TiN–TiB2 сeramics degradation in the region of a steady-state laser heating

TiN–TiB2 сeramics degradation in the region of a steady-state laser heating

Accepted Manuscript TiN–TiB2 сeramics degradation in the region of a steady-state laser heating M. Vlasova, M. Kakazey, P.A. Marquez Aguilar, R. Guar...

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Accepted Manuscript TiN–TiB2 сeramics degradation in the region of a steady-state laser heating

M. Vlasova, M. Kakazey, P.A. Marquez Aguilar, R. Guardian Tapia, M.C. Reséndiz-González, A. Castro Hernandez, I.V. Mel'nikov, Ya. Fironov PII: DOI: Reference:

S0257-8972(19)30681-4 https://doi.org/10.1016/j.surfcoat.2019.06.058 SCT 24738

To appear in:

Surface & Coatings Technology

Received date: Revised date: Accepted date:

26 March 2019 26 May 2019 19 June 2019

Please cite this article as: M. Vlasova, M. Kakazey, P.A.M. Aguilar, et al., TiN–TiB2 сeramics degradation in the region of a steady-state laser heating, Surface & Coatings Technology, https://doi.org/10.1016/j.surfcoat.2019.06.058

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ACCEPTED MANUSCRIPT TiN–TiB2 сeramics degradation in the region of a steady-state laser heating M. Vlasova1*, M. Kakazey1, P. A. Marquez Aguilar1, R. Guardian Tapia1, M. C. ReséndizGonzález1, A. Castro Hernandez1, I. V. Mel'nikov2,3, Ya. Fironov3 1

Center of Investigation in Engineering and Applied Sciences of the Autonomous University of the State of Morelos (CIICAp–UAEMor), Av. Universidad, 1001, Cuernavaca, Mexico. 2

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Research Center for Marine Geophysics, Moscow Institute of Physics and Technology, Nauchny Per. 4, Dolgoprudny, Region of Moscow 141700, Russian Federation 3

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School of Radiotechnics and Computer Technology, Moscow Institute of Physics and Technology, Pervomayskaya ul. 3, Dolgoprudny, Region of Moscow 141700, Russian Federation

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Abstract

In the work, the process of local laser heating of TiN–TiB2 ceramics in air is considered. It has

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been established that the development of high-temperature processes in the irradiation zone (T ≥ 2000 °C) is accompanied by the decomposition of TiN and TiB2 into TiNx, TiB, Ti, and B and by

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the formation of vaporous ablation products, which are oxidized to TiO2 and B2O3 depending on the length of the flight path. As a result of the deposition of these oxides with different

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TiO2/B2O3 ratio on the substrate, TixByOz composite films form. Depending on the type and temperature of particles deposited on the substrate, it is possible to obtain films in the form of a

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continuous vitreous layer, mixture of vitreous islands and spherical particles, and chains of

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spherical particles of different diameter.

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Key words: TiN–TiB2 ceramics, laser treatment, ablation products, films

1. Introduction

Refractory non-oxygen compounds such as carbides, nitrides, and borides are extensively useful in design and production of new materials due to their high melting point, hardness, electric conductivity, etc., which are determined by the corresponding chemical bonds [1–7]. The synthesis of composite ceramics based on these compounds extends considerably area of application of this type of materials. A powder of such compounds meets an extensive application as a wear-resistant coating for cutting tools [8–12]. As a rule, coatings of this type are deposited by the PVD (physical vapor deposition), PECVD (plasma-enhanced chemical vapor

ACCEPTED MANUSCRIPT deposition), СVD (chemical vapor deposition), sputter deposition, ion beam assisted deposition, and magnetron-sputtering methods [13–18], laser CVD (LCVD) and laser cladding are used [19– 24]. All the evidence indicated that the deposition methods of coatings can be done in vacuum or an appropriate gas atmosphere to prevent oxidation processes of components. As a rule, some of the above technologies allow coating made of a simple (single-phase) composition [21]. To obtain coatings of complex composition, labor consuming technologies are being developed [23,

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24]. The method of laser-assisted sputtering targets made of refractory oxygen-free compounds

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is rarely used. However, as shown in [25-27], the LCVD method in air allows implementing

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fundamentally new coatings/films of complex composition with a number of properties that expands their fields of application.

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The purpose of this paper is to study: 1) phase transformations that occur in the zone of local high-power stationary laser heating of TiN - TiB2 ceramics in the air, and 2) morphology and

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composition of films formed from the ablation products. The aim 1) is of interest from the standpoint of degradation of composite ceramics at high temperatures under the conditions of the

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formation of a narrow crater, which is difficult for the atmosphere oxygen to enter. The aim 2) is

2. Experimental Technique

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of interest as a new LCVD method of coating a complex composition by sprayed ceramics.

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An 80 wt. % TiN – 20 wt. % TiB2 ceramics was obtained from a homogenized powder mixture by hot pressing under a pressure of 4 GPa at a temperature of 1400 °C during 3 min

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[28]. The obtained cylindrical specimens had a diameter d = 5 mm and a length l = 10 mm. Laser treatment was carried out with an YLS-1000-SM (IPG Photonics) single-mode fiber

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laser model operating at 1070 nm and an average power of 1 kW. The laser was operated in a continuous wave (cw) regime. The sample is treated for 5 s. The ablation products are deposited on an infrasil (optical quartz) substrate located in parallel with the top surface of the sample (target) at a distance of 20 mm. This type of substrate was chosen to avoid absorption of the laser light and so heating of the substrate, and the appearance of products of interaction of the material of the film and substrate, too. The scheme of the experiment is shown in Fig. 1 a. As a result of the irradiation, a stain of ablation products is formed on the substrate, the shape and size of which is shown in Fig. 1b.

ACCEPTED MANUSCRIPT The treated samples and deposited ablation products are investigated by the X-ray diffraction method (D2 PHASER diffractometer, Bruker) and scanning electron microscopy in combination with micro chemical analyses by using an energy dispersive spectroscope (EDS) of a Hitachi SU 5000 and a ZEISS-FIB-SEM. EDS measurements are carried out in various regimes: local microanalysis, on the area of 20x20 mm and mapping. A comparison of the results can allow not

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only identifying the elements, but also their spatial distribution.

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3. Results and discussion

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3.1. Characterization of ceramics

According to the obtained XRD data, the main phases found in the ceramics are TiN and TiB2 (Fig. 2, I a). The ceramics consists of TiN and TiB2 grains (Fig. 3). As it follows from the

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microanalysis data (see Table 1), TiN is concentrated predominantly, in light areas, whereas, TiB2 dominates in gray areas. The presence of oxygen indicates the insignificant oxidation of the

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surface in long-term storage of specimens in air (for ~10 years).

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3.2. Laser treatment of ceramics 3.2.1. Target

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As a result of laser treatment, a conical crater of 3-mm depth is made on the top side of the sample. The diameter of the hole in the upper part of the crater is 1.3 mm. At the same time,

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3.2.1.1. X-ray data

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ablation products appear both there and being deposited on the substrate.

According to the XRD data, after irradiation, along with TiN and TiB2, in the crater and

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zone adjacent to the crater, the TiNx and TiB were recorded (Fig. 2, I b). The appearance of TiNx was caused by the development of the oxidation processes of TiN [29-31]: TiN + O2 → TiNx + Ti + TiO2 (rutile and anatase) + N2↑ (1).

A part of released Ti interacts with TiB2 with the formation TiB [3]: TiB2 + Ti → TiB (2). 3.2.1.2. SEM, EDS data Along with depositing highly dispersed particles, spherical particles turned out to present on the target surface (Fig. 4). The surface of the ceramics adjacent to the crater also have signs of

ACCEPTED MANUSCRIPT degradation of TiN grains (Fig. 4 a, a’, b-b’’). According to the EDS data (see Table 1) and the micrograph shown in Fig. 4 b’’, correspondingly, an oxidation processes of the TiN grains and the TiB2 intercrystalline interlayers develop on the top surface of the ceramics near the crater. Only Ti and O are detected among these interlayers, whereas in the TiN grains, an insignificant amount of nitrogen remains (see left and right part of Fig. 4 b’’). Since TiB2 has a low oxidation resistance, titanium oxide interlayers form exactly on TiB2 base. Their composition is close to

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Ti2O3 (see Table 1).

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With an increase in the distance from the crater, an intensive deposition of nanoparticles on

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the surface of the target is observed (see Fig. 4 b, b’, c, c’). Accordingly, microanalysis showed that as the distance from the crater to the edge of the end face of the target increases, the total

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composition of the coating of the target changes: the Ti content decreases, whereas the B and O contents increase. In other words, the gradual transition from TiO2:B to B2O3:Ti through

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intermediate TixByOz states occurs. Similar transformations also occur in deposited spherical particles (see Table 1).

The development of the process of oxidation of ceramics is also notably on the surface of the

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crater walls (Fig. 5). However, it has a “gradient character”: the top part of the crater is enriched

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with titanium and oxygen, and in the bottom part of the conical crater, titanium prevails, boron, nitrogen, and a small amount of oxygen are also present (see Table. 1). Thus, in the top part of

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the crater, the processes of oxidation of the ceramic composite are actively developing, which are

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described by reactions 1, 3-5 [3, 29]:

In this case, B2O3 as a high volatility component readily moves away from the crater zone, and the crater itself is enriched with titanium oxide. As can be seen from Fig. 5, globules (spherical particles), consisting mainly of Ti and O, are present on the crater walls. In the bottom narrow part of the crater, which is characterized by higher heating temperatures, the processes of dissociation of TiN and TiB2 develop, leading to the formation of gaseous products [32]:

ACCEPTED MANUSCRIPT 2TiNsolid → 2Tigas+ N2 (6), TiB2solid→ Tigas+ 2Bgas (7). As a result, this crater zone is enriched with gaseous products Ti, B, N2, which gradually enter/diffuse up into the top part of the crater, riched with TiO2. This sweeps nitrogen away from the crater. The titanium and boron atoms are partially oxidized and erupt from the crater. A small

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number of boron atoms diffuse into the titanium oxide melt (see Table 1, inside crater).

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Since nitrogen is not detected by EDS analysis in the ablation products deposited on the

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target surface (see Table 1), one may conclude that an oxidation process dominates not only in the crater zone, but also in scattering flow of ablation products into the space, what leads to the

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formation of complex compounds of titanium oxyborides. Such factors as oxidation of ablating components and volatility some of them are likely to set conditions of TixByOz compounds

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formation with different ratios x, y, and z and pre-determine the composition of the deposition

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products on the target surface.

3.2.2.1. X-ray data of ablation products on substrate

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The X-ray diffraction patterns of the ablation products show (Fig. 2, II) that the amorphized material that corresponds to vitreous B2O3 with different TiO2 content is the major phase [33,

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34]. Nevertheless, on the halo, a number of weak narrow peaks that can be assigned to TiO2 (anatase and rutile) [35] and H3BO3 [34, 36] are present. The obtained data indicate that

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reactions (3–5) are preferable.

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3.2.2.2. SEM and EDS data of ablation products on the substrate By study the ablation products deposited on the substrate, it was established that, with an increase in the distance from the center of the substrate located above the crater to the edge of the substrate, the morphology of the film changes substantially: the transition from the continuous vitreous coating to the island-type coating and then to the globular-fractal one (Fig. 6 a, a’-c, c’) occurs. The size of spherical particles decreases with distance from the center to the edge of the substrate. The microanalysis data show that Ti, B, and O are the main elements (see Table 2 and Fig. 7). By moving away from the сenter of substrate to the edge of the substrate (from zone I to zone

ACCEPTED MANUSCRIPT III), in the deposition products (films), the Ti content gradually decreases, whereas the B and O contents increase. That is, the trend of changing the content of elements is the same as in the products of deposition on the surface of the target. With increasing in the length of flight, the composition of the ablation products deposited on the substrate changes from TixByOz to B2O3: Ti. For spherical particles, a similar tendency is observed. Due to the presence of a temperature gradient in a spreading plasma-dust cloud, ablation

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products are deposited on the surface of a substrate with different temperatures. This leads to the

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formation of films of different morphology.

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Since the ablation, products are deposited both on the substrate and on the target itself, it worth trying to compare the deposition products in both cases. It is noticable that major products

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of the ablation are TiO2 and B2O3. For TiO2 Tmelt. = 1870 °C, and for B2O3 Tmelt. = 450 °C. Due to the different volatility of oxides, B2O3 precipitates quite far away from the eruption

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source of ablation products (crater) on both the substrate and the target. This corresponds to the zone III on the substrate and the edge of the target top (see Table 1, 2 and Fig. 4 c, Fig. 6, zone III). As the length of the flight through the ambient air increases and the B2O3 vapor cools down,

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the vapor → liquid (drops) → solid (spherical particles) transition takes place. As a result,

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spherical particles of various sizes are deposited on the substrate/surface of the target. The presence of a small amount of Ti there (see Fig. 7, zone III) suggests us to consider the

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composition of spherical particles/globules as B2O3 doped with Ti (or B2O3: Ti). Titanium oxide is predominantly deposited on the substrate in the zone I, located above the

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crater. The presence of a small amount of boron (see Table 2) indicates that here it is deposited both TiO2 doped with boron, and TiO2 – B2O3 composite mixture (see Fig. 6 a ’). As a result, the

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obtained film can be represented as TiO2:B, or TixByOz. Note that the globules of composition TiO2: B were found: on the film of zone I (see Fig. 7, zone I), on the surface of the target near the crater (see Fig. 4 a, b), and also on the surface of the crater (see Fig. 5). It can be assumed that drops of various sizes of boron doped titanium oxide directly erupt from the crater. The biggest of are cools down more slowly during the flight and take the form of "petals" when these at high speed collide with the surface of the substrate. The zone II on the substrate is intermediate between zone I and zone III. In this zone the smaller-size TiO2:B droplets that experiences longer flights drops are gathered (see Table 2 zone

ACCEPTED MANUSCRIPT II and Fig. 7 zone II). This also applies to ablation products deposited on the target surface at the distance of ~ 1.4 mm from crater (see Table 1 and Fig. 4b I). That is, the intense steady-state heating enables us growing TixByOz films as with a variety of morphologies and with different ratios of x, y, and z. A simplified scheme of the product distribution is shown in Fig. 8. The basis for obtaining such films/coatings of complex composition are the processes of degradation/dissociation of TiN and TiB2, that occur under

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oxygen deficiency and subsequent oxidation of ablation products to TiO2 and B2O3 with

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simultaneous doping of the corresponding oxides with boron or titanium in different temperature

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zones.

Note that TiO2 –B2O3 coatings/films are well exploited in solar cell production [33] as

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protective coatings [43]. In turn, TiO2: B films are exploited to enhance the photo catalytic activity of TiO2 [34, 44, 45], as a functional oxide coating on heat-sensitive substrates [46]. The

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B2O3:Ti glass seals have great potential for biomedical and aerospace applications [47, 48]. Each specific application requires specific technology for producing films with particular composition.

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Here, various types of films are shown to be obtained within the same technology of the LCVD by simple changing the distance from the target to the substrate. Thus, the zone I film

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corresponds to TiO2: B; films zone III - B2O3:Ti. Zone II films may have properties inherent to both TiO2: B and B2O3: Ti films. It is noticeable the stationary cw irradiation regime opens up

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the possibility of deposition of films of different thickness by changing the irradiation time.

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4. Conclusions

In summary, this paper demonstrates that the stationary cw mode of laser heating of TiN -

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TiB2 ceramics in the air is accompanied by the composite degradation, in turn, leading to the formation of a narrow cone-shaped crater. The presence of the temperature gradient in the crater leads to development of significantly different processes: the dissociation of TiN, TiB2 compounds and the formation of Ti, B and N↑ prevail in the bottom zone of the crater. In the top zone of the crater, oxidation of TiN and TiB2 and Ti and B coming out of the bottom zone prevail, which leads to the formation of TiO2:B and B2O3. The ejection of all newly formed products from the crater and corresponding spread in the ambient air is the basis of formation of TixByOz films. Depending on the length of the flight of the ablation products and the place of deposition, the composition of the films can be considered

ACCEPTED MANUSCRIPT as a gradual transition from TiO2:B films to B2O3:Ti through a number of intermediate states. This means that films of different composition with different properties can be obtained by changing the distance from the target to the substrate.

Acknoledgement The work is the MIPT was supported by the Russian Ministry of Educationand Science, grant

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8.12870.2018/12.1, and by the joint grant 18-42-130005 of the Republic of Mordovia and RFBR

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[43] P. Zurlini, A. Lorenzi, Il. Alfieri, G. Gnappi, A. Montenero, N. Senin, R. Groppetti, P. Fabbri, Titanium and zirconium hard coatings on glass substrates prepared by thesol–gel method, Thin Solid Films 517 (2009) 5881–5887. doi:10.1016/j.tsf.2009.03.211 [44] L. Artiglia, D. Lazzari, S. Agnoli, G. Andrea Rizzi, G. Granozzi, Searching for the Formation of Ti−B Bonds in B‑ Doped TiO2−Rutile, J. Phys. Chem. C, 117 (2013) 13163−13172. dx.doi.org/10.1021/jp404520z.

ACCEPTED MANUSCRIPT [45] M. Bettinelli, V. Dallacasa, D. Falcomer, P. Fornasiero, V. Gombac, T. Montini, L. Romanò, A. Speghini, Photocatalytic Activity of TiO2 Doped with Boron and Vanadium, J. Hazard. Mater. 146 (2007) 529−534. [46] M. Quesada-Gonz ́alez, K. Baba, C. Sotelo-V ́azquez, P. Choquet, C.J. Carmalt, I.P. Parkin, N.D. Boscher, Interstitial boron-doped anatase TiO2 thin-films on optical fibres: atmospheric pressure-plasma enhanced chemical vapour deposition as the key for functional oxide coatings temperature-sensitive

substrates,

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(2017),

10836.

DOI:

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10.1039/c7ta02029e.

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[47] S.K. Saha, H.Jam, J.I. Goldstein, A.S. Miller, R.K. Brow, Reaction between titanium and B2O3 melt/glass, Phys.Chem.Glassey, 39(2) (1998)118-121.

E. H. Schemitsch, M. Towler, Titanium addition influences

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[48] O. Rodriguez, W. Stone,

antibacterial activity of bioactive glass coatings on metallic implants, Heliyon, 3(10) (2017)

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e00420. DOI: 10.1016/j.heliyon.2017.e00420

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Figure captions

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Fig. 1. The scheme of sample irradiation (a) and the deposition of ablation products on the substrate. The spot diameter of precipitated ablation products is 10 mm. Zone I is on the distance

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20 mm over the crater. Zone II is at distance ~2 mm from the center of the substrate plate. Zone III is at distance ~ 4 mm from the center of the substrate plate.

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Fig. 2. X-ray diffraction patterns of ceramics obtained from the 80 wt. % TiN – 20 wt. % TiB2 mixture (I) and ablation products on the substrate (II). For I: a) the initial ceramics; b) after laser

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treatment. For II: a) precipitated products of the substrate in zone II; b) in zone III. Fig. 3. SEM secondary-electron micrograph of the TiN–TiB2 ceramics (a, b). Light gray

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areas correspond to aggregates of TiN grains, dark gray areas correspond to a mixture of TiN and TiB2 grains, and black holes are pores.

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Fig. 4. SEM micrographs of the TiN–TiB2 ceramic surface at different distances from point of irradiation (crater). For a, a’ the distance from crater is ~0.5 mm. For b, b’ the distance from

indicated areas.

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crater is ~1.4 mm. For c, c’ the distance from crater is ~2.4 mm. On b’’: content of elements in

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Fig. 5. Distribution of elements on the crater surface. Arrows marked TiO2 globule. Fig. 6. SEM micrographs of ablated products deposited at different distances from the center to the edge of the substrate. Zone I is at the distance 20 mm over the crater. Zone II is at distance ~2 mm from the center of the substrate plate. Zone III is at distance ~ 4 mm from the center of the substrate plate. Fig. 7. Distribution of elements in different zones of deposition of ablation products (see Fig. 6 a, b, c). Zone I at the distance 20 mm over the crater. Zone II at distance ~2 mm from the center of the substrate plate. Zone III at distance ~ 4 mm from the center of the substrate plate.

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TiN–TiB2 ceramics.

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Table 1.

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Large area Light gray areas Dark gray areas For pure TiN For pure TiB2 For pure [40]: BO B4O5 B2O3 BO2 For pure [40]: Ti2O TiO Ti2O3 TiO2 For pure [41,42]: TiBO3 Ceramic surface after irradiation Near the crater (Fig. 4 a-a’’): Inside grain Intercrystalline boundaries

Ti 74.51 78.56 64.02 77.37 60 – – – – 85.68 74.95 66.6 59.94 44.87

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Initial ceramic surface (Fig. 2a)

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Elemental composition of the TiN–TiB2 ceramics, individual compounds, and irradiated surface of ceramics.

On a 20×20 μm square Spherical particles Midway between the crater and

Content of elements, wt. % N B O 11.35 4.29 11.04 14.48 2.78 4.77 8.31 3.38 14.78 22.63 – – – 40 – – 40.32 59.68 – 35.08 64.92 – 31.06 68.94 – 25.25 74.75 – – 14.34 – – 25.05 – – 33.4 – – 40.06 – 10.13 44.99 Ti/B

70.76 67.67

10.25 –

4.94 –

14.05 32.33

87.57 53.12

– –

7.36 4.57

5.07 40.31

11.898 11.62

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42.66 52.52

– –

19.14 37.81

38.20 9.67

2.23 1.39

On the edge of the sample: On a 20×20 μm square Spherical particles

0.11 0.03

– –

24.08 31.07

75.81 68.9

0.0046 0.000965

Inside crater on a 20×20 μm square: Top part Bottom part

59.50 80.31

– 9.70

0.77 9.47

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sample edge: On a 20×20 μm square Spherical particles

39.73 0.52

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Note: For “near crater” the distance from crater is ~0.5 mm. For “midway” the distance from crater is ~1.4 mm. For “on the edge” the distance from crater is ~2.4 mm.

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Table 2. Elemental composition of deposited ablation products in different areas of the substrate in the cw regime

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Content of elements, wt. % N B O

Ti/B

26.55 23.21

– –

6.70 6.79

66.75 70.00

3.96 3.41

17.03 15.3

– –

6.52 4.02

76.46 80.38

2.612 3.8

0.03 0.05

– –

31.96 31.07

68.01 68.88

0.00094 0.0016

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Zone I Over the crater (Fig. 5 a): On a 20×20 μm square Spherical particles

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Zones of analysis

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Zone II In the middle part of the substrate (Fig. 5 b) On a 20×20 μm square Spherical particles Zone III On the edge of the substrate (Fig. 5 c): On a 20×20 μm square Spherical particles

Note: Zone I on the distance 20 mm over the crater. Zone II on distance ~2 mm from the center of the substrate plate. Zone III on distance ~4 mm from the center of the substrate plate.

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Fig. 1. The scheme of sample irradiation (a) and the deposition of ablation products on the

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substrate. The spot diameter of precipitated ablation products is 10 mm. Zone I is on the distance

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20 mm over the crater. Zone II is at distance ~2 mm from the center of the substrate plate. Zone

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III is at distance ~ 4 mm from the center of the substrate plate.

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Fig. 2. X-ray diffraction patterns of ceramics obtained from the 80 wt. % TiN – 20 wt. % TiB2 mixture (I) and ablation products on the substrate (II). For I: a) the initial ceramics; b) after laser

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treatment. For II: a) precipitated products of the substrate in zone II; b) in zone III.

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Fig. 3. SEM secondary-electron micrograph of the TiN–TiB2 ceramics (a, b). Light gray

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areas correspond to aggregates of TiN grains, dark gray areas correspond to a mixture of

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TiN and TiB2 grains, and black holes are pores.

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Fig. 4. SEM micrographs of the TiN–TiB2 ceramic surface at different distances from point of irradiation (crater). For a, a’ the distance from crater is ~0.5 mm. For b, b’ the distance from

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crater is ~1.4 mm. For c, c’ the distance from crater is ~2.4 mm. On b’’: content of elements in indicated areas.

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Fig. 5. Distribution of elements on the crater surface. Arrows marked TiO2 globule.

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Fig. 6. SEM micrographs of ablated products deposited at different distances from the center to the edge of the substrate. Zone I is at the distance 20 mm over the crater. Zone II is at distance ~2

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mm from the center of the substrate plate. Zone III is at distance ~ 4 mm from the center of the

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substrate plate.

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Fig. 7. Distribution of elements in different zones of deposition of ablation products (see Fig. 6 a, b, c). Zone I at the distance 20 mm over the crater. Zone II at distance ~2 mm from the center of the substrate plate. Zone III at distance ~ 4 mm from the center of the substrate plate.

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Fig. 8. Simplified scheme of formation and spread of ablation products in laser treatment of the

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TiN–TiB2 ceramics.

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Content of elements, wt. % N B O 11.35 4.29 11.04 14.48 2.78 4.77 8.31 3.38 14.78 22.63 – – – 40 – – 40.32 59.68 – 35.08 64.92 – 31.06 68.94 – 25.25 74.75 – – 14.34 – – 25.05 – – 33.4 – – 40.06 – 10.13 44.99

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Large area Light gray areas Dark gray areas For pure TiN For pure TiB2 For pure [40]: BO B4O5 B2O3 BO2 For pure [40]: Ti2O TiO Ti2O3 TiO2 For pure [41,42]: TiBO3 Ceramic surface after irradiation Near the crater (Fig. 4 a-a’’): Inside grain Intercrystalline boundaries

Ti 74.51 78.56 64.02 77.37 60 – – – – 85.68 74.95 66.6 59.94 44.87

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Initial ceramic surface (Fig. 2a)

Ti/B

10.25 –

4.94 –

14.05 32.33

87.57 53.12

– –

7.36 4.57

5.07 40.31

11.898 11.62

Midway between the crater and sample edge: On a 20×20 μm square Spherical particles

42.66 52.52

– –

19.14 37.81

38.20 9.67

2.23 1.39

On the edge of the sample: On a 20×20 μm square Spherical particles

0.11 0.03

– –

24.08 31.07

75.81 68.9

0.0046 0.000965

Inside crater on a 20×20 μm square: Top part Bottom part

59.50 80.31

– 9.70

0.77 9.47

39.73 0.52

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On a 20×20 μm square Spherical particles

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70.76 67.67

Note: For “near crater” the distance from crater is ~0.5 mm. For “midway” the distance from crater is ~1.4 mm. For “on the edge” the distance from crater is ~2.4 mm.

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26.55 23.21

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Zone II In the middle part of the substrate (Fig. 5 b) On a 20×20 μm square Spherical particles

17.03 15.3

– –

Zone III On the edge of the substrate (Fig. 5 c): On a 20×20 μm square Spherical particles

0.03 0.05

6.70 6.79

Ti/B

66.75 70.00

3.96 3.41

6.52 4.02

76.46 80.38

2.612 3.8

31.96 31.07

68.01 68.88

0.00094 0.0016

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Zone I Over the crater (Fig. 5 a): On a 20×20 μm square Spherical particles

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Zones of analysis

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Note: Zone I on the distance 20 mm over the crater. Zone II on distance ~2 mm from the center

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of the substrate plate. Zone III on distance ~4 mm from the center of the substrate plate.

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Graphical abstract

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Highlights: 1. Intensive stationary laser heating of TiN-TiB2 ceramics in air.

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2. Features of distribution of ceramics decomposition products inside crater.

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3. Formation TixByOz compounds inside and outside crater

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4. The change morphology of precipitated films depending on deposition site on substrate.

Figure 1

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Figure 4

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Figure 7