Next Article in Journal
Enhancing the Raveling Resistance of Polyurethane Mixture: From the Perspective of Polyurethane Adhesive
Previous Article in Journal
Smart Food Packaging: An Umbrella Review of Scientific Publications
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Coatings
Volume 12
Issue 12
10.3390/coatings12121951
coatings-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Structural, Mechanical, and Thermal Properties of the TiAlTaN/TiAlBN Multilayer

by
Zheng Li
1,
Li Chen
1,2,*,
Jie Zhang
1 and
Xu Sun
1
1
State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, China
2
Zhuzhou Cemented Carbide Cutting Tools Co., Ltd., Zhuzhou 412007, China
*
Author to whom correspondence should be addressed.
Coatings 2022, 12(12), 1951; https://doi.org/10.3390/coatings12121951
Submission received: 12 November 2022 / Revised: 8 December 2022 / Accepted: 9 December 2022 / Published: 12 December 2022
(This article belongs to the Section Corrosion, Wear and Erosion)
Browse Figures
Versions Notes

Abstract

:
A multilayer structure and incorporation of the fourth element are promising strategies to improve the properties of TiAlN coatings. In this study, the structural, mechanical, and thermal properties of the Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer, as well as the Ti0.34Al0.48Ta0.18N and Ti0.42Al0.54B0.04N monolithic coatings, were carefully researched. Coherent growth of the multilayer structure induces a single-phase cubic structure of the Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer, even though the Ti0.34Al0.48Ta0.18N and Ti0.42Al0.54B0.04N coatings have a single-phase cubic structure and a mixed cubic and wurtzite structure, respectively. The Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer reveals a higher hardness of 38.2 ± 0.9 GPa due to interfacial strengthening, corresponding to 32.4 ± 0.6 GPa of Ti0.34Al0.48Ta0.18N and 32.7 ± 0.9 GPa of Ti0.42Al0.54B0.04N. During annealing, our three kinds of coating demonstrate an age-hardening effect. The Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer presents a hardness peak of 40.0 ± 0.9 GPa at 1000 °C, whereas the Ti0.34Al0.48Ta0.18N and Ti0.34Al0.48Ta0.18N coatings show the hardness peaks of 37.1 ± 0.7 and 35.0 ± 0.6 GPa at 900 °C, respectively. Furthermore, the improved oxidation resistance is obtained by the Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer.

1. Introduction

Metastable TiAlN coatings have been used extensively in the machining industry to improve the cutting performance of cutting tools for their superb mechanical and thermal properties [1,2,3]. The thermal decomposition process of TiAlN coatings attracts researchers’ attention. On the hand, the spinodal decomposition of supersaturated cubic TiAlN into nanosized Al-rich and Ti-rich domains leads to an excellent age-hardening effect [4,5]. On the other hand, with further increase in thermal load, the metastable cubic (c) Al-rich domain would gradually transform into stable wurtzite (w) AlN phase [6], which worsens its mechanical properties [7]. Furthermore, the oxidation resistance is another critical factor for surface-covered coatings in several significant industrial properties [8]. The oxidation resistance of TiAlN coatings is inadequate to meet the current growing demand, as the oxidation temperature is lower than 850 °C [9].
Numerous modification methods have been developed to improve the performance of TiAlN coatings. Alloying various elements into TiAlN coatings have been one of the main strategies [10], such as Ta [11,12,13,14], B [15,16,17,18], V [19], Zr [20], Si [15,21], etc. For instance, many reports show that TiAlN alloying with Ta can increase its hardness and fracture toughness [22,23]. Ta-incorporation also improves thermal stability by delaying the w-AlN formation and perfects the oxidation resistance via inhibiting the formation of a-TiO2 [13,14,24]. B-addition can modify the properties of TiAlN coatings based on theoretical calculations and experiments. From our previous studies, the addition of B positively affects oxidation resistance by promoting the generating of α-Al2O3 [16,25]. Nevertheless, alloying with B reduces the solid solubility of Al in c-TiN and thus promotes the formation of wurtzite AlN phases, which weakens its hardness [16].
Multilayered architecture is another promising strategy to enhance its properties, which can effectively improve its hardness, wear resistance, and thermal stability, etc. [26,27]. Some studies have reported that TiAlTaN/TiAlN [11], TiAlN/TaAlN [14], and TiAlBN/TiAlN [28] multilayers demonstrate superior mechanical and thermal properties than their corresponding monolithic coatings. Multilayers can combine the advantages of corresponding monolithic coatings [23,28]. Moreover, coherent interfaces promote spinodal decomposition due to the interface-directed effect, which refines the thermal stability of the coating [29,30].
Based on these effective methods, we committed to building a TiAlTaN/TiAlBN multilayer that can combine the advantages of both TiAlTaN and TiAlBN coatings. Correspondingly, for TiAlTaN/TiAlBN multilayer and TiAlTaN, TiAlBN monolithic coatings, we scientifically studied their structure, mechanical, and thermal properties.

2. Materials and Methods

The TiAlTaN/TiAlBN multilayer and TiAlTaN and TiAlBN monolithic coatings were synthesized by commercial cathodic arc evaporation equipment (Oerlikon Balzers INNOVA, Balzers, Liechtenstein) with the deposition parameters of an N2 pressure of ~3.2 Pa, a temperature of 550 °C, a substrate bias of −40 V, and a target current of 180 A. A variety of substrates were used to meet different experimental requirements, including cemented carbide (WC-6 wt.% Co), low alloy steel foils, polycrystalline corundum plates, and tungsten (W) sheets. Before deposition, all these substrates were cleaned by the ultrasonic wave in alcohol and acetone and then etched in an atmosphere of argon. TiAlTaN and TiAlBN monolithic coatings were deposited by Ti0.30Al0.60Ta0.10 and Ti0.35Al0.60B0.05 powder metallurgical targets (99.99% purity), respectively. Meanwhile, TiAlTaN/TiAlBN multilayers were prepared from two Ti0.30Al0.60Ta0.10 and two Ti0.35Al0.60B0.05 targets by spinning substrates with a rotary speed of 2.2 r/min. More information about the preparation of the multilayer is outlined in reference [31]. Figure 1 displays the deposition schematic diagram of TiAlTaN/TiAlBN multilayers in the arc evaporation equipment.
Coating powder samples were prepared to eliminate the impact of the substrate on the annealing and oxidation experiments. To eliminate the intervention of the substrate, coatings deposited on low-alloyed steel sheets were etched by 10 mol% nitric acids to separate the coating from the substrate. After filtration, cleaning, drying, and grinding, pure powder samples were obtained. Coating powder samples were executed by a differential scanning calorimeter (DSC, Netzsch QMS 403 Aëolos, Netzsch, Selb, Germany) in pure Ar gas (99.99% purity, 20 sccm flow rate) to the specified temperatures (Ta = 800, 900, 1000, 1100, 1200, 1300, and 1450 °C) at a programming rate of 10 K/min and then immediately cooling down to room temperature at a rate of 50 K/min. Coated W pieces were annealed in a vacuum furnace (COD533R, pressure ≤ 10−3 Pa) for 30 min at given temperatures with a heating rate of 10 K/min and then cooled in the furnace.
Powder samples were oxidized at the target temperature (Set a Ta every 100 °C from 800 to 1200 °C)to evaluate the oxidation resistance of our coatings. The process was conducted with a heating rate of 10 K/min and then a cooling rate of 50 K/min in a synthetic air (79 vol% N2, 21 vol% O2, 20 sccm flowing rate) atmosphere by DSC equipment. Coated corundum sheets were isothermally oxidized in the DSC device with synthetic air at 950 °C for 10 h. Moreover, reference [19] provides more information on the annealing and oxidation treatments.
The fracture cross-section of the deposited and oxide coatings was conducted by scanning electron microscopy (SEM, Zeiss Supre 55, Zeiss, Jena, Germany). Energy dispersive X-ray spectroscopy (EDX), equipped with SEM, was utilized to investigate the chemical composition and line scan profiles. Moreover, light element B was recharacterized using inductively coupled plasma mass spectrometry (ICP-mass, ELAN DRC-e, ELAN, Hsinchu, China) to compensate for the insufficiency of EDX measurement. XRD measurements with Cu (Kα) radiation using a Bruker D8 in Bragg-Brentano arrangement operated at 40 mA and 40 kV were employed to investigate the structural evolution of powder specimens in different experiments during annealing and oxidation. Transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM, FEI Titan G2 60–300, FEI, Hillsborough, NC, USA) with a field emission gun operating at 300 kV were applied to determine the microstructure of the TiAlTaN/TiAlBN multilayer in detail. Before TEM and STEM characterization, the dual-beam focused ion beam (FIB) system (FEI Helios Nanolab 600I, FEI, Hillsborough, NC, USA) was used to strip the atoms on the sample’s surface, and the thickness of the piece was thinned to less than 50 nm. The nanoindenter with a Berkovich diamond indenter tip was used to measure the hardness and elastic modulus. Measurements were under an applied load of 15nN following the Oliver and Pharr method [32]. The average and error values were conducted and calculated from more than twenty indents on each sample.

3. Results and Discussion

3.1. Microstructure and Mechanical Properties

To simplify notations, the atomic ratios of (Ti + Al + Ta)/N and (Ti + Al + B)/N are approximately normalized to 1:1. According to EDX and ICP-mass, the nominal components of TiAlTaN and TiAlBN monolithic coatings are Ti0.34Al0.48Ta0.18N and Ti0.42Al0.54B0.04N, respectively. The ionization rates of various elements during arc evaporation, gas scattering, and the resputtering procedure are the main reasons for the minor composition variation between the coating and the corresponding target [33]. The XRD patterns of Ti0.42Al0.54B0.04N, Ti0.34Al0.48Ta0.18N monolithic, and Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayered coatings are shown in Figure 2, and the inserted image in Figure 2 is a partially enlarged view of the XRD pattern of Ti0.42Al0.54B0.04N coating at this position.
The Ti0.42Al0.54B0.04N coating emerges as a cubic and wurtzite dual-phase structure. However, the Ti0.34Al0.48Ta0.18N coating exhibits a single cubic structure. It agrees with the previous research; the Ta and B additions have a reverse effect on the solid solubility of Al in c-TiN (ICDD 00-038-1420) [16,34,35]. The single cubic structure of the Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer suggests the epitaxial growth between the Ti0.34Al0.48Ta0.18N and Ti0.42Al0.54B0.04N sublayers. The substitution solution of Ta with a larger atomic radius (1.46 Å) induces a larger lattice constant of 4.192 ± 0.001 Å, compared to 4.150 ± 0.001 Å for Ti0.42Al0.54B0.04N. The diffraction peaks of our multilayer are situated between these two monolithic coatings, corresponding to the lattice constant of 4.163 ± 0.001 Å. The growth morphology of the Ti0.34Al0.48Ta0.18N, Ti0.42Al0.54B0.04N, and Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N coatings are demonstrated in the SEM fracture cross-section of Figure 3.
The Ti0.34Al0.48Ta0.18N coating (~3.66 μm) shows a distinct columnar growth morphology. As shown in Figure 3b, a distinct difference in the growth morphology of the Ti0.42Al0.54B0.04N coating (~3.04 μm) can be observed. The competitive growth of cubic and wurtzite phases interrupts the columnar growth and thus leads to a featureless morphology. However, the Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N coating (~2.77 μm) reveals a columnar growth morphology again. It is related to the signal cubic structure arising from the coherent growth between the Ti0.34Al0.48Ta0.18N and Ti0.42Al0.54B0.04N sublayers.
Crossing TEM analyses were conducted to further investigate the interfacial structure of Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer interfacial structure. The TEM bright-field (BF) image demonstrates a clear columnar growth with well-defined alternating bright Ti0.42Al0.54B0.04N and dark Ti0.34Al0.48Ta0.18N layers, depicted in Figure 4a. The selected area electron diffraction (SAED) image specifically indicates a single-phase cubic structure, consistent with the above XRD results. According to the high-resolution transmission electron microscope (HRTEM) image in Figure 4b, the coherent growth between the Ti0.34Al0.48Ta0.18N and Ti0.42Al0.54B0.04N sublayers can be affirmed by the continuing lattice fringes across several adjacent bilayer periods. It is illustrated more clearly in the filtered inverse fast Fourier transformation (IFFT) image. The Z-contrast STEM high angle annular dark-field (HAADF) image in Figure 4c explicates that the bilayer period is ~6.5 nm, consisting of bright Ti0.34Al0.48Ta0.18N (~3.6 nm) and dark Ti0.42Al0.54B0.04N (~2.9 nm) sublayers.
As shown in Figure 5, the deposition hardness, elastic modulus, and H3/E2 ratio of our Ti0.34Al0.48Ta0.18N, Ti0.42Al0.54B0.04N, and Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N coatings are exhibited. The Ti0.34Al0.48Ta0.18N and Ti0.42Al0.54B0.04N monolithic coatings exhibit a similar hardness, with values of 32.4 ± 0.9 and 32.7 ± 0.9 GPa, respectively. The interfacial strengthening and grain refinement causes a higher hardness of 38.2 ± 0.9 GPa for the Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer [23,36,37]. Furthermore, this hardening can be attributed to its overall cubic structure, corresponding to the mixed c/w-Ti0.42Al0.54B0.04N coating. The w-AlN formation of the Ti0.42Al0.54B0.04N coating induces the lowest indentation modulus of 418.8 ± 8.9 GPa, whereas the indentation modulus of the Ti0.34Al0.48Ta0.18N and Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N coatings are 457.6 ± 10.4 and 486.4 ± 14.0 GPa, respectively. Consequently, the Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer reveals a maximum H3/E2 ratio of 0.24, which means it has the best resistance of materials to plastic deformation [38].

3.2. Thermal Stability

Figure 6 displays the XRD patterns of the powdered samples after annealing. As shown in Figure 6a, the original diffraction peaks of Ti0.34Al0.48Ta0.18N slightly move to higher 2θ angles after annealing at Ta = 800 and 900 °C, suggesting the recovery and relaxation processes. When Ta reaches 1000 and 1100 °C, the shoulder peaks of (111) and (200) matrix diffraction peaks mean the spinodal decomposition towards metastable c-Ti(Ta)N-rich and c-AlN-rich domains. The c-AlN-rich domain conversion into stable w-AlN occurs at Ta = 1200 °C, where a tiny diffraction signal at ~33.2 and ~36.1° can be observed. At Ta = 1300 and 1450 °C, the Ti0.34Al0.48Ta0.18N decomposes entirely into the stable phases c-Ti(Ta)N and w-AlN. Annealing of Ti0.42Al0.54B0.04N between 900 and 1000 °C leads to a broader diffraction peak of the cubic structured matrix phase, (see Figure 6b,) indicative of the spinodal decomposition. Simultaneously, a slight move to a higher 2θ position and an increased intensity in the diffraction peaks of wurtzite structured matrix phases means the decomposition towards stable phases c-TiN and w-AlN. With further annealing at Ta ≥ 1200 °C, the Ti0.34Al0.48Ta0.18N almost decomposes into its stable phases c-Ti(B)N and w-AlN. The Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer behaves in a similar thermal decomposition process with Ti0.34Al0.48Ta0.18N, (see Figure 6c,) where the spinodal decomposition and w-AlN formations temperatures are 1000 and 1200 °C, respectively, followed by an entire decomposition at Ta = 1300 and 1450 °C.
The structural evolutions proceeding during the annealing of investigated coatings lead to the change in hardness. All coatings reveal an age-hardening effect, (see Figure 7) which arises from the coherent strain between the products of spinodal decomposition (c-TiN-rich and c-AlN-rich domains) and remaining matrix [39]. The Ti0.34Al0.48Ta0.18N and Ti0.42Al0.54B0.04N coatings reach the hardness peaks of 35.0 ± 0.6 GPa and 37.1 ± 0.7 GPa at Ta = 900 °C, respectively, while the peak hardness of 40.0 ± 0.9 GPa for the Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer appears at Ta = 1000 °C. Further annealing with raised temperature leads to a drop in hardness due to the coarsening of c-TiN-rich and c-AlN-rich domains along with the transition towards w-AlN. By contrast, the hardness of Ti0.34Al0.48Ta0.18N coating presents a mild downtrend. Ultimately, as Ta = 1200 °C, the hardness of Ti0.34Al0.48Ta0.18N, Ti0.42Al0.54B0.04N, and Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N coatings are 33.5 ± 0.7 GPa, 29.5 ± 0.7 GPa, and 32.94 ± 1.3 GPa, respectively.

3.3. Oxidation Resistance

As shown in Figure 7, XRD determinations of powdered coatings after oxidation at specific temperatures in the synthetic air are performed to investigate the oxidation resistance. No oxidic product can be observed after the oxidation of Ti0.34Al0.48Ta0.18N at 800 °C, see Figure 8a. Further oxidation at 900 and 1000 °C brings about the formation of rutile (r-) TiO2 (ICDD 00-021-1276) as well as the concomitant spinodal decomposition. Except for the enhanced intensity of r-TiO2 diffraction peaks, the diffraction peaks of corundum (α-) Al2O3 (ICDD 00-046-1212) appear with oxidation temperature increased to 1100 °C. Here, the diffraction peaks of the remaining coatings can be still observed. Eventually, the Ti0.34Al0.48Ta0.18N has been fully oxidized, leaving the oxidation products of r-TiO2, α-Al2O3, and h-Ta2O5 (ICDD 00-018-1304) at 1200 °C. After oxidation of Ti0.42Al0.54B0.04N at 800 °C, (see Figure 7b,) the appearance of metastable anatase (a-) TiO2 (ICDD 00-021-1272) hints the worse oxidation resistance than Ti0.34Al0.48Ta0.18N. The transformation of metastable anatase a-TiO2 into its stable r-TiO2 occurs at 900 °C. Further oxidation at 1000 °C leads to the α-Al2O3 formation. With the oxidation temperature increasing to 1100 °C, the Ti0.42Al0.54B0.04N has been completely oxidized, where the TiO2 transformation finishes. Additionally, the orthorhombic (o-)Al5(BO3)O6 (ICD 00-034-1039) of B-containing oxide can be observed. The Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer presents a similar oxidation process with Ti0.34Al0.48Ta0.18N except for the anatase-to-rutile TiO2 transformation instead of the direct formation r-TiO2 (see Figure 7c). This difference can be ascribed to the lower Ta content [13,14,24]. The onset temperatures of r-TiO2 and α-Al2O3 are 900 and 1100 °C, respectively, where the end temperatures of anatase-to-rutile TiO2 transformation and complete oxidation are 1100 and 1200 °C.
Further oxidation of coated polycrystalline corundum plates was conducted at 950 °C for 10 h in synthetic air to better explore their oxidation resistance. Figure 9 exhibits the cross-sectional SEM line scan images of Ti0.34Al0.48Ta0.18N and Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N coatings, where the Ti0.42Al0.54B0.04N coating has been completely oxidized (not shown). Ti0.34Al0.48Ta0.18N and Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N coatings state a bilayer oxide scale with an Al-rich top-layer and Ti-rich interlayer. The oxide scales of Ti0.34Al0.48Ta0.18N and Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N coatings are ~2.07 and ~1.25 μm, respectively, which indicates that the Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer possesses the best oxidation resistance. This drop in the oxide scale is mainly attributed to the Ti-rich interlayer, which suggests the combined effect of Ta and B retards the growth of the Ti-rich interlayer.

4. Conclusions

In this work, the structural, mechanical, and thermal properties of Ti0.34Al0.48Ta0.18N, Ti0.42Al0.54B0.04N, and Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N coatings are studied. The Ti0.34Al0.48Ta0.18N coating shows a single cubic structure, while the Ti0.42Al0.54B0.04N coating demonstrates a cubic and wurtzite dual-phase structure. The templating effect of the cubic Ti0.34Al0.48Ta0.18N sublayer brings a single-phase cubic structure to the Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer. The interfacial strengthening of the multilayer leads to a significantly increased hardness to 38.2 ± 0.9 GPa for the Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer, where the hardness of the Ti0.34Al0.48Ta0.18N and Ti0.42Al0.54B0.04N coatings are 32.4 ± 0.9 and 32.7 ± 0.9 GPa, respectively. All coatings during annealing present age-hardening abilities due to spinodal decomposition. The hardness peak of the Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer with the value of 40.0 ± 0.9 GPa appears at 1000 °C, whereas the Ti0.34Al0.48Ta0.18N and Ti0.34Al0.48Ta0.18N coatings at 900 °C show hardness peaks of 37.1 ± 0.7 and 35.0 ± 0.6 GPa, respectively. This indicates a better thermal stability of the multilayer. Furthermore, the Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer behaves with the best oxidation resistance. After oxidation at 950 °C for 10 h, the Ti0.42Al0.54B0.04N has been completely oxidized, whereas the oxide scales of Ti0.34Al0.48Ta0.18N and Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N coatings are ~2.07 and ~1.25 μm, respectively.

Author Contributions

Visualization, writing—original draft, Z.L.; conceptualization, methodology, funding acquisition, L.C.; investigation, J.Z. and X.S. All authors have read and agreed to the published version of the manuscript.

Funding

This study was financially supported by the National Natural Science Foundation of China: 51775560.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Acknowledgments

Li Chen is grateful for the support of the State Key Laboratory of Powder Metallurgy of Central South University.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Coll, B.F.; Sathrum, P.; Fontana, R.; Peyre, J.P.; Duchateau, D.; Benmalek, M. Optimization of arc evaporated (Ti,Al)N film composition for cutting tool applications. Surf. Coat. Technol. 1992, 52, 57–64. [Google Scholar] [CrossRef]
  2. Hörling, A.; Hultman, L.; Odén, M.; Sjölén, J.; Karlsson, L. Mechanical properties and machining performance of Ti1−xAlxN-coated cutting tools. Surf. Coat. Technol. 2005, 191, 384–392. [Google Scholar] [CrossRef]
  3. Prengel, H.G.; Santhanam, A.T.; Penich, R.M.; Jindal, P.C.; Wendt, K.H. Advanced PVD-TiAlN coatings on carbide and cermet cutting tools. Surf. Coat. Technol. 1997, 94–95, 597–602. [Google Scholar] [CrossRef]
  4. Chen, L.; Du, Y.; Mayrhofer, P.H.; Wang, S.Q.; Li, J. The influence of age-hardening on turning and milling performance of Ti–Al–N coated inserts. Surf. Coat. Technol. 2008, 202, 5158–5161. [Google Scholar] [CrossRef]
  5. Mayrhofer, P.H.; Hörling, A.; Karlsson, L.; Sjölén, J.; Larsson, T.; Mitterer, C.; Hultman, L. Self-organized nanostructures in the Ti–Al–N system. Appl. Phys. Lett. 2003, 83, 2049–2051. [Google Scholar] [CrossRef]
  6. Endrino, J.L.; Århammar, C.; Gutiérrez, A.; Gago, R.; Horwat, D.; Soriano, L.; Fox-Rabinovich, G.; Martín y Marero, D.; Guo, J.; Rubensson, J.E.; et al. Spectral evidence of spinodal decomposition, phase transformation and molecular nitrogen for-mation in supersaturated TiAlN films upon annealing. Acta Mater. 2011, 59, 6287–6296. [Google Scholar] [CrossRef]
  7. Bartosik, M.; Rumeau, C.; Hahn, R.; Zhang, Z.L.; Mayrhofer, P.H. Fracture toughness and structural evolution in the TiAlN system upon annealing. Sci. Rep. 2017, 7, 16476. [Google Scholar] [CrossRef] [Green Version]
  8. Vaz, F.; Rebouta, L.; Andritschky, M.; Da Silva, M.; Soares, J. Thermal oxidation of Ti1−xAlxN coatings in air. J. Eur. Ceram. Soc. 1997, 17, 1971–1977. [Google Scholar] [CrossRef]
  9. Chen, L.; Paulitsch, J.; Du, Y.; Mayrhofer, P.H. Thermal stability and oxidation resistance of Ti-Al-N coatings. Surf. Coat. Technol. 2012, 206, 2954–2960. [Google Scholar] [CrossRef] [Green Version]
  10. Derflinger, V.H.; Schütze, A.; Ante, M. Mechanical and structural properties of various alloyed TiAlN-based hard coatings. Surf. Coat. Technol. 2006, 200, 4693–4700. [Google Scholar] [CrossRef]
  11. Yang, Y.; Xu, Y.X.; Chen, L.; Mayrhofer, P.H. Improved Ti-Al-N coatings through Ta alloying and multilayer architecture. Surf. Coat. Technol. 2017, 328, 428–435. [Google Scholar] [CrossRef]
  12. Hemmati, A.; Abdoos, M.; Veldhuis, S.C. Developing Ti-Al-Ta-N based coatings: Thermal stability, oxidation resistance, ma-chining performance and adaptive behavior under extreme tribological conditions. Mater. Today Commun. 2022, 31, 103373. [Google Scholar] [CrossRef]
  13. Hollerweger, R.; Riedl, H.; Paulitsch, J.; Arndt, M.; Rachbauer, R.; Polcik, P.; Primig, S.; Mayrhofer, P.H. Origin of high tem-perature oxidation resistance of Ti–Al–Ta–N coatings. Surf. Coat. Technol. 2014, 257, 78–86. [Google Scholar] [CrossRef] [Green Version]
  14. Koller, C.M.; Hollerweger, R.; Sabitzer, C.; Rachbauer, R.; Kolozsvári, S.; Paulitsch, J.; Mayrhofer, P.H. Thermal stability and oxidation resistance of arc evaporated TiAlN, TaAlN, TiAlTaN, and TiAlN/TaAlN coatings. Surf. Coat. Technol. 2014, 259, 599–607. [Google Scholar] [CrossRef]
  15. Pfeiler, M.; Zechner, J.; Penoy, M.; Michotte, C.; Mitterer, C.; Kathrein, M. Improved oxidation resistance of TiAlN coatings by doping with Si or B. Surf. Coat. Technol. 2009, 203, 3104–3110. [Google Scholar] [CrossRef]
  16. Zhou, J.; Hu, C.; Zhang, J.; Chen, L.; Kong, Y. Effect of B-doping on the mechanical properties, thermal stability and oxida-tion resistance of TiAlN coatings. Int. J. Refract. Hard Met. 2021, 98, 105531. [Google Scholar] [CrossRef]
  17. Park, J.-K.; Cho, J.-Y.; Jeon, H.-T.; Baik, Y.-J. Structure, hardness and thermal stability of TiAlBN coatings grown by alternat-ing deposition of TiAlN and BN. Vacuum 2009, 84, 483–487. [Google Scholar] [CrossRef]
  18. Moraes, V.; Bolvardi, H.; Kolozsvári, S.; Riedl, H.; Mayrhofer, P.H. Thermal stability and mechanical properties of Ti-Al-B-N thin films. Int. J. Refract. Hard Met. 2018, 71, 320–324. [Google Scholar] [CrossRef]
  19. Xu, Y.X.; Chen, L.; Pei, F.; Yue, J.L.; Du, Y. Thermal stability and oxidation resistance of V-alloyed TiAlN coatings. Ceram. Int. 2018, 44, 1705–1710. [Google Scholar] [CrossRef]
  20. Yang, B.; Chen, L.; Xu, Y.X.; Peng, Y.B.; Fen, J.C.; Du, Y.; Wu, M.J. Effect of Zr on structure and properties of Ti-Al-N coat-ings with varied bias. Int. J. Refract. Met. Hard Mater. 2013, 38, 81–86. [Google Scholar] [CrossRef]
  21. Pei, F.; Liu, H.J.; Chen, L.; Xu, Y.X.; Du, Y. Improved properties of TiAlN coating by combined Si-addition and multilayer architecture. J. Alloys Compd. 2019, 790, 909–916. [Google Scholar] [CrossRef]
  22. Seidl, W.M.; Bartosik, M.; Kolozsvári, S.; Bolvardi, H.; Mayrhofer, P.H. Influence of Ta on the fracture toughness of arc evaporated Ti-Al-N. Vacuum 2018, 150, 24–28. [Google Scholar] [CrossRef]
  23. Waldl, H.; Tkadletz, M.; Czettl, C.; Pohler, M.; Schalk, N. Influence of multilayer architecture on microstructure and fracture properties of arc evaporated TiAlTaN coatings. Surf. Coat. Technol. 2022, 433, 128098. [Google Scholar] [CrossRef]
  24. Grossmann, B.; Jamnig, A.; Schalk, N.; Czettl, C.; Pohler, M.; Mitterer, C. Tailoring age hardening of Ti1−xAlxN by Ta alloying. J. Vac. Sci. Technol. 2017, 35, 060604. [Google Scholar] [CrossRef]
  25. Rebholz, C.; Monclus, M.A.; Baker, M.A.; Mayrhofer, P.H.; Gibson, P.N.; Leyland, A.; Matthews, A. Hard and superhard TiAlBN coatings deposited by twin electron-beam evaporation. Surf. Coat. Technol. 2007, 201, 6078–6083. [Google Scholar] [CrossRef]
  26. Shuai, J.; Zuo, X.; Wang, Z.; Guo, P.; Xu, B.; Zhou, J.; Wang, A.; Ke, P. Comparative study on crack resistance of TiAlN mon-olithic and Ti/TiAlN multilayer coatings. Ceram. Int. 2020, 46, 6672–6681. [Google Scholar] [CrossRef]
  27. Xu, Y.X.; Chen, L.; Pei, F.; Chang, K.K.; Du, Y. Effect of the modulation ratio on the interface structure of TiAlN/TiN and TiAlN/ZrN multilayers: First-principles and experimental investigations. Acta Mater. 2017, 130, 281–288. [Google Scholar] [CrossRef]
  28. Sun, X.; Chen, L.; Zhou, J. Structure, mechanical and thermal properties of TiAlBN/TiAlN multilayers. Surf. Coat. Technol. 2022, 441, 128512. [Google Scholar] [CrossRef]
  29. Povstugar, I.; Choi, P.-P.; Tytko, D.; Ahn, J.-P.; Raabe, D. Interface-directed spinodal decomposition in TiAlN/CrN multilayer hard coatings studied by atom probe tomography. Acta Mater. 2013, 61, 7534–7542. [Google Scholar] [CrossRef]
  30. Chen, L.; Xu, Y.X.; Du, Y.; Liu, Y. Effect of bilayer period on structure, mechanical and thermal properties of TiAlN/AlTiN multilayer coatings. Thin Solid Films 2015, 592, 207–214. [Google Scholar] [CrossRef]
  31. Wang, H.T.; Xu, Y.X.; Chen, L. Optimization of Cr-Al-N coating by multilayer architecture with TiSiN insertion layer. J. Alloys Compd. 2017, 728, 952–958. [Google Scholar] [CrossRef]
  32. Oliver, W.C.; Pharr, G.M. An improved technique for determining hardness and elastic modulus using load and displace-ment sensing indentation experiments. J. Mater. Res. 1992, 7, 1564–1583. [Google Scholar] [CrossRef]
  33. Freller, H.; Haessler, H. TixAl1−xN films deposited by ion plating with an arc evaporator. Thin Solid Films 1987, 153, 67–74. [Google Scholar] [CrossRef]
  34. Rachbauer, R.; Holec, D.; Mayrhofer, P.H. Increased thermal stability of Ti-Al-N thin films by Ta alloying. Surf. Coat. Technol. 2012, 211, 98–103. [Google Scholar] [CrossRef]
  35. Rachbauer, R.; Holec, D.; Mayrhofer, P.H. Phase stability and decomposition products of Ti-Al-Ta-N thin films. Appl. Phys. Lett. 2010, 97, 151901. [Google Scholar] [CrossRef]
  36. Kong, M.; Zhao, W.; Wei, L.; Li, G. Investigations on the microstructure and hardening mechanism of TiN/Si3N4 nanocompo-site coatings. J. Phys. D 2007, 40, 2858. [Google Scholar] [CrossRef]
  37. Schlögl, M.; Kirchlechner, C.; Paulitsch, J.; Keckes, J.; Mayrhofer, P.H. Effects of structure and interfaces on fracture tough-ness of CrN/AlN multilayer coatings. Scr. Mater. 2013, 68, 917–920. [Google Scholar] [CrossRef]
  38. Chen, X.; Du, Y.; Chung, Y.-W. Commentary on using H/E and H3/E2 as proxies for fracture toughness of hard coatings. Thin Solid Film. 2019, 688, 137265. [Google Scholar] [CrossRef]
  39. Koehler, J.S. Attempt to Design a Strong Solid. Phys. Rev. B 1970, 2, 547–551. [Google Scholar] [CrossRef]
Coatings 12 01951 g001 550
Figure 1. A schematic diagram of the deposition system containing the sample fixture and positions of targets for TiAlTaN/TiAlBN multilayers.
Figure 1. A schematic diagram of the deposition system containing the sample fixture and positions of targets for TiAlTaN/TiAlBN multilayers.
Coatings 12 01951 g001
Coatings 12 01951 g002 550
Figure 2. The (a) XRD patterns and (b) lattice constants of Ti0.42Al0.54B0.04N, Ti0.34Al0.48Ta0.18N and Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N coatings.
Figure 2. The (a) XRD patterns and (b) lattice constants of Ti0.42Al0.54B0.04N, Ti0.34Al0.48Ta0.18N and Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N coatings.
Coatings 12 01951 g002
Coatings 12 01951 g003 550
Figure 3. SEM fracture cross-sections of the (a) Ti0.34Al0.48Ta0.18N, (b) Ti0.42Al0.54B0.04N, and (c) Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N coatings.
Figure 3. SEM fracture cross-sections of the (a) Ti0.34Al0.48Ta0.18N, (b) Ti0.42Al0.54B0.04N, and (c) Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N coatings.
Coatings 12 01951 g003
Coatings 12 01951 g004 550
Figure 4. (a) Cross-sectional TEM bright-field with an inset of SAED pattern, (b) the HRTEM image with the IFFT image, and (c) the STEM HAADF picture of the Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer.
Figure 4. (a) Cross-sectional TEM bright-field with an inset of SAED pattern, (b) the HRTEM image with the IFFT image, and (c) the STEM HAADF picture of the Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayer.
Coatings 12 01951 g004
Coatings 12 01951 g005 550
Figure 5. The hardnesses (H), elastic moduli (E), and H3/E2 ratios of Ti0.34Al0.48Ta0.18N, Ti0.42Al0.54B0.04N monolithic, and Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayered coatings.
Figure 5. The hardnesses (H), elastic moduli (E), and H3/E2 ratios of Ti0.34Al0.48Ta0.18N, Ti0.42Al0.54B0.04N monolithic, and Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayered coatings.
Coatings 12 01951 g005
Coatings 12 01951 g006 550
Figure 6. XRD patterns of (a) Ti0.34Al0.48Ta0.18N, (b) Ti0.42Al0.54B0.04N, and (c) Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N after annealing at setting temperatures.
Figure 6. XRD patterns of (a) Ti0.34Al0.48Ta0.18N, (b) Ti0.42Al0.54B0.04N, and (c) Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N after annealing at setting temperatures.
Coatings 12 01951 g006
Coatings 12 01951 g007 550
Figure 7. The hardness of Ti0.34Al0.48Ta0.18N, Ti0.42Al0.54B0.04N monolithic, and Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayered coatings as a function of annealing temperatures.
Figure 7. The hardness of Ti0.34Al0.48Ta0.18N, Ti0.42Al0.54B0.04N monolithic, and Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayered coatings as a function of annealing temperatures.
Coatings 12 01951 g007
Coatings 12 01951 g008 550
Figure 8. XRD patterns of (a) Ti0.34Al0.48Ta0.18N, (b) Ti0.42Al0.54B0.04N, and (c) Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N after oxidation in synthetic air at setting temperatures.
Figure 8. XRD patterns of (a) Ti0.34Al0.48Ta0.18N, (b) Ti0.42Al0.54B0.04N, and (c) Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N after oxidation in synthetic air at setting temperatures.
Coatings 12 01951 g008
Coatings 12 01951 g009 550
Figure 9. The SEM fracture cross-sections and EDX line scan profiles of (a) Ti0.34Al0.48Ta0.18N monolithic and (b) Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayered coatings after isothermal oxidation in synthetic air at 950 °C for 10 h.
Figure 9. The SEM fracture cross-sections and EDX line scan profiles of (a) Ti0.34Al0.48Ta0.18N monolithic and (b) Ti0.34Al0.48Ta0.18N/Ti0.42Al0.54B0.04N multilayered coatings after isothermal oxidation in synthetic air at 950 °C for 10 h.
Coatings 12 01951 g009
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Li, Z.; Chen, L.; Zhang, J.; Sun, X. Structural, Mechanical, and Thermal Properties of the TiAlTaN/TiAlBN Multilayer. Coatings 2022, 12, 1951. https://doi.org/10.3390/coatings12121951

AMA Style

Li Z, Chen L, Zhang J, Sun X. Structural, Mechanical, and Thermal Properties of the TiAlTaN/TiAlBN Multilayer. Coatings. 2022; 12(12):1951. https://doi.org/10.3390/coatings12121951

Chicago/Turabian Style

Li, Zheng, Li Chen, Jie Zhang, and Xu Sun. 2022. "Structural, Mechanical, and Thermal Properties of the TiAlTaN/TiAlBN Multilayer" Coatings 12, no. 12: 1951. https://doi.org/10.3390/coatings12121951

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop