**3.1. Millings 1 and 2: wet**

The diffractograms of millings 1 and 2 (**Figure 2**) show the characteristic peaks of Rutile (TiO<sup>2</sup> ), in which 2θ is equal to 28, 36, 39, and 57° approximately, and it is presented as a tetragonal structure that indicates that the largest amount of powder corresponding to the initial material. The presence of characteristic graphite peaks with a hexagonal structure, in which 2θ is equal to approximately 24, 26, and 70°, is also observed. The most representative titanium carbide peaks have a cubic structure at approximate angles of 2θ that is equal to 36, 41, 61, 72, and 91°. Also, the characteristic peaks of aluminum (Al) of cubic structure in 2θ occurred, being equal to 9, 39, and 78° approximately. Alumina peaks (Al<sup>2</sup> O3 ) with a cubic structure at 2θ equal to 13, 21, and 50° also occurred.

The diffractograms for millings 1 and 2 (**Figure 2**) showed that small amounts of TiC were formed. Milling 2, with a more milling time (7 h) was the one that had the highest intensity TiC peaks, 146 a.u. approximately and at an angle of 2θ = 36°.

#### **3.2. Milling 3: dry and vacuum**

In the diffractograms (**Figure 3**), the characteristic peaks of the Rutile phase or titanium dioxide TiO<sup>2</sup> , the titanium carbide (TiC), and the carbon for each of the samples are observed. The titanium carbide peaks, TiC, occur with their intensity maximums in 2θ equal to 36, 41, 60, 72, and 76°. With these peaks, it was evidenced that the highest intensity occurred at the angle of 2θ being equal to 36° in sample 1, with an approximate intensity of 247 a.u.

#### **3.3. Final milling**

The diffractogram for the powders with an 18-h milling time (**Figure 4**) shows characteristic peaks of rutile, titanium carbides, mica, and hydrated elements that facilitate the formation of hydrides and carbides. The characteristic peaks of titanium carbide (TiC) occurred with an intensity of 150 a.u. at 36°, but also at 2θ being equal to 41, 60, 72, and 76°.

For the 36-h milling time, the intensity of the characteristic peak of TiC at 36° increasing to 350 a.u. was observed (**Figure 5** and **Table 7**). Peaks at 2θ being equal to 41, 60, 72, and 76° were also diffracted, which were observed in the diffractogram for the 18-h milling.

from the oven, it fractured. This result shows that the material at this temperature did not sinter completely. The target subjected to a 1000°C temperature had a yellow color; this change in color is possibly due to the fact that, in the beginning, the pores are full of air, and as it was in oxidizing conditions, when opening the oven, it was discolored by the attack of oxygen on

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In the micrographs (**Figure 6**) for the unsintered and 36-h milling time powders, the presence of two types of particles was observed; some of them had a spherical shape with an approximate

the surface [13]. This target showed a higher consistency than the sintering at 700°C.

**Figure 2.** Diffractograms of millings 1 and 2.

As the milling time increased, the peaks of the X-ray diffractograms widened to twice their height, evidencing a process of internal stress accumulation.

In the sintering process, it was observed that the target subjected to a 700°C sintering temperature turned to a light gray color, and when trying to take it with the tweezers to remove it

**Figure 2.** Diffractograms of millings 1 and 2.

Scanning electron microscopy (SEM) (JSM-5910LV) tests were performed on the powder material with a 36-h milling time and the material sintered at 1000°C to determine size, distri-

The diffractograms of millings 1 and 2 (**Figure 2**) show the characteristic peaks of Rutile (TiO<sup>2</sup>

in which 2θ is equal to 28, 36, 39, and 57° approximately, and it is presented as a tetragonal structure that indicates that the largest amount of powder corresponding to the initial material. The presence of characteristic graphite peaks with a hexagonal structure, in which 2θ is equal to approximately 24, 26, and 70°, is also observed. The most representative titanium carbide peaks have a cubic structure at approximate angles of 2θ that is equal to 36, 41, 61, 72, and 91°. Also, the characteristic peaks of aluminum (Al) of cubic structure in 2θ occurred,

The diffractograms for millings 1 and 2 (**Figure 2**) showed that small amounts of TiC were formed. Milling 2, with a more milling time (7 h) was the one that had the highest intensity

In the diffractograms (**Figure 3**), the characteristic peaks of the Rutile phase or titanium diox-

titanium carbide peaks, TiC, occur with their intensity maximums in 2θ equal to 36, 41, 60, 72, and 76°. With these peaks, it was evidenced that the highest intensity occurred at the angle of

The diffractogram for the powders with an 18-h milling time (**Figure 4**) shows characteristic peaks of rutile, titanium carbides, mica, and hydrated elements that facilitate the formation of hydrides and carbides. The characteristic peaks of titanium carbide (TiC) occurred with an

For the 36-h milling time, the intensity of the characteristic peak of TiC at 36° increasing to 350 a.u. was observed (**Figure 5** and **Table 7**). Peaks at 2θ being equal to 41, 60, 72, and 76°

As the milling time increased, the peaks of the X-ray diffractograms widened to twice their

In the sintering process, it was observed that the target subjected to a 700°C sintering temperature turned to a light gray color, and when trying to take it with the tweezers to remove it

were also diffracted, which were observed in the diffractogram for the 18-h milling.

2θ being equal to 36° in sample 1, with an approximate intensity of 247 a.u.

intensity of 150 a.u. at 36°, but also at 2θ being equal to 41, 60, 72, and 76°.

height, evidencing a process of internal stress accumulation.

, the titanium carbide (TiC), and the carbon for each of the samples are observed. The

O3

) with a cubic structure at

),

bution, particle shape, and local chemical composition.

being equal to 9, 39, and 78° approximately. Alumina peaks (Al<sup>2</sup>

TiC peaks, 146 a.u. approximately and at an angle of 2θ = 36°.

2θ equal to 13, 21, and 50° also occurred.

**3.2. Milling 3: dry and vacuum**

ide TiO<sup>2</sup>

**3.3. Final milling**

**3. Results**

122 Powder Technology

**3.1. Millings 1 and 2: wet**

from the oven, it fractured. This result shows that the material at this temperature did not sinter completely. The target subjected to a 1000°C temperature had a yellow color; this change in color is possibly due to the fact that, in the beginning, the pores are full of air, and as it was in oxidizing conditions, when opening the oven, it was discolored by the attack of oxygen on the surface [13]. This target showed a higher consistency than the sintering at 700°C.

In the micrographs (**Figure 6**) for the unsintered and 36-h milling time powders, the presence of two types of particles was observed; some of them had a spherical shape with an approximate

**Figure 4.** Diffractogram for the powders with an 18-h milling time.

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**Figure 5.** Diffractogram for the powders with a 36-h milling time.

**Figure 3.** Diffractograms of dry and vacuum milling.

4-μm size (**Figure 6c**) and other particles of elongated shape of an approximate 1-μm size (**Figure 6e**). In general, it was found that the powders had an irregular particle size.

For the compacted and sintered material (36-h milling), a regular form of grain size was observed in the micrographs (**Figure 7**), with an average grain size of 5 μm (**Figure 7d**), and with a more regular particle size than the powder material. In the grain distribution, the growth of some grains can be seen at the expense of others, which means that a diffusion

**Figure 4.** Diffractogram for the powders with an 18-h milling time.

**Figure 5.** Diffractogram for the powders with a 36-h milling time.

4-μm size (**Figure 6c**) and other particles of elongated shape of an approximate 1-μm size

For the compacted and sintered material (36-h milling), a regular form of grain size was observed in the micrographs (**Figure 7**), with an average grain size of 5 μm (**Figure 7d**), and with a more regular particle size than the powder material. In the grain distribution, the growth of some grains can be seen at the expense of others, which means that a diffusion

(**Figure 6e**). In general, it was found that the powders had an irregular particle size.

**Figure 3.** Diffractograms of dry and vacuum milling.

124 Powder Technology

**Figure 6.** Micrographs for the unsintered and 36-h milling time powders: (a) 1000×, (b) 2000×, (c) 3000×, (d) 5000×, and (e) 10,000×.

**Figure 7.** Micrographs for the compacted and sintered material (36-h milling): (a) 1000×, (b) 2000×, (c) 3000×, (d) 5000×,

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and (e) 10,000×.

**Figure 6.** Micrographs for the unsintered and 36-h milling time powders: (a) 1000×, (b) 2000×, (c) 3000×, (d) 5000×, and

(e) 10,000×.

126 Powder Technology

**Figure 7.** Micrographs for the compacted and sintered material (36-h milling): (a) 1000×, (b) 2000×, (c) 3000×, (d) 5000×, and (e) 10,000×.

process between particles occurred. The former issue showed that the 1000°C sintering favored the homogenization of grain size.

The chemical analysis performed on the powder material (36-h milling) showed the presence of elements such as silicon (Si), potassium (K), aluminum (Al), titanium (Ti), iron (Fe), and oxygen (O) (**Figure 8**). A high atomic percentage of oxygen and titanium was found (**Table 9**), which was followed by aluminum, silicon, and potassium.

For the sintered target (36-h milling), the chemical analysis (**Figure 9**) showed the presence of elements such as Al, Si, and Ti, which confirms the phases that were revealed in the X-ray diffractograms (**Figure 5**). Such present elements as calcium, potassium, and iron (**Table 10**)

**Figure 8.** Scanning electron microscopy for the powder material (36-h milling).


come from the material being found in the milling jars, as well as some impurities that the

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The presence of alumina in millings 1 and 2 means that the aluminum reacted with oxygen causing oxidation in the material and did not meet its main objective, which was to react with

material absorbed during the sintering process.

**Table 10.** Percentage of elements within the sintered powders.

**Figure 9.** Scanning electron microscopy for the sintered target (36-h milling).

**Element Weight (%) Atomic (%)** O 42.26 64.28 Al 11.61 10.39 Si 6.23 5.36 K 0.54 0.33 Ti 36.76 18.34 Fe 1.75 0.76 Ca 0.55 0.33 Total 100.00 100.00

**4. Discussion**

**Table 9.** Percentage of elements within the powders.

**Figure 9.** Scanning electron microscopy for the sintered target (36-h milling).


**Table 10.** Percentage of elements within the sintered powders.

come from the material being found in the milling jars, as well as some impurities that the material absorbed during the sintering process.

#### **4. Discussion**

process between particles occurred. The former issue showed that the 1000°C sintering

The chemical analysis performed on the powder material (36-h milling) showed the presence of elements such as silicon (Si), potassium (K), aluminum (Al), titanium (Ti), iron (Fe), and oxygen (O) (**Figure 8**). A high atomic percentage of oxygen and titanium was found (**Table 9**),

For the sintered target (36-h milling), the chemical analysis (**Figure 9**) showed the presence of elements such as Al, Si, and Ti, which confirms the phases that were revealed in the X-ray diffractograms (**Figure 5**). Such present elements as calcium, potassium, and iron (**Table 10**)

favored the homogenization of grain size.

128 Powder Technology

which was followed by aluminum, silicon, and potassium.

**Figure 8.** Scanning electron microscopy for the powder material (36-h milling).

**Table 9.** Percentage of elements within the powders.

**Element Weight (%) Atomic (%)** O 45.89 67.14 Al 10.26 8.90 Si 7.62 6.35 K 0.33 0.20 Ti 34.00 16.62 Fe 1.90 0.80 Total 100.00 100.00

> The presence of alumina in millings 1 and 2 means that the aluminum reacted with oxygen causing oxidation in the material and did not meet its main objective, which was to react with

titanium dioxide, to form titanium carbide, as was intended (Eq. (2)). The ethanol added to the mixture of millings 1 and 2, as dispersing liquid, added more oxygen to the material, making it difficult to extract the O<sup>2</sup> molecules from the titanium dioxide.

**References**

Ir Pubns Ltd; 1989

457-462

1423-1431

Weinheim: Wiley-VCH; 1996

[1] Koch CC. The synthesis and structure of nanocrystalline materials produced by mechan-

Titanium Carbide (TiC) Production by Mechanical Alloying

http://dx.doi.org/10.5772/intechopen.76690

131

[2] Murty BS, Ranganathan S. Novel materials synthesis by mechanical alloying/milling.

[3] DCNM by MA Techniques. New Materials by Mechanical Alloying Techniques. Oberursel:

[4] Cahn RW. Materials Science and Technology, Processing of Metals and Alloys. Vol. 15.

[5] Zhang L, Shen H-F, Rong Y, Huang T-Y. Numerical simulation on solidification and thermal stress of continuous casting billet in mold based on meshless methods. Materials

[6] Ye LL, Quan MX. Synthesis of nanocrystalline TiC powders by mechanical alloying.

[7] Hack GAJ. Dispersion strengthened alloys for aerospace. Metals and Materials. 1987;**3**(457):

[8] Dossett JL, Luetje RE. Heat Treating: Proceedings of the 16th Conference. ASM Inter-

[9] Froes FH, DeBarbadillo JJ. Structural Applications of Mechanical Alloying: Proceedings of an ASM International Conference; Myrtle Beach, South Carolina; 27-29 March 1990.

[10] Botero F, Torres JG, Jaramillo HE, de Sanchez NA, Sanchez SH. Diseño de un molino de bolas tipo atritor. Latin American Journal of Metallurgy and Materials. 2009;**S1**(4):

[11] El-Eskandarany MS. Mechanical Alloying: Nanotechnology, Materials Science and

[12] Lü L, Lai MO. Mechanical Alloying. NY, USA: Springer Science & Business Media; 2013 [13] Angelo PC, Subramanian R. Powder Metallurgy: Science, Technology and Applications.

ical attrition: A review. Nanostructured Materials. 1993;**2**(2):109-129

International Materials Reviews. 1998;**43**(3):101-141

Science and Engineering: A. 2007;**466**(1):71-78

Powder Metallurgy. NY, USA: Elsevier Ltd; 2015

New Delhi, India: PHI Learning Private Limited; 2008

Nanostructured Materials. 1995;**5**(1):25-31

national. OH, USA: ASM Press; 1996

ASM International; 1990

The highest concentration of TiC in milling 3 (sample 1), which corresponds to the powder adhered to the milling spheres, can be explained because, at this place, the highest impact energy occurs; consequently, the adhered material is in constant collision with all the parts that make up the milling bowl and this favors the creation of TiC.

The SEM micrographs of the 36-h milling powders showed a wide particle distribution, from about 200 nm through about 1 μm, while the sintered samples showed particles of spherical shape and regular distribution of grains with a size less than 5 μm. This grain distribution was produced by the growth of some grains at the expense of others, that is to say, a diffusion process occurred, and an effective sintering at a 1000°C temperature also took place.
