<?xml version="1.0" encoding="UTF-8"?><!DOCTYPE article  PUBLIC "-//NLM//DTD Journal Publishing DTD v3.0 20080202//EN" "http://dtd.nlm.nih.gov/publishing/3.0/journalpublishing3.dtd"><article xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" dtd-version="3.0" xml:lang="en" article-type="research article"><front><journal-meta><journal-id journal-id-type="publisher-id">OALibJ</journal-id><journal-title-group><journal-title>Open Access Library Journal</journal-title></journal-title-group><issn pub-type="epub">2333-9705</issn><publisher><publisher-name>Scientific Research Publishing</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="doi">10.4236/oalib.1110902</article-id><article-id pub-id-type="publisher-id">OALibJ-130123</article-id><article-categories><subj-group subj-group-type="heading"><subject>Articles</subject></subj-group><subj-group subj-group-type="Discipline-v2"><subject>Biomedical&amp;Life Sciences</subject><subject> Business&amp;Economics</subject><subject> Chemistry&amp;Materials Science</subject><subject> Computer Science&amp;Communications</subject><subject> Earth&amp;Environmental Sciences</subject><subject> Engineering</subject><subject> Medicine&amp;Healthcare</subject><subject> Physics&amp;Mathematics</subject><subject> Social Sciences&amp;Humanities</subject></subj-group></article-categories><title-group><article-title>
 
 
  Effect of Titanium Content on the Structure, Electrical Conductivity and Mechanical Properties of Cu-3wt%Si Alloys
 
</article-title></title-group><contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>C.</surname><given-names>W. Onyia</given-names></name><xref ref-type="aff" rid="aff1"><sup>1</sup></xref></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>E.</surname><given-names>E. Nnuka</given-names></name><xref ref-type="aff" rid="aff2"><sup>2</sup></xref></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>C.</surname><given-names>N. Nwambu</given-names></name><xref ref-type="aff" rid="aff2"><sup>2</sup></xref></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>C.</surname><given-names>M. Ekwedigwe</given-names></name><xref ref-type="aff" rid="aff2"><sup>2</sup></xref></contrib></contrib-group><aff id="aff1"><addr-line>Department of Metallurgical and Materials Engineering, Enugu State University of Science and Technology, Enugu, Nigeria</addr-line></aff><aff id="aff2"><addr-line>Department of Metallurgical and Materials Engineering, Nnamdi Azikiwe University, Awka, Nigeria</addr-line></aff><pub-date pub-type="epub"><day>04</day><month>12</month><year>2023</year></pub-date><volume>10</volume><issue>12</issue><fpage>1</fpage><lpage>14</lpage><history><date date-type="received"><day>21,</day>	<month>October</month>	<year>2023</year></date><date date-type="rev-recd"><day>24,</day>	<month>December</month>	<year>2023</year>	</date><date date-type="accepted"><day>27,</day>	<month>December</month>	<year>2023</year></date></history><permissions><copyright-statement>&#169; Copyright  2014 by authors and Scientific Research Publishing Inc. </copyright-statement><copyright-year>2014</copyright-year><license><license-p>This work is licensed under the Creative Commons Attribution International License (CC BY). http://creativecommons.org/licenses/by/4.0/</license-p></license></permissions><abstract><p>
 
 
  In the present study, the effect of titanium content on the structure, electrical conductivity and mechanical properties of Cu-3wt%Si alloys were investigated. The experimental alloys were produced with various titanium concentrations of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2% and 3% by weight using permanent mould casting technique. Tensile, hardness, impact and conductivity tests were carried out on the cast samples. Micro-structures of the specimens were also analyzed using optical microscopy. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses were used to characterize the cast specimens. The results indicated that the addition of titanium to Cu-3wt%Si alloy refined and modified the structure of the alloy resulting in improvement in the ultimate tensile strength, yield strength, hardness and Young’s modulus of the experimental alloy by 442.3%, 425%, 70.59%, 53.9%, respectively at 1.5wt%Ti content and percentage elongation, impact strength and electrical conductivity by 186.24%, 187.67% and 7.26% respectively at 0.1wt%Ti content. The addition of titanium also led to the formation of CuTi
  <sub>2</sub> phase which further contributed to the increase in strength and hardness of the alloy.
 
</p></abstract><kwd-group><kwd>Cu-3wt%Si Alloys</kwd><kwd> Titanium</kwd><kwd> Electrical Conductivity</kwd><kwd> Mechanical Properties</kwd></kwd-group></article-meta></front><body><sec id="s1"><title>1. Introduction</title><p>Copper and its alloys are among the most commercially important metals because of their relatively good properties, ease of manufacture and numerous applications. They are normally exploited because of their good electrical and thermal conductivity, outstanding resistance to corrosion and ease of fabrication. Copper alloys are generally non-magnetic with medium values of strength and fatigue resistance (Caron, 2001 [<xref ref-type="bibr" rid="scirp.130123-ref1">1</xref>] ; Nwambu et al., 2017 [<xref ref-type="bibr" rid="scirp.130123-ref2">2</xref>] ).</p><p>Structural applications are mostly based on ferrous materials, steels in particular (Nnuka, 1991) [<xref ref-type="bibr" rid="scirp.130123-ref3">3</xref>] but findings have shown that copper alloys (bronzes) are quickly replacing contemporary steel materials for some specific applications especially in components for marine/subsea applications (Nwambu et al., 2017) [<xref ref-type="bibr" rid="scirp.130123-ref4">4</xref>] . Silicon bronze is a copper-based alloy containing silicon as the major alloying element. The commercial silicon bronzes contain 1 to 3wt%Si (Russell &amp; Lee, 2005) [<xref ref-type="bibr" rid="scirp.130123-ref5">5</xref>] . The addition of silicon decreases the density, electrical conductivity and melting point of the alloy. It also improves fluidity and gives excellent welding qualities to Cu-Si alloys.</p><p>Silicon bronzes find applications in electronics, electrical, automobile and building industries for the fabrication of connectors, bolts, electrical conduits, screws, tie rods, lead frames, etc (Kulczyk et al., 2012 [<xref ref-type="bibr" rid="scirp.130123-ref6">6</xref>] ; Ilona et al., 2016 [<xref ref-type="bibr" rid="scirp.130123-ref7">7</xref>] ). Silicon bronzes are also used for tanks, pressure vessels, marine construction, and hydraulic pressure lines (Avner, 1974) [<xref ref-type="bibr" rid="scirp.130123-ref8">8</xref>] .</p><p>Addition of Sn to Cu-Ni alloys with subsequent aging heat treatment has been found to yield Cu-Ni-Sn alloys with good mechanical properties and electrical conductivity (Shankar &amp; Sellamuthu, 2017 [<xref ref-type="bibr" rid="scirp.130123-ref9">9</xref>] ; Kim et al., 1999 [<xref ref-type="bibr" rid="scirp.130123-ref10">10</xref>] ; Plewes, 1975 [<xref ref-type="bibr" rid="scirp.130123-ref11">11</xref>] ; Cribb et al., 2013 [<xref ref-type="bibr" rid="scirp.130123-ref12">12</xref>] ; Cribb &amp; Grensing, 2011 [<xref ref-type="bibr" rid="scirp.130123-ref13">13</xref>] ; Rhu et al., 1999 [<xref ref-type="bibr" rid="scirp.130123-ref14">14</xref>] ). However, some previous researchers (Cribb &amp; Grensing, 2011) [<xref ref-type="bibr" rid="scirp.130123-ref13">13</xref>] reported that a serious segregation phenomenon of Sn element exists in the conventional casting process for Cu-Ni-Sn alloys, which has a negative influence on the subsequent processing and mechanical properties of the alloys. Titanium has been shown to significantly improve the tensile properties of Cu-15Ni-8Sn alloys. Tensile elongation increased from 2.7% for the alloy without Ti to 17.9% for the alloy with 0.3% Ti, while tensile strength increased from 935 MPa to 1024 MPa (Zhao et al., 2017) [<xref ref-type="bibr" rid="scirp.130123-ref15">15</xref>] . Watanabe et al. (2015) [<xref ref-type="bibr" rid="scirp.130123-ref16">16</xref>] found that the addition of 0.04wt%Ti enhanced the strength of Cu-2.0wt%Ni - 0.5wt%Si alloy without reducing its electrical conductivity. The addition of zinc (Nnakwo et al., 2017a) [<xref ref-type="bibr" rid="scirp.130123-ref17">17</xref>] and tin (Nnakwo et al., 2017b) [<xref ref-type="bibr" rid="scirp.130123-ref18">18</xref>] to Cu-3wt%Si alloys resulted in an increase in the hardness and ultimate tensile strength of the alloys. This work will report the effect of titanium additions on the physic-mechanical properties of Cu-3wt%Si alloys.</p></sec><sec id="s2"><title>2. Materials and Method</title><p>The base alloy for this study was produced from commercial pure copper (99.99%) and commercial pure silicon (99.98%). The doped silicon bronze was produced by the addition of titanium in concentrations of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2% and 3% by weight using permanent mould casting technique. A bailout crucible furnace was used for the melting process. For the production of the control alloy cast samples, the required amounts of pure copper in the form of copper wire were first charged into the preheated furnace and melted. A predetermined amount of silicon in powder form was added to the molten copper and stirred. The melt was held for about 10 min to ensure complete dissolution of silicon in the copper melt and stirred again to achieve homogeneity before pouring into preheated permanent mould and allowed to cool to ambient temperature. Subsequently, the Cu-3wt%Si alloys with the additives were produced by repeating the above-described procedure and introducing the different concentrations of titanium.</p><p>A tensile test was carried out on the cast specimens using a Universal Testing Machine (model WDW-10) as per ASTM E8/E8M-22 standard to determine the ultimate tensile strength, yield strength, % elongation and Young’s modulus. Hardness test was carried out on 10 mm &#215; 10 mm long cylindrical test bars machined from the cast samples, using a digital Rockwell hardness tester (model HRS-150) according to ASTM E18-22 standard. Charpy impact testing was performed on the cast samples following the ASTM E23 standard using an impact tester (model JB-300B). The resistivity and conductivity of the experimental alloys were determined based on standard Ohm’s experiment. Structural analysis was carried out on the cast alloy specimens. Prior to the structural analysis, the surfaces of the specimens were ground with different grades of emery papers from rough to fine grades (400, 600, 800 and 1200 μm). After grinding, the specimens were polished to mirror finish using an aluminum oxide powder, rinsed with water and dried using a hand drier. The dried samples were etched with a solution of 10 g of iron (III) chloride, 30 cm<sup>3</sup> of hydrochloric acid and 120 cm<sup>3</sup> of water for 60 seconds. Finally, the surface morphology of the etched samples was examined using an optical metallurgical microscope (Model: L2003A). Scanning electron microscopy (SEM)/energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) analyses of the experimental alloys were carried out on the samples using a TESCAN scanning electron microscope, model number (VEGA III LMH) and a PANalytical X’Pert PRO X-ray diffractometer (XRD) respectively.</p></sec><sec id="s3"><title>3. Results and Discussion</title><sec id="s3_1"><title>3.1. Mechanical Properties and Conductivity of Cu-3wt%Si Alloy</title><p>Figures 1-7 show the effect of titanium addition on the electrical conductivity and mechanical properties ? ultimate tensile strength (UTS), yield strength, percentage elongation, hardness, Young’s modulus and impact strength of the alloy. It is observed from the Figures that the ultimate tensile strength, yield strength, hardness and Young’s modulus increased with increasing concentration of titanium up to 1.5% before decreasing with further increase in concentration of the additive. The addition of 1.5wt%Ti to Cu-3wt%Si alloy resulted in improvement in the ultimate tensile strength, yield strength, hardness and Young’s modulus of</p><p>the experimental alloy by 442.3%, 425%, 70.59% and 53.9% respectively. Maximum ultimate tensile strength, yield strength, hardness and Young’s modulus values obtained were 282 MPa, 210 MPa, 87 HRB and 135 GPa at 1.5wt%Ti content respectively. The addition of 0.1wt%Ti resulted in an improvement in the percentage elongation, impact strength and electrical conductivity of the alloy by 186.24%, 187.67% and 7.26% respectively. Maximum percentage elongation, impact strength and electrical conductivity values obtained were 31.2%, 128.3 J and 24.96 Sm<sup>−</sup><sup>1</sup> at 0.1wt%Ti content respectively. The improvement in the strength and hardness of the alloys was attributed to the presence of refined and modified intermetallic phases in the structure of the alloys. The decrease in the strength and hardness of the alloys at high titanium concentrations was attributed to the coarsening of the grains.</p></sec><sec id="s3_2"><title>3.2. Optical, Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD) Analyses of the Alloys</title><p>The optical, scanning electron microscopy and X-ray diffraction analyses of the alloys are presented in Figures 8-21. <xref ref-type="fig" rid="fig8">Figure 8</xref> presents the micrograph of undoped Cu-3wt%Si alloy casting showing microstructures in which the primary α-copper phase (solid solution of silicon in copper), γ-Cu<sub>0.83</sub>Si<sub>0.17</sub> (Cu<sub>5</sub>Si) and ε-Cu<sub>15</sub>Si<sub>4</sub> intermetallic phases are present. Coarse γ-Cu<sub>0.83</sub>Si<sub>0.17</sub> intermetallic phase (<xref ref-type="fig" rid="fig18">Figure 18</xref>) can be observed at the grain boundaries in the microstructure of the alloy (<xref ref-type="fig" rid="fig8">Figure 8</xref>) and owing to this, the mechanical properties of the undoped alloy are poor.</p><p>Figures 9-17 reveal the presence of Cu<sub>0.83</sub>Si<sub>0.17</sub>, Cu<sub>15</sub>Si<sub>4</sub>, and CuTi<sub>2</sub> intermetallic phases in the structure of the alloys doped with titanium. X-ray diffraction (XRD) analyses of the alloy samples also indicate the presence of these intermetallics in the structure of the alloys (<xref ref-type="fig" rid="fig19">Figure 19</xref> and <xref ref-type="fig" rid="fig21">Figure 21</xref>). It can be observed that</p><p>addition of titanium refines and modifies the morphology of the intermetallic compounds with attendant increase in ultimate tensile strength, yield strength, percentage elongation, hardness, impact strength and Young’s modulus. The grain size decreases with increase in concentration of titanium up to 1.5wt%Ti. The small grain sizes result to increased number of grain boundaries which served as increased impediment to motion of dislocations and consequently increased the ultimate tensile strength, yield strength, hardness and Young’s modulus with corresponding decrease in percentage elongation and impact strength of the</p><p>alloys. Increase in concentration of titanium beyond 1.5wt%coarsened the morphology of the intermetallic compounds which resulted to decrease in the ultimate tensile strength, yield strength and hardness of the alloy. The presence of CuTi<sub>2</sub> compounds in the structure of the alloy further improved the strength and hardness of the alloy.</p></sec></sec><sec id="s4"><title>4. Conclusions</title><p>The effect of titanium content on the structure, electrical conductivity and mechanical properties of Cu-3wt%Si alloy has been investigated. The following conclusions can be made from the experimental results and theoretical analysis:</p><p>・ Undoped Cu-3wt%Si alloy has low mechanical properties due to the presence of coarse γ-Cu<sub>0.83</sub>Si<sub>0.17</sub> intermetallic phase at the grain boundaries of the alloy.</p><p>・ The addition of titanium to Cu-3wt%Si alloy successfully refined and modified the structure of the alloys which resulted in improvement in the ultimate tensile strength, yield strength, hardness, Young’s modulus, percentage elongation, impact strength and electrical conductivity of the experimental alloy by 442.3%, 425%, 70.59%, 53.9%, 186.24%, 187.67% and 7.26% respectively.</p><p>・ The addition of titanium also resulted in the formation of CuTi<sub>2</sub> which further contributed to the increase in strength and hardness of the alloy.</p><p>・ Maximum ultimate tensile strength, yield strength, hardness, Young’s modulus, percentage elongation, impact strength and electrical conductivity values of 282 MPa, 210 MPa, 87 HRB, 135 GPa, 31.2%, 128.3 J and 24.96 Sm<sup>−1</sup> respectively were obtained.</p></sec><sec id="s5"><title>Conflicts of Interest</title><p>The authors declare no conflicts of interest.</p></sec><sec id="s6"><title>Cite this paper</title><p>Onyia, C.W., Nnuka, E.E., Nwambu, C.N. and Ekwedigwe, C.M. (2023) Effect of Titanium Content on the Structure, Electrical Conductivity and Mechanical Properties of Cu-3wt%Si Alloys. Open Access Library Journal, 10: e10902. https://doi.org/10.4236/oalib.1110902</p></sec></body><back><ref-list><title>References</title><ref id="scirp.130123-ref1"><label>1</label><mixed-citation publication-type="other" xlink:type="simple">Mahajan, S., Buschow, K.H.J., Cahn, R., et al. (2001) Encyclopedia of Materials: Science and Technology. Pergamon, Bergama, 1652-1660.  
https://doi.org/10.1016/B0-08-043152-6/00289-8</mixed-citation></ref><ref id="scirp.130123-ref2"><label>2</label><mixed-citation publication-type="other" xlink:type="simple">Nwambu, C.N. and Nnuka, E.E. (2017) Microstructures and Physio-Mechanical Properties of Sand Cast Copper-10%Aluminium Alloys. Journal of Engineering and Applied Sciences, 12, 44-53.</mixed-citation></ref><ref id="scirp.130123-ref3"><label>3</label><mixed-citation publication-type="journal" xlink:type="simple"><name name-style="western"><surname>Nnuka</surname><given-names> E.E. </given-names></name>,<etal>et al</etal>. (<year>1991</year>)<article-title>The Effect of Micro Additives on the Quality and Distribution Pattern of the Secondary Phase in Aluminium-Copper Alloy System</article-title><source> The Nigerian Engineer</source><volume> 26</volume>,<fpage> 30</fpage>-<lpage>37</lpage>.<pub-id pub-id-type="doi"></pub-id></mixed-citation></ref><ref id="scirp.130123-ref4"><label>4</label><mixed-citation publication-type="other" xlink:type="simple">Nwambu, C.N., Anyaeche, I.M., Onwubiko, G.C. and Nnuka, E.E. (2017) Modification of the Structure and Mechanical Properties of Aluminium-Bronze (Cu-10%Al) Alloy with Zirconium and Titanium. International Journal of Scientific &amp; Engineering Research, 8, 1048-1057.</mixed-citation></ref><ref id="scirp.130123-ref5"><label>5</label><mixed-citation publication-type="other" xlink:type="simple">Russell, A.M. and Lee, K.L. (2005) Structure-Property Relations in Nonferrous Metals. John Wiley &amp; Sons, Inc., Hoboken. https://doi.org/10.1002/0471708542</mixed-citation></ref><ref id="scirp.130123-ref6"><label>6</label><mixed-citation publication-type="other" xlink:type="simple">Kulczyk, M., Skiba, J., Przybysz, S., Pachla, W., Bazarnik, P. and Lewandowska, M. (2012) High Strength Silicon Bronze (C65500) Obtained by Hydrostatic Extrusion. Archives of Metallurgy and Materials, 57, 859-862.  
https://doi.org/10.2478/v10172-012-0094-4</mixed-citation></ref><ref id="scirp.130123-ref7"><label>7</label><mixed-citation publication-type="other" xlink:type="simple">Ilona, E.I., Nwambu, C.N. and Nnuka, E.E. (2016) Effect of Modification on the Structure and Mechanical Properties of Aluminium-12% Silicon Alloy. International Journal of Scientific and Engineering Research, 7, 471-475.</mixed-citation></ref><ref id="scirp.130123-ref8"><label>8</label><mixed-citation publication-type="other" xlink:type="simple">Avner, S.H. (1974) Introduction to Physical Metallurgy. 2nd Edition, Mcgraw-Hill Book Company, New York.</mixed-citation></ref><ref id="scirp.130123-ref9"><label>9</label><mixed-citation publication-type="other" xlink:type="simple">Shankar, K.V. and Sellamuthu, R. (2017) Determination on the Effect of Tin Content on Microstructure, Hardness, Optimum Aging Temperature and Aging Time for Spinodal Bronze Alloys Cast in Metal Mold. International Journal of Metalcasting, 11, 189-194. https://doi.org/10.1007/s40962-016-0034-6</mixed-citation></ref><ref id="scirp.130123-ref10"><label>10</label><mixed-citation publication-type="other" xlink:type="simple">Kim, S.S., Rhu, J.C., Jung, Y.C., Jung, Y.C., Han, S.Z. and Kim, C.J. (1999) Aging Characteristics of Thermomechanically Processed Cu-9Ni-6Sn Alloy. Scripta Materialia, 40, 1-6. https://doi.org/10.1016/S1359-6462(98)00400-X</mixed-citation></ref><ref id="scirp.130123-ref11"><label>11</label><mixed-citation publication-type="other" xlink:type="simple">Plewes, J.T. (1975) High-Strength Cu-Ni-Sn Alloys by Thermomechanical Processing. Metallurgical Transactions A, 6, Article No. 537.  
https://doi.org/10.1007/BF02658411</mixed-citation></ref><ref id="scirp.130123-ref12"><label>12</label><mixed-citation publication-type="other" xlink:type="simple">Cribb, W.R., Gedeon, M.J. and Grensing, F.C. (2013) Performance Advances in Copper-Nickel-Tin Spinodal Alloys. Advanced Materials &amp; Processes (ASM International), 171, 20-25. https://doi.org/10.31399/asm.amp.2013-09.p020</mixed-citation></ref><ref id="scirp.130123-ref13"><label>13</label><mixed-citation publication-type="other" xlink:type="simple">Cribb, W.R. and Grensing, F.C. (2011) Spinodal Copper Alloy C72900—New High Strength Antifriction Alloy System. Canadian Metallurgical Quarterly, 50, 232-239.  
https://doi.org/10.1179/1879139511Y.0000000012</mixed-citation></ref><ref id="scirp.130123-ref14"><label>14</label><mixed-citation publication-type="other" xlink:type="simple">Rhu, J.C., Kim, S.S., Jung, Y.C., Han, S.Z. and Kim, C.J. (1999) Tensile Strength of Thermomechanically Processed Cu-9Ni-6Sn Alloys. Metallurgical and Materials Transactions A, 30, 2649-2657. https://doi.org/10.1007/s11661-999-0305-4</mixed-citation></ref><ref id="scirp.130123-ref15"><label>15</label><mixed-citation publication-type="other" xlink:type="simple">Zhao, C., Zhang, W., Wang, Z., Li, D., Luo, Z., Yang, C. and Zhang, D. (2017) Improving the Mechanical Properties of Cu-15Ni-8Sn Alloys by Addition of Titanium. Materials, 10, Article 1038. https://doi.org/10.3390/ma10091038</mixed-citation></ref><ref id="scirp.130123-ref16"><label>16</label><mixed-citation publication-type="other" xlink:type="simple">Watanabe, C., Takeshita, S. and Monzen, R. (2015) Effects of Small Addition of Ti on Strength and Microstructure of a Cu-Ni-Si Alloy. Metallurgical and Materials Transactions A, 46, 2469-2475. https://doi.org/10.1007/s11661-015-2870-z</mixed-citation></ref><ref id="scirp.130123-ref17"><label>17</label><mixed-citation publication-type="other" xlink:type="simple">Nnakwo, K.C., Okeke, I.U. and Nnuka, E.E. (2017) Effect of Zinc Content on the Structure and Mechanical Properties of Silicon Bronze. International Journal of Scientific Research in Science, Engineering and Technology, 3, 179-183.</mixed-citation></ref><ref id="scirp.130123-ref18"><label>18</label><mixed-citation publication-type="other" xlink:type="simple">Nnakwo, K.C., Okeke, I.U. and Nnuka, E.E. (2017) Structural Modification and Mechanical Properties of Cu-3wt%Si-xwt%Sn Alloy. International Journal of Scientific Research in Science, Engineering and Technology, 3, 184-187.</mixed-citation></ref></ref-list></back></article>