The effect of NiO catalyst on reduction, synthesis and binder content of TiC-Ni nanocomposite

Journal Pre-proof The effect of NiO catalyst on reduction, synthesis and binder content of TiC-Ni nanocomposite

Danial Davoodi, Reza Miri, Amir Hossein Emami, Morteza Tayebi, Saman Salahshour PII:

S0263-4368(19)30907-2

DOI:

https://doi.org/10.1016/j.ijrmhm.2019.105175

Reference:

RMHM 105175

To appear in:

International Journal of Refractory Metals and Hard Materials

Received date:

24 November 2019

Revised date:

13 December 2019

Accepted date:

16 December 2019

Please cite this article as: D. Davoodi, R. Miri, A.H. Emami, et al., The effect of NiO catalyst on reduction, synthesis and binder content of TiC-Ni nanocomposite, International Journal of Refractory Metals and Hard Materials(2019), https://doi.org/ 10.1016/j.ijrmhm.2019.105175

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© 2019 Published by Elsevier.

Journal Pre-proof

The Effect of NiO catalyst on reduction, synthesis and binder content of TiC-Ni nanocomposite Danial Davoodi*a,b, Reza Mirib, Amir Hossein Emamic, Morteza Tayebid, Saman Salahshourc

a

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Young Researchers and Elite Club, Najafabad Branch, Islamic Azad University, Najafabad, Iran. b

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Kherad Sanat Arvand Company, Research and Development Unit, Engineering Department, Khorramshahr, Iran. c

-p

Advanced Materials Research Center, Department of Materials Engineering, Najafabad Branch, Islamic Azad University, Najafabad, Iran. d

lP

re

Young Researchers and Elites Club, Science and Research Branch, Islamic Azad University, Tehran, Iran.

Corresponding author: Danial Davoodi

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Tel.: +98 9380051762; fax: +98 3142253789. E-mail: [email protected]; [email protected]

Reza Miri E-mail: [email protected], Tel: +989128462404 Amir Hossein Emami E-mail: [email protected], Tel: +98913 2266369 Morteza Tayebi E-mail: [email protected]; [email protected], Tel: +989130316573 Saman Salahshour E-mail: [email protected], Tel: +989302619829

1

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Abstract In the present study, synthesis of TiC-Ni nanocomposite via magnesiothermic method was investigated. The effects of catalyst content on the mechanisms of TiO 2 reduction and synthesis of TiC-Ni nanocomposite were evaluated. For this purpose, the powder mixture was milled at different NiO content. By adding 0.1-0.3 at.% NiO to the mixture and milling after combustion, it was found that the synthesis did not completely occur. In 0.4 at.% NiO to the mixture, the synthesis was completed and after leaching pure TiC was synthesis. Additionally, the effect of

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NiO on the binder content composite synthesis was examined. It was observed by increasing

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NiO content, combustion time decreased and Ni content in nanocomposite increased. TEM observations confirmed for 0.4 at.% NiO at initial powder pour TiC with spherical morphology

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and for more than 0.5 at.% NiO at initial powder TiC-Ni nanocomposite with semi- spherical

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morphology was synthesis.

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1. Introduction

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Keywords: TiC-Ni nanocomposite; Magnesiothermic reactions; NiO Catalyst; Binder; TiC powder

TiC is one the most attractive materials which is under investigation to be used in industries

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due to special characteristics such as high melting point, great phasic stability, significant hardness, low friction coefficient, outstanding chemical resistance, excellent resistance to

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corrosion and oxidation in rough environments, high elastic modulus and low density [1-3]. However, due to low ductility the application of TiC is restricted [4, 5]. For this reason, it was tried to increase the ductility of TiC by combining with metallic materials like Mo and Ni which have good wettability in contact with TiC. Additionally, the ductility can be modified by creation of nanostructure, so it could be used in cutting tools, high-temperature heat exchangers, different turbine components and heat-resistance coatings in the form of powder or bulk [6, 7]. TiC is synthesized by different methods including direct reaction of Ti and C in temperatures higher than 2000 ˚C [8-12], thermal plasma synthesis [13], carbothermal reduction [14, 15], chemical vapor deposition (CVD) [16, 17], petroleum coke salt bath [18] and self-propagating hightemperature synthesis (SHS) [12, 19-23]. According to Table 1, all of the mentioned methods require high temperature, expensive equipment and long-time process. For this purpose, 2

Journal Pre-proof researchers have shown interest in mechanically inducing self-sustaining reactions (MSR) method, so as to be able to synthesize TiC or its composites and cermets just by mixing raw oxide materials plus carbon and magnesium by mechanical milling at ambient temperature. In this process synthesis is done because of occurring combustion of raw materials and successive cold-weld and fracture cycles during the milling [24]. MSR technique is a complex technique with aspects and details of which are not fully investigated, yet. Therefore, it is not still used in industrial applications. One of the complexities of this procedure is lack of full-control during the process. Because the process takes place in the form of combustion in a sealed container, it is

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hard to control the reaction progress and TiC-to-metallic binder ratio. Thus, in the present

ro

investigation, attempts were made to prepare high purity nanosized TiC-Ni composite using TiO2 , NiO, Mg, and graphite raw materials through mechanochemical synthesis during the

re

-p

shortest possible time.

Temp.

Time

Product

Ref.

RT

30 min

TiC-Al2 O3 TiC

[25]

TiC-Ni TiC-Ni-Mo

[11]

TiC/multilayer graphene

[26]

Ti, C, Ni, Mo powder

RT 2000 °C

24 hours

Thermal plasma

Titanium ethoxide, Titanium isopropoxide, Titanium butoxide

168-231 °C

10 min

Direct reaction

Carbon nanotubes, Ti powder

1300 °C

30 hours

Ultrasonication, wet milling and SPS

MWCNTs, Ti powder

1050 °C

5 min

Melting-casting process

Graphite, Cu powder, Ti

700 °C 1150 °C ~ 1250 °C

Milling

Titanium and asphalt

RT

SPS

Ti, Ni and C powder

Milling, SPS

Ti, Ni and activated carbon

Milling, thermal explosion

Ti, Al and C powder

Milling

Ti, activated carbon powder

2 hours 30 s 30 hours 45 hours 5 min 2 min 8 hours 8 min 6 hours 185–186 s 48-144 hours

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Direct reaction

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SHS

Reactant Mg, Al, wood dusts, activated carbon, TiO2 powders

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Method

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Table 1 Different method and combustions time

1100 °C 1200 °C RT 1000 C-1250 °C RT 700 °C ~RT

3

TiC Nanotubes, TiC Nanowires, Carbon Nanotubes TiC-modified carbon nanotubes, TiC nanotubes, TiC nanorods

[7]

[27]

Cu-TiC

[28]

TiC

[29]

Ni–TiC

[30]

TiC-Ni

[31]

Al-TiC

[32]

TiC

[33]

Journal Pre-proof TiC

[34]

Al, Ti, nanodiamonds

RT

6-8 hours

TiC-Al

[35]

Fe, Cu, Ti, Graphite

RT 200 °C 1100 °C

6 hours 2 min 6 min

Fe-Cu-TiC

[36]

NiO and TiO2 , nano-sized carbon powder

RT 1000 °C

4 hours 3 hours

Ni-TiC

[6]

TiCl4 and CaC2

500 °C

8 hours

TiC

[1]

Titanium(IV) isopropoxide, Polyvinylpyrroliodine, cobalt acetate tetrahydrate

850 °C

6 hours

Co-TiC-CNFs

[37]

Al, Ti, carbon nanotubes

RT

8 hours

TiC-Al–Zn–Mg–Cu

[38]

Ti, graphite powder

RT

24 hours

TiC-Ti

[3]

Al, Fe2 O3 , Cr2 O3 , NiO, ZrO2 , Y2 O3 , Ti, and graphite

RT 110℃

2 hours 2 hours

ZTA-TiC-FeCrNi

[4]

2. Experimental

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2.1. Nanocomposite synthesis

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30 min

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Combustion synthesis and hot press Milling and cladding process High-gravity combustion synthesis

1400 °C

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Electrospinning of a sol-gel

TiO2 , carbon black powder

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Carbothermal reduction Mechanical alloying Mechanical alloying and combustion synthesis Electrochemical ly in molten chlorides Directly synthesized

TiO2 , NiO, Mg and graphite powders were used to synthesize TiC-Ni nanocomposite samples

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based on reaction of Eq. 1. Details and morphologies of the raw materials are presented in Table 2 and Fig. 1, respectively. Synthesis process was carried out using milling at 600 rpm with

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powder-to-ball ratio of 1:20 under argon atmosphere (99.99% purity). In order to avoid the elevation of temperature during milling, the mill process was stopped every 45 min for 15 min. To improve the efficiency of the synthesis progress and reduction of TiC-Ni nanocomposite, preactivation was employed to produce finer particles. Details of the mentioned process is brought in an earlier investigation [39]. (

)

(

)

Table 2 Properties of initial powders 4

(x= 0-1)

(1)

Journal Pre-proof Particle size (μm) 50 40 20 5

Purity (%) 99.8 99.8 99 99

Company Merck Merck Merck Merck

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Material TiO 2 NiO Mg Graphite

2.2. Leaching process

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Fig. 1 Morphology of initial powder: (a) TiO2 , (b) NiO, (c) graphite, and (d) Mg

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Mg powder was utilized as a reduction agent in the magnesiothermic reaction to reduce the oxide materials. After the reaction it was converted to MgO as the reaction byproduct. To

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eliminate the undesirable phase from the final product, a leaching process was carried out at 80 °C by HCl 9% solution for 30 min [39-41]. 2.3. Characterization X-ray diffraction (XRD) analysis (Philips model PW30-40, Netherlands) was utilized to characterize the present phases in the nanocomposite samples with 2θ=10–80° and step size of 0.05° under the working current and voltage of 30 mA and 30 kV, respectively. For all the experiments, Cu-Kα radiation (λ=1.5405 Å) was employed. To determine the existent phases in the prepared nanocomposite samples, X'pert HighScore Software was used. Additionally, scanning electron microscope (SEM) (Camscan model MV2300, USA) and transmission

5

Journal Pre-proof electron microscopy (TEM) (Philips model CM120, Netherlands) were employed to investigate the morphology and particle size of the prepared nanocomposite samples, respectively. 2.4. Thermodynamic studies Thermodynamic calculations were carried out based on free energy, enthalpy of formation and reactions adiabatic temperatures. The attained data were analyzed by HSC Chemistry Software (Version 5.0), consistent with Eq. 2 [42]. (

)

∑

∫

(

)

Eq. 2

of

∫ ∑

Where, ΔH˚298 , ΔHm , ΔQ and Cp are representations of change of standard formation enthalpy at

ro

298 °C, change of melt latent heat, total heat of reaction and specific thermal capacity,

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respectively. Crystallographic studies including internal strain (induced during milling process) and crystallite size of TiC-Ni nanocomposite samples were also carried out. The analyzes were

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done by Rietveld method via MAUD Software. They were carried out by means of precise fitting

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3. Results and discussion

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of the XRD patterns. The fitting was done using GoF function.

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3.1. Thermodynamic characterization and possible reactions To evaluate the thermodynamic behavior of the synthesis process, occurrence of possible

process,

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reaction was determined. Additionally, in order to conclude the nature of mechanochemical theoretical

adiabatic

temperatures

of

the

reactions

were

determined

using

thermodynamic data and the reaction type in the milling vial. Theoretical approach of TiC-Ni nanocomposite preparation by mechanochemical process and use of oxide raw materials is described in the following sections. Also, it should be mentioned that synthesis process occurred in a millisecond after combustion in the vial. 3.1.1. Carbothermic reactions Thermodynamically, in presence of carbon, reduction of TiO2 and NiO is not spontaneous. Standard enthalpy and Gibbs free energy values of these reaction are displayed in Table 3. The reactions are considered endothermic and they are not spontaneous as MSR. Hence, long-time 6

Journal Pre-proof milling for the raw materials or a finalizing process e.g. a heat treatment is required for occurrence of reaction [43]. The reduction of oxide phase in the ternary system of graphite, TiO2 and NiO is not basically achieved by graphite. Table 3 Thermodynamic data of carbothermic reduction reactions No.

∆G (

Reaction ( )

3

( )

4

+723.663

+495.082

+551.242 +539.161

+434.256

6

( ) ( ) ( )

366.740

+708.588

+760.245

+74.433

+129.158

+28.836

+85.895

+509.500

+594.190

+689.546

+852.821

-p

9

+314.225

ro

8

of

( ) ( )

( )

re

10

( )

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11

)

+615.113

5 7

∆H (

)

In presence of magnesium the reaction type is different, i.e. reaction of NiO and TiO2 with

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Mg is extremely exothermic. As it can be seen in Table 4, reduction of NiO and TiO2 powders is spontaneous in a way that they release 361900 J/mol and 258452 J/mol heat, respectively. The

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calculated adiabatic temperatures for reaction of Mg with NiO and TiO2 were 3106 K and 2219 K, respectively. This reveals the likelihood of self-progressive reaction synthesis at elevated

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temperatures. By studying the thermodynamic data for simultaneous reaction of NiO and TiO2 with Mg, it can be interpreted that the reaction is exothermic and its adiabatic temperature is 2853 K that means the possibility of reaction occurrence during milling. Table 4 Thermodynamic data of magnesiothermic reduction reactions No

∆G (

Reaction

)

∆H (

)

(K)

12

-357.769

-361.900

3106

13

-249.292

-258.452

2219

14

-607.061

-620.352

2853

7

Journal Pre-proof Regarding Table 5, after reduction of NiO and TiO2 the reaction with graphic was studied and it was revealed that TiO2 presence in the system can result in formation of TiC. The reactions of 15 and 16 with graphite are both exothermic with adiabatic temperatures of 3670 K and 3077 K, respectively. additionally, they are both spontaneous. Table 5 Thermodynamic data of the synthesi reactions ∆G (

Reaction

)

∆H (

)

(K)

-180.857

-184.502

3670

16

-430.149

-442.954

3077

17

-787.918

-804.854

3297

ro

15

of

No

-p

3.2. XRD characterization

XRD patterns of Eq.1 reaction with different NiO atomic percentages (x=0-0.4) are brought in

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Fig. 2. As it can be seen, the XRD pattern of initial mixture powder (Fig. 2a), the peaks of TiO2 ,

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NiO, Mg and graphite are present. After milling with x=0.1, the peaks of TiO2 were still existing (Fig. 2b), but their intensities decreased and the peaks are broadened, which is due to finer particle sizes, creation of crystalline defects and enhancement of lattice strains [44]. The

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combustion did not occurred after milling for 1000 min. This is attributed to low amount of catalyst, requiring very prolonged milling times for the combustion to occur [39]. For x=0.2, the

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XRD pattern is presented in Fig. 2c, that MgO, TiC and Ni peaks are evident in the pattern. As it

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is evident in the figure, TiO2 peaks are still observed in the pattern since the reaction did not progressed completely. Based on the pattern in Fig. 2d, it is obvious that small amount of TiO2 was still present in the system and the synthesis did not progress completely (x=0.3). Moreover, the peak intensities decreased considerably and they were broadened. This confirms the nanoscale dimensions of the particles or crystalline structure. In order to complete the synthesis procedure, another sample with 0.4 at% NiO was milled. Regarding Fig. 2e, it resulted in formation of TiC, Ni and MgO phases without TiO 2 . Afterwards, the specimen was leached to remove MgO phase. The related XRD pattern is shown in Fig. 2f and it can be seen that pure TiC remained. Since the oxide raw materials reduced by magnesium, presence of a catalyst is essential for progress of the reaction.

8

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TiO2 G NiO Mg

TiC Ni MgO

(e)

(d)

of

Intensity (a. u.)

(f)

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(c)

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(b)

20

30

lP

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(a)

40

50

60

70

80

90

na

2 Theta (deg.)

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Fig. 2 XRD patterns of TiO2 , NiO and graphite powder mixtures with addition of NiO: (a) 0 at.%, (b) 0.1 at.%, (c) 0.2 at.%, (d) 0.3 at.%, (e) 0.4 at.%, and (e) 0.4 at.% after leaching

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To evaluate the effect of catalyst increase on the synthesis time and binder content, x=0.5-1 NiO was added to the system according to Eq. 1. XRD patterns of the powder mixtures with different NiO contents were displayed in Fig. 3. By rising the NiO content from 0.5 to 1 at%, combustion time decreased from 100 to 30 min, respectively. On the other side, enhancement of the catalyst content in the system after the combustion resulted in increase of the Ni atomic fraction. Moreover, by improving the NiO content in the system and formation of TiC and CO, the milling process enhanced the possibility of contact between Mg and oxide particles, which resulted in completion of reduction reactions and increase of Ni after the combustion. Indeed, presence of NiO and its reduction by graphite is a high exothermic reaction, which causes the released heat in the system to increase. The high amount of released heat is the main reason for

9

Journal Pre-proof NiO to be recognized as the catalyst that provides the requiring energy for completion of the reaction.

TiC Ni MgO (i)

of

(e)

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(d)

(c)

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Intensity (a. u.)

(f)

re

(b)

30

40

50

60

70

80

90

100

2 Theta (deg.)

ur

20

na

lP

(a)

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Fig. 3 XRD patterns of TiO 2 , NiO and graphite powder mixtures with addition of NiO: (a) 0.5 at.%, (b) 0.6 at.%, (c) 0.7 at.%, (d) 0.8 at.%, (e) 0.9 at.%, (f) 1 at.%, and (g) 1 at.% after leaching

It should be mentioned that no intermetallic phases are formed in the system, it is related to the preactivation process and increase of effective surface of the powder particles. On the other hand, in the system Mg and graphite powder particles randomly covered the surface of oxide particles. Basically, graphite prevented the contact of Mg and oxide particles. This phenomenon plays role in the combustion time. In fact, with improving the contact of Mg and oxide particles, combustion time shortens. To determine the binder content after combustion, the system was examined with various NiO atomic fractions. When NiO catalyst content was selected as 0-0.3 at%, the synthesis did not 10

Journal Pre-proof complete, hence the calculations were done for 0.5-1 at%. For this reason, Ni content was calculated after the synthesis by XRD patterns based on the NiO amount (Fig. 3). By fitting the graph in the figure to a polynomial function, an experimental correlation was obtained (Eq. 18 and 19). It is apparent that Ni content was elevated by increasing the NiO fraction, while the

30

140

25

120

of

ro

20

15

100

80

y = -70.57+200.39x-101.79x2

-p

Ni content, at.%

y = 332-483.46x+176.78x2

60

re

10

Combustion time Ni content

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5 0.5

0.6

0.7

Combustion time , min

combustion time declined. Both of the trends were nonlinear.

40

20 0.8

0.9

1.0

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NiO content, at.%

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Fig. 4 Fitting of combustion time and Ni content mathematical function based on added NiO with experimental data. Solid points represent experimental data and continuos line represents mathematical model

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3.6. FESEM and TEM observations One of the main challenges in composite preparation is to achieve uniform distribution of the reinforcement in the matrix [45]. Hence, FE-SEM equipped with X-ray mapping analysis was utilized to investigate the distribution of TiC phase in the nickel matrix and evaluate the influence of leaching process on the complete removal of MgO phase before and after the process for x=1. As it is shown in Fig. 5, the analysis of magnesium and oxygen elemental mapping confirms the existence of MgO phase before the process; however, MgO phase is not visible in the mapping analysis after the leaching (Fig. 6). According to XRD pattern and elemental mapping analysis, it is evident that MgO phase was completely removed after the process. In addition, based on the fact that in the micrographs, every color spot characterizes an 11

Journal Pre-proof individual element in that specific area (e.g. C and Ti represent TiC phase), it can be suggested that TiC reinforcement particles were uniformly distributed in the Ni matrix, both before and

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after the leaching process.

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Fig. 5 FE-SEM micrograph and elemental mappings of milled sample for 1 at.% NiO before leaching

12

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Fig. 6 FE-SEM micrograph and elemental mappings of milled sample for 1 at.% NiO after leaching Rietveld method uses analytical functions to model the XRD patterns and attributes the peak intensity to crystalline structure. This method presents a simulated pattern by considering the crystalline parameters, XRD peak shape and width, and background parameters. In this technique, parameters of 2θ correction, peak broadening and peak symmetry were computed according to a reference pattern. Thus, crystallite size and internal strain of the particles can be calculated by comparing the peak positioning and peak broadening to the reference pattern. In this study, the data of crystallite size and lattice strain were determined for TiC-Ni nanocomposite samples and it was found that the crystallite size changed from 12 nm to 21 nm for Ni particles, while it varied from 27 nm to 51 nm for TiC particles. On the other side, the lattice strain for Ni and TiC crystallites varied from 0.0009 to 0.00025 and from 0.00093 to 13

Journal Pre-proof 0.00115, respectively. Interestingly, it was observed that the lowest crystallite size was attributed to sample, which was synthesized gradually. TEM micrographs of TiC-Ni nanocomposite and pure TiC samples containing NiO= 1 and 0.4 are shown in Fig. 7, respectively. Fig. 7a reveals that during synthesis with NiO=1, the nanocomposite sample had semi-spherical morphology with particle size of 64±2 nm. Fig. 7b represents the microstructure of the sample with NiO=0.4. The particle size of this sample (38±5 nm) was finer along with spherical morphology compared to the sample that was synthesized with NiO=1. The results revealed that catalyst had a strong influence on coarsening of the

of

particles that can be due to prolonged milling time, which resulted in formation of fine spherical

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particles.

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Fig. 7 TEM micrograph of synthesized sample: (a) TiC, (b) TiC-Ni nanocomposite

4. Conclusions

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For 0.1 at% NiO addition to the system as catalyst and milling for 1000 min no combustion occurred. The synthesis did not completely occur in the range of 0.2 to 0.3 at%, while at catalyst amount of 0.4 at%, the synthesis was completed in a way that after leaching, pure TiC was obtained. Increasing the NiO content not only resulted in shortening the synthesis time, but also enhanced the Ni binder in the nanocomposite after removal of MgO during leaching process. TEM results confirmed that when x=0.4 and 1, fine particles with the size of 38±5 nm and 64±2 nm, and spherical and semi-spherical morphologies were obtained, respectively, which is ideal for coating applications.

14

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Highlights

TiC-Ni nanocomposite was prepared by magnesiothermic reaction with 64±2 nm size

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TEM images confirmed that the obtained pure TiC had spherical morphology

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It was found that NiO acted as both catalyst and binder of TiC-Ni nanocomposite

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By increasing the NiO content from 0 to 0.4 pure TiC was obtained

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Pure TiC and TiC-Ni nanocomposite were produced by NiO=0.4 and Ni>0.4,

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

respectively

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Journal Pre-proof Highlights



TiC-Ni nanocomposite was prepared by magnesiothermic reaction with 64±2 nm size



TEM images confirmed that the obtained pure TiC had spherical morphology



It was found that NiO acted as both catalyst and binder of TiC-Ni nanocomposite



By increasing the NiO content from 0 to 0.4 pure TiC was obtained



Pure TiC and TiC-Ni nanocomposite were produced by NiO=0.4 and Ni>0.4,

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respectively

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Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

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☒The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:

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There is no financial interests/personal relationships.

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Prime Novelty Statement

MSR technique is a complex technique which its aspects and details are not fully investigated, yet. Therefore, it is not still used in industrial applications. One of the complexities of this procedure is lack of full-control during the process. Because the process is taken place in the form of combustion in a sealed container, so it is hard to control the reaction progress and TiC-

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to-metallic binder ratio. Thus, in this investigation it was attempted to formulate the reaction

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progress based on required nickel content by changing the catalyst amount. Therefore, the

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reaction progress could be controlled by adjusting the amount of the initial catalyst.

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We have no conflict of interest to declare.

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