Titanium Oxide and their Effects on Structure, Physical Properties and Electrochemical Corrosion Parameters of Alloys

Materials are so significant in the development of civilization. Almost no metals are used in pure form, but they are always combined with each other to recover one or more properties. An alloy may be defined as a substance that has the metallic properties and is composed of two or more chemical elements of which at least one is a metal. Most alloys are great importance in industry and in the arts than are the pure metals. Several researches reported that, modification structure by adding alloying elements to tin or bismuth-based alloys caused minor/ or major effects on measured physical properties such as elastic modulus, hardness, meting temperature, internal friction, spreading, resistivity and electrochemical corrosion behavior with corrosion parameters [1-17]. Microstructure, mechanical and thermal properties of bismuth or tin based alloys are studied [18-23] studied at different conditions. Matrix structure of these alloys is changed which effects on all measured physical properties.

Titanium and some of its alloys are used as biomaterials for dental and orthopedic applications. Titanium is used in condensers and turbine blades in electric power plants. It is also incorporated into the architecture of buildings, roofs, piping and cable. Titanium dioxide has a wide range of applications, from paint to sunscreen to food coloring. It has eight modifications rutile, anatase, brookite, α-PbO2-like, baddeleyite like, cotunnite -like, orthorhombic OI and cubic phases) also exist. Titanium Dioxide has high gloss, good whiteness, good discernibility, good liquidity, extraordinary hiding power and good coloring power, good weather resisting property and chalk resistance performance. It has the highest refractive index. Titanium dioxide melts at 1843 °C and its density is 4.23gm/cm³.

Sn_82-xBi₁₅Zn₃Ti₂O_x (x= 0.3, 0.6, 0.9 and 1.2) alloys consist of tetragonal β-Sn phase, hexagonal Bi phase, Zn phase with undetected Ti₂O or intermetallic compounds and solid solution from dissolved atoms that changed alloy matrix structure. Adding different ratio (0.5 to 1.5 wt. % at the expense of bismuth) from titanium oxide (TiO₂) to Bi_50-xPb₁₅Sn₂₂Cd₃In₁₀ alloy caused a change in matrix structure such as feature formed phases, crystal size, lattice distortion, lattice parameters, (a and c), and unit volume cell (V) [9] as listed in Table 1. Scanning electron micrographs, SEM, of Bi_{50- x}Pb₁₅Sn₂₂In₁₀Cd₃(TiO₂)_x (x=0 to 1.5 wt.%) alloys show heterogeneous structure (different feature for formed phases with different grain size beside a solid solution) as shown in Figure 1 which agreed with x-ray analysis.

Figure 1: SEM of Bi_50-xPb₁₅Sn₂₂In₁₀Cd3(TiO₂)_x alloys [9].

Table 1: Crystal size, lattice parameters and lattice distortion of rhombohedral Bi phase [9].

Sn_82-xBi₁₅Zn₃Ti₂O_x (x= 0.3, 0.6, 0.9 and 1.2) alloys consist of tetragonal β-Sn phase, hexagonal Bi phase, Zn phase with undetected Ti₂O or intermetallic compounds and solid solution from dissolved atoms that changed alloy matrix structure. From SEM, Figure 2, adding Ti₂O to Sn₈₂Bi₁₅Zn₃ alloy caused a change in its matrix microstructure (quantity, size and orientation of formed phases) [24]. Lattice microstrain, ε, determined from draw the relation between full width half maximum, FWHM, and 4tanθ using Williamson and Hall equation. Lattice microstrain of Sn₈₂Bi₁₅Zn₃ alloy increased after adding titanium dioxide as listed in Table 2.

Table 2: Lattice microstrain of Sn_82-xBi₁₅Zn₃Ti₂)_x alloys [24].

Sn₆₀Bi_30-xSb₆Zn₄Cu_0.7Ti₂O_x (x=0, 0.3, 0.6, 0.9 and 1.2) alloys consist of tetragonal β-Sn phase, hexagonal Bi phase, Zn phase, undetected phases such as Ti₂O or Sb or Cu or intermetallic compounds and solid solution from dissolved atoms [26]. Lattice microstrain of Sn₆₀Bi₃₀Sb₆Zn₄Cu_0.7 alloys varied after adding titanium oxide as listed in Table 3. SEM of Sn₆₀Bi_30-xSb₆Zn₄Cu_0.7Ti₂O_x alloys show heterogeneous structure from formed phases in matrix structure as shown in Figure 3 which agree with x-ray analysis.

Table 3: Lattice microstrain of Sn_82-xBi₁₅Zn₃Ti₂)_x alloys [24].

The Sn₇₆Al₁₀Bi_10-xCu₂Zn₂(TiO₂)_x (x=0.5 to 1.5 wt.%) alloys consist of tetragonal β-Sn phase and hexagonal Bi phase with formed a solid solution or undetected phases. The crystallinity, crystal size and orientations for formed phases of Sn₇₆Al₁₀Bi₁₀Cu₂Zn₂ alloy changed after adding titanium oxide nanoparticles [26]. The estimated crystal size was given through measured diffraction pattern broadening by Scherer formula. Crystal size of β-Sn phase in Sn₇₆Al₁₀Bi₁₀Cu₂Zn₂ alloy varied after adding titanium dioxide as presented in Table 4. Lattice microstrain of Sn₇₆Al₁₀Bi₁₀Cu₂Zn₂ alloy decreased after adding titanium oxide up to 1wt. % and then increased as listed in Table 4. The Sn₇₆Al₁₀Bi₉Cu₂Zn₂(TiO₂)₁ alloy has lower microstrain value. SEM show that adding different ratio from TiO₂ nanoparticles to Sn₇₆Al₁₀Bi₁₀Cu₂Zn₂ alloy changed the shape and size of dendrite structure and disturbed dissolved atoms as grains in it as seen in Figure 4. SEM analysis for used alloys shows heterogeneity structure and that is agreed with x-ray analysis [26].

Figure 2: SEM of Sn_82-xBi₁₅Zn₃Ti₂O_x alloys [24].

Figure 3: SEM of Sn₆₀Bi_30-xSb₆Zn₄Cu_0.7Ti₂O_x alloys [25].

Figure 4: SEM of Sn₇₆Al₁₀Bi_10-xCu₂Zn₂(TiO₂)_x alloys [26].

Table 4: Crystal size of β-Sn and lattice microstrain in Sn₇₆Al₁₀Bi_10-xCu₂Zn₂(TiO₂)_x alloys [26].

Sn₆₁Bi₂₅Sb₅Zn₄Al_3-xAg₂(TiO₂)_x (x=0.3 to 1.2 wt.%) alloys consist of β-Sn phase, hexagonal Bi phase and dissolved Sb, Zn, Al, Ag atoms with TiO₂ nanoparticles or undetected phases in matrix [27]. Crystal size of β-Sn phase in Sn₆₁Bi₂₅Sb₅Zn₄Al₃Ag₂ alloy varied after adding TiO₂ nanoparticles as listed in Table 5. Sn₆₁Bi₂₅ Sb₅Zn₄Al_2.4Ag₂(TiO₂)_0.6 alloy has higher lattice microstrain and lower β-Sn phase crystal size. SEM of Sn₆₁Bi₂₅Sb₅Zn₄Al_3-xAg₂(TiO₂)_x alloys [27], Figure 5, show that the matrix structure of Sn₆₁Bi₂₅Sb₅Zn₄Al₃Ag₂ alloy changed after adding TiO₂ which agree with x-ray analysis and affected all measured properties.

Figure 5: SEM of Sn₆₁Bi₂₅ Sb₅Zn₄Al_3-xAg₂(TiO₂)_x alloys [27].

Sn₈₀Sb₁₅Pb₅ alloy consists of β-Sn and SbSn intermetallic phases. After adding different ratio of titanium oxide (TiO₂) nanoparticles to Sn₈₀Sb₁₅Pb₅ alloy, SbSn intermetallic phase disappeared with changing matrix microstructure [29]. Lattice parameters, (a and c), unit volume cell (V) and crystal size (t) of β-Sn phase in Sn_80-xSb₁₅Pb₅(TiO₂)_x (x= 0, 0.5, 1 and 1.5 wt. %) alloys are determined and then recorded in Table 6. Little variation occurred in lattice parameters and unit volume of β-Sn in Sn_80-xSb₁₅Pb₅(TiO₂)_x alloys but a major variation in β-Sn crystal size after adding titanium oxide nanoparticles. Scanning electron micrographs, SEM, of Sn₈₀Sb₁₅Pb₅ and Sn_78.5Sb₁₅Pb₅(TiO₂)_1.5 alloys show heterogeneous structure as shown in Figure 6 and that agreed with x-ray analysis. Adding TiO₂ caused a change in matrix microstructure of Sn₈₀Sb₁₅Pb₅ alloy.

Table 5: Crystal size of β-Sn and lattice microstrain in Sn₆₁Bi₂₅sb₅Zn₄Al_3-xAg₂(TiO₂)_x alloys [27].

Table 6: Matrix parameters (a, b, c, V and t) of Sn_80-xSb₁₅Pb₅(TiO₂)_x alloys [28].

Figure 6: SEM of Sn_80-xSb₁₅Pb₅(TiO₂)₂ alloys [28].

Sn_60-xAl₂₀Sb₁₅Pb₅(TiO₂)_x (x= 0.5, 1 and 1.5 wt.%) alloys consist of β-Sn, Pb and SbSn intermetallic phases [28]. The determined lattice parameters, unit volume cell and crystal size of β-Sn phase in Sn_60-xAl₂₀Sb₁₅Pb₅(TiO₂)_x recorded in Table 7. A little variation happened in lattice parameters and unit volume of β-Sn in Sn_80-xSb₁₅Pb₅(TiO₂)_x alloys after adding titanium oxide nanoparticles but a major variation occurred in β-Sn crystal size. That is because TiO₂ nanoparticles dissolved in matrix alloy formed a solid solution and resultant in disappeared or appeared phases with changed the shape of rest phases. Dissimilar structure for Sn₆₀Sb₁₅Pb₅Al₂₀ and Sn_58.5Sb₁₅Pb₅Al₂₀(TiO₂)_1.5 alloys are shown in scanning electron micrographs, Figure 7, which agreed with x-ray analysis. That is meant adding TiO₂ caused a change in matrix microstructure [28].

Figure 7: Sn_60-xAl₂₀Sb₁₅Pb₅(TiO₂)_x alloys [28].

 Sn_645-xAg_3.5Bi₃₀In₂(TiO₂)_x (x=0.5, 1 and 1.5 wt. %) alloys consist of β-Sn, Ag₃Sn and hexagonal Bi phases [30]. That is meant that in atoms and TiO₂ nanoparticles dissolved in alloy matrix forming a solid solution with changing microstructure. Lattice parameters, unit volume cell and crystal size of β-Sn in Sn_645-xAg_3.5Bi₃₀In₂(TiO₂)_x alloys are determined and then presented in Table 8. Unit cell volume of β-Sn in Sn_645-xAg_3.5Bi₃₀In₂(TiO₂)_x alloys decreased but lattice parameter, a, and crystal size varied after adding TiO₂ nanoparticles. The internal lattice microstrain of Sn_645-xAg_3.5Bi₃₀In₂(TiO₂)_x alloys also was determined then show in Table 8. Lattice strain of Sn_645-xAg_3.5Bi₃₀In₂(TiO₂)_x increased with increasing TiO₂ nanoparticles ratio.

Table 7: Matrix parameters (a, b, c, V and τ) of Sn_60-xAl₂₀Sb₁₅Pb₅(TiO₂)_x alloys [28]

Table 8: Matrix parameters (a, c, V, τ and ε) of Sn_645-xAg_3.5Bi₃₀In₂(TiO₂)_x alloys [29].

Sn_87-xSb₁₀Pb₃(TiO₂)_x (x=0.5, 1 and 1.5 wt. %) alloys consist of β-Sn, Pb/or Sb and SbSn intermetallic phases [31]. Adding TiO₂ to Sn₈₇Sb₁₀Pb₃ alloy caused a change in Sn matrix structure such as lattice parameters and formed crystal structure (crystallinity, crystal size and the orientation) as seen in Table 9. That is because TiO₂ nanoparticles dissolved in Sn matrix formed a solid solution and other accumulated particles formed a trace of phases. Also Sn_80-xAl₂₀(TiO₂)_x (x=0.5, 1and 1.5 wt.%) alloys consist of β- Sn and Al phases [31]. Adding TiO₂ to Sn₈₀Al₂₀ alloy caused a change in Sn matrix such as lattice parameters and formed crystal structure (crystallinity and crystal size) as seen in Table 10.

Table 9: Matrix parameters (a, c, V and τ) of Sn_645-xAg_3.5Bi₃₀In₂(TiO₂)_x alloys [30].

Table 10: Matrix parameters (a, c, V and τ) of Sn_80-xSb₁₅Pb₅(TiO₂)₂ alloys [30].

Measurement of thermal parameters is very inertial for their applications, particularly in the construction of devices. The melting temperature value of Bi_50-xPb₁₅Sn₂₂In₁₀Cd₃(TiO₂)_x alloys increased after adding TiO₂ nanoparticles which dependent on alloy compositions or alloy structure as presented in Table 11. The melting temperature value of Sn₈₂Bi₁₅Zn₃ alloy is decreased after adding different ratio from titanium oxide as listed in Table 12. The melting temperature value of Sn₆₀Bi₂₉Sb₆Zn₄Cu_0.7 alloy is varied after adding different ratio from titanium oxide as shown in Table 13. But no significant effect on melting temperature value of Sn₇₆Al₁₀Bi₁₀Cu₂Zn₂ alloy after adding titanium dioxide nanoparticles as presented in Table 14.

Table 11: Melting temperature of Bi_50-xPb₁₅Sn₂₂In₁₀Cd₃(TiO₂)_x alloys [9].

Table 12: Melting temperature of Sn_82-xBi₁₅Zn₃Ti₂O_x alloys [25].

Table 13: Melting temperature of Sn₆₀Bi_30-xSb₆Zn₄Cu_0.7(Ti₂O)_x alloys [26].

Table 14: Melting temperature of Sn₇₆Al₁₀Bi_10-xCu₂Zn₂(TiO₂)_x alloys [27].

Melting temperature of Sn₆₁Bi₂₅Sb₅Zn₄Al₃Ag₂ alloy varied after adding TiO₂ nanoparticles as listed in Table 15. It is increased up to 0.9 wt. % TiO₂ nanoparticles and then it’s decreased. Melting temperature of Sn₈₀Sb₁₀Pb₅ alloy decreased after adding TiO₂ nanoparticles as presented in Table 16. Melting temperature of Sn₆₀Al₂₀Sb₁₅Pb₅ alloy varied after adding TiO₂ nanoparticles as presented in Table 17. That is because TiO₂ nanoparticles due a change in matrix microstructure of Sn₆₀Al₂₀Sb₁₅Pb₅ alloy. But melting temperature of Sn_64.5-xAg_3.5Bi₃₀In₂(TiO₂)_x (x=0.5, 1 and 1.5 wt. %) alloys varied after adding TiO₂ nanoparticles as listed in Table 18.

Table 15: Melting temperature of Sn₆₁Bi₂₅Sb₅Zn₄Al_3-xAg₂(TiO₂)_x alloys [28].

Table 16: Melting temperature of Sn_80-xSb₁₅Pb₅(TiO₂)_x alloys [29].

Table 17: Melting temperature of Sn_60-xAl₂₀Sb₁₅Pb₅(TiO₂)_x alloys [29].

Table 18: Melting temperature of Sn_645-xAg_3.5Bi₃₀In₂(TiO₂)_x alloys [30].

Melting temperature of Sn₈₇Sb₁₀Pb₃ alloy decreased after adding TiO₂ nanoparticles as shown in Table 19. The melting temperature of Sn₈₀xAl₂₀(TiO₂)_x (x= 0.5 to 1.5 wt.%) alloys are listed in Table 20. Little increased in melting temperature of Sn₈₀Al₂₀ alloy after adding TiO₂ nanoparticles.

Table 19: Melting temperature of Sn_645-xAg_3.5Bi₃₀In₂(TiO₂)_x alloys [31].

Table 20: Melting temperature of Sn_80-xAl₂₀(TiO₂)_x alloys [31].

A significant change in elastic modulus of Bi_50-xPb₁₅Sn₂₂Cd₃In₁₀(TiO₂)_x (x=0.5 to 1.5 wt.%) alloys with adding different ratio from TiO₂ nanoparticles. Vickers hardness and calculated maximum shear stress of Bi₅₀Pb₁₅Sn₂₂Cd₃In₁₀ alloy increased after adding (TiO₂) as listed in Table 21.

Table 21: Elastic modulus, hardness and maximum shear stress of Bi_50-xPb₁₅Sn₂₂In₁₀Cd₃(TiO₂)_x alloys [24].

Vickers hardness and calculated maximum shear stress of Sn₇₆Al₁₀Bi_10-xCu₂Zn₂(TiO₂)_x alloys at 10 gram force and indentation time 5 sec are presented in Table 22. Vickers hardness value of Sn₇₆Al₁₀Bi₁₀Cu₂Zn₂ alloy varied after adding titanium oxide nanoparticles.

Table 22: Vickers hardness and maximum shear stress of Sn₇₆Al₁₀Bi_10-xCu₂Zn₂(TiO₂)_x alloys [27].

Table 23: Elastic modulus of Sn_80-xSb₁₅Pb₅(TiO₂)_x alloys [29].

Elastic modulus value of Sn_80-xSb₁₅Pb₅(TiO₂)_x (x= 0, 0.5, 1 and 1.5 wt. %) alloys is listed in Table 23. Elastic modulus of Sn₈₀Sb₁₅Pb₅ alloy increased after adding TiO₂ nanoparticles because it’s dissolved in alloy matrix. The stress exponent values of Sn_80-xSb₁₀Pb₅(TiO₂)_x alloys which calculated using Mulheam-Tabor method are given in Table 24. These exponent values are in the range of 2.16 to 3.07 depending on the composition of alloy and that agreed with the pervious results [32,33]. The change in stress exponent values are attributable to microstructural features (such as change in lattice parameters, solid solution, size and distribution of strengthening phases, intermetallic phases) and that is agree with the pervious results [34].

Table 24: Stress exponent (n) of Sn_80-xSb₁₅Pb₅(TiO₂)_x alloys [29].

Elastic modulus of Sn_60-xAl₂₀Sb₁₅Pb₅(TiO₂)_x (x= 0.5, 1 and 1.5 wt.%) alloys are registered in Table 25. Elastic modulus of Sn₆₀Al₂₀Sb₁₅Pb₅ alloy varied after adding TiO₂ nanoparticles. The stress exponent Sn₆₀Al₂₀Sb₁₅Pb₅ alloy decreased after adding TiO₂ nanoparticles as shown in Table 26. These exponent values are in the range of 2.44 to 5.75 depending on the composition of used alloy. Elastic modulus and Vickers hardness values of Sn_64.5Ag_3.5Bi₃₀In₂ alloy decreased after adding TiO₂ nanoparticles as shown in Table 27.

Table 25: Elastic modulus of Sn_60-xAl₂₀Sb₁₅Pb₅(TiO₂)_x alloys [29].

Table 26: Stress exponent (n)of Sn_60-xAl₂₀Sb₁₅Pb₅(TiO₂)_x alloys [29].

Table 27: Elastic modulus and Vickers hardness of Sn_64.5-xAg_3.5Bi₃₀In₂(TiO₂)_x alloys [30].

The elastic constants are directly related to atomic bonding and structure. Elastic modulus and Vickers hardness values of Sn_87-xSb₁₀Pb₃(TiO₂)_x alloys are listed in Table 28. Elastic modulus and Vickers of Sn₈₇Sb₁₀Pb₃ alloy increased after adding different ratio from TiO₂ nanoparticles. Elastic modulus and Vickers hardness values of Sn_80-xAl₂₀(TiO₂)_x (x= 0.5 to 1.5 wt. %) alloys are listed in Table 29. Elastic modulus of Sn₈₀Al₂₀ alloy increased after adding different ratio from TiO₂ nanoparticles. Also, little variation occurred in Vickers hardness at 10-gram force and indentation time 5 sec of Sn₈₀Al₂₀ alloy after adding TiO₂ nanoparticles.

Table 28: Elastic modulus and Vickers hardness of Sn_645-xAg_3.5Bi₃₀In₂(TiO₂)_x alloys [31].

Table 29: Elastic modulus and Vickers hardness of Sn_80-xAl₂₀(TiO₂)_x alloys [31].

The corrosion potential (E_Corr), corrosion current (I_Corr) and corrosion rate (Corr_Rate) of Sn_82-xBi₁₅Zn₃Ti₂O_x (x=0.3 to 1.2 wt. %) alloys are presented in Table 30. Corrosion rate and corrosion current of Sn₈₂Bi₁₅Zn₃ alloy decreased after adding (Ti₂O). The corrosion potential, corrosion current and corrosion rate of Sn₆₀Bi_30-xSb₆Zn₄Cu_0.7(Ti₂O)_x (x= 0.3 to 1.2 wt.%) alloys are listed in Table 31. Corrosion rate and corrosion current of Sn₆₀Bi₃₀Sb₆Zn₄Cu_0.7 alloy varied after adding different ratio from (Ti₂O)_x. Sn₆₀Bi_28.4Sb₆Zn₄Cu_0.7(Ti₂O)_0.9 alloy has better corrosion resistance.

Table 30: Corrosion parameters of Sn_82-xBi₁₅Zn₃Ti₂O_x alloys [25].

Table 31: Corrosion parameters of Sn₆₀Bi_30-xSb₆Zn₄Cu_0.7(Ti₂O)_x alloys [26].

The corrosion current, corrosion potential and corrosion rate of Sn₇₆Al₁₀Bi_10-xCu₂Zn₂(TiO₂)_x (x=0.5 to 1.5 wt.%) alloys in 0.25M HCl are presented in Table 32. Corrosion rate and corrosion current of Sn₇₆Al₁₀Bi₁₀Cu₂Zn₂ alloy decreased after adding 0.5 and 1.5wt. % titanium oxide nanoparticles but increased after adding 1wt. %.

Table 32: Corrosion parameters of Sn₇₆Al₁₀Bi_10-xCu₂Zn₂(TiO₂)_x alloys [27].

Table 33 presents the corrosion potential, corrosion current, and corrosion rate of Sn₆₁Bi₂₅Sb₅Zn₄Al_3-xAg₂(TiO₂)_x (x=0.3 to 1.2 wt.%) alloys. Corrosion rate of Sn₆₁Bi₂₅Sb₅Zn₄Al₃Ag₂ alloy varied decreased up to 0.9wt. % titanium dioxide nanoparticle and then increased with increasing the ratio of titanium dioxide nanoparticle. That is because adding titanium dioxide nanoparticle caused heterogeneous microstructure with affected on microsegregation and reactivity of atoms with HCl solution. The Sn₆₁Bi₂₅Sb₅Zn₄Al_1.5Ag ₂(TiO₂)_1.5 alloy has high corrosion resistance.

Table 33: Corrosion parameters of Sn₆₁Bi₂₅Sb₅Zn₄Al_3-xAg₂(TiO₂)_x alloys [28].

Adding titanium oxide which has low density, high refractive index with higher melting temperature to tin or bismuth-based alloys improved their properties due changed its matrix structure for make it used in different industrial applications.

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