Titanium carbide includes nickel oxide hybrid nanocomposites and preparation method

Abstract

The invention relates to Titanium Carbide (TiC) doped Nickel Oxide (NiO) hybrid nanocomposites and theirs preparation method. The nanocomposite of TiC nanoparticles on NiO nanoparticles provides electrical, dielectric and mechanical properties superior to the pure form of NiO nanoparticles, which are widely used as semiconductor materials.

Description

[0001] TITANIUM CARBIDE INCLUDES NICKEL OXIDE HYBRID NANOCOMPOSITES AND PREPARATION METHOD

[0002] TECHNICAL FIELD

[0003] The invention relates to Titanium Carbide (TiC) doped Nickel Oxide (NiO) hybrid nanocomposites and theirs preparation method.

[0004] PRIOR ART

[0005] Nanotechnology, the basic technology of today's and the following centuries' industrial era, is known as the science of controlling matter at the atomic and molecular level. Nanotechnology, which is based on scientific determination and experience, makes a very high contribution to the preservation of the world's habitability as a result of its contribution to the environment, energy, material durability and appropriate consumption. Today, high value-added technology is very important for business lines that require intense competition such as defense industry, medicine, automotive and electronics applications. In recent years, nanotechnological discoveries have made significant progress, especially in materials science and many new products or processes that have entered our lives. Especially when attention is focused on the nanoscale, elements, a very promising class of materials, are expected to develop further in all areas as they completely change their physical, chemical, electrical, optical and mechanical properties. In recent years, nanomaterials have attracted great attention due to their excellent electronic, optical, magnetic, chemical, and thermal properties. Many researchers have recently.

[0006] Nanomaterials have attracted great attention in recent years due to their excellent electronic, optical, magnetic, chemical and thermal properties. Recently, many researchers have focused on the synthesis of crystalline metal oxides at the nanoscale due to their higher surface areas and superior properties. In addition, reducing the synthesis and overall production costs of these nano-metal oxides is of great importance.

[0007] Oxide nanoparticles exhibit extraordinary and unique properties that can be used in many applications. Among them, nickel oxide (NiO) is one of the outstanding p-type semiconductor materials with cubic face-centered cubic (FCC) structure due to Ni2+ vacancies. Besides, it exhibits a large exciton binding energy with a wide band gap (3.6-4.3 eV). NiO nanoparticles (NPs) exhibit excellent chemical stability, durability, low toxicity, cheaper and higher ionization energy and outstanding physical properties. In the known art, it is well known that Ni (3d) states constitute the lowest energy levels of the conduction band in NiO, while 0 (2p) states constitute the highest energy levels of the valence band. It is also known that the hybridization of Ni (3d) and 0 (2p) in the NiOe octahedron of NiO results in the electronic structure. Also, NiO is an antiferromagnetic material with a high electrical resistivity of 1013 (ohm / cm) and a Neel temperature of 523K. Due to to its unique physical properties and chemical stability, NiO nanoparticles can be used in various applications such as optoelectronic devices, photodetectors, solar cells, gas sensors, and solid oxide fuel cells. In addition to these applications, NiO can also be used in electrochemical sure capathe the citors, smart wind and ows, and catalysts. Therefore, NiO is an important transition metal oxide. The electrical conductivity of NiO nanoparticles is attributed to the holes associated with Ni2+vacancies. The stoichiometric composition of NiO shows strong electrical resistance, but the resistance is greatly reduced with Ni2+vacancies. However, the conductivity of NiO can be increased by increasing the Ni vacancies (VNi) and oxygen interstitials (Vo) either by controlling the synthesis process or by appropriate doping of metals. The formation energy for nickel vacancies is the lowest for all defects / substitutions, leading to p-type conductivity of NiO. However, the existence of p-type conductivity of NiO is associated with interstitial oxygen.

[0008] Titanium carbide (TiC) is one of the important carbides formed by the reaction of the titanium element, which is in the fourth group of the periodic table, with carbon. Titanium carbide, which is among the refractory carbides, has been the subject of research for over a hundred years and is expected to be included in research in the coming years. TiC, which is chemically very stable, has a face-centered cubic (FCC) crystal structure. TiC has become a much-studied material in recent years due to its excellent combination of physical properties such as high melting point, low density, hardness and durability, good heat and electrical conductivity. Due to the attractive properties of TiC, it can be used as a nano-structural reinforcement for polymer, metal and ceramic matrix composites; it has widespread application in catalysis, microelectronics and industry. There are studies on the examination of the structure and morphology of TiC nanoparticles and their combination with different compositions. However, studies are needed on the determination of the dielectric properties of TiC nanoparticles. Studies conducted using NiO and TiC materials separately are given below.

[0009] In known technique; NiO nanoparticles were prepared by calcining malate gel using basic nickel carbonate (BNC) and malic acid as raw materials and H2O as solvent. The reaction was examined by TG-DTA, XRD and FT-IR. The particle size and morphology of NiO nanoparticles were a charaa cter zed b,y TEM. It shows that nickel malate can be formed by the reaction of BNC and malic acid; the gel consists of nickel malate and residual malic acid; the precursor can be completely transformed into NiO nanoparticles in air at 400 °C and the prepared sample has a cubic crystal structure with an average diameter of approximately 14 nm according to the Scherrer formula. NiO calcined at 400 °C for 1 h had narrow particle size distribution, weak agglomeration and small particle size. The particle size of NiO increased with increasing temperature. In another study, NiO nanoflakes with an average size of about 2 pm and an average thickness of about 20 nm were successfully synthesized by a simple two-step method. The electrochemical properties of NiO nanoflakes synthesized as anode electrodes of lithium-ion batteries were investigated by conventional charge / discharge tests and showed initial discharge and charge capacities of 1213 mAh g -1 and 902 mAh g -1 at a current density of 100 mA g -1. After 50 cycles, the discharge and charge capacities of the NiO nanoflakes electrode were 1015 and 990 mAh g -1, respectively. The initial discharge and charge capacities of the prepared NiO electrode were 749 and 541 mAh g -1 at a current density of 800 mA g -1 , while after 50 cycles they were 578 and 567 mAh g -1 , respectively.

[0010] Nanoneedle-assembled hierarchical and nanosheet-assembled hierarchical NiO nanoflowers (nanoflowers) were successfullphotocatalysts via a facile hydrothermal method followed by calcination, and we determined their growth mechanism and effects on gas sensing properties. We demonstrated that the gas sensing properties of NiO nanocrystals can be significantly enhanced by tailoring the nanoscale building blocks In ally, it wthe as noticed that nanoneedle-assembled hierarchical NiO structures exhibited faster gas response and recovery than nanosheet-assembled ones. Nanosheet-assembled hisothermscal NiO nanoflowers showed higher gas response to ethanol. In a different study with NiO nanocrystals; they were prepared by calcination of Ni(OH)2 precursor synthesized through a facile ion diffusion controlled by ion exchange membrane without adding any solvent or template.Brunauer-Emmett-Teller (BET) izotermi, X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) isotherm, X-ray photoelectron spectroscopy (XPS) and Ultraviolet-visible (UV-vis) analysis were used to further study the crystallinity, morphology, surface and porosity properties, chemical composition and optical properties. The pseudocapacitive behavior of NiO samples was investigated by cyclic voltammograms (CV) and galvanostatic charge-discharge tests in 2 M KOH. The result analysis reveals that both specific capacitance and surface area decrease with increasing calcination temperatures. Among the NiO samples, NiO-400 nanoflakes calcined at 400 °C have the highest specific capacitance of 381 F g-1 at 2Ag-1 current density, but much lower than that of Ni(OH)2 sample. In addition, UV-vis analysis shows that the absorption peak shifts to red with increasing temperature for the three NiO samples, and NiO-400 has a wide band gap of 3.3 eV, which makes the material interesting for application in photocatalyst.

[0011] The reduction of TiO2 by graphite or metallic titanium was monitored in a graphite resistor X-ray furnace under continuous vacuum. This involved the formation of various oxides, oxycarbides and titanium carbides, which are likely to form between 293 and 2300 K, in a four-step reaction mechanism. In the case of the Ti2O3 phase, an inextinguishable reduced form and an oxidized form were observed, which emerged independently of each other. On the other hand, for the observed Magneli suboxides TinO2n-1, the evolution of the 'crystallographic shift' within their structure was confirmed originally, using the linear variation of their measured molar volumes concerning.

[0012] Ceramic nanoparticles of TiC were successfully synthesized in a SiO2 matrix by high energy ball milling followed by heat treatment. The milling procedure involved milling a mixture of TiO2, Si, and graphite powders at ambient temperature in an inert gas (Ar) atmosphere. Structural evaluation of the powder particles was carried out by XRD, TEM, SEM, EDX, and DSC. XRD results indicate that TiC-SiO2 nonocomposite was produced after 10 h of mechanical activation followed by 7 min of heat treatment at 1473 K (1200 °C). According to the results, TiC-SiO2 nanocomposite was synthesized after 10 h of mechanical activation with heat treatment at 1473 K (1200 °C) for 7 min. The pressure test showed that the TiC-SiO2 composite powder with ceramic matrix had higher toughness (i.e. , less brittleness) than the ceramic material used in single-phase form TiC. TEM results showed that TiC and SiO2 crystallites were in nano-size. The mechanical activation of the powder mixture caused the lattice parameter of titanium carbide to deviate from the standard value. This was due to the increase in the amount of stress and the synthesis of non-stoichiometric ratio of titanium carbide.

[0013] Pure and (% 10, 20 and 30 wt.) titanium carbide (TiC) doped zinc oxide (ZnO) nanoparticles were produced by sol-gel synthesis method. Sol-gel nanoparticle synthesis was carried out by dissolving the solvents in a magnetic stirrer at 90 °C for 4 h. Filtration, drying, mortaring and annealing processes were carried out for the synthesized nanoparticles. The structural and morphological properties of the synthesized ZnO and TiC doped nanoparticles were investigated by field emission scanning electron microscope (FE-SEM), X-ray diffraction (XRD), energy dispersive spectrum (EDX) and Fourier transform infrared spectroscopy (FT-IR) analyses. The dielectric properties of the produced nanoparticles were also investigated. As a result of the analysis, characteristic peaks of TiC and ZnO nanoparticles were observed in XRD analysis. In the XRD analysis results, increases and shifts occurred in the characteristic peaks of TiC with the increase in the amount of TiC additive. As a result of FE-SEM analysis, it was observed that TiC nanoparticles grew in the ZnO structure with the increase in TiC additive. It was observed that TiC doping positively affected the dielectric properties and AC conductivity values of ZnO nanoparticles. In another study, nickel oxide (NiO) nanoparticles were synthesized by sol-gel method. The solution pH was controlled at 11 and the calcination temperature at 450 °C. The structure, morphology and particle size of NiO were investigated. Structural analysis confirmed that the cubic structure of NiO was formed without impurities. Morphological and elemental analyses revealed the ratio of NiO, Ni and O. Morphological analysis showed NiO nanoparticles with an average diameter of approximately 32.9 nm.

[0014] Titanium carbide (TiC) particles reinforced with aluminum alloy (A 6063) were produced using the stir casting method. Titanium carbide was added to the aluminum alloy at 2, 4, 6, 8 and 10 percent by weight. It was observed that the density, hardness and tensile strength of the composites increased to a maximum of 7.8%, 20% and 19.55%, respectively, when titanium carbide particles were added. As a result of mechanical and impact tests performed on titanium carbide (TiC) reinforced hybrid composite plates, it was observed that 3% wt TiC reinforced composite plates had 15% improvement in elasticity modulus and 6% more energy absorption in impact resistance compared to the pure composite plate. In another study; the processing of a multi-phase composite consisting of e-glass fiber reinforced epoxy resin and TiC particles and the solid particle erosion behavior of the composite were investigated. As the TiC particle percentage (0-10-15-20 wt.%) increased, the hardness value increased from 29 to 53 HV and the erosion wear behavior improved significantly, and it was observed that the impact velocity significantly affected the TiC ratio and the impact angle.

[0015] In the known technique, the mechanical and tribological behaviors of epoxy matrix composite reinforced with TiC particles at different ratios (%0-5-10-15-20-25 wt.) were investigated. It was determined that the best results were obtained at 15% wt. ratios for hardness and tensile strength, 10% wt. ratios for wear resistance and 20% wt. In another study produced with hot pressing technique, studies were conducted on estimating the mechanical and physical properties of Cu-TiC composites with artificial neural networks (ANN) model. All the features of TiC effect in density, hardness, electrical conductivity, transverse rupture strength, friction coefficient and wear rate values brought much superior results.

[0016] With the increase in TiC content, both microhardness and ultimate tensile strength of aluminum metal matrix composites were found to increase significantly compared to the base alloy. In the studies on the evaluation of fatigue and impact behavior of titanium carbide reinforced metal matrix composites, it was observed that the fatigue and impact behavior of the composites increased significantly with TiC reinforcement.

[0017] BRIEF DESCRIPTION OF THE INVENTION

[0018] The invention relates to the synthesis and preparation method of hybrid nanocomposites with Titanium Carbide (TiC) nanoparticles as reinforcement element to Nickel Oxide (NiO) nanoparticles. The nanocomposite of TiC nanoparticles on NiO nanoparticles provides electrical, dielectric and mechanical properties superior to the pure form of NiO nanoparticles, which are widely used as semiconductor materials.

[0019] Our invention will easily meet the needs in the defense industry, medicine, automotive, textile and electrical fields thanks to its high bending, tensile and compression strength, high hardness and wear resistance, low density, high thermal conductivity, high resistance to high temperatures and easy machinability. Thus, the deficiencies of the materials used today in these fields are eliminated and it is in competition with equivalent materials. Our invention becomes a nanocomposite material with the metal material it is combined with powder metallurgy when used in the defense industry and provides higher mechanical strength, tribological properties, resistance to high temperatures, better friction and wear conditions with its lubricating properties compared to its equivalents. It has the feature of being used in electronic parts and battery and solar energy panel applications with its high electrical conductivity and high thermal conductivity.

[0020] LIST OF FIGURES

[0021] Figure 1. Views of the Appearance of NiO-TiC Nanomaterial Production Scheme Figure 2. Views of the Appearance of XRD Analysis Results of Nanoparticles A)

[0022] NiO-TiC B) NiO, C) TiC

[0023] Figure 3. Views of the Appearance of Raman Spectra of Nanoparticles A) NiO- TiC B) NiO, C) TiC

[0024] Figure 4. Views of the Appearance of FT-IR Spectra of NiO / TiC Nanoparticles Figure 5. Views of the FE-SEM Appearance of Nanoparticles - 1) A) NiO, B) TiC Figure 6. Views of the FE-SEM Appearance of Nanoparticles - 2 A) NiO-1 TiC, B)

[0025] NiO-5TiC, C) NiO-1 OTiC

[0026] Figure 7. Views of the Appearance of EDX Spectra of Nanoparticles A) NiO, B)

[0027] NiO-1TiC, C) NiO-5TiC, D) NiO-1 OTiC, E) TiC

[0028] Figure 8. View of the EDX mapping of TiC nanoparticles (10 pm magnification)

[0029] A) NiO-1TiC, B) NiO-5TiC, C) NiO-10TiC

[0030] Figure 9. View of the frequency dependence of A) dielectric constant (s'), B) dielectric loss (s"), and C) conductivity (oac) for nanocomposites Figure 10. View of A) l-V curves, B) current-TiC composition for NiO composites containing TiC (1 to 10 wt%) nanoparticles

[0031] Figure 11. View of DC conductivity (ode) of NiO-TiC nanocomposite A) NiO-5TiC,

[0032] B) NiO-1 OTiC

[0033] Corresponding Numbers in Figures

[0034] 1) 1. Beaker

[0035] 2) 2. Beaker

[0036] 3) 3. Beaker

[0037] 4) 4. Beaker

[0038] 5) 5. Beaker DETAILED DESCRIPTION OF THE INVENTION

[0039] With the invention, the production of pure NiO and TiC doped NiO nanoparticles by sol-gel synthesis method was started by adding 0.5 M Nickel (II) acetate tetrahydrate (C^uNiOs) into 25 ml of methanol to the 1st beaker (1) to form Mixture-1 (Methanol+ C^uNiOs) and stirred with a magnetic stirrer until dissolved. Mixture-2 (Methanol+NaOH) was formed by adding 2.5 M Sodium Hydroxide (NaOH) to 25 ml of methanol to the 2nd beaker (2) and stirred with a magnetic stirrer until dissolved by ensuring the pH balance of the solution. These two solutions were combined in the 3rd Beaker (3) and 10 ml more methanol was added to the mixture to form Mixture-3 (NiO). The solution was stirred on a magnetic stirrer at 90°C for four hours. After stirring, the solution was allowed to reach room temperature. The nanoparticles were then filtered with filter paper and washed with alcohol. After the filtration and washing process, the nanoparticles were dried in the oven at 70 ° C. The dried nanoparticles were crushed in a mortar without annealing in the oven at 500 ° C for one hour and then the annealing process was carried out. Thus, pure NiO nanoparticles samples were produced and the same process steps were repeated to produce TiC added NiO nanoparticles. In TiC reinforced nanoparticles, nano-TiC particles were added to 20 ml methanol (1, 5, 10%) in weight percentages and then mixed in the 4th Beaker (4) using an ultrasonic homogenizer for 30 minutes to form Mixture-4 (Methanol + TiC). Mixture-3 and Mixture-4 were added to the 5th Beaker (5) to form Mixture-5 (NiO + TiC) and all procedures performed to obtain pure NiO were repeated to obtain TiC reinforced NiO nanocomposites. The names of the produced nanoparticles with their additive amounts are given in Table 1.

[0040] Sample Contents

[0041] TiC 100% TiC

[0042] NiO 100% NiO

[0043] NiO-1TiC 1% TiC, 99% NiO

[0044] NiO-5TiC 5% TiC, 95% NiO

[0045] NiO-10TiC 5% TiC, 90% NiO

[0046] Table 1. Nomenclature of synthesized nanoparticles and additive amounts

[0047] The functional groups of the synthesized pure and NiO doped TiC nanoparticles were characterized using FT-IR measurements. The analysis was carried out using a FT-IR spectrometer with a scanning range of 4000-500 cm-1 and the XRD peaks of the produced nanoparticles were obtained in the scanning range of 2 = 10 to 80° at 40 kV / 40 mA in CuKa (=1.5406A) radiation. A Raman spectrometer system with excitation wavelengths of 532 and 325 nm was used to produce non-resonant and RRS results, respectively. FE-SEM and EDX analyses were used to analyze the form and chemical content of the nanoparticles, as well as particle sizes and doping degree. Conductivity (Gp), loss factor (DF) and capacitance (Cp) measurements of TiC doped NiO nanoparticles were carried out on 13 mm diameter disks at room temperature. Dielectric properties were investigated using an impedance analyzer with a frequency range of 1 kHz to 2000 kHz.

[0048] The structural information and crystal size of TiC reinforced and pure NiO nanoparticles were investigated by XRD analysis. When the 29 degrees of NiO nanoparticles were examined, it showed five diffraction peaks at 26 of 37.202°, 43.221 °, 62.795°, 75.220° and 79.305° which were related to the COD data of NiO 96-101-0096. These peak values are the characteristic peaks of NiO nanoparticles. According to these data, the Miller indices of NiO correspond to (111), (200), (220), (311) and (222). The obtained results were well matched with the standard monoclinic structure of NiO (03-065-6920) and the JCPDS of the C2 / m space group. Intense peaks corresponding to 35.918°, 41.674°, 60.412°, 72.342°, 76.118° 29 degrees in pure TiC nanoparticles were observed to preserve their characteristic peaks when combined with NiO nanoparticles. With the increase in TiC doping, increases and shifts occurred in the characteristic peaks of NiO and TiC nanoparticles. Diffraction planes in nanoparticles with TiC doping are shown in Table 3.

[0049] Sample / Diffraction NiO NiO-1TiC NiO-5TiC NiO-10TiC Plane

[0050] (111) 37.202 37.233 37.295 37.341

[0051] (200) 43.221 43.268 43.329 43.360

[0052] (220) 62.795 62.811 62.934 62.950

[0053] (311) 75.220 75.282 75.360 75.390

[0054] (222) 79.305 79.352 79.414 79.475 Table 2.29 values of the diffraction planes of the synthesized NiO nanoparticles Sample / Diffraction TiC NiO-1TiC NiO-5TiC NiO-10TiC Plane

[0055] (111) 35.918 35.949 36.010 36.026

[0056] (200) 41.674 41.689 41.798 41.828

[0057] (220) 60.412 60.443 60.551 60.567

[0058] (311) 72.342 72.373 72.420 72.435

[0059] (222) 76.118 76.164 76.242 76.303

[0060] Table 3. 26 values of diffraction planes of synthesized TiC nanoparticles

[0061] The Debye-Scherrer formula given below was used to determine the average crystallite size of NiO nanoparticles. Preferential orientation is observed along the (200) plane.

[0062] D = — (1) Pcos ' '

[0063] Here, D is the average crystallite size of the nanoparticle, k is a constant of ~0.9, A is the wavelength of Cu-ka radiations with energy of 8.04 keV used in XRD measurements, [3 is the full width at half maximum (FWHM) intensity of the peaks and 9 is the Bragg angle. Bragg's law of X-ray diffraction and the interplanar spacing formula for the cubic system given below were used to calculate the lattice constant of NiO nanocrystals.

[0064] nA = 2dsin0 (2)

[0065] and

[0066] 1 > h2+k2+l2

[0067] d2“2(3)

[0068] The lattice parameter of the synthesized nanoparticles was obtained as 4.17 A, which is in good agreement with previous results. To obtain information about the texture and orientation, the texture coefficients for the (hkl) plane were calculated by the formula (TC(hkl)).

[0069] khkl) 'o(hkl)1 L(hkl) - x TC(hki) (4)

[0070]

[0071] N2jTC(hkl) Here, l(hkl) represents the relative density of the considered (hkl), lo(hkl) is the standard density taken from JCPDS card number 47-1049 and N is the number of planes considered. The obtained values are in the range of 0.94 to 1.04. Since TC(hkl)~1, we conclude that the crystallites are randomly oriented. It is calculated using the dislocation density (8) which gives an idea about the disorder of the crystal structure.

[0072]

[0073] Here, D is the crystallite size. 5 was found to be 2.26 X 1015 Iines / m2.

[0074] The lattice parameters of the synthesized TiC-doped NiO nanoparticles are shown in Table 4. As the TiC content increases, the full width half maximum (FWHM) of the peaks changes and an angular shift is observed for the (200) peak compared to NiO due to the change in the ionic radius of Ni2+ (0.69 A). Therefore, surface and strain forces due to the expansion of the NiO lattice can be expected, contributing to the enhancement of the optical and conductivity aspects of NiO nanostructures.

[0075] It is shown that the crystallinity of NiO nanostructures is improved by dual doping, which is attributed to the reduction of defects in NiO nanocrystals. When several previous studies are examined, it has been shown that the doping of transition metal to NiO causes the improvement of NiO crystallinity. When the synthesized nanoparticles are examined, it is observed that with the increase in the amount of TiC doping, there are decreases in lattice parameters, unit cell and crystallite size values.

[0076] Sample 2theta(200) p= FWHM(°) a=b=c(A) D(nm) V(A3) NiO 43.221 0,67812 4,464 22,666 28,890 NiO-1TiC 43.268 0,64041 4,459 16,876 28,800 NiO-5TiC 43.329 0,60303 4,453 16,843 28,685 NiO-10TiC 43.360 0,56077 4,450 16,834 28,626

[0077] Table 4. Calculated a, D and V values of synthesized nanoparticles

[0078] The room temperature Raman spectra of NiO showed a combined phonon (1 P) 1TO and 1LO mode at (-570 cm-1), a two-phonon (2P) 2TO mode at -730 cm-1, (2P)TO, LO mode at -906 cm-1, 2LO mode at -1090 cm-1 and the strongest two-magnon (2M) scattering band at -1490 cm-1. The Raman spectra of NiO nanoparticles showed a broad peak between 300-600 cm-1 which was attributed to two overlapping peaks at 390 cm-1, 534 cm-1 corresponding to 1TO and 1LO optical mode of NiO, respectively. The weak bands around 724 cm-1 and 1069 cm-1 correspond to the 2TO and 2LO stretching modes of NiO, respectively. The disappearance of the 2 M band indicates the decrease of the antiferromagnetic bonding strength in pure NiO nanoparticles due to disorder caused by smaller crystallites and defects. Purely stoichiometric cubic or rhombohedral NiO does not show first-order Raman scattering (1TO and 1LO modes). Therefore, the presence of first-order Raman scattering peaks can be attributed to the disorder caused by nickel or interstitial oxygen vacancies, surface effects and imperfections of the synthesized nanoparticles. Since Raman spectroscopy is considered as one of the most sensitive tools to study the structural properties of carbonaceous materials, it is further used to confirm the presence of graphitic structure in nanocomposites Raman spectrum provides information about the crystal perfection of graphite-based materials. The Raman spectra of TiC nanoparticles synthesized with NiO contain additional three peaks at about 250 cm-1 , 400 cm-1 and 600 cm-1 , which further confirms the formation of TiC.

[0079] According to the FT-IR spectrum, transmittance graph (%) and wave number (cm-1) corresponding peak values of NiO nanoparticles, the broad peak corresponding to 2366 cm-1 can be attributed to O-H stretching vibration. In addition, the peak at 980 cm-1 is attributed to C-0 stretching, implying that ultrafine NiO clusters lead to strong physical adsorption of CO2 and H2O. The strong intense peak located at 521 cm-1 can be attributed to the stretching of Ni-0 bond (Table 5). FT-IR spectra varied with TiC, TiC particles having a peak at 501 cm-1 attributed to Ti-C vibration.

[0080] Bant poison Conclusion

[0081] 2366 cm"1O-H stretching vibrations

[0082] 980 cm"1C-0 stretching vibrations

[0083] 521 cm"1Ni-0 bond grilles

[0084] 1105 cm-1, 1031 cm-1Carbonyl Group

[0085] 1380 Grubu

[0086] 871 cm-1NO-(3A- ) Vibration, Nitro

[0087] group

[0088] 501 cm”1Ti-C stretching vibrations

[0089] Table 5. FT-IR band position and band assignment of NiO-TiC nanoparticles The weight contribution amounts of the elements in the EDX analysis results are shown in Table 6.

[0090] According to the SEM images, it was observed that the particles were nanosized and the TiC nanoparticles were evenly distributed on the NiO nanorods and plates. SEM images revealed that the NiO-TiC particles were synthesized in nanosized. Ni, 0, Ti, and C elements were detected in the EDX spectra. The particle size distributions of spherical NiO nanoparticles were clearly defined and the sizes were well matched with XRD.

[0091] SEM images showed a slight change from nanospheres to nanorods with increasing doping percentage. From the SEM images of NiO and TiC: NiO nanopowders, it was found that highly porous nanoparticles were molded, which was beneficial to the development of active sites on NiO and highlighted the sensing ability of the synthesized samples. FE-SEM images reveal that the nanoparticles change from a regular, layered arrangement to an asymmetric structure of varying sizes with a rough and discontinuous morphology of the layers. This morphology is associated with the application of ultrasound. The passage of ultrasound waves through the dispersed material in a liquid medium leads to the formation of bubbles that collapse when their volume increases, releasing a large amount of energy that can break the material structure. When the distribution of TiC nanoparticles on the NiO structure is examined, TiC nanoparticles maintain their original layered structure; however, they have a very heterogeneous size and shape distribution with some particles being much larger than others, as well as defective lamellae caused by the oxidation process, as evidenced by the irregular ends of the sheets and agglomerates. As a result of EDX analysis, increases in the amounts of Ti and C were observed with the increase of the doping ratio. In the EDX analysis results, it was observed that Ni, 0, Ti and C elements were present in the samples. Sample Content (% by weight)

[0092] Ni O Ti C

[0093] TiC - - 77.10 22.90 NiO 88.07 11.93

[0094] NiO-1TiC 79.26 5.08 3.40 1.78

[0095] NiO-5TiC 71.13 6.07 5.48 3,25

[0096] NiO-10TiC 64.70 7.25 6.41 5.59

[0097] Table 6. EDX analysis results of nanocomposites

[0098] Dielectric constants and dielectric loss factors were measured in the frequency range of 20 Hz to 3 MHz at room temperature. It was found that the values of Dielectric Constant and Dielectric Loss decreased with increasing frequency and the nanocomposite samples showed better electrical properties compared to the pure form of the compounds. The dielectric constant at 1 kHz for the pure form of the compound was found to be 362. For the obtained composite, it was found to be 133.

[0099] As can be seen, the dielectric constant of the composite was observed at a lower value than the composite. From the AC electrical properties results, it was confirmed that the multiple interfaces in the composite samples improved the dielectric properties compared to the composites. In addition, according to another study, it was found that the synthesized NiO-Fe2O3 composite (maximum de conductivity 0.0039 S cm-1) showed higher de conductivity compared to the composite. In other similar studies, the contribution of metals such as lanthanum, cerium, copper and chromium to the dielectric and electrical properties was investigated. Significant improvements in electrical properties were found as a result of the contribution. In this study, the obtained and calculated s', s" and oac values of NiO-TiC nanoparticles for increasing frequencies are shown in Figure 8. These figures show that s' and E" values decrease as frequency increases and reach constant numbers when higher frequencies are reached. It was found that the composite with the highest dielectric constant at low frequencies is the nanoparticle with the highest TiC doping by weight. It was observed that the detected s' values were higher compared to several previous reports and also to the results obtained for the pure form of NiO. The increase in s' values can be attributed to the quantum size state occurring in the synthesized NiO nanoparticles. The E" value also tends to decrease with frequency and is lowest at high frequencies. These values can be explained by the defects in the prepared nanostructures, so a higher value means larger defects in the samples. Table 7 contains the values of dielectric constant, dielectric loss factor and ac conductivity observed at 1 kHz frequency. When the values at 1 kHz frequencies are analyzed, it is seen that there is an improvement in the electrical properties as the TiC content increases.

[0100] Sample Dielectric Dielectric oacAC Constant Loss (E') conductivity conductivity (£') (S / cm) (Log oac) (S / cm) NiO 2Log28 30,639 1,808x1 O’8-7,742 1wt% TiC, 99% NiO 25,548 34,140 2,015x10’8-7,695 5wt% TiC, 95% NiO 47,013 58,009 3,529x1 O’8-7,452 10wt% TiC, 90% 49,596 256,242 1,250x1Q-7-6,902 NiO

[0101] TiC 54,835 9905,399 4,681x1 O’6-5,329

[0102] Table 7. Electrical analysis results at 1 kHz

[0103] As the TiC doping ratio by weight increases, a significant increase in the current value is observed both at constant voltage and at increasing voltages. Table 8 shows the numerical indicators of the change in the current values of NiO and NiO nanoparticles at different voltages.

[0104] Sample 0,1 V 2V 5V 10V

[0105] NiO 2.00x1 O’78.04x1 O'72.23x1 O’65.53x1 O’6

[0106] 1wt% TiC, 99% NiO 2.02x10’79.40x10’73.31x10’61.13x10’5

[0107] 5wt% TiC, 95% NiO 5.01X10’71.04x10’73.23x10’69.55X10’5

[0108] 10wt% TiC, 90% NiO 4.05X10’61.02x10’72.62x10’45.61x10’4

[0109] Table 8. Current values of NiO nanocomposites in different voltage ranges. The change in DC conductivity of NiO composites doped with 5 and 10 wt% TiC was investigated from room temperature to 350 K. As a characteristic property of semiconductor materials, the ode value of TiC doped NiO composites increases with temperature. The composites showed a linear change compared to the change in Ino-1000 / T. This relationship is described by the Arrhenius formula. Here oo is the preexponential factor, Ea is the activation energy, kB is the Boltzmann constant and T is the temperature. The activation energies were found to be 0.038 eV for the 5 and 10 wt% TiC doped composites and 0.023 eV for the 10 wt% TiC doped composites.

[0110] (Ea \ *^dc (6

[0111]

[0112] exP I \FKBF 1 / ) )

Claims

CLAIMS1. It is a hybrid nanocomposite material, characterized by; containing Titanium Carbide (TiC) and Nickel Oxide (NiO) nanoparticles.

Images