent times have also used free electron
(FEL) [88,89], diode [82,86,90], and Ytterbium lasers [83] to perform nitriding of titanium. Lisiecki [90]
lists higher absorption and more uniform heating as some of the main advantages of using a diode
laser with a rectangular beam mode over more conventional laser sources such as the CO2 laser
with a Gaussian beam mode. Finally, two-dimensional (2D) finite element models of the heat and
mass transfer occurring during laser nitriding were developed by Kuznetsov and Nagornova [91],
Dahotre et al. [92], Xuan et al. [93], and Höche et al. [88]; while the first two papers neglected fluid
flow, Höche et al. [88] considered both convection and diffusion in their model, and calculated several
important dimensionless numbers such as the Peclet number (ratio of convective heat transfer to
conductive heat transfer, value close to 10), Reynolds number (ratio of inertial forces to viscous forces,
Coatings 2019, 9, 283 8 of 22

value close to 500), and the Marangoni number (ratio of the Marangoni surface tension gradient forces
to the viscous forces, value close to 5000) in the melt pool. Using their 2D model, Höche et al. [88]
were able to predict surface deformation due to Marangoni flow, and recognized the tradeoff between
high melt depths and low surface roughness, since the convective effects responsible for transporting
nitrogen deeper into the melt pool were also responsible for deforming the surface and reducing
surface quality.

3.2.2. Role of Near-Surface Plasma in Laser Nitriding of Titanium

If the laser energy density is high enough (of the order of 1010 W/m2 [52]), the irradiated area
of the substrate melts and vaporizes, leading to the formation of a plasma plume near the surface.
A simplified description of the formation of such a laser-induced plasma is presented below [94]:

• In a metal where the first ionization potential is typically low, the metal vapor is easily ionized by
the high intensity of the laser beam, giving rise to primary free electrons near the surface. Free
electrons can also be generated by thermionic emission and the photoelectric effect [95].
• These primary free electrons gain energy by absorbing the laser radiation through a process called
inverse bremsstrahlung. The energetic free electrons then collide with the neutral atoms and
molecules of the processing gas, causing dissociation and ionization and producing secondary
free electrons and ions in the process. This triggers a cascade ionization process in the gas, leading
to gas breakdown and plasma formation. Gas breakdown is said to have occurred when the
free electron density is of the order of 1024 /m3 [96]. The presence of the primary free electrons
reduces the threshold intensity required to cause optical breakdown of the processing gas by
about four orders of magnitude [97], as well as the effective ionization potential of the processing
gas [94]. According to Grigoryants [94], the threshold power density for a CO2 laser to cause
optical breakdown is approximately 6 × 109 W/m2 .
• The absorption of the laser energy by the plasma increases with the degree of ionization (i.e., the
free electron density); if the laser is operated in the CW mode, a steady state can be reached when
the absorbed laser energy is balanced by losses due to plasma re-radiation. In the steady state, the
laser energy can sustain the plasma in a coaxial flow of the processing gas even when the original
source of free electrons, the metal substrate, is removed from the laser beam path. Such a plasma
has been referred to as a “continuous optical discharge” (COD) plasma [98] or a “laser-sustained
plasma” (LSP) [99] in the literature; the latter terminology will be used in this paper.
• Peak temperatures in the range of 15000–17000 K have been measured at the core of steady-state
argon LSP’s [99,100]. Although it is more difficult to characterize a nitrogen LSP, its peak
temperature is expected to be the same order of magnitude. This makes the LSP an interesting
tool from the standpoint of high-temperature materials processing.

Although plasma formation is a commonly encountered phenomenon in laser materials

processing [52,101], it has received limited attention in the laser nitriding literature. Morton et al. [54],
probably drawing an analogy from laser welding processes, differentiated between two regimes of
melting during laser nitriding: “normal melting” below laser power densities of 109 W/m2 where energy
transfer occurred through photons impinging upon the surface with an efficiency of less than 50%,
and “keyhole melting” above power densities of 109 W/m2 where plasma formation resulted in energy
transfer efficiencies close to 100%. Although higher melt depths were achieved within the keyhole
melting regime, it was fraught with problems such as high surface roughness, specimen distortion,
and crack formation, and was thus deemed undesirable by the authors [54]. Thomann et al. [97]
studied the laser-induced plasma that formed during pulsed CO2 and XeCl laser nitriding of CP-Ti
substrates; they found that the CO2 laser-induced plasma occurred due to gas breakdown and was
rich in ionic and atomic nitrogen species. The investigators also concluded that near-surface plasma
formation enabled better energy coupling between the laser and the substrate and was hence necessary
for the nitriding process [97]. Geetha et al. [78] observed near-surface plasma formation in their pulsed
Coatings 2019, 9, 283 9 of 22

Nd:YAG laser nitriding experiments in both pure and dilute nitrogen atmospheres; they noted that
nitrogen dissociation in the plasma led to greater nitrogen diffusion rates into the melt pool. Moreover,
the researchers reported that in an argon-diluted nitrogen atmosphere, ionic argon in the Ar-N2 plasma
hindered the diffusion of nitrogen, leading to a dendrite-free microstructure; as noted earlier, this effect
has been observed before in the laser nitriding literature [59,60,69], albeit in the absence (or without
the mention) of plasma formation. Höche et al. [102] and Ohtsu et al. [103] also argued that plasma
formation aided the nitrogen dissociation process leading to the formation of nitrogen radicals that
can diffuse faster into the titanium melt pool; plasma formation was thus dubbed beneficial to the
laser nitriding process. Yu and Sun [104] conducted laser nitriding of titanium using a CO2 laser in
the presence and absence of a nitrogen plasma struck and sustained using an independent plasma
gun. They found that at the same laser power density (109 W/m2 ), the presence of the nitrogen
plasma significantly enhanced the nitriding efficiency; this was attributed to the greater nitrogen intake
occurring due to the presence of ionic and atomic nitrogen in the plasma.
On the other hand, Abboud et al. [73] took precautions to avoid plasma formation in their CO2
laser nitriding experiments of Ti64, because the plasma (a) absorbed the laser radiation and hence
reduced laser absorption on the titanium substrate, and (b) occasionally caused the focusing lens to
break. Chen et al. [72] reported that the titanium-rich plasma pushed the nitrogen gas flow away
from the titanium substrate and hence acted as a barrier between the nitrogen flow and the titanium
substrate; consequently, they recommended that the laser power density be maintained at low values to
prevent metal evaporation and subsequent plasma formation. However, Ohtsu et al. [105] found that
the titanium-rich plasma could be confined to the substrate by maintaining a high enough pressure of
nitrogen gas (100 kPa); at such high pressures, nitrogen radicals could effectively interact with the melt,
leading to efficient coupling between the nitrogen gas flow and the substrate and, as a consequence,
thicker nitrided layers. A recent study by Chan et al. [74] also proved that a stable, “low-brightness”,
laser-sustained plasma can improve the nitriding quality and reduce oxygen contamination, in contrast
to a “high-brightness” plasma that can cause defects (cracks, craters, etc.) in the nitrided layer.
A summary of commonly encountered issues, their causes, and proposed solutions in the laser nitriding
literature can be found in Table 1.

Table 1. Summary of commonly encountered issues in laser nitriding of titanium.

Issue Cause Proposed Solutions References

Preheating titanium substrate [54,61,62]
Crack formation in Residual tensile Diluting nitrogen flow with argon [54,59,60,62,66,73,75]
nitrided layer stresses
Laser remelting 1 [106]

Surface roughness Low laser power, high scan speeds,

Marangoni [54,73,88]
and melt pool nitrogen dilution with argon
convection
inhomogeneity Laser remelting [60,106]
Covering thrice the melt pool width with N2 flow [54]
Oxygen High affinity of Controlled N2 atmosphere [56–58,60,61,73,75,107]
contamination of titanium to oxygen Specially designed gas flow devices,
nitrided layer above 600 ◦ C avoid turbulent flow
[66,72–76]

Nitriding in the presence of plasma 1 [104,108–110]

To be avoided (energy attenuation to substrate,
risk of lens breakage, insufficient contact between [54,72,73]
Cascade ionization titanium substrate and nitrogen gas flow)
Plasma formation
due to high laser
during nitriding To be encouraged (better energy coupling between
energy density
substrate and laser, higher diffusion rates of nitrogen
[74,97,102,103,105,108–110]
in melt pool, enhanced nitriding efficiency,
reduced surface oxidation 1 )
1 See Section 4 for more details.
 Coatings 2019, 9, 283 10 of 22
Coatings 2019, 9, x FOR PEER REVIEW 10 of 22

4.4.Laser-sustained
Laser-sustainedPlasma
Plasma(LSP)
(LSP)Nitriding
NitridingofofTitanium
Titanium

4.1.Background
4.1. Background
Therole
The roleplayed
playedby bynear-surface
near-surfaceplasma plasmaduring
duringCW CWCO CO2 2laser
lasernitriding
nitridingofofcommercially
commerciallypure pure
titanium (CP-Ti) was
titanium wasinvestigated
investigated in great detail
in great in thein
detail Center for Multi-scale
the Center Wave-Material
for Multi-scale Interaction
Wave-Material
(CMWMI) (CMWMI)
Interaction at the Pennsylvania State University
at the Pennsylvania State[100,106,108–112] in recent years,
University [100,106,108–112] inresulting in the
recent years,
development
resulting in theofdevelopment
the so-called “LSP
of thenitriding”
so-called process that was process
“LSP nitriding” capable of improving
that was capable the wear resistance
of improving
of CP-Ti
the in open and
wear resistance of uncontrolled
CP-Ti in openatmosphere with minimal
and uncontrolled surface
atmosphere oxidation.
with minimalUsing a combination
surface oxidation.
of charge-couple
Using a combination device (CCD) imaging
of charge-couple and optical
device (CCD) spectroscopy,
imaging and Nassar et al. [108] characterized
optical spectroscopy, Nassar et al.the
near-surface
[108] plasma
characterized theformed duringplasma
near-surface the laser nitriding
formed process
during as a function
the laser nitriding of scanning
process as aspeed and
function
ofoff-focal
scanning distance
speed and(OFD). They distance
off-focal found three main
(OFD). processing
They regimes
found three mainpertinent
processing to plasma
regimes formation:
pertinent
to plasma formation:
• At low scanning speeds and small OFD’s (i.e., conditions favoring higher power densities and
• At low scanning
longer speeds and
beam-substrate small OFD’s
interaction times),(i.e., conditions
a Ti-rich favoring
plasma formed higher
nearpower densities
the surface andand
did
longer beam-substrate
not allow the nitrogen interaction
gas flow times), a Ti-rich
to interact with plasma formedresulting
the substrate, near the surface
in surfaceandoxidation
did not
allow
(e.g., the nitrogen
Figure gasChen
4, left); flow et to al.
interact with the
[72] made substrate,
a similar resultingand
observation in surface
argued oxidation (e.g.,
against plasma
Figure 4, left);
formation Chen
since theyetbelieved
al. [72] made
that thea similar
Ti-rich observation
plasma baffled and argued
the contactagainst
between plasma formation
nitrogen and the
since they substrate.
titanium believed that the Ti-rich plasma baffled the contact between nitrogen and the titanium
• substrate.
At higher scan speeds and larger OFD’s, the near-surface plasma became richer in nitrogen
• At highersuch
species scan asspeeds
N and N and+ ; this
larger OFD’s,
ensured the near-surface
sufficient interactionplasma
between became
the gas richer in nitrogen
and the substrate
species such as N and N +; this ensured sufficient interaction between the gas and the substrate
and resulted in near-stoichiometric golden-colored titanium nitride layers on the substrate
and resulted
(e.g., Figure in near-stoichiometric
4, middle). This regimegolden-colored
can be thoughttitanium nitride
of as similar layers
to the one on the substrate
studied (e.g.,
by researchers
Figure 4, middle). This regime can be thought of as similar to the one
such as Thomann et al. [97] who concluded that plasma formation was necessary for efficient laser studied by researchers
such as Thomann
nitriding, et al. [97]
as mentioned who
earlier in concluded
Section 3.2.2.that plasma formation was necessary for efficient
• laser nitriding, as mentioned earlier
Finally, at high scan speeds and/or large OFD’s, in Section 3.2.2.
near-surface titanium plasma was not observed.
• Finally, at high scan speeds and/or large OFD’s, near-surface titanium plasma was not observed.

Regime 1 Regime 2 Regime 3

(8 mm OFD, 10 mm/s speed) (4 mm OFD, 90 mm/s speed) (8 mm OFD, 90 mm/s speed)

Figure4.4.(a)(a)
Figure Atomic
Atomic nitrogen
nitrogen species
species (CCD
(CCD image),
image), (b) (b) atomic
atomic titanium
titanium species
species (CCD(CCD image),
image), and and
(c)
(c) photograph
photograph of the
of the top top surface
surface of nitrided
of nitrided trail
trail shown
shown forfor Regime
Regime 1 (left),
1 (left), Regime2 2(middle),
Regime (middle),and
and
Regime3 3(right)
Regime (right) during
during LSPLSP nitriding.
nitriding. Reprinted
Reprinted withwith permission
permission fromfrom Ref. [108].
Ref. [108]. Copyright
Copyright 2012
2012 IOP
IOP Publishing.
Publishing.

Nassaretetal.al.
Nassar [108]
[108] thus
thus found
found a processing
a processing window
window of speeds
of scan scan speeds and (Regime
and OFD’s OFD’s (Regime
2) where2)
where a nitrogen-rich near-surface plasma struck during laser nitriding CP-Ti. Further,
a nitrogen-rich near-surface plasma struck during laser nitriding CP-Ti. Further, using X-ray using X-ray
photoelectronspectroscopy
photoelectron spectroscopy(XPS),
(XPS),Nassar
Nassaretetal.
al.[108]
[108]observed
observedthatthatnitriding
nitridingininthe
thepresence
presenceofof
nitrogen-rich plasma (Regime 2) in an open and uncontrolled atmosphere reduced
nitrogen-rich plasma (Regime 2) in an open and uncontrolled atmosphere reduced surface oxidationsurface oxidation
in the nitrided layers, which was attributed to the gettering action of the plasma whereby
in the nitrided layers, which was attributed to the gettering action of the plasma whereby the active the active
nitrogenspecies
nitrogen speciesreacted
reactedwith
withatmospheric
atmosphericoxygen.
oxygen.Additionally,
Additionally,microstructural
microstructuralcharacterization
characterizationofof
the nitrided layers revealed no evidence of energy attenuation of the laser beam in the presence of
Coatings 2019, 9, x FOR PEER REVIEW 11 of 22
Coatings 2019, 9, 283 11 of 22
plasma (Figure 5a,b); this was because the laser energy absorbed by the LSP was transferred to the
substrate via two mechanisms: (a) energetic nitrogen species in the plasma colliding with the
the nitrided layers revealed no evidence of energy attenuation of the laser beam in the presence of
substrate, and (b) low-wavelength ultraviolet re-radiation by the LSP that is absorbed more efficiently
plasma (Figure 5a,b);
Coatings 2019, this
9, x FOR was
PEER because the laser energy absorbed by the LSP was transferred
REVIEW of 22 to the
by the titanium substrate compared to the CO2 laser radiation (10.64 µm wavelength)11[108]. The
substrate via two mechanisms: (a) energetic nitrogen species in the plasma colliding with the substrate,
presence of nitrogen-rich plasma
plasma (Figure 5a,b);
was thus found
this was because the laserby
toenergy
be beneficial
absorbed
for the
theLSPlaser nitriding process.
and (b) low-wavelength ultraviolet re-radiation the LSP that by
is absorbed wasmore
transferred to the by the
efficiently
Furthermore, to reap the benefits of nitriding in the presence
substrate via two mechanisms: (a) energetic nitrogen species in the plasma colliding withof nitrogen-rich plasma beyond
the the
titanium substrate compared to the CO2 laser radiation (10.64 µm wavelength) [108]. The presence of
processing conditions
substrate, and (b) oflow-wavelength
Regime 2, Nassar et al.
ultraviolet [108] alsobyconducted
re-radiation the LSP that is nitriding
absorbed experiments
more efficientlyin the
nitrogen-rich plasma
titaniumwas thus found to be
to beneficial forradiation
the laser nitriding process. [108]. The
presence byof athepre-struck substrate compared
laser-sustained the CO
plasma 2 laser
(LSP) in coaxial (10.64 µm gas
nitrogen wavelength)
flow. Laser-sustained
Furthermore,
presence to reap the benefits
of nitrogen-rich of nitriding in
to the presenceforofthe nitrogen-rich plasma beyond the
plasma (LSP) is plasma that isplasma
generatedwas thus
andfound
sustained be beneficial
near the focal laser nitriding
plane of aprocess.
laser beam in a
gaseous atmosphere away from any potentially interacting surface. A freestanding nitrogen LSPinhad
processing conditions of Regime 2, Nassar et al. [108] also conducted nitriding experiments the
Furthermore, to reap the benefits of nitriding in the presence of nitrogen-rich plasma beyond the
processing conditions of Regime 2, Nassar et al. [108] also conducted
presence of a pre-struck laser-sustained plasma (LSP) in coaxial nitrogen gas flow. Laser-sustained nitriding experiments in the
a tear-drop shapeofwith
presence dimensions
a pre-struck of approximately
laser-sustained plasma (LSP) 15inmm in the
coaxial axialgas
nitrogen direction and 5 mm in the
flow. Laser-sustained
plasma (LSP)
radial direction is plasma
(Figure that
6b). Thisis generated
approach, and sustained near the focal plane of a laser beam thein a
plasma (LSP) is plasma that is generated henceforth
and sustainedreferred near the to asplane
focal LSP ofnitriding,
a laser beamallowed
in a
gaseous gaseous
atmosphere
investigators to access away
atmosphere
from scan
the high any any
away from
potentially
speed/large interacting
potentiallyOFD
surface.
processing
interacting
A freestanding
surface. conditions
A freestanding
nitrogen
of nitrogen
Regime LSP had4,a
3 (Figure
LSP had
tear-drop shape
a tear-drop
right) in the with
presence shapedimensions of approximately
with dimensionsplasma.
of nitrogen-rich of approximately 15
Nassar et mm in
15 al. the
mm[108] axial
in thethus direction
axialdeveloped and 5
direction andthe mm
5 mm in the
the radial
LSPinnitriding
direction
method that (Figure
radial
enabled 6b).
direction This approach,
(Figure
laser 6b). This
nitriding henceforth
approach,
of CP-Ti referred
henceforth
in open to as LSP nitriding,
referred to asatmosphere
and uncontrolled allowed the
LSP nitriding,inallowedinvestigators
the
the presence of
investigators to access the high scan speed/large OFD processing of conditions of3Regime 3 (Figure 4,
nitrogen-rich plasma over a broad processing window of scan speeds and OFD’s (Regimes 2 andin3 the
to access the high scan speed/large OFD processing conditions Regime (Figure 4, right) in
presence right) in the presenceplasma.
of nitrogen-rich of nitrogen-rich
Nassarplasma. Nassar
et al. [108] et al.
thus [108] thus developed
developed the LSP nitriding
the LSP nitriding method that
Figure 5c).
method that enabled laser nitriding of CP-Ti in open and uncontrolled atmosphere in the presence of
enabled laser nitriding of CP-Ti in open and uncontrolled atmosphere in the presence of nitrogen-rich
nitrogen-rich plasma over a broad processing window of scan speeds and OFD’s (Regimes 2 and 3 in
plasma over
Figurea 5c).
broad processing window of scan speeds and OFD’s (Regimes 2 and 3 in Figure 5c).

(Regime 2)
(Regime 2)

(Regime 3)
(Regime 3)

(Regime 1)
(Regime 1)

(c)(c)
Figure
Figure5.5.Optical
Figure 5. micrograph
Optical Optical
micrograph micrograph of transverse
ofoftransverse
transverse cross-sectionofof
cross-section
cross-section titanium
oftitanium
titanium nitrided (a)(a)
nitrided
nitrided using a LSP,
(a)using
using and
a aLSP, (b)
LSP, and(b)
and (b)
without a LSP (i.e., only the laser beam) at otherwise identical processing conditions; (c) processing
withoutaaLSP
without LSP(i.e.,
(i.e.,only
onlythe thelaser
laserbeam)
beam)atatotherwise
otherwiseidentical
identicalprocessing
processingconditions;
conditions;(c) (c)processing
processing
window of Nassar et al. [108] showing different regimes during LSP nitriding of pure titanium, where
windowof
window ofNassar
the
Nassar etetrepresent
triangles al.al.[108]
[108]processing
showingdifferent
showing different used
regimes
conditionsregimes
during
during
by Kamat
LSPnitriding
et LSP
nitriding
al. [109] ofofpure
to compare
pure titanium, where
lasertitanium,
nitriding inwhere
thetriangles
the triangles represent
represent
the presence and processing
processing conditions
absence of conditions
the used
nitrogen used
LSP. by
Thebyscale
Kamat
Kamat barsetet al.
inal. [109]
(a)[109] totocompare
and (b) compare
read laser
laser
200 µm. nitridinginin
nitriding
Reprinted
thepresence
the presence
withandandabsence
absence
permission fromofof the
the
Ref. nitrogen
nitrogen
[108]. LSP.
LSP.
Copyright The
The
2012 scale
scale
IOP barsinin(a)
bars
Publishing. (a,b)
andread 200 µm.
(b) read Reprinted
200 µm. with
Reprinted
permission
with fromfrom
permission Ref. Ref.
[108]. Copyright
[108]. Copyright 20122012
IOP IOP
Publishing.
Publishing.

(a) (b) (c)

Figure 6. (a) Schematic of Nassar et al.’s [108] LSP nitriding process with the substrate perpendicular
to the laser beam, (b) CCD image of freestanding nitrogen LSP, and (c) schematic of Black et al.’s [111]
LSP nitriding process (a)
with the substrate parallel(b) (c) 6a,b reprinted with
to the laser beam. Figure
permission from Ref. [108]. Copyright 2012 IOP Publishing. Figure 6c reprinted with permission from
Figure
Figure6.6.(a)
(a)Schematic
SchematicofofNassar
Nassaretetal.’s
al.’s [108]
[108] LSP
LSP nitriding process with
nitriding process withthethesubstrate
substrateperpendicular
perpendicularto
Ref. [111]. Copyright 2017 Elsevier.
tothe
thelaser
laserbeam,
beam,(b)
(b)CCD
CCD image
image ofof freestanding
freestanding nitrogen
nitrogen LSP,
LSP, andand
(c) (c) schematic
schematic of Black
of Black et al.’s
et al.’s [111]
[111] LSP
LSP nitriding
nitriding process
process with with the substrate
the substrate parallelparallel to the
to the laser laserFigure
beam. beam.6a,bFigure 6a,b with
reprinted reprinted with
permission
permission from Ref.
from Ref. [108]. [108]. Copyright
Copyright 2012 IOP Publishing.
2012 IOP Publishing. Figure 6c Figure 6c reprinted
reprinted with permission
with permission from Ref.from[111].
Ref. [111]. Copyright
Copyright 2017 Elsevier.
2017 Elsevier.
Coatings 2019, 9, 283 12 of 22

4.2. Effect of Nitrogen

Coatings LSP
2019, 9, x FOR onREVIEW
PEER Heat and Mass Transfer During Nitriding 12 of 22

Black et al. [111] studied the interaction between a nitrogen LSP and a CP-Ti substrate by orienting
4.2. Effect of Nitrogen LSP on Heat and Mass Transfer During Nitriding
the CP-Ti substrate parallel to the axis of the CO2 laser beam (Figure 6c); these experiments differed
Black et al. [111] studied the interaction between a nitrogen LSP and a CP-Ti substrate by
from Nassar et al.’s [108] research (Figure 6a) where the substrate was normal to the laser beam.
orienting the CP-Ti substrate parallel to the axis of the CO2 laser beam (Figure 6c); these experiments
In Black et al.’s [111] configuration, the nitrogen LSP (Figure 6b) was the sole heating source since the
differed from Nassar et al.’s [108] research (Figure 6a) where the substrate was normal to the laser
laser beam
beam.did not irradiate
In Black the substrate,
et al.’s [111] thus
configuration, allowing
the nitrogenthem to isolate
LSP (Figure 6b) and
was study
the solethe interaction
heating source of the
nitrogen LSP
since thewith
laserthe CP-Ti
beam didsubstrate. When
not irradiate the axis ofthus
the substrate, theallowing
parallel them
nitrogen LSP was
to isolate and brought
study thewithin
2–2.5 mm of the of
interaction CP-Ti substrate
the nitrogen LSPand maintained
with there forWhen
the CP-Ti substrate. 5 s, the
the substrate
axis of the melted
parallel and incorporated
nitrogen LSP
wasfrom
nitrogen broughtthewithin
plasma,2–2.5 mm of thein
resulting CP-Ti substrate and
the synthesis of maintained
TiN layersthere
up tofor300
5 s, the
µmsubstrate meltedon the
in thickness
andwith
substrate incorporated nitrogengradation
compositional from the plasma, resulting
of nitride in the synthesis
concentration (Figureof 7a)
TiN and
layers up to 300
faceted µm in
crystal growth
thickness on the substrate with compositional gradation of nitride concentration (Figure 7a) and
on the surface (Figure 7b). Such rapid growth of TiN crystals on the CP-Ti substrate without any direct
faceted crystal growth on the surface (Figure 7b). Such rapid growth of TiN crystals on the CP-Ti
radiation from the CO2 laser beam demonstrated the utility of the nitrogen LSP as a high-energy source
substrate without any direct radiation from the CO2 laser beam demonstrated the utility of the
of active nitrogen
nitrogen LSP species.
as a high-energy source of active nitrogen species.

(a) (b)

FigureFigure
7. SEM7. SEM images
images of the
of the titaniumsubstrate
titanium substrate nitrided
nitridedininthe
theparallel configuration
parallel (Figure
configuration 6c)
(Figure 6c)
showing: (a) longitudinal cross-section having four distinct layers of the nitrided titanium substrate,
showing: (a) longitudinal cross-section having four distinct layers of the nitrided titanium substrate,
and (b) faceted crystal growth at the nitrided surface. Reprinted with permission from Ref. [111].
and (b) faceted crystal growth at the nitrided surface. Reprinted with permission from Ref. [111].
Copyright 2017 Elsevier.
Copyright 2017 Elsevier.
To study the effects of the nitrogen LSP on heat transfer to the substrate, the temperature of the
To study the effects of the nitrogen LSP on heat transfer to the substrate, the temperature of the
CP-Ti substrate (3.175 mm thick) was measured in both Nassar et al.’s perpendicular (Figure 6a) [109]
CP-Ti substrate
and Black et (3.175 mm thick)
al.’s parallel was
(Figure 6c)measured in both Nassar
[113] configurations et al.’sthermocouples
using K-type perpendicular (Figure
welded 6a) [109]
to the
and Black et al.’s parallel (Figure 6c) [113] configurations using K-type thermocouples
back of the substrate. In the perpendicular configuration, Kamat et al. [109] conducted nitriding welded to
the back of the substrate.
experiments In theand
in the presence perpendicular configuration,
absence of a nitrogen LSP (i.e., Kamat et al. and
LSP nitriding [109] conductedlaser
conventional nitriding
experiments
nitriding,inrespectively)
the presence andand absence
found that atof a nitrogen
similar LSP conditions
processing (i.e., LSP nitriding
(8 mm OFDand andconventional
90 mm/s scan laser
speed),
nitriding, the peak temperatures
respectively) and found measured by a thermocouple
that at similar located directly
processing conditions (8 mm beneath
OFD the
andlaser trail scan
90 mm/s
(on the backside of the CP-Ti coupon) were similar in both cases; moreover,
speed), the peak temperatures measured by a thermocouple located directly beneath the laser trail the peak temperature
recorded by a thermocouple located 13 mm away from the laser trail (again, on the back face of the
(on the backside of the CP-Ti coupon) were similar in both cases; moreover, the peak temperature
substrate) was higher in the presence of the LSP. These observations suggested that the nitrogen LSP
recorded by a thermocouple located 13 mm away from the laser trail (again, on the back face of the
broadened the energy distribution incident upon the substrate without attenuating energy incident
substrate)
uponwasit. Inhigher in the
the parallel presence of[113],
configuration the LSP. These observations
two thermocouples suggested
were attached that
to the backthe nitrogen
face of the LSP
broadened the energy distribution incident upon the substrate without attenuating
substrate (3.175 mm thick) so that the first (TC1) was directly horizontal with respect to the laser focalenergy incident
upon it. In the
point while parallel
the secondconfiguration
(TC2) was 10 [113], two thermocouples
mm below the first one; thewere attached
nitrogen LSP was to maintained
the back face at a of the
distance
substrate (3.175 d from the substrate
mm thick) so thatfor
the5 first
s, where
(TC1) d was
wasvaried from
directly 5 to 15 mm
horizontal (Figure
with 8a).to
respect Asthe
seen in focal
laser
Figure 8b, the thermocouple TC1 located at the back of the substrate recorded
point while the second (TC2) was 10 mm below the first one; the nitrogen LSP was maintained at a a temperature rise of
close to 500 °C after five seconds; treating the nitrogen LSP as a radiating sphere, using appropriate
distance d from the substrate for 5 s, where d was varied from 5 to 15 mm (Figure 8a). As seen in
radiation view factors for the sphere-rectangle geometry, and using the lumped heat capacitance
Figure 8b, the thermocouple TC1 located at the back of the substrate recorded a temperature rise of
assumption for the titanium substrate for d ≥ 9 mm (i.e., when the substrate could be assumed to be
close to ◦ C after five seconds; treating the nitrogen LSP as a radiating sphere, using appropriate
at 500
a uniform temperature as seen in Figure 8b), Kamat [113] modeled the transient heat transfer
radiation view factors for the sphere-rectangle geometry, and using the lumped heat capacitance
assumption for the titanium substrate for d ≥ 9 mm (i.e., when the substrate could be assumed to
be at a uniform temperature as seen in Figure 8b), Kamat [113] modeled the transient heat transfer
Coatings 2019, 9, 283 13 of 22
Coatings 2019, 9, x FOR PEER REVIEW 13 of 22

between
between
Coatings the9,LSP
the2019,
LSP and
x FORand
the the substrate
substrate
PEER REVIEW andand estimated
estimated that
that thethe nitrogen
nitrogen LSP
LSP waswas equivalenttotoa a13
equivalent heat
heat source
of 22
source of 998 Watts within an error bar of ±10% for a laser power of 3.5
of 998 Watts within an error bar of ±10% for a laser power of 3.5 kW. Since calorimetric measurements kW. Since calorimetric
measurements
between showed
the nitrogen
LSP thatsubstrate
and LSP
the the nitrogen LSP absorbed about
the 38% (1.33 kW) of theequivalent
3.5 kW laser topower
showed that the absorbedand estimated
about 38% (1.33that kW) nitrogen
of the 3.5LSP kWwas laser a heat it, it
power sustaining
sustaining it, it was concluded that the LSP re-radiated close to 75% of the
source of 998 Watts within an error bar of ±10% for a laser power of 3.5 kW. Since calorimetricpower it absorbed from
was concluded that the LSP re-radiated close to 75% of the power it absorbed from the laser, with the
the laser, with the remaining 25% power used for heating the nitrogen gas exiting
measurements showed that the nitrogen LSP absorbed about 38% (1.33 kW) of the 3.5 kW laser power the LSP. Further,
remaining
the 25% power
presence usedalso
forfound
heating the nitrogen gas exiting the LSP. Further,
and toitthe presence of LSP
sustaining it,ofitLSP
waswas
concluded thatto increase
the the width
LSP re-radiated of thetonitrided
close 75% of trails
the power reduce surface
absorbed from
was oxidation
also found
the laser, to increase
[109].
with the width
the remaining of theused
25% power nitrided trails and
for heating to reduce
the nitrogen gassurface
exiting oxidation [109].
the LSP. Further,
the presence of LSP was also found to increase the width of the nitrided trails and to reduce surface
oxidation [109].

(b)
(a)
Figure
Figure 8. (a)
8. (a) Schematicofoftemperature
Schematic temperature measurement
measurement ininparallel configuration
parallel with
configuration location
(b) with of theof the
location
thermocouples; (a)
thermocouples; (b)(b) temperature
temperature rise, ΔT
rise, ∆T(°C), recorded
(◦ C), by two
recorded thermocouples
by two TC1 andTC
thermocouples TC2and
1
at theTC
endat the
2
of 5 s. 8. (a) Schematic of temperature measurement in parallel configuration with location of the
Figure
end of 5 s.
thermocouples; (b) temperature rise, ΔT (°C), recorded by two thermocouples TC1 and TC2 at the end
To
of 5quantify
To quantify s. the effect the effect
of the of LSP
the onLSPnitrogen
on nitrogenintake intake intomelt
into the the melt
pool,pool,Kamat Kamat
et al.et[109]
al. [109]
measured
measured the weight increase of the titanium coupons after nitriding
the weight increase of the titanium coupons after nitriding in the presence and absence of a nitrogen in the presence and absence of
a nitrogen LSP,
To quantify i.e., during
the effect LSP and
of the LSP conventional
on nitrogen laser nitriding, respectively; the processing
LSP, i.e., during LSP and conventional laser nitriding,intake into the melt
respectively; pool, Kamatconditions
the processing et al. [109](laser
conditions
measured (laserthe weightpower, scan speed,
increase of theOFD)
titanium were maintained
coupons after the same to
nitriding in ensure a fair comparison.
the presence and absence It of
power,
was
scan speed,the
found that
OFD) were maintained
nitrogen
the same to ensure a fair comparison. It was found that
a nitrogen LSP, i.e., duringuptakeLSP and was conventional
consistently higher in the caserespectively;
laser nitriding, of LSP nitriding for all the
the processing
the nitrogen
tested uptake was
conditions; consistently examination
a microstructural higher in the ofcase
the top of LSP
surfacenitriding
of to for all the
theensure
nitrided tested
layers conditions;
indicated
conditions (laser power, scan speed, OFD) were maintained the same a fair comparison. It
a microstructural
that
wasLSPfound thatexamination
nitriding the produced of
nitrogenauptake the porous
more top
wassurfacesurfaceofconsisting
consistently the nitrided
higher ofthe
in layers
case ofindicated
“expulsion sites”
LSP that that
nitriding wereLSP
for allnitriding
absent
the
produced
in
tested aconditions;
more porous
conventional laser surface consisting
nitriding
a microstructural (Figure 9). of
The
examination “expulsion
pore formation
of the sites”
top thatattributed
was
surface were
of absent inlayers
conventional
to oversaturation
the nitrided indicatedof laser
nitriding
molten (Figure
that LSP titanium 9). The
nitriding with pore formation
energetic
produced nitrogen
a more porous wassurface
attributed
species from to oversaturation
the
consisting plasma, wherein
of “expulsion sites” of molten
the excess
that were titanium
absent with
nitrogen
recombined
energetic nitrogen
in conventional andspecies
bubbled out of
from
laser nitriding the
the melt 9).
plasma,
(Figure pool surface,
wherein
The porethe resulting
excessin
formation volcano-like
nitrogen
was porous
recombined
attributed defects at the
and bubbled
to oversaturation of out
top
of the surface
molten
melt pool (white
titaniumsurface, arrows
with in Figure
energetic
resulting in 9b,d). In
nitrogen a subsequent
species
volcano-like from the
porous publication,
plasma,
defects Kamat
wherein
at the et
theal.excess
top surface [110] reported
(whitenitrogen
arrows in
that reducingand
Figurerecombined
9b,d). In a the concentration
bubbled
subsequent out of nitrogen
of the
publication,melt pool
Kamatabove theresulting
surface,
et al. melt pool,
[110] either by reducing
in volcano-like
reported porous the
that reducing the incident
defects at the
concentration
energy
top density
surface (e.g.,
(white by increasing
arrows in Figure the scan
9b,d). In speed)
a or by diluting
subsequent publication,the nitrogen
Kamat et flow
al. withreported
[110] argon,
of nitrogen above the melt pool, either by reducing the incident energy density (e.g., by increasing the
eliminated
that reducing the formation
the concentrationof pores of onnitrogen
the top surface.
above the While meltthepool,
dilution
eitherof bynitrogen
reducing withthe argon was
incident
scanfound
speed) or by dilutingtothe nitrogen flow with argon, eliminated the surface,
formation of pores on the top
energytodensity
be necessary eliminate pore
(e.g., by increasing and crack
the scan speed)formation
or by dilutingat the top
the nitrogen itflow
led towitha drastic
argon,
surface. While the
reduction dilution of nitrogen with argon wasoffound to be necessary to eliminate pore and
eliminatedinthe nitrogen
formation uptake (e.g., on
of pores an 11thevol.% dilution
top surface. While nitrogen in the
the dilution ofLSP reduced
nitrogen withtheargon
nitrogen
was
crackintake
formation
foundintoto be at the
thenecessary top surface,
melt pooltobyeliminate it
70%) dueporeled to a
to reduceddrastic
and crack reduction
Marangoni
formation in
convection nitrogen
at the top uptake
in surface,
the meltitpool (e.g.,
led [110]. an 11 vol.%
to a drastic
dilution of nitrogen
reduction in theuptake
in nitrogen LSP reduced
(e.g., an the nitrogen
11 vol.% intake
dilution into thein
of nitrogen melt
the pool by 70%)the
LSP reduced due to reduced
nitrogen
Marangoni
intake into Laser
convection
the melt Nitriding
in the
pool (no LSP)
bymelt
70%) pool
due to [110].
reduced Marangoni convection LSP Nitriding
in the melt pool [110].
(a) (b)
Laser Nitriding (no LSP) LSP Nitriding
(a) (b)

Figure 9. Cont.
Coatings 2019, 9, 283 14 of 22
Coatings 2019, 9, x FOR PEER REVIEW 14 of 22

(c) (d)

FigureFigure 9. Comparison
9. Comparison ofofLSP
LSPand
and conventional
conventional laser nitriding
laser processed
nitriding underunder
processed similarsimilar
conditions: (a)
conditions:
and (c) scanning electron (SE) micrograph and optical profile of top surface of laser-nitrided trail,
(a) and (c) scanning electron (SE) micrograph and optical profile of top surface of laser-nitrided trail,
respectively; (b,d) SE micrograph and optical profile of top surface of LSP-nitrided trail, respectively.
respectively; (b,d) SE micrograph and optical profile of top surface of LSP-nitrided trail, respectively.
The pores formed due to nitrogen expulsion from the melt pool in (b,d) are indicated by white arrows.
The pores formed due to nitrogen expulsion from the melt pool in (b,d) are indicated by white arrows.
Reprinted with permission from Ref. [109]. Copyright 2016 John Wiley and Sons.
Reprinted with permission from Ref. [109]. Copyright 2016 John Wiley and Sons.
4.3. Two-step “LSP Nitriding-Remelting” Process
4.3. Two-Step “LSP Nitriding-Remelting” Process
The nitrogen flow dilution approach described above reduced surface cracking and porosity at
The nitrogen
the cost flowthe
of limiting dilution approach
nitrogen described
concentration in theabove reduced
melt pool, surface
resulting cracking and porosity
in microstructures consistingat the
cost of
oflimiting
a thin (~5the µm) nitrogen
TiN layer concentration
at the top, with in athe melt pool, martensitic
dendrite-free, resulting intitanium
microstructures
region deeperconsisting
in the of a
thin (~5
meltµm)pool.TiN layer
Since theatthin
the TiN
top, layer
with is a dendrite-free,
expected to be martensitic
removed during titanium region deeper
a post-processing in the melt
finishing
pool. operation,
Since the thisthinmicrostructure
TiN layer is expected to be removed
could not sufficiently during
improve a post-processing
the hardness of titaniumfinishing operation,
and performed
poorly in preliminary wear tests. To overcome this reduced control
this microstructure could not sufficiently improve the hardness of titanium and performed over the microstructure of the
poorly
nitrided surface
in preliminary wearlayers,
tests. Kamat et al. [106]
To overcome developed
this reducedacontrol
two-stepoverdeep-case hardening process
the microstructure (Figure
of the nitrided
10a):
surface in theKamat
layers, first step, a nitrided
et al. layer was deposited
[106] developed a two-step on deep-case
a titanium substrate
hardening in process
the presence of a 10a):
(Figure
prestruck, pure-nitrogen LSP, with the laser beam oriented normal to the substrate surface, while in
in the first step, a nitrided layer was deposited on a titanium substrate in the presence of a prestruck,
the second step, the nitrided layer from the first step was remelted under a prestruck pure-argon LSP
pure-nitrogen LSP, with the laser beam oriented normal to the substrate surface, while in the second
at speeds low enough to partially or fully melt the dendrites. The remelting step recirculated the
step, the nitrided
nitrogen in thelayermeltfrom theforming
pool, first step was remelted
a crack-free under a prestruck
and homogenous pure-argon
nitrided layer (FigureLSP 10c)
at speeds
with low
enough to partially or fully melt the dendrites. The remelting step recirculated
lower surface roughness (Figure 10e,g); however, this came at the cost of reduced average case the nitrogen in the melt
pool, hardness
forming of a crack-free
the nitridedand homogenous
layer, nitrided
since the remelting steplayer (Figure
diluted 10c) with
the nitrided layerlower surface roughness
by introducing fresh
titanium
(Figure 10e,g);from the substrate
however, into the
this came at nitrogen-rich melt pool.
the cost of reduced Moreover,
average casethehardness
two-step approach offeredlayer,
of the nitrided
sincemore control over
the remelting the diluted
step microstructure, since the
the nitrided TiNby
layer phase fraction (and
introducing hence
fresh averagefrom
titanium case hardness)
the substrate
and case depth could be varied by varying the LSP nitriding
into the nitrogen-rich melt pool. Moreover, the two-step approach offered more controland/or remelting scan speeds, resulting
over the
in microstructures ranging from a two-phase mixture of TiN dendrites embedded in a martensitic α’-
microstructure, since the TiN phase fraction (and hence average case hardness) and case depth could be
Ti matrix to a solid solution of nitrogen in α’-Ti as identified through a combination of energy
varied by varying the LSP nitriding and/or remelting scan speeds, resulting in microstructures ranging
dispersive spectroscopy (EDS) and X-ray diffraction (XRD). Optimal processing conditions were
from identified
a two-phase mixture of TiN dendrites embedded in a martensitic α’-Ti matrix to a solid solution
that formed homogeneous and crack-free nitrided layers of case depths up to 800 µm and
of nitrogen in α’-Ti
average case hardness as identified
up to 560through a combination
HV, showing of energy
a 250% hardness dispersive
increase compared spectroscopy (EDS) and
to the untreated
X-rayCP-Ti
diffraction
substrate (XRD). Optimal
(hardness ~160 processing conditions
HV). The two-step LSP were identified that
nitriding-remelting formed
process homogeneous
developed by
and crack-free
Kamat et al.nitrided
[106] thus layers of casean
represented depths up to 800
improvement overµm and average
conventional lasercase hardness
nitriding up todue
processes 560 HV,
to itsa ability
showing to form deep,
250% hardness crack-free,
increase compared homogenous, nitrided cases
to the untreated CP-Tiofsubstrate
any desired thickness
(hardness ~160on HV).
titanium substrates; moreover, due to the oxygen-gettering effect of the
The two-step LSP nitriding-remelting process developed by Kamat et al. [106] thus represented an LSP [108], the process did not
require a controlled
improvement nitrogen atmosphere,
over conventional thus overcoming
laser nitriding processes due the issues
to its listed
ability in to
Tableform1. deep, crack-free,
homogenous, nitrided cases of any desired thickness on titanium substrates; moreover, due to the
oxygen-gettering effect of the LSP [108], the process did not require a controlled nitrogen atmosphere,
thus overcoming the issues listed in Table 1.
Coatings 2019, 9, 283 15 of 22
Coatings 2019, 9, x FOR PEER REVIEW 15 of 22

(a)
Schematic

(b) (c)
Optical

200 µm 200 µm

(d) (e)
SEM (Top Surface)

(f) (g)
Surface Profile

Figure
Figure 10.
10. (a)(a)
Process
Processschematic
schematicof two-step LSP LSP
of two-step nitriding and remelting
nitriding process;
and remelting transverse
process; cross-
transverse
sectional microstructure (b) before remelting and (c) after remelting; surface microstructure
cross-sectional microstructure (b) before remelting and (c) after remelting; surface microstructure (d) (d) before
remelting and (e) after
before remelting remelting;
and (e) surface roughness
after remelting; across theacross
surface roughness widththe
of the trailof(f)the
width before
trail remelting
(f) before
and (g) after
remelting andremelting. White arrows
(g) after remelting. Whiteinarrows
(d) point topoint
in (d) surface cracks.cracks.
to surface Reprinted with permission
Reprinted from
with permission
Ref.
from[106]. Copyright
Ref. [106]. 2017 Elsevier.
Copyright 2017 Elsevier.

In a subsequent study, Kamat et al. [112] used the two-step processing approach to deposit
multiple overlapping trails to perform case hardening of CP-Ti over wider areas. Processing was
conducted at different nitriding speeds and the same remelting speed, resulting in nitrided layers of
different TiN dendrite volume fractions (Figure 11, where NX refers to a sample nitrided at a speed
Coatings 2019, 9, 283 16 of 22

In a subsequent study, Kamat et al. [112] used the two-step processing approach to deposit
multiple overlapping trails to perform case hardening of CP-Ti over wider areas. Processing was
conducted 9,
Coatings at different nitriding speeds and the same remelting speed, resulting in nitrided layers of
Coatings 2019,
2019, 9, xx FOR
FOR PEER
PEER REVIEW
REVIEW 16
16 of
of 22
22
different TiN dendrite volume fractions (Figure 11, where NX refers to a sample nitrided at a speed of
X mm/s)
of
of X
X mm/s)
mm/s) and,and,
and,subsequently, different
subsequently,
subsequently, case case
different
different hardness
case values;
hardness
hardness the measured
values;
values; the near-surface
the measured
measured hardness
near-surface
near-surface values
hardness
hardness
of samples
values
values of N45, N60,
of samples
samples N45,and
N45, N60,
N60,N75
andshown
and N75 in Figure
N75 shown
shown in 11 were
in Figure
Figure 11870,
11 were621,
were 870,and
870, 547
621,
621, HV,
and
and 547respectively.
547 HV, While
HV, respectively.
respectively.
While the N45 sample showed evidence of surface cracking in SE micrographs, samples N60 and were
the
WhileN45thesample
N45 showed
sample evidence
showed of surface
evidence of cracking
surface in SE
cracking micrographs,
in SE samples
micrographs, N60
samples and
N60 N75
and N75
N75
foundfound
were
were to be to
found crack-free.
to be
be crack-free.
crack-free.

300
300 µm
µm

(a)
(a) (b)
(b) (c)
(c)
Figure
Figure 11.
Figure 11. Optical
11. Opticalmicrographs
Optical micrographsof
micrographs oftransverse
of transversecross-section:
transverse cross-section:(a)
cross-section: (a)N45
(a) N45(870
N45 (870HV,
(870 HV,surface
HV, surfacecracks),
surface cracks),(b)
cracks), (b)N60
(b) N60
N60
(621
(621 HV,
(621 HV, no
HV, no surface
surface cracks),
cracks), and
and (c)
(c) N75
(c) N75 (547
N75 (547 HV,
(547 HV, no
HV, no surface
surface cracks).
cracks). Reprinted
Reprintedwith
Reprinted withpermission
with permissionfrom
permission from
from
Ref.
Ref.[112].
Ref. [112]. Copyright
[112]. Copyright2017
Copyright 2017Elsevier.
2017 Elsevier.
Elsevier.

Theprocessed
The
The processed samples
processed samples were
samples were then
were thensubjected
then subjectedto
subjected toreciprocating
to reciprocating ball-on-flat
reciprocating ball-on-flat wear
ball-on-flat wear tests
wear testswith
tests withalumina
with alumina
alumina
balls
balls used
balls used
used as as the
as the counterbody.
the counterbody.
counterbody. Similar Similar
Similar to to
to thethe single
the single trail
single trail experiments
trail experiments
experiments [106], [106],
[106], thethe remelting
the remelting
remelting step step
step waswas
was
found to
found
found toeliminate
to eliminateboth
eliminate boththe
both thesurface
the surfacemicrocracks
surface microcracksand
microcracks andhot
and hottearing
hot tearingmacrocracks
tearing macrocrackspenetrating
macrocracks penetratingthrough
penetrating throughthe
through the
the
depth
depth
depth of of the
of the nitrided
the nitrided layer
nitrided layer that
layer that formed
that formed during
formed during multi-trail
during multi-trail LSP nitriding.
multi-trail LSP Figure
LSP nitriding. 12
nitriding. Figure provides
Figure 12 a summary
12 provides
provides aa
of the
summary wear test results; the treated samples showed enhanced
summary of the wear test results; the treated samples showed enhanced tribological properties
of the wear test results; the treated samples showed tribological
enhanced properties
tribological compared
properties to
the untreated
compared to CP-Ti
the sample
untreated by
CP-Ti resisting:
sample (a)
by oxidative
resisting: wear
(a) of titanium
oxidative
compared to the untreated CP-Ti sample by resisting: (a) oxidative wear of titanium and hence the wear and
of hence
titanium the formation
and hence and
the
material transfer
formation
formation and of TiO debris
and material
material transfer
transfer to the
of
of TiOalumina
TiO debris
debris ball,
to and
to the (b) plasticball,
the alumina
alumina deformation
ball, and
and (b) from three-body
(b) plastic
plastic deformation
deformation abrasive
from
from
wear by
three-body the TiO debris because of their increased surface hardness,
three-body abrasive wear by the TiO debris because of their increased surface hardness, resulting in
abrasive wear by the TiO debris because of their increased resulting
surface in a
hardness,wear scar volume
resulting in
aareduction
wear scarinvolume
wear scar the range
volume of 70%–80%
reduction
reduction in the(Figure
in the range
range of 12a)
of on par with
70%–80%
70%–80% (Figure
(Figurea tool
12a)steel
12a) on
on parsample
par withtested
with toolunder
aa tool steel similar
steel sample
sample
conditions.
tested
tested under
under Moreover,
similar itconditions.
similar was found Moreover,
conditions. that the more
Moreover, it homogeneous
it was
was found
found that the microstructure
that the
the more
more homogeneous (N75), the lower
homogeneous the
the
the friction
microstructure coefficient
(N75), recorded
the lower during
the the
friction wear test
coefficient (Figure
recorded 12b);
during the
microstructure (N75), the lower the friction coefficient recorded during the wear test (Figure 12b); the higher
the wear coefficients
test (Figure of friction
12b); the
recorded
higher
higher for the N60
coefficients
coefficients of and N45
of friction
friction cases were
recorded
recorded for
for the attributed
the N60
N60 andandto N45hard
N45 TiNwere
cases
cases regions
were that did
attributed
attributed to not
to harddissolve
hard TiN
TiN regionsafter
regions
the remelting
that
that did
did not step and
not dissolve
dissolve after
aftercaused
the uneven wear
the remelting
remelting step
step and as evident
and causedfrom
caused uneven
uneven their
wear
wearrespective
as
as evident
evidenttransverse
from
from their wear
their profiles
respective
respective
(Figure
transverse 12d).
wear Crack-free
profiles nitrided
(Figure layers,
12d). with
Crack-free depths up
nitrided to 600
layers, µm,with
transverse wear profiles (Figure 12d). Crack-free nitrided layers, with depths up to 600 µm, average average
depths case
up hardness
to 600 µm, values
average up
to
case 641 ± 86
case hardness HV,
hardness values and
values upa wear
up to resistance
to 641
641 ±± 8686 HV, improvement
HV, andand aa wear of 70%–80%
wear resistance over
resistance improvement that
improvement of of the
of 70%–80% untreated
70%–80% over titanium
over that
that of
of
substrate,
the untreated were thus
titanium obtained
substrate, usingwere the LSP
thus nitriding-remelting
obtained using the
the untreated titanium substrate, were thus obtained using the LSP nitriding-remelting process. process.
LSP nitriding-remelting process.

(a)
(a) (b)
(b)

Figure 12. Cont.

Coatings 2019, 9, 283 17 of 22
Coatings 2019, 9, x FOR PEER REVIEW 17 of 22

(c) (d)

Unmelted TiN
Reciprocating direction Reciprocating direction normal to plane

Figure
Figure 12.
12.Effect
Effectofof
two-step
two-step nitriding-remelting
nitriding-remelting on on
wear resistance
wear of CP-Ti:
resistance (a) measured
of CP-Ti: wearwear
(a) measured scar
volumes; (b) variation
scar volumes; of coefficient
(b) variation of friction
of coefficient over over
of friction the test
the duration; wearwear
test duration; scar scar
profiles in the
profiles (c)
in the
longitudinal and and
(c) longitudinal (d) transverse directions.
(d) transverse The symbol
directions. NX inNX
The symbol thein
figures denotes
the figures “nitrided
denotes at X mm/s
“nitrided at X
speed” i.e., higher
mm/s speed” the number
i.e., higher X, lower
the number the nitrogen
X, lower content
the nitrogen andand
content hardness
hardnessof of
the
thenitrided
nitridedlayer.
layer.
Reprinted
Reprinted with
with permission
permission from
from Ref.
Ref. [112].
[112]. Copyright
Copyright2017
2017 Elsevier.
Elsevier.

5. Summary
5. Summaryand
andFuture
FutureDirections
Directions
In this
In this paper,
paper, aa critical
critical literature
literature review
review of of the
the laser
laser nitriding
nitriding of of titanium
titanium was was presented,
presented, with with aa
special emphasis on the role of near-surface plasma. Surface
special emphasis on the role of near-surface plasma. Surface cracking, oxygen contamination ofcracking, oxygen contamination of the
the
nitrided layer,
nitrided layer,surface
surfaceroughness,
roughness, andand meltmelt
pool pool
inhomogeneity
inhomogeneity were identified as the main
were identified as challenges
the main
in the three decades of research performed on the laser nitriding
challenges in the three decades of research performed on the laser nitriding of titanium. Moreover, of titanium. Moreover, the role of
plasma
the role was found was
of plasma to befound
a source of aconfusion
to be source ofamongconfusion researchers, with some viewing
among researchers, with some it asviewing
beneficial it for
as
enhancing nitrogen intake in the melt pool, while others taking precautions
beneficial for enhancing nitrogen intake in the melt pool, while others taking precautions to avoid it to avoid it to prevent energy
attenuation
to prevent energy to the attenuation
substrate due totothelaser energydue
substrate absorption
to laser by energythe plasma.
absorption Recent research
by the plasma.conducted
Recent
at the Pennsylvania State University studied the role played
research conducted at the Pennsylvania State University studied the role played by near-surface by near-surface plasma in detail, and
revealedinthat
plasma conducting
detail, laser nitriding
and revealed in the presence
that conducting laser of a pre-struck,
nitriding in the nitrogen-rich,
presence oflaser-sustained
a pre-struck,
plasma (LSP) in open and uncontrolled atmosphere
nitrogen-rich, laser-sustained plasma (LSP) in open and uncontrolled atmosphere increased nitrogen intake increased
into the melt pool,
nitrogen
minimized
intake into surface
the meltoxidation, and broadened
pool, minimized the incident
surface oxidation, energy anddistribution
broadenedprofile without causing
the incident energy
any energy attenuation. Furthermore, the pre-struck nitrogen
distribution profile without causing any energy attenuation. Furthermore, the pre-struck nitrogenLSP was found to be a potent source
of thermal energy and active nitrogen species, capable of forming
LSP was found to be a potent source of thermal energy and active nitrogen species, capable of forming thick TiN-rich layers on titanium
substrates
thick TiN-rich oriented
layersparallel to the laser
on titanium beam axis
substrates i.e., without
oriented parallelany direct
to the laserlaser irradiation.
beam axis i.e.,The attractive
without any
properties of the LSP were further used to develop a novel two-step
direct laser irradiation. The attractive properties of the LSP were further used to develop a novel two- “LSP nitriding-remelting” case
hardening
step technique which afforded
“LSP nitriding-remelting” greater control
case hardening technique overwhichthe microstructure
afforded greater of the nitrided
control overlayer
the
microstructure of the nitrided layer than conventional laser nitriding without the need to processthe
than conventional laser nitriding without the need to process in controlled nitrogen atmospheres; in
developed nitrogen
controlled process was able to formthe
atmospheres; wide-area,
developed crack-free,
processhomogeneous
was able to nitrided layers (upcrack-free,
form wide-area, to 600 µm
thick and 641 HV
homogeneous hardness)
nitrided layersthat(up
improved
to 600the µm reciprocating
thick and wear 641 HV resistance of CP-titanium
hardness) that improved substrates
the
by 70%–80%, thus representing a significant improvement over conventional
reciprocating wear resistance of CP-titanium substrates by 70%–80%, thus representing a significant laser nitriding processes.
Future research
improvement directions can
over conventional laserfocus on a fundamental
nitriding processes. characterization of the nitrogen LSP using
a combination
Future research of optical spectroscopy
directions can focus andon computational modeling. Insights
a fundamental characterization into
of the the LSP-substrate
nitrogen LSP using
interaction can be gained by modeling the gas flow and heat
a combination of optical spectroscopy and computational modeling. Insights into the transfer occurring during theLSP-substrate
LSP nitriding
process using
interaction canapproaches
be gained by such as finitethe
modeling element
gas flow analysis (FEA)transfer
and heat or computational
occurring during fluid dynamics
the LSP
(CFD) to obtain the temperature and nitrogen species (N , N, N + , and so on) concentration as a
nitriding process using approaches such as finite element analysis (FEA) or computational fluid
2
function of position, similar to prior approaches adopted in the literature
dynamics (CFD) to obtain the temperature and nitrogen species (N2, N, N , and so on) concentration to study
+ laser-sustained argon
plasmas
as a function[100]. The plasma-substrate
of position, similar to prior energy transferadopted
approaches can alsoinbethe modeled
literature analytically by solving the
to study laser-sustained
inverse heat conduction problem, wherein the energy profile
argon plasmas [100]. The plasma-substrate energy transfer can also be modeled analyticallyof the LSP can be estimated using accurate by
solving the inverse heat conduction problem, wherein the energy profile of the LSP can configuration,
temperature measurements such as the ones obtained in Figure 8. The “perpendicular” be estimated
whereinaccurate
using the laser temperature
beam does notmeasurements
directly irradiatesuch the substrate
as the (Figure 6c), also represents
ones obtained in Figurean 8. exciting
The
direction to pursue in order to exploit the nitrogen LSP as an energetic
“perpendicular” configuration, wherein the laser beam does not directly irradiate the substrate source nitrogen species. Another
promising
(Figure 6c), direction lies inan
also represents further
exciting development
direction to of the two-step
pursue in order LSP nitriding-remelting
to exploit the nitrogen LSP process;
as an
although this process was successful in producing thick, crack-free,
energetic source nitrogen species. Another promising direction lies in further development of the and wear-resistant nitrided layers,
two-step LSP nitriding-remelting process; although this process was successful in producing thick,
crack-free, and wear-resistant nitrided layers, further testing (e.g., rolling contact fatigue testing of
Coatings 2019, 9, 283 18 of 22

further testing (e.g., rolling contact fatigue testing of cylindrical titanium specimens treated using
the two-step approach) and process optimization are recommended to evaluate the feasibility of
this processing technique as a viable and repeatable case-hardening method for high contact stress
applications such as gears and bearings.

Author Contributions: A.M.K. wrote the manuscript; A.E.S., S.M.C., and J.A.T. reviewed and edited it.
Funding: This research was supported by the Office of Naval Research (No. N00014-07-1-0121), the National
Science Foundation Graduate Research Fellowship Program, the Penn State Electro-Optics Center, and the P.B.
Breneman Chair of Engineering Science and Mechanics at the Pennsylvania State University.
Acknowledgments: The authors acknowledge helpful discussions with Amber Black (Los Alamos National
Laboratory) and Abdalla Nassar (Penn State Applied Research Laboratory).
Conflicts of Interest: The authors declare no conflict of interest.

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