Review On Thin Film Coatings For Precision Glass Molding

Surfaces and Interfaces 30 (2022) 101903
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Review on thin film coatings for precision glass molding

Awais Akhtar, Haihui Ruan *
Department of Mechanical Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, China
A R T I C L E I N F O A B S T R A C T
Keywords: Precision glass molding (PGM) is an advanced glass manufacturing technology employed by the optical industry
Coatings for the large-scale production of lenses and other precision glass components. One of the key breakthroughs is the
Sputtering use of anti-sticking coatings that extend the tool life and render a molded glass surface polish-free. In the
Anti-sticking property
literature, various protective coatings, including noble metals, ceramics, and diamond-like carbon (DLC) coat
Substrate
Mechanical property
ings, have been attempted. These coatings met with varying degree of success and have finite service life due to
various degradation mechanisms. Noble metal coatings, although expensive, are the most preferred owing to
their simplicity of fabrication and high operating temperatures. Their degradation starts from the diffusion and
segregation of active elements along grain boundaries. Most of the attempted ceramic coatings are deteriorated
because the oxidation of metallic elements—that occurs more easily than noble metals—develops an oxide scale
that is adhesive to glass. DLC coatings exhibit poor thermal stability at high temperatures (> 600 ◦ C) owing to
the strong tendency of graphitization and inadequacy in developing high sp3-content; their application in PGM is
limited. The improvement in oxidation resistance and anti-sticking of coatings is a continuous development task,
particularly when the PGM technology is to be adapted for glasses with high glass transition temperature. This
paper reviews the state of the art of these coatings with a focus on their deposition techniques, anti-sticking,
microstructural and mechanical properties, and their degradation mechanisms in glass molding cycles. With
these explorations, a perspective on further improving the reliability of PGM coatings is provided.
1. Introduction properties required in optical, magnetic, and electrical applications

[9–12]. Among them, an important coating development is to enable
With the increasing applications of optical components in various molded precision optics that shift the optical industry from the con
fields, such as consumer electronics, lasers, and medical technology, the ventional expensive and time-consuming manufacturing processes via
precision glass manufacturing that achieves superior surface quality and grinding, polishing, and lapping [13,14] to an efficient and scalable
optical effectiveness is in large demand in the industry [1–3]. Compared PGM technology. Surface protective coatings for PGM are critical for
with traditional grinding and polishing methods, precision glass mold advancing PGM into a single-step process in mass production [15],
ing (PGM) is currently the most appropriate and widely recognized which must withstand thermomechanical stresses and a corrosive ther
technology for the cost-effective mass production of precision glass mochemical environment owing to the softened glass at molding tem
components such as lenses and optical switches [4–6]. In a PGM process, peratures [8]. Therefore, the structural behaviors of these coatings
high-precision mold inserts directly contact heated glass above its glass should exhibit sufficient strength and hardness to resist thermal shocks,
transition temperature (Tg) under mechanical loading. The occurrence adhesion, and wear at high temperatures [16].
of physical diffusion and chemical reactions on the glass–mold contact For PGM, three major groups of surface protective coatings are used:
area at molding temperatures results in premature mold failure and (i) noble metal coatings [17], (ii) ceramic hard coatings [18], and (iii)
significantly affects the surface quality of the glass [7]. Thus, the carbon-based (e.g., diamond-like carbon (DLC)) coatings [19]. Several
application of protective coating is critical for extending the service studies on various anti-adhesion surface coatings have been conducted
lifespan of the molds and increasing the surface quality of molded glass with varying degrees of success for particular glass types. However,
lenses [8]. The synthesis of protective surface coatings has gained glass-sticking, thermal instability, and oxidation of the coating elements
increasing popularity owing to their exceptional physicochemical at molding temperatures—at which the viscosity of glass reduces to 107 -
* Corresponding author.
E-mail address: [email protected] (H. Ruan).
https://doi.org/10.1016/j.surfin.2022.101903
Received 30 September 2021; Received in revised form 3 February 2022; Accepted 20 March 2022
Available online 26 March 2022
2468-0230/© 2022 Elsevier B.V. All rights reserved.
A. Akhtar and H. Ruan Surfaces and Interfaces 30 (2022) 101903
109 Pa.s—remain major challenges. evaporation, and ion beam deposition.

Although several coatings for PGM have been used, their failure
mechanisms have been fragmentedly discussed in the literature. As the 2.1.1. Sputtering
current trend of PGM migrates towards glass with high glass transition Sputtering is a vacuum coating technique in which cathodic targets
points, such as the aluminosilicate glass used in portable electronics, (source materials) are bombarded by energetic ions of inert gases such as
there is a need to consolidate the existing know-how and, if possible, to argon or helium. The development of cations is caused by the plasma
improve the high-temperature performance for more stringent applica that ignites between the targets (cathode) and substrates (anode). The
tions. Therefore, this paper reviews studies on coatings for PGM. We positive ions (cations) being accelerated in an electric field strike the
describe the deposition techniques, microstructural evolutions, and surface of a target [28]; the transfer of kinetic energy to the target atoms
their mechanical performances, and then present our perspective on the establishes a thin film onto a substrate surface (Fig. 2). This process has
optimization of coating durability, cost-effectiveness, and high- several advantages, such as high purity, remarkable adhesion, high
temperature performance. deposition rates, and simplicity of depositing either metallic or ceramic
coatings. Sputtering also facilitates the formation of materials with a
2. Deposition techniques high melting point. Reactive gases, such as oxygen or nitrogen, can be
added to form metal oxides, nitrides, or other compound films. Gener
Thin films exhibit distinctive performances compared with bulk ally, the sputtering process has common types: direct current (DC) and
materials because the majority of the deposition processes are radio frequency (RF) sputtering. In a DC sputtering system, the glow
nonequilibrium in nature; thus, a thin film formation can be outside the discharge is maintained by a DC current between the metallic electrodes.
permissible region of the corresponding (equilibrium) phase diagram However, in RF sputtering, an AC current is applied to neutralize the
[20–22]. Deposition techniques practically determine the properties of a charge build-up in an insulating target material.
thin film and can be used to modify the properties of the bulk material. Table 1 lists the PGM coatings reported in the literature. We can
These techniques require proper consideration according to the area of observe that sputtering is the most extensively applied in the develop
utilization because they do not result in identical properties, such as ment of PGM coatings owing to its simplicity and flexibility to offer a
surface morphology, microstructure, hardness, and corrosion resistance broad range of material deposition.
[23]. Thin film deposition is broadly categorized into two main groups:
physical vapor deposition (PVD) and chemical vapor deposition (CVD) 2.1.2. Electron beam evaporation
(Fig. 1). For PGM, the coatings developed based on them in the open An intensive electron beam (e-beam), produced from a filament and
literature have been summarized in Table 1. driven by both magnetic and electric fields, can also vaporize a target
material in a vacuum (Fig. 3). Even materials with high melting points
2.1. Physical vapor deposition (e.g., metal oxides) can be effectively vaporized with e-beams [30].
E-beam evaporation is a rapid process with deposition rates of several
PVD encompasses a broad range of vapor-phase technologies, where micrometers per second, although the quality and adhesion of the
atoms or molecules are physically ejected from a material and subse developed film on a substrate may suffer from the low energy of the
quently condensed and nucleated onto a substrate [24]. Generally, PVD vaporized particles. Therefore, more sophisticated evaporation methods
methods are employed in film deposition with thicknesses ranging from utilize excess plasma. The vaporized particles passing through the
several nanometers to several micrometers. Their applications include plasma region ionize, consequently, they can be accelerated to produce a
graded composition deposits, multilayer coatings, free-standing struc film [31] denser than the columnar grains resulting from the conven
tures, and dense deposits. Owing to their versatile features, sustainable tional e-beam deposition because high-energy ionized particles can
and environment-friendly PVD methods have received increasing in disrupt columnar growth. Thin films developed by this technique are of
terest in modern times [25]. It is employed primarily to improve the high quality and purity [32].
tribological, optical, and mechanical properties of a substrate material
[26,27]. The main PVD processes are sputtering, electron beam
Fig. 1. Classification of deposition techniques.
2
Table 1
Deposition of coatings for PGM applications.
Reference Coating Substrate Deposition Annealing Glass type Major findings
(Year) material / technique a temperature (◦ C)
Interlayer
Wu et al. PtIr, IrRe, WC RF-M.S. 500 ◦ C - Thermal stability of the Ir-based coatings was observed at 500 ◦ C
[40] IrReCrN /-
(2003)
Lin et al. CrN, CrWN / - Si, WC IBAD 750 ◦ C - Cr2O3 formation caused the increase in surface roughness of
[41] coatings and higher content of W in CrWN coatings demonstrated
(2006) improvement in hardness
Chen et al. MoRu / Ni WC DC-M.S. 600 ◦ C - Adequate thermal stability under 600 ◦ C was observed w.r.t
[42] hardness and surface roughness
(2006)
Kang et al. MoRu / Ni WC DC-M.S. 550 ◦ C - An increase in surface roughness of the coatings was observed with
[9] an increase in interlayer (Ni) thickness and a decrease in hardness
(2007) with a decrease in Mo content at 550 ◦ C
Wen et al. NiRu /- Si wafer E.B.E. 600 ◦ C - Substantial reduction in hardness at 600 ◦ C was observed owing to
[43] the breakdown of the periodical multilayer structure
(2008)
Chen et al. MoRu / Cr, Ti WC RF-M.S. 600 ◦ C - Better oxidation resistance and higher hardness with the increase
[44] (O) in Ru content were observed at 600 ◦ C
(2009)
Chien et al. PtIr / TaN WC/Co M.S. 700 ◦ C L-BAL42 Restriction of WC/Co diffusion with the TaN interlayer was
[45] observed
(2010)
Bobzin et al. PtIr / Ni, Cr WC PVD - - Evaluation of the protective coatings via a nanoimpact test
[46] revealed the better adhesion property with Cr interlayer than Ni
(2010) interlayer
Sakurai et al. PtZrNi / - WC RF-M.S. 450 ◦ C BK7 An increase in Zr content in PtZrNi coatings deteriorated the anti-
[47] sticking performance
(2010)
Fischbach PtIr, TiAlN / Ni WC, Si DC-M.S. 550 ◦ C P-SK57 Superior anti-sticking performance was observed with PtIr coating
et al. [48] than TiAlN coating in actual PGM condition
(2010)
Masuda et al. PtIr, IrRe / Ni Steel RF-M.S. 570 ◦ C - Faster Ni diffusion in PtIr coating was observed than in IrRe
[49] coating after heat treatment at the same temperatures
(2011)
Chen et al. TaN / - WC-Co DC-M.S. 500–800 ◦ C - Diffusion of oxygen occurred through the columnar structure of the
[50] annealed TaNx coatings above 500 ◦ C, making the TaN-based
(2011) coatings unapplicable for PGM
Tseng et al. PtIr, NiIr / Cr WC ISAMSS 700 ◦ C L-LAH83, Less oxidation resistance with NiIr coating than PtIr coating at
[51] N-KZFS5, 700 ◦ C
(2011) K-LaK8
Klocke et al. PtIr / Ni, Cr WC PVD - - Improvement in adhesion and effective strength with either Ni or
[52] Cr interlayer (Cr interlayer is relatively more effective)
(2011)
Bobzin et al. PtIr / Cr WC/Co MSIP-PVD 650 ◦ C P-LASF47, N-FK5 Diffusion of Cr interlayer was observed into the PtIr coating,
[53] increased glass defects at the glass–coating contact zone with the
(2012) increase in interlayer thickness
Lin et al. CrWN / - Si, WC M.S. 500 ◦ C K-PG325 CrWN coatings demonstrated improved anti-sticking with glass at
[54] 400 ◦ C
(2013)
Chao et al. PtIr / Ta WC/Co M.S. 596–607 ◦ C N-PK, N-FK, P-SK, PtIr coating displayed enhanced anti-sticking performance for
[14] L-NB, N-PS different optical glasses.
(2013)
Liu et al. ReIr / - Si M.S. 600 ◦ C - The annealed ReIr coating with increased Ir content exhibited
[55] better thermal stability at 600 ◦ C
(2013)
Bobzin et al. PtIr / Ni, Cr WC/Co M.S. 590–645 ◦ C L-BAL42, Severer interfacial reaction between coating and glass with an
[17] P-LASF47, N-FK5 increase in Co content in the substrate
(2014)
Chen et al. TaSiN / - Si DC-M.S. 600 ◦ C - The preferential oxidation of Si occurred in TaSiN coatings. During
[56] 600 ◦ C annealing, the inward diffusion of oxygen was restricted by
(2014) the development of Si oxide scales.
Chen et al. TaN, CrTaN, Si wafer M.S. 600 ◦ C BK7 Thermal stability of as-deposited Ta-nitride coatings (TaN, CrTaN,
[57] TaSiN, CrTaSiN TaSiN, CrTaSiN) after cyclic annealing were evaluated. CrTaSiN
(2014) /- demonstrated the best mechanical properties with the lowest
roughness, making it a suitable candidate for glass molding.
Chen et al. CrTaSiN / - Si, WC M.S. 600 ◦ C SiO2-ZnO-La2O3 Increased nanohardness was observed for CrTaSiN coatings in
[58] and SiO2-B2O3- comparison with Cr-free coatings and outward diffusion of glass
(2014) BaO glasses elements (Ca, Na, Zn) during thermal cycling resulted in the
reduction of coatings (CrTaSiN) surface quality.
Zhu et al.[59] ReIr / Ta WC/Co RF-M.S. 631 ◦ C D-ZK3 The Re/Ir multilayer exhibited better anti-stick performance than
(2015) Re and Ir monolayers for barium crown optical glass.
CrWN / Cr Si, WC DC-M.S. 600 C
◦
SiO2-B2O3-BaO- Higher W content resulted in the reduction of nano hardness at
based glass 600 ◦ C, owing to WO3 formation.
(continued on next page)
3
Table 1 (continued )
Reference Coating Substrate Deposition Annealing Glass type Major findings
(Year) material / technique a temperature (◦ C)
Interlayer
Chen et al.
[60]
(2015)
Klocke et al. PtIr / Ni WC M.S. 640 ◦ C B270 Selective oxidation of Ni was occurred owing to the grain boundary
[61] diffusion.
(2016)
Peng et al. PtIr / Cr, Ni WC M.S. 630 ◦ C - Outward diffusion phenomena were observed for Ni and Cr
[62] interlayer owing to grain boundary segregation in which Ni
(2017) diffusion is faster than that of Cr.
Chang et al. ZrSiN / Ti Si, WC DC-M.S. 600 ◦ C SiO2-B2O3-BaO ZrSiN coatings with higher Si contents (>30 at. %) exhibited an
[63] based glass amorphous phase with increased hardness, which was ascribed to
(2018) the variation in the bonding characteristics.
Lee et al.[64] AlCrN / - WC M.S. 800–900 ◦ C - The atomic ratio of Al/Cr was nonuniform, causing a detrimental
(2018) effect on the oxidation resistance at higher temperatures.
Wei et al. ReIr / Ta WC M.S. 631 ◦ C D-ZK3 Enhancement in mechanical performances and restriction of
[65] atomic diffusion were observed with a Re/Ir multilayer compared
(2019) with Re and Ir monolayers.
Friedrichs PtIr / Cr WC DC-M.S. 640 ◦ C B270 PtIr coating surface deteriorates (increasing defects) with
et al. [66] increased molding cycles.
(2020)
Huang et al. CrWN / - Si, WC PEMS 650 ◦ C BK7 Severe oxidation of the annealed coatings occurred in air and the
[67] higher W content increased the surface roughness and coating
(2020) thickness.
Chen et al. CrSiN, TaSiN, WC DC-M.S. 600 ◦ C SiO2-B2O3-BaO- ZrSiN coatings exhibited better anti-sticking in glass molding than
[68] ZrSiN / Cr, Ti based glass CrSiN and TiSiN coatings.
(2020)
Zhang et al. α-Al2O3 / TiN WC CVD 280 ◦ C, D-ZK3, IRG206 α-Al2O3 multilayer coatings developed using CVD exhibited better
[69] 540 ◦ C anti-sticking properties with D-ZK3 glass and chalcogenide glass
(2020) compared with DLC coatings
Li et al. [70] CrWN / - WC PEMS 650 ◦ C BK7 Increased W content resulted in the enhancement of Young’s
(2020) modulus and nanohardness and a decrease in the surface
roughness.
Guo et al. CrWN / - Si, WC PEMS 650 ◦ C - The as-deposited coatings exhibited the nonuniform distribution of
[71] the solid-solution matrix, whereas annealing caused
(2020) homogenization, resulting in considerable age-hardening.
a
RF-M.S.: radio frequency magnetron sputtering; DC-M.S.: direct current magnetron sputtering; E.B.E: Electron beam evaporation; PEALD: Plasma enhanced atomic
layer deposition; PVD: Physical vapor deposition; M.S.: Magnetron sputtering; ISAMSS: Ion source assisted magnetron sputtering system; MSIP-PVD: magnetron
sputter ion plating physical vapor deposition; PEMS: plasma-enhanced magnetron sputtering; IBAD: ion beam assisted deposition; CVD: chemical vapor deposition.
Fig. 2. Illustration of sputtering procedure on an atomic scale [29].
2.1.3. Ion beam deposition of ions eliminates the columnar microstructure (which is commonly
Similar to e-beam evaporation, energetic ions ejected from an ion observed in low-temperature PVD) to establish very dense and adherent
source can also sputter material off a target, which, after plume for films.
mation, is deposited onto the substrate surface. A schematic of the ion
beam deposition (IBD) is shown in Fig. 4(a). Technically, the signifi 2.2. Chemical vapor deposition
cance of IBD is the controllability of ionic energies and the impact of ion
occurrence on a developing surface. An additional ion gun can be uti CVD is a general term for preparing thin films through a series of
lized to assist deposition through bombardment with a developing film, chemical reactions. In CVD, the material synthesis process occurs when
called ion-beam assisted deposition (IBAD). Dual ionic beams facilitate the target constituents in the vaporized state react near the surface or
stoichiometry control in thin films [34]. In addition, the bombardment into the substrate surface, resulting in film growth [36]. Various factors
4
Fig. 3. Schematic of e-beam evaporation [33].
Fig. 4. Schematic of (a) IBD and (b) IBAD [35].
of this process are responsible for film quality, such as temperature, 3. Anti-sticking and durability
pressure, flow rate, and reactor geometry [37,38]. The main distinctive
features of CVD are its resourcefulness in producing either simple or 3.1. Overview of coating materials
complex compounds with comparative ease in terms of frequently low
temperature, outstanding throwing power, uniform coating thickness, Among the various coatings developed for PGM, as identified in
high growth rate, and the simplicity of epitaxial growth. CVD can be several papers [40,72], noble metal coatings are generally employed in
used to deposit materials that are difficult to vaporize, and it is more industries because of their superior oxidation and corrosion resistance
adaptable to depositing on substrates of complex shapes than other and better reliability than other coatings. Noble metals are nonreactive
deposition techniques [24,39]. Major CVD techniques include with cations, anions, and network atoms in glasses in the temperature
plasma-enhanced atomic layer deposition (PEALD), plasma-enhanced range for PGM (typically 600–700 ◦ C) [40]. Another advantage over
CVD, and metal-organic CVD. other coatings is that the coating process for noble metals is simple, as an
industrial sputtering facility can serve this purpose. Klocke et al. [73]
compared nitride and noble metal coatings on tungsten carbide (WC)
substrates and observed that noble metal coatings exhibited a
5
significantly better resistance to oxidation and anti-sticking properties applied to promote adhesion between the noble metal coatings and
than nitride coatings at or below 700 ◦ C. Another study by Tseng et al. substrates, and PVD, in particular magnetron sputtering, is extensively
[51] demonstrated that PtIr coatings have better mechanical properties applied to develop coatings. However, considering the high cost of noble
than NiIr coatings on WC substrates. Fischbach et al. [48] compared PtIr metals and the further elevated PGM temperatures, efforts are still
and TiAlN coatings on WC and Si substates in industrial glass molding required to develop ceramic coatings or a combination of ceramic and
atmospheres and observed that PtIr coatings exhibited significantly metallic coatings. In the following section, we review the existing
better anti-sticking properties than TiAlN coatings. Table 1 shows the coatings and their performance in PGM applications.
different coating types, substrate materials, interlayer materials, and
deposition techniques that were employed in previous PGM applica
3.2. Noble metal coatings
tions. It is evident that the PtIr coating is the most widely adopted
among the noble metal coatings, owing to its chemical inertness and
3.2.1. Anti-sticking property
anti-sticking property. Additionally, WC is extensively employed as a
In a PGM process, glass–mold sticking at molding temperatures is a
substrate material owing to its remarkable wear resistance and thermal
critical problem that results in limitations in the quality of molded glass
stability, and nickel (Ni) or chromium (Cr) interlayers are the most
products and the lifetime of molds [59]. In addition, molding tools
Fig. 5. SEM surface analysis and EDX data of four different PtIr coating systems [66].
6
undergo cyclic thermomechanical and chemical loads. Therefore, coat governed primarily by the outward diffusion of W and second
ings are required to protect and improve the service lifespans of molding arily by the diffusion of Cr.
tools. Friedrichs et al. [66] investigated the glass adhesion properties of
four different PtIr protective coatings on cemented WC substrates. Wei et al. [65] examined the anti-sticking property by applying the
Energy-dispersive X-ray spectroscopy (EDX or EDS) data obtained from sessile drop technique (wetting test). In the wetting test, D-ZK3 glass
scanning electron microscopy (SEM) of four different PtIr-coated sam balls were positioned on the coated substrates in a vacuum. The tem
ples with and without the Cr interlayer after multiple molding cycles are perature was increased to 631 ◦ C, 120 ◦ C above the Tg, for one hour.
shown in Fig. 5. When there was no interlayer, several small regions of Fig. 6 shows the wetting angle of the glass ball on the substrate with
damage appeared on the coating surface. The corresponding EDX data different coatings. They observed that at 631 ◦ C, a slight adhesion
revealed that adhesion occurred as a significant level of glass elements occurred between the glass ball and both the Ir and Re coatings. Sur
was identified on the surface. They observed that the degradation of the prisingly, the Re/Ir multilayer coating resulted in minimum adhesion;
molding tool was due to the outward diffusion of W atoms. With the the glass sample remained approximately spherical with a contact angle
employment of a 20 nm Cr interlayer, glass adhesion was further of 168.1◦ , significantly larger than those resulting from Re and Ir
reduced and the Cr oxide scale formed on the coating surface owing to monolayers and WC (without coating). After the wetting test on the
the outward diffusion of Cr resulting in a roughness change and some monolayer-coated samples, the surface of the glass ball became slightly
glass adhesion. Comparing the interlayers of 20- and 5-nm Cr for opaque. High temperatures promoted inter-diffusion (or reactions) be
600-nm PtIr coatings, they observed that the thinner interlayer resulted tween the glass and coating. Moreover, the diffusion of active substrate
in larger surface defects caused by glass adhesion. Tungsten (W) was elements towards the surface initiated the reaction, resulting in a
identified in the adhesion areas, implying that before the deterioration decrease in the wetting angle [74]. Conversely, the adherence of the
of the Cr layer, substrate degradation occurred because of the outward optical glass ball with the substrate was reduced considerably after the
diffusion and accumulation of W on the surface. Such a coating failure multilayer Re and Ir coatings were developed, by which the glass ball
mechanism was further corroborated based on the result of thinner remained fully transparent and no apparent sticking occurred after the
coatings, i.e., 300-nm PtIr and 20-nm Cr interlayer, which were rapidly wetting tests at 631 ◦ C. Thus, a Re/Ir multilayer coating was suggested
damaged and spalled. in [65]. Furthermore, this result indicated that multilayer coatings may
The study of Friedrichs et al. indicted the following challenges with be superior to monolayer coatings in terms of anti-sticking performance.
the PtIr/Cr/WC system: For monolayers, diffusion is facilitated by grain boundaries [75,76],
whereas in multilayers [59,77,78], the interfaces of disparate elements
I Glass adhesion is primarily due to the diffusion of W and Cr to enhance the resistance to diffusion, and therefore, better suppress the
wards the coating surface. outward migration of substrate elements to react with the glass. Addi
II Selective oxidation of Cr after Cr atoms reach the surface causes tionally, Refs. [79,80] demonstrated that the ordered nanostructure
an increase in surface roughness, which is the initial stage of resulted in higher resistance to the penetration of cations in glass (e.g.,
degradation. This oxide scale impairs the anti-sticking perfor Ca, Ba) into the protective coatings, thereby facilitating the anti-sticking
mance, resulting in glass adhesion fragments on the surface. The performance.
internal consumption of Cr in the interlayer causes Kirkendall The primary function of protective coatings is to increase the lifespan
voids [62], which impairs PtIr coating adhesion. of the mold by establishing a chemical barrier to prevent the most
III In addition to the Cr oxide scale, glass adhesion also occurs in frequent failure, i.e., glass sticking. The above-mentioned studies indi
areas containing a large amount of W atoms emanating from the cated that at high temperatures in glass molding, the diffusion of active
substrate. The existence of W resulted in more severe glass elements in the interlayer and substrate via the grain boundaries of the
adhesion than the Cr oxide scale. protective coatings towards the surface is the most common phenome
IV The service lifespans of coated WC-based molding tools, indi non that results in glass sticking. Therefore, the multilayer structure of
cated by the extent of loss of anti-sticking performance, are noble metal coatings may bring about a notable improvement in anti-
Fig. 6. Wetting angle of different coatings at high temperatures [65].
7
sticking performance, which is attributed to the impediment of atomic Cr interlayer is caused by the nuclei growth of such intermetallic com
diffusion caused by the addition of interfaces. pounds and oxide scale formation on the surface. When the Cr interlayer
is fully consumed, the activity of Cr decreases, and the (Pt,Ir)3Cr2 for
3.2.2. Degradation mechanisms mation stops. Subsequently, Cr atoms diffuse out from the intermetallic
PGM tools with protective coatings must undergo several hundred to phase, resulting in the shrinkage of the (Pt,Ir)3Cr2 phase, which may
thousand pressing cycles to justify their economic benefits over tradi change to the Cr-lean phase of (Pt,Ir)3Cr or completely vanishes. This
tional material removal processes. This can result in changes in the phenomenon of second phase formation and depletion induced by
surface topology, inertness, and even mechanical failure (e.g., spall supply limitation has also been observed in several previous studies
ation). Therefore, knowledge about the mechanism of coating failure is [91–97].
vital. Zirong et al. [62] examined the degradation mechanism of At the later stage of coating degradation, the involvement of the WC
Pt0.3Ir0.7 coatings on WC substrates with Cr as the adhesive interlayer at substrate in the diffusion process causes the development of W-enriched
630 ◦ C. The degradation evolution based on the experimental obser intermetallic compounds. Additionally, at the interfacial area, these
vations is depicted in Fig. 7. The outward transportation and segregation intermetallic compounds form numerous voids, known as the Kirkendall
of Cr atoms along the grain boundaries of the protective coating was effect [98], in which imbalance mass transportation as a consequence of
suggested as the leading degradation mechanism. From a thermody the difference in diffusion rates creates free volumes. During the out
namic perspective, diffusion is driven by chemical potential gradients ward diffusion of Cr-dominant species, vacancies drift in the opposite
and activities across the interfaces of disparate materials. However, direction. These additional vacancies may condense into voids [99,100],
grain boundaries provide fast channels, along which diffusion is a few which play a crucial role in the commencement of WC degradation.
orders of magnitude faster than within a grain [81]. Therefore, at a Klocke et al. [61] investigated the degradation of a PtIr coating with
higher temperature of 630 ◦ C and in a short period [82,83], the outward Ni as an adhesive interlayer. The PtIr-coated samples covered with B270
transport of interlayer atoms occurs primarily through grain boundary glass were heated at 640 ◦ C for several heating cycles in a vacuum or
diffusion, which forms oxide scales on the coating surface. The devel nitrogen environment. The resulting coatings and glass are shown in
opment of surface oxides is strongly influenced by the interior material Fig. 9(a). The marked regions in Fig. 9(a) were subjected to X-ray
transport. First, the decoration of solutes in PtIr grain boundaries is photoelectron spectroscopy (XPS) analysis, and the results are shown in
directed by the Gibbs adsorption isotherm, that is, the reduction in Fig. 9(b). The study observed that Ni oxides formed only on the surface.
interfacial energy owing to the decoration of solutes. This results in a At a depth of 20 nm, only metallic Ni was observed in the PtIr film. This
diffusion flux into the grain boundaries. When diffusive species arrive at demonstrated that external and selective oxidation occurred after the
the surface of the film, oxidation processes occur to eliminate the sol outward diffusion of Ni. Additionally, W and, to a smaller extent, cobalt
utes, in particular, those from the decorated area at the grain boundaries (Co) oxides formed on the surface, indicating the oxidation of these
owing to their trapping in the oxide scale. This impact results in the species. The diffusion of nickel likely occurred through the grain
decrease in the solute chemical potential in the grain boundaries; thus, a boundary diffusion mechanism [49]. After sputtering to remove the 20
chemical potential gradient towards the surface is established, which nm layer, nickel oxide was eliminated, and only metallic Ni was iden
promotes further outward diffusion [84–89]. If the oxide scale is suffi tified. An XPS analysis at a depth of 20 nm also demonstrated a
ciently dense to stop oxidation, the outward transport of the diffusive considerable reduction in Co and W concentrations, which were signif
species can be slowed down [90]. icantly smaller than the Ni concentration. Therefore, it was hypothe
Fig. 8 shows a three-dimensional element distribution of a heat- sized that the existence of Co and W on the surface is not the result of
treated (at 630 ◦ C) PtIr/Cr/WC system obtained using atom probe to diffusion through the layers of PtIr and Ni. Instead, open craters were
mography. The appearance of Cr enrichment at both the grain bound identified on the coating surface, where large fractions of W and Co were
aries of the protective coating and the interfacial areas are shown in detected. The dimensions of the craters were 1–30 μm, suggesting that
Fig. 8(b) and 8(c), respectively. The diffusion of Cr results in the for the PtIr/Ni layer was deformed and fractured by the media resulting
mation of intermetallic phases, which are initially Cr-rich compounds from underneath, possibly because of the invasion of oxygen and the
with a stoichiometry of (Pt, Ir)3Cr2 formed at the PtIr/Cr interfacial area. formation of W and Co oxides. Additionally, a high content of carbon
With continuous thermal exposure, the continuous consumption of the was also identified using XPS analysis (zone 2); however, owing to the
Fig. 7. Illustration of degradation evolution mechanism of PtIr/Cr/WC at 630 ◦ C [62].
8
Fig. 8. Typical characterization results acquired from the interfacial area of PtIr/Cr/WC specimen after heat-treatment at 630 ◦ C: (a) Scanning trasnmission electron
micrroscopy (STEM) image and 3D atomic mappings of (b) PtIr layer bottom part, (c) PtIr/Cr interfacial area, and (d) Cr/WC interfacial area [62].
chemical inertness of carbon, it was not involved in glass adhesion with respectively.
the surface [101,102]. Above studies have shown that the degradation of coated molds is
Liu et al. [103] examined the chemical inertness of IrRe protective primarily influenced by the interfacial areas of interlayers with protec
coatings developed on silicon (Si) substrates with B2O3-ZnO-L2O3 tive (noble metal) coatings and with substrate. Owing to thermal
glasses in the temperature range of 270–600 ◦ C. The results revealed instability, outward movement and segregation of the interlayer mate
that the invasion of Zn from the glass reduced the coating performance. rial along the grain boundaries of the protective coatings appears to be
Additionally, the formation of Zn compounds on the coating surface the beginning of the degradation process at glass-molding temperatures.
resulted in a significant increase in the surface roughness. In another In addition, the creation of voids at the interlayer/substrate interface
study [49], IrRe and PtIr coatings were employed on Ni-P molds, and the owing to the departure of interlayer materials results in the weakening
results indicated that the diffusion of Ni was promoted in the grain of coating-substrate adhesion as well as the outward diffusion of sub
boundaries of Ni and Ni3P intermetallic in the plating structure towards strate materials. As the service lifespan of the coated molds is vital to
the coating surface. However, Ni diffusion was suppressed in the IrRe PGM application, further research is suggested to focus on quantitative
coating owing to the smaller diffusion coefficient of Ni in the IrRe alloy modeling of the above degradation mechanisms to predict the lifespan of
than in the PtIr alloy. MoRu coatings deposited on WC substrates have coated models for given coating structure and molding temperature.
exhibited significant thermal stability in terms of surface characteristics
and phase evolution, including hardness and roughness, after annealing 3.2.3. Ruthenium as a metal coating
at 600 ◦ C [42]. Chen et al.[104] studied the annealing effect (at 600 ◦ C) Ru, which is a cost-effective noble metal, has gained interest because
of TaRu and MoRu coatings in an oxygen-containing environment. They its oxidation resistance is even higher than that of other noble metals,
observed that the preferential internal oxidation phenomena occurred such as platinum (Pt) and iridium (Ir) [105]. Chen et al. [44] employed
for tantalum (Ta) and molybdenum (Mo) in the coatings; however, the MoRu coatings on WC substrates; after annealing at 600 ◦ C, they
ruthenium (Ru) element remained in its metallic state. Owing to internal observed that coatings with high Ru content (at least higher than Mo
oxidation, the resulting laminated oxide structures converted TaRu and content) exhibited superior oxidation resistance and higher hardness.
MoRu coatings into alternating layers of (Ta2O5, Ru) and (MoO2, Ru), Their results indicated that Ru is a suitable coating material for
9
Fig. 9. Evaluation of PtIr/Ni/WC: (a) optical images of specimens after heating tests with glass covers, and (b) XPS analysis of coating surfaces and subsurface [61].
high-temperature applications. Ru has been used as a metallic film for that CVD Ru films have higher thermal stability than ALD Ru films.
contact switching in microelectromechanical systems (MEMS) with Chen et al. [109] developed TaRu coatings on WC substrates with a
enhanced mechanical properties compared to Pt, gold (Au), rhodium Cr interlayer using DC magnetron co-sputtering. Four alloy coatings
(Rh), and silver (Ag) [106]. Although Ru, along with Pt, primarily ap (Ta35Ru65, Ta45Ru55, Ta55Ru45, Ta64Ru36) were achieved with pure
pears as an electrocatalyst in the literature [107], owing to its higher metal targets (Ta, Ru, Cr) at 400 ◦ C. To investigate the stability of TaRu
oxidation resistance, it can be a coating material for PGM when an in coatings, they annealed the coatings in an oxygen-containing environ
crease in chemical inertness is required, specifically when high-Tg ment at 600 ◦ C for 4 h and then cooled them to room temperature.
glasses are subjected to molding. Fig. 11 shows the XRD, SEM, and TEM analyses of the as-deposited and
Han et al.[108] deposited Ru thin films on Si substrates using pulsed annealed TaRu coatings. In the as-deposited state, the XRD patterns
CVD and ALD with the same thickness to compare the thermal stability revealed the reflections of hexagonal Ru, tetragonal β-Ta, and hexagonal
of the surface characteristics before and after thermal annealing (Fig RuTa (Fig. 11(a)), whereas the annealed coatings exhibited reflections of
10). The surface roughness and morphology were examined using Ru, RuTa, and Ta2O5, indicating the oxidation of tantalum at 600 ◦ C. The
atomic force microscopy (AFM). Fig. 10(a) shows the variation in cross-sectional SEM images demonstrated the columnar morphology of
roughness with rapid thermal annealing (RTA). In the as-deposited state, the TaRu coatings on the substrate and the formation of an oxide scale
Ru thin films grown using pulsed CVD exhibited a smaller roughness on the top surface of the coatings after annealing. The developed TaRu
than those grown by ALD owing to the smaller grain size. The AFM coatings with a relatively higher Ru content exhibited fewer thickness
images of the annealed state (Fig. 10(b)) indicated that the small changes after annealing. With the minimum amount of Ru, the overall
roughness of the CVD Ru films was maintained up to a high temperature thickness of the coating Ta64Ru36 increased from 702 to 740 nm due to
of 800 ◦ C, whereas the ALD Ru films had a significant increase in the oxidation, which resulted in a layered structure (Fig. 11(e)). Because the
roughness. In addition, ALD Ru films demonstrated void formation Ta64Ru36 coating was annealed in an oxygen environment, the inward
owing to the excessive growth of grains, whereas a minor increase in oxygen diffusion was faster than the outward Ta diffusion. In addition,
grain size was observed for CVD Ru films. These results clearly indicated Ta formed an oxide more easily than Ru, resulting in internal oxidation
10
Fig. 10. (a) Roughness comparison of Ru films deposited using p-CVD and ALD (inset AFM images), and (b) AFM images (upper part) at 800 ◦ C and SEM images
(lower part) at 700 ◦ C of Ru films [108].
[110,111]. Cr35W18N47 coating in the contact region with glass (Fig. 13(h)) and
Chen et al. [112] fabricated CrRu protective coatings using magne noncontact region (Fig. 13(i)) were 12.3 and 14.6 nm, respectively. The
tron co-sputtering with Ti as an interlayer on Si substrates. The CrRu increase in the surface roughness of the noncontact region, associated
coatings were deposited at 400 ◦ C and then annealed in a 50 ppm O2-N2 with cracks, was caused by oxidation at high temperatures. The same
environment for 2 h at 600 ◦ C. Fig. 12 shows the cross-sectional phenomena were also observed for other coatings (Cr27W24N49,
microstructural behavior of the Cr47Ru53 and Cr65Ru35 coatings in the Cr18W28N54, and Cr13W31N56). The extent of oxidation in the contact
as-deposited and annealed state. After co-sputtering, Cr47Ru53 and regions was relatively small because the cover glass inhibited the oxygen
Cr65Ru35 exhibited compact polycrystalline morphologies and columnar accessibility. Huang et al. [67] synthesized CrWN coatings with varying
structures, respectively. After annealing, thick oxide scales formed on W contents using magnetron sputtering and examined the molding
the surfaces of both co-sputtered coatings and the columnar structure performance of the coatings in a nitrogen environment at 650 ◦ C for 6
transformed into a polycrystalline structure in the Cr65Ru35 coating. The min. The fabricated coatings with varying W contents were
size of the recrystallized grains was limited by the original columnar Cr34.45W20.94N44.61, Cr28.03W33.29N38.68, Cr18.90W40.13N40.97, and
grain boundaries, resulting in smaller grains in the Cr65Ru35 coating Cr15.73W44.94N39.33. In the Cr34.45W20.94N44.61 coating, with a low W
than in Cr47Ru53. The electron diffraction patterns indicated that the content, a coarse granular morphology was observed with many
CrRu and oxide scale regions consisted of Ru-based alloys and Cr2O3, noticeable micro-sized pores. Although the deposition techniques were
respectively. different, the effects of W content were the same as those revealed by Li
et al. [70], that is, the increase in W content results in grain refinement
3.3. Ceramic coatings and a smoother surface, but it aggravates oxidation.
Li et al. [70] schematically revealed the degradation mechanism of
While noble metal coatings are more advantageous than ceramic CrWN coatings (Fig. 14). At the molding temperature in the PGM, the
ones in prolonging the lifetime of PGM tools, the research on ceramic top surface of the coatings experienced high pressure. As the number of
coatings has not stopped because of the lower cost that can potentially thermal cycles increased, the columnar voids of the coated structure
achieve a better combination of cost and durability, particularly when provided diffusion channels for oxygen. In addition to the formation of
higher temperatures in PGM are required. Li et al. [70] fabricated CrWN surface oxide layers, internal oxidation also occurred. The aggravation
(Cr35W18N47, Cr27W24N49, Cr18W28N54, and Cr13W31N56) coatings on of W and Cr oxidation significantly reduced the integrity of the coatings.
WC substrates using co-sputtering Cr and W targets in a plasma sput The anti-adhesion and mechanical properties decreased abruptly, and
tering system. The coating surfaces were analyzed using AFM before and cracks were observed owing to the interfacial reaction, sticking, and
after the pressing cycles of glass molding at a maximum temperature of oxidation. With the increase in thermomechanical cycles, the cracked
650 ◦ C. As the W content increased, finer particle sizes and decreased coatings eventually fell off owing to the sticking and demolding forces.
surface roughness of the CrWN coatings were observed. The addition of Chen et al. [56] prepared TaSiN coatings via magnetron
W to CrN resulted in the formation of a dense and fine-grained structure co-sputtering on Si substrates. The cross-sectional TEM images of the
of the coatings because the addition of W atoms in co-sputtering caused coating before and after annealing at 600 ◦ C are shown in Fig. 15. The
an enhancement in the collision of Cr and N. Additionally, mobility and selected-area diffraction pattern (SADP) demonstrated a noncrystalline
diffusivity could be restrained by the higher W content. Previous studies phase. High resolution transmission electron microscopy (HRTEM)
[113,114] reported that the increase in the energy of the (sputtering) W image revealed the stacking of the coating constitution with periodic
target caused a decrease in the surface roughness of the coatings. For the gradient concentration; however, the lattice fringes were not identified.
Cr35W18N47 coating, the maximum and minimum particle sizes were In the annealed state, the Ta27Si20N53 coating exhibited an oxide scale
337 and 107 nm, respectively. In addition, the formation of finer par formed on the surface. Underneath the oxide scale, the amorphous
ticles occurred in other coatings (Cr27W24N49, Cr18W28N54, and structure of the coatings was maintained (inset of Fig. 15(c)). The oxide
Cr13W31N56) if the W target power was increased. Fig. 13 shows the scale continued to expand during prolonged heating and remained
surface morphology of the Cr35W18N47 coating before and after thermal amorphous, whereas the internal part of the coating demonstrated
pressing cycles in a nitrogen environment. The surface roughness of the crystalline domains embedded in the amorphous matrix. The crystalline
11
Fig. 11. Study of Ta64Ru36 coatings: XRD patterns of the (a) as-deposited and (b) annealed coatings, cross-sectional SEM images of the (c) as-deposited and (d)
annealed coatings, and (e) cross-sectional TEM image of the annealed coatings [109].
domains were identified based on the apparent lattice fringes attributed maximum diameter of 200 nm, as observed in the contact region.
to the Ta2N and TaN phases. Moreover, the original granular morphology was maintained in the
Chen et al. [68] further investigated the chemical inertness of noncontact region. After 600 thermal cycles, the TEM image (Fig. 16(f))
silicon-nitride-based (Cr28Si17N55, Ta26Si14N60, Zr16Si20N64) coatings in of the Ta26Si14N60 coatings revealed the formation of an oxide scale on
contact with SiO2-B2O3-BaO glass at temperatures between 270 and the coating surface and the expansion of the interlayer area. Based on
600 ◦ C (Fig. 16). For the Cr28Si17N55 coatings, significant glass adhesion the EDS analysis of the surface oxide, no identification of Ti was
was observed after the first ten thermal cycles. After 100 thermal cycles, observed, which indicated that the Ta26Si14N60/Ti/WC coating
the optical microscopy (OM) and SEM images revealed a damaged sur restricted the outward diffusion of Ti. After being heated for 400 cycles,
face, indicating adhesiveness with glass. The WC substrate underneath the Zr16Si20N64 coatings became translucent, i.e., the granular
was exposed, which was also confirmed using EDS analysis. After 400 morphology underneath the coatings could be partially observed. This
thermal cycles in the Ta26Si14N60 coatings, the contact region of the was because the island oxides were smaller (~20 nm) than those in the
coating with glass became opaque (the as-deposited coatings were heated Ta26Si14N60 coatings. With continued annealing after 600 and
transparent), possibly because of the formation of oxide islands with a 800 thermal cycles, the oxide particles further expanded to 20–40 nm
12
Fig. 12. Study of Cr47Ru53 and Cr65Ru35 coatings characterized by cross-sectional SEM images of (a, b) as-deposited and (c, d) annealed coatings, and cross-sectional
TEM images of (e, f) annealed coatings [112].
and 150 nm, respectively (Fig. 16(h) and 16(i), respectively). The 60% [101]) of sp3-modification without any hydrogen are known as
elemental mapping of the Ta26Si14N60 coatings in the contact region tetrahedral amorphous carbon (ta-C) coatings. These coatings have
indicated that the oxide particles had high amounts of Ba and O with low excellent properties, including high hardness, high density, low abrasion
levels of N and Zr. These results indicated that the Zr16Si20N64 coatings rates, and low chemical reactivity. Generally, PVD processes such as
demonstrated better chemical inertness than Cr28Si17N55 and conventional sputtering can only induce less than 40% content of sp3
Ta26Si14N60 against BK7 optical glass. Chang et al. [63] also studied the because the carbon ions are unable to gain sufficient energy and are
oxidation resistance of ZrSiN coatings at 600 ◦ C. Their results indicated deposited on the substrate’s surface with little momentum, resulting in
that the improved oxidation resistance was attributed to the formation inadequacy in the formation of sp3 bonds. Consequently, most carbon
of dense Zr-Si-O oxide scales that inhibited oxygen diffusion. particles accumulate in small grains, resulting in graphite modification
[116]. The deposition of (ta-C) DLC coatings with a high sp3 content
requires specialized deposition techniques such as filtered cathodic
3.4. Diamond-like carbon (DLC) coatings vacuum arc (FCVA) deposition, which are not commonly used in the
industry. Bernhardt et al. [101] developed ta-C coatings with an sp3
DLC coatings encompass a wide range of carbon-based protective ratio of approximately 60% using magnetron sputtering ion plating
coatings. Owing to their high wear resistance and low coefficient of (MSIP) on a WC substrate for glass molding applications and annealed in
friction, they are generally used as protective layers against friction and a vacuum environment with glass at different temperatures of 590 and
various applications in which low friction is required [19]. The different 630 ◦ C. Most of the coated surfaces corrugated after annealing because
properties of DLC coatings, such as chemical and mechanical properties, of residual stresses; only few of them kept a good smoothness of the
are determined by the sp2/sp3 content ratio as well as hydrogen content. surfaces. Zhang et al. [69] fabricated DLC coatings on WC substrates
The DLC coatings containing a high content (more than 40% [115] or
13
Fig. 13. AFM study of CrWN coatings: (a–d) surface morphologies of as-deposited (Cr35W18N47, Cr27W24N49, Cr18W28N54, and Cr13W31N56) coatings, respectively,
(g–j) surface morphology of annealed Cr35W18N47 coating [70].
using FCVA and ion-assisted magnetron sputtering methods and re are determined based on the recorded force-indentation curve.
ported that the occurrence of graphitization at temperatures above Nanoindentation is considered one of the fastest and simplest
450 ◦ C dramatically affects the lifespan of coated molds in PGM. methods for obtaining information about the mechanical properties of
Although DLC coatings offer good self-lubrication with improved thin films [119]. To avoid the influence of the substrate, a general rule of
anti-wear properties, their poor thermal stability and the requirement of thumb to obtain precise measurements of hardness (H) and Young’s
the dedicated coating facility restricts their applications in the glass modulus (E) of thin films is that the indentation depth must be less than
molding industry [101,117]. Additionally, although a few attempts have one-tenth of the overall coating thickness [120]. During the process of
been made to employ DLC coatings for PGM applications, owing to the loading and unloading in the nanoindentation method, the machine
graphitization, it tends to oxidize at high temperatures and in an in continually records the load (P) against indentation depth (h). After
dustrial production environment (e.g., with a constant N2 flow), recording the P–h curve, the H can be determined from Eq. (1) as [121]
rendering it unsuitable for glasses with high Tg (e.g., Tg ≥ 550 ◦ C).
Pmax
H= (1)
A
4. Tribological performances
where Pmax is the maximum indentation load, and A represents the
In addition to thermal/chemical stability and anti-stick performance, projected contact area between the specimen and indenter. The effective
coatings must also have high toughness, high hardness, and low friction modulus (Eff) can be calculated by Eq. (2) as [121]
for PGM applications that involve the flow of glass on a coating surface. √̅̅̅
π dp 1
Among these, hardness is the most important for industrial coating ap Eeff = √̅̅̅̅ (2)
2 dh A
plications involving contact and sliding [118]. Nanoindentation is
employed to quantify it, in which a diamond-tipped indenter is forced
where dp/dh is the slope of the (load–displacement) unloading curve at
into a coating surface. Subsequently, the elastic properties and hardness
14
Fig. 14. Illustration of the degradation mechanism of CrWN coatings in contact with BK7 optical glass [70].
Fig. 15. Cross-sectional TEM and HRTEM images of Ta27Si20N53 coatings in the (a, b) as-deposited and (c, d) annealed states [56].
the maximum indentation depth. The elastic modulus of the indented properties of the multilayered coating was determined to be primarily
material can then be calculated by substituting Eeff in the Eq (3). due to dislocation blockage by interfaces [122]. In addition, as the grain
size is constrained by the layer thickness, the hindrance of dislocation
1 1 − υ2 1 − υ2i
= + (3) increases with refinement in grain size, which results in higher hardness.
Eeff E Ei Moreover, the multilayer structure can also contribute to the coating
toughness [80] because the interfaces result in an enhancement in the
where Ei and υi are the elastic modulus and Poisson’s ratio of indenter,
resistance to crack propagation. Based on a series of studies on Re/Ir
respectively, and E is the elastic modulus of the indented material.
coatings, it appears that the multilayer design has an overwhelming
Wei et al. [65] performed nanoindentation for monolayer and
advantage over monolayer coatings in terms of both tribological and
multilayer Re/Ir coatings and observed that the multilayer Re/Ir coating
chemical properties.
exhibited a higher Young’s modulus and hardness than those of the
The nanoscratch test is also commonly used to determine the adhe
monolayers (Re or Ir). The significant enhancement in the mechanical
sive properties of coatings and thin films [123,124], in which the lateral
15
Fig. 16. Study of SiN-based coatings: (a) schematic of glass/sample in heating test, SEM images of (b–c) Cr28Si17N55 coatings, (d–f) Ta26Si14N60 coatings, and (g–i)
Zr16Si20N64 coatings after heating [68].
force is measured while moving an indenter tip that has been forced into structure to withstand repetitive impact loading. Conversely, the coat
the specimen [125]. Using a constant rate of increase in the normal force ings without adhesive interlayer coatings failed rapidly during the
and a constant scratching speed, Klocke et al. [52] investigated the in impact tests.
fluence of the interlayer material and its thickness on the adhesion of the Huang et al. [67] determined the mechanical properties of CrWN
PtIr film. They observed that in the absence of an interlayer, a steep coatings through nanoindentation. They observed that co-sputtered
increase in the indentation depth was developed in the early stage of coatings with increased W content after annealing at 650 ◦ C resulted
scratching and that the adhesion and hardness of the PtIr film were in higher hardness, and coatings with a high H/E (i.e., hardness over
improved after depositing the Ni or Cr interlayer. The critical scratch Young’s modulus) ratio demonstrated good fracture toughness. In
load increased with the interlayer thickness, and the 50-nm Cr interlayer another study, Huang et al. [127] compared the mechanical perfor
performed the best in resisting exfoliation. The probable reasons for the mance of CrWN coatings heated at 650 ◦ C in vacuum, nitrogen, and air
improvement in adhesion are the enhanced compatibility of the me environments. The evaluation using nanoindentation demonstrated that
chanical properties between the coating and substrate and the estab the vacuum-annealed coatings exhibited a noticeable age-hardening
lishment of stronger bonds at the interfacial area of the material. effect, and therefore, the significant improvement in mechanical prop
In the load-control mode, a nanoindenter tip can repeatedly hit a erties was ascribed to spinodal decomposition. In contrast, the CrWN
coating surface with a prescribed maximum load. This is called a coatings annealed in nitrogen and air environments suffered from sub
nanoimpact test [126], which may determine the toughness of the stantial mechanical degradation caused by oxidative damage. Chang
coatings. In the nanoimpact test, a solenoid is employed to drag the et al. [128] evaluated the hardness of Hf-Si-N coatings using nano
indenter from the surface and perform the re-acceleration from a short indentation and observed that the hardness of the coatings after
distance opposite to the film. The repetition of impacts at the same annealing (at 600 ◦ C) initially increased and then decreased with
location is enabled by proper automation. The development of inden continuous annealing (100 h), owing to the formation of an oxide scale
tation depth against repetitive impacts is continually monitored. Thus, on the surface. Guo et al. [71] examined the mechanical performance of
the progress of film deformation is captured. For the PtIr coatings, CrWN coatings before and after annealing at 650 ◦ C under vacuum and
nanoimpact tests have been performed to study the effects of interlayers concluded that both the nanohardness and Young’s modulus increased
(Cr and Ni) with varying thicknesses [52]. The interlayer was observed after annealing owing to the occurrence of an age-hardening mecha
to improve the resistance to repetitive impacts. In particular, with the nism. Although these studies have demonstrated the tribological per
employment of a Cr interlayer of 50 nm, the imprint depth remained formances of the various PGM coatings, it is unclear how the
almost unchanged up to nearly 1500 impacts. This result was ascribed to room-temperature performances correlate with high-temperature ones
the plastic deformation of the film during several initial impacts and the or with the lifetime of coatings in PGM cycles. The measurements of
work hardening effect to resist further impacts. For all other examined high-temperature tribological performances and the development of
scenarios, a progressive film fracture occurred as the number of impacts quantitative models revealing the influence of various degradation
increased, resulting in a continuous increase in the imprint depth. mechanisms are therefore suggested for the future studies.
Consequently, it was concluded that the Cr interlayer with a thickness of
50 nm provided a significant toughening effect on the entire coating
16
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Surfaces and Interfaces 30 (2022) 101903

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Surfaces and Interfaces

Review on thin film coatings for precision glass molding

1. Introduction properties required in optical, magnetic, and electrical applications

109 Pa.s—remain major challenges. evaporation, and ion beam deposition.

Fig. 1. Classification of deposition techniques.

Fig. 2. Illustration of sputtering procedure on an atomic scale [29].

Fig. 3. Schematic of e-beam evaporation [33].

Fig. 4. Schematic of (a) IBD and (b) IBAD [35].

Fig. 6. Wetting angle of different coatings at high temperatures [65].

Fig. 7. Illustration of degradation evolution mechanism of PtIr/Cr/WC at 630 ◦ C [62].

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