<?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">AMPC</journal-id><journal-title-group><journal-title>Advances in Materials Physics and Chemistry</journal-title></journal-title-group><issn pub-type="epub">2162-531X</issn><publisher><publisher-name>Scientific Research Publishing</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="doi">10.4236/ampc.2021.1112021</article-id><article-id pub-id-type="publisher-id">AMPC-114259</article-id><article-categories><subj-group subj-group-type="heading"><subject>Articles</subject></subj-group><subj-group subj-group-type="Discipline-v2"><subject>Chemistry&amp;Materials Science</subject><subject> Physics&amp;Mathematics</subject></subj-group></article-categories><title-group><article-title>
 
 
  Structural Features and Properties of the Vitreous Part of the System 50P&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt;-25CaO-(25-x)Na&lt;sub&gt;2&lt;/sub&gt;O-xCoO (with 0 ≤ x ≤ 25; mol%)
 
</article-title></title-group><contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Brahim</surname><given-names>Bachachir</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>Yassine</surname><given-names>Er-Rouissi</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>Radouane</surname><given-names>Makhlouk</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>Achraf</surname><given-names>Harrati</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>Abdeslam</surname><given-names>El Bouari</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>Said</surname><given-names>Aqdim</given-names></name><xref ref-type="aff" rid="aff1"><sup>1</sup></xref><xref ref-type="corresp" rid="cor1"><sup>*</sup></xref></contrib></contrib-group><aff id="aff1"><addr-line>Faculty of Sciences Ain Chock, Laboratory of Materials Engineering for Environment and Valorization, Hassan II University, Casa-blanca, Morocco</addr-line></aff><aff id="aff2"><addr-line>Faculty of Sciences Ben-M’sik, Laboratory Physical-Chemistry of Applied Materials, Hassan II University, Casablanca, Morocco</addr-line></aff><pub-date pub-type="epub"><day>28</day><month>12</month><year>2021</year></pub-date><volume>11</volume><issue>12</issue><fpage>254</fpage><lpage>266</lpage><history><date date-type="received"><day>13,</day>	<month>October</month>	<year>2021</year></date><date date-type="rev-recd"><day>26,</day>	<month>December</month>	<year>2021</year>	</date><date date-type="accepted"><day>29,</day>	<month>December</month>	<year>2021*</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>
 
 
  The glass series
   
  50P<sub>2</sub>O<sub>5</sub>-25CaO-(25
  -
  x)Na<sub>2</sub>O-xCoO (with (0 ≤ x ≤ 25; mol%)
  , has been prepared by direct melting at 1080&#176;C
   
  &#177;
   
  20&#176;C
  . The introduction
   
  of cobalt in calcium phosphate glasses is use
  d
   to compare its
   
  effect with calcium in inhibition corrosion. The dissolution rate has been investigated. It indicated an improvement of chemical durability when the cobalt oxide increases in the network glass at the expense of Na<sub>2</sub>O content. Both, IR spectroscopy and X-ray diffraction have confirmed the structure changes when the CoO content increases in the glass. This change results in the disappearance of isolated orthophosphate groups follow
  ed
   
  of a polymerizing of the structure from isolated orthophosphate towards pyrophosphate chains (Q<sup>1</sup>) by promoting the formation of olygophosphates
   
  (mixed
   
  Q<sup>1</sup>-Q<sup>2</sup>) 
  rich in pyrophosphates. Analysis of the density values, showed an increase of density with the increase CoO content. The covalent radius values of oxygen
   
  r
  <sub>cal</sub>
   
  (O<sup>2-</sup>) indicate a significant decrease and therefore a relatively high reinforcement of the metal-oxygen-phosphorus (Co-O-P) bonds. SEM micrograph confirms the evolution of the glass structural morphology. The sample having a maximum CoO content confirms a homogeneous glass phase with quite crystalline particles.
   
  This property is prerequisite for many interesting industrial applications.
 
</p></abstract><kwd-group><kwd>Chemical Durability Phosphate Glasses</kwd><kwd> Cobalt Oxide</kwd><kwd> Density</kwd><kwd> DTA</kwd><kwd> DRX</kwd><kwd> IR</kwd><kwd> SEM Micrograph</kwd></kwd-group></article-meta></front><body><sec id="s1"><title>1. Introduction</title><p>Due to their poor chemical durability phosphate glasses have rather limited technological application despite their investigation so far conducted by many researchers [<xref ref-type="bibr" rid="scirp.114259-ref1">1</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref2">2</xref>]. However, several phosphate glasses with high aqueous corrosion resistance have been reported [<xref ref-type="bibr" rid="scirp.114259-ref3">3</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref4">4</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref5">5</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref6">6</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref7">7</xref>]. Their properties (low melting point, high thermal expansion coefficient, bioactivity, optical properties etc.) make these glasses serious potential candidates for many technological applications. It has been found that the introduction of oxides, such as ZnO, Fe<sub>2</sub>O<sub>3</sub>, Al<sub>2</sub>O<sub>3</sub>, PbO, CaO and Cr<sub>2</sub>O<sub>3</sub>, results in the formation of, Zn-O-P, Fe-O-P, Pb-O-P, Al-O-P, Ca-O-P and Cr-O-P bonds, leading to improvement of phosphate glasses chemical durability [<xref ref-type="bibr" rid="scirp.114259-ref5">5</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref7">7</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref8">8</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref9">9</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref10">10</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref11">11</xref>]. The synergy of phosphate glasses with some types of nuclear waste has indicated the possibility of a form of waste with a lower corrosion rate than borosilicate glasses [<xref ref-type="bibr" rid="scirp.114259-ref8">8</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref12">12</xref>]. As a result of high chemical durability, iron phosphate glasses have been considered as better candidates for the vitrifying of some type of nuclear wastes when compared with borosilicate glasses [<xref ref-type="bibr" rid="scirp.114259-ref4">4</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref5">5</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref6">6</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref8">8</xref>]. The aim of the present work is to synthesize and select phosphate glasses in the system 50P<sub>2</sub>O<sub>5</sub>-25CaO-(25−x)Na<sub>2</sub>O-xCoO (with 0 ≤ x ≤ 25; mol%) for two reasons:</p><p>&#183; the first reason is to analyze glasses, with low cobalt content, by different techniques arranged for further later studies in the biomedical field [<xref ref-type="bibr" rid="scirp.114259-ref13">13</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref14">14</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref15">15</xref>];</p><p>&#183; the second reason is to compare the effect of cobalt with that of iron in inhibition of corrosion [<xref ref-type="bibr" rid="scirp.114259-ref3">3</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref6">6</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref16">16</xref>]. The studied series indicated the structural change when cobalt content increases and causes an important tendency polymerization from orthophosphates to pyrophosphate groups which are at the origin of the improvement of chemical durability.</p></sec><sec id="s2"><title>2. Experimental Section</title><p>Phosphate glasses are prepared by direct melting of the (NH<sub>4</sub>)H<sub>2</sub>PO<sub>4</sub> (98,99% pure), CaCO<sub>3</sub> (99.5% pure), Na<sub>2</sub>O (99% pure), CoCO<sub>3</sub>, xH<sub>2</sub>O (Co 43% - 47% pure) mixtures with suitable proportions. The reagents are intimately crushed then introduced into a porcelain crucible. They were initially heated at 300˚C for 2 h and then kept at 500˚C for 1 h to complete the decomposition. The reaction mixture was then heated at 850˚C. for 1 h and finally at 1080˚C for 30 minutes. The homogeneous liquid was poured in aluminum plate previously heated to 200˚C to avoid thermal shock. Pellets about 5 to 10 mm in diameter and 1 to 3 mm thick were obtained. The samples were polished with carbon Silica sandpaper (with CSI of sufficiently high level), cleaned with acetone and immersed in pyrex beakers containing 100 ml of distilled water and carried to 90˚C. The sample surface must be constantly submerged in distilled water for 21 consecutive days. The dissolution rate was evaluated from the mass loss as a function of time. The IR spectra of the studied phosphate glasses were determined in the frequency range between 400 and 1600 cm<sup>−1</sup> with a resolution of 2 cm<sup>−1</sup> using a Fourier transform infrared spectrometer (IR AFFINITY-1S). The samples were finally ground and mixed with KBr (potassium bromide), which is transparent in the IR and serves as a template. The ratio of the matter/KBr in the pellets was 10% by weight. The vitreous state was first evidenced from the shiny and transparency aspect, which was confirmed by X-ray diffraction patterns (XRD type BRUKER D8 ADVANCE). The glasses S<sub>0</sub>, S<sub>2</sub> and S<sub>4</sub> were annealed at 540˚C, 551˚C and 660˚C, respectively, for 72 hours. Differential thermal analysis (DTA) was performed using a DTG-60 SUMULTANEOUS DTA-DTG Apparatus, at a heating rate of 10˚C/min in atmospheric air with alumina crucibles. The Archimedes method was used to measure the density of glasses using orthophthalate as a floating medium. The microstructures of the sample glasses were characterized by scanning electron microscopy (SEM), equipped with a full system micro-analyser (EDX-EDAX).</p></sec><sec id="s3"><title>3. Results and Discussion</title><sec id="s3_1"><title>3.1. Analysis of Chemical Durability of Series Glasses 50P<sub>2</sub>O<sub>5</sub>-25CaO-(25−x)Na<sub>2</sub>O-xCoO</title><p>The chemical durability (D<sub>R</sub>) of the glass series 50P<sub>2</sub>O<sub>5</sub>-25CaO-(25−x)Na<sub>2</sub>O-xCoO (with 0 ≤ x ≤ 25 mol%) was determined from the dissolution rate (D<sub>R</sub>) of the samples immersed in 100 ml of distilled water at 90˚C for 21 consecutive days. The dissolution rate is defined as the weight loss of the glass expressed in g∙cm<sup>−2</sup>∙min<sup>−1</sup>. The values of D<sub>R</sub> and of pH of the leaching aqueous solution are represented respectively, in figures 1 and grouped in <xref ref-type="table" rid="table1">Table 1</xref>. In <xref ref-type="fig" rid="fig1">Figure 1</xref>, the shape of the D<sub>R</sub> curve indicates a progressive improvement of the chemical durability of the glass from 5.44 &#215; 10<sup>−5</sup> to 8.60 &#215; 10<sup>−7</sup> (g∙cm<sup>−2</sup>∙min<sup>−1</sup>) when the CoO content varies from 0 to 25 mol% [<xref ref-type="bibr" rid="scirp.114259-ref10">10</xref>].</p></sec><sec id="s3_2"><title>3.2. Density and Molar Volumes</title><p>Density measurements allowed us to follow the evolution of the molar volume</p><table-wrap id="table1" ><label><xref ref-type="table" rid="table1">Table 1</xref></label><caption><title> Compositions, calculated O/P ratio, D<sub>R</sub> and transition temperature (Tg) of the series 50P<sub>2</sub>O<sub>5</sub>-25CaO-(25−x)Na<sub>2</sub>O-xCoO glasses versus CoO (mol%)</title></caption><table><tbody><thead><tr><th align="center" valign="middle"  rowspan="2"  >Glass Sample</th><th align="center" valign="middle"  colspan="4"  >Starting glass composition (mol%)</th><th align="center" valign="middle"  rowspan="2"  >Ratio O/P</th><th align="center" valign="middle"  rowspan="2"  >D<sub>R</sub> (g/cm<sup>2</sup>∙min)</th><th align="center" valign="middle" >Tg (˚C)</th><th align="center" valign="middle" >T<sub>C</sub> (˚C)</th><th align="center" valign="middle" >T<sub>C</sub>-T<sub>G</sub></th><th align="center" valign="middle" >pH</th></tr></thead><tr><td align="center" valign="middle" >CoO</td><td align="center" valign="middle" >Na<sub>2</sub>O</td><td align="center" valign="middle" >CaO</td><td align="center" valign="middle" >P<sub>2</sub>O<sub>5</sub></td><td align="center" valign="middle"  colspan="3"  >(&#177;5˚C)</td><td align="center" valign="middle" >&#177;0.5</td></tr><tr><td align="center" valign="middle" >S<sub>0</sub></td><td align="center" valign="middle" >0</td><td align="center" valign="middle" >25</td><td align="center" valign="middle" >25</td><td align="center" valign="middle" >50</td><td align="center" valign="middle"  rowspan="5"  >3</td><td align="center" valign="middle" >(5.40 &#177; 0.20) &#215; 10<sup>−5</sup></td><td align="center" valign="middle" >377</td><td align="center" valign="middle" >505</td><td align="center" valign="middle" >128</td><td align="center" valign="middle" >6,2</td></tr><tr><td align="center" valign="middle" >S<sub>1</sub></td><td align="center" valign="middle" >5</td><td align="center" valign="middle" >20</td><td align="center" valign="middle" >25</td><td align="center" valign="middle" >50</td><td align="center" valign="middle" >(1.69 &#177; 0.20) &#215; 10<sup>−5</sup></td><td align="center" valign="middle" >405</td><td align="center" valign="middle" >524</td><td align="center" valign="middle" >119</td><td align="center" valign="middle" >6,6</td></tr><tr><td align="center" valign="middle" >S<sub>2</sub></td><td align="center" valign="middle" >10</td><td align="center" valign="middle" >15</td><td align="center" valign="middle" >25</td><td align="center" valign="middle" >50</td><td align="center" valign="middle" >(4.83 &#177; 0.20) &#215; 10<sup>−6</sup></td><td align="center" valign="middle" >434</td><td align="center" valign="middle" >555</td><td align="center" valign="middle" >121</td><td align="center" valign="middle" >8,4</td></tr><tr><td align="center" valign="middle" >S<sub>3</sub></td><td align="center" valign="middle" >15</td><td align="center" valign="middle" >10</td><td align="center" valign="middle" >25</td><td align="center" valign="middle" >50</td><td align="center" valign="middle" >(1.55 &#177; 0.20) &#215; 10<sup>−6</sup></td><td align="center" valign="middle" >455</td><td align="center" valign="middle" >570</td><td align="center" valign="middle" >115</td><td align="center" valign="middle" >8,6</td></tr><tr><td align="center" valign="middle" >S<sub>4</sub></td><td align="center" valign="middle" >25</td><td align="center" valign="middle" >0</td><td align="center" valign="middle" >25</td><td align="center" valign="middle" >50</td><td align="center" valign="middle" >(8.60 &#177; 0.20) &#215; 10<sup>−7</sup></td><td align="center" valign="middle" >528</td><td align="center" valign="middle" >661</td><td align="center" valign="middle" >133</td><td align="center" valign="middle" >8,8</td></tr></tbody></table></table-wrap><p>depending on the composition of the system 50P<sub>2</sub>O<sub>5</sub>-25CaO-(25−x)Na<sub>2</sub>O-xCoO. The density measurements were completed at room temperature. As can be observed from <xref ref-type="fig" rid="fig2">Figure 2</xref>, the variation in density versus CoO content (mol%) indicates an increase of density. On the other hand, it was possible to deduce the value of the molar volume and oxygen radius from density measurements, calculated from the approximate hypothesis of the close packing of oxygen anions, O<sup>2−</sup>, each having r<sub>cal</sub> (O<sup>2−</sup>) recapitulated for each composition in <xref ref-type="table" rid="table2">Table 2</xref> [<xref ref-type="bibr" rid="scirp.114259-ref4">4</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref10">10</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref16">16</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref17">17</xref>]. The molar volume of oxygen and the radius of anions of oxygen (O<sup>2−</sup>) in the glass have been determined from Equations (1) and (2), respectively.</p><table-wrap id="table2" ><label><xref ref-type="table" rid="table2">Table 2</xref></label><caption><title> Density and related molar data of the 48P<sub>2</sub>O<sub>5</sub>-30CaO-(21−x)Na<sub>2</sub>O-xTiO<sub>2</sub> system</title></caption><table><tbody><thead><tr><th align="center" valign="middle" >Samples</th><th align="center" valign="middle" >Molar formula Oxyg&#232;ne/Mol (N<sub>O</sub>)</th><th align="center" valign="middle" >Density ρ<sub>v</sub> (g∙cm<sup>−3</sup>)</th><th align="center" valign="middle" >Molar Mass (g/mol)</th><th align="center" valign="middle" >Molar Volume (&#197;)<sup>3</sup> V O M = M ρ N A N 0</th><th align="center" valign="middle" >Calculated oxygen radius (O<sup>2−</sup>) (&#197;) r c a l ( O − 2 )</th></tr></thead><tr><td align="center" valign="middle" >S<sub>0</sub></td><td align="center" valign="middle" >25Na<sub>2</sub>O-25CaO-50P<sub>2</sub>O<sub>5 </sub> (300)</td><td align="center" valign="middle" >2.588</td><td align="center" valign="middle" >10,051.95</td><td align="center" valign="middle" >21.5</td><td align="center" valign="middle" >1.390</td></tr><tr><td align="center" valign="middle" >S<sub>1</sub></td><td align="center" valign="middle" >5CoO-20Na<sub>2</sub>O-25CaO-50P<sub>2</sub>O<sub>5 </sub> (300)</td><td align="center" valign="middle" >2.637</td><td align="center" valign="middle" >10,116.615</td><td align="center" valign="middle" >21.2</td><td align="center" valign="middle" >1.384</td></tr><tr><td align="center" valign="middle" >S<sub>2</sub></td><td align="center" valign="middle" >10CoO-15Na<sub>2</sub>O -25CaO-50P<sub>2</sub>O<sub>5 </sub> (300)</td><td align="center" valign="middle" >2.709</td><td align="center" valign="middle" >10,181.28</td><td align="center" valign="middle" >20.8</td><td align="center" valign="middle" >1.375</td></tr><tr><td align="center" valign="middle" >S<sub>3</sub></td><td align="center" valign="middle" >15CoO-10Na<sub>2</sub>O -25CaO-50P<sub>2</sub>O<sub>5 </sub> (300)</td><td align="center" valign="middle" >2.720</td><td align="center" valign="middle" >10,245.945</td><td align="center" valign="middle" >20.6</td><td align="center" valign="middle" >1.372</td></tr><tr><td align="center" valign="middle" >S<sub>4</sub></td><td align="center" valign="middle" >25CoO-25CaO-50P<sub>2</sub>O<sub>5</sub> (300)</td><td align="center" valign="middle" >2.819</td><td align="center" valign="middle" >10,375.275</td><td align="center" valign="middle" >20.3</td><td align="center" valign="middle" >1.364</td></tr></tbody></table></table-wrap><p>V O M = M / ρ N A * N 0 (1)</p><p>r c a l ( O − 2 ) = V O M 3 2 (2)</p><p>With M = molar mass, ρ = density, N<sub>A</sub> = Avogadro number; *N<sub>0</sub> = number of oxygen atoms in the molecular formula. A detailed analysis of the data in <xref ref-type="table" rid="table2">Table 2</xref> shows that the molar volume decreases increasing of the CoO content. The covalent radius value of the oxygen atom (O<sup>2−</sup>), calculated by the molar volume using the Equation (2) for each composition, decrease, also, indicating a reinforcement of the metal-oxygen-phosphorus (Co-O-P) bond with increasing of CoO content.</p></sec><sec id="s3_3"><title>3.3. Structural Approach by Infrared Spectroscopy</title><p>Infrared spectra of glass series 50P<sub>2</sub>O<sub>5</sub>-25CaO-(25−x)Na<sub>2</sub>O-xCoO (0 ≤ x ≤ 25; mol%) are shown in <xref ref-type="fig" rid="fig3">Figure 3</xref>. The assignments of the vibration bands are given in <xref ref-type="table" rid="table3">Table 3</xref>. All vibration bands of treated phosphate glasses are shown in the range of frequencies between 400 and 1600 cm<sup>−1</sup>. The band at 490 - 510 cm<sup>−1</sup> is attributed to skeletal deformation δ<sub>ske</sub> (P-O-P) [<xref ref-type="bibr" rid="scirp.114259-ref3">3</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref4">4</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref5">5</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref6">6</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref18">18</xref>]. The frequency band located at 770 - 786 cm<sup>−1</sup> is attributed to the symmetrical mode of vibration ν<sub>sym</sub> (P-O-P) of the pyrophosphate groups (Q1) [<xref ref-type="bibr" rid="scirp.114259-ref4">4</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref18">18</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref19">19</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref20">20</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref21">21</xref>], while the bands at 880 - 910 are assigned to the asymmetric vibration mode ν<sub>asym</sub> (P-O-P) [<xref ref-type="bibr" rid="scirp.114259-ref4">4</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref8">8</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref22">22</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref23">23</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref24">24</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref25">25</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref26">26</xref>]. The band that appears around 1015 cm<sup>−1</sup> is attributed to the asymmetric vibration mode ν<sub>asym</sub> (P-O-P) of the isolated orthophsphate groups (Q˚) [<xref ref-type="bibr" rid="scirp.114259-ref5">5</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref19">19</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref21">21</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref23">23</xref>]. The band at 1280 cm<sup>−1</sup> is attributed to asymmetric stretching of two non-bridging oxygens ν<sub>sym</sub> PO<sub>2</sub>. Analysis of the IR spectra obtained (<xref ref-type="fig" rid="fig3">Figure 3</xref>) indicates that the vibration band ν<sub>asym</sub> P-O-P at 1015 cm<sup>−1</sup> attributed to the isolated orthophosphate groups decreases with increasing cobalt oxide at the expense of Na<sub>2</sub>O content. This band disappears completely when the CoO content reaches 15 mol%. On the other hand the shift, at the</p><table-wrap id="table3" ><label><xref ref-type="table" rid="table3">Table 3</xref></label><caption><title> The assignments of different vibration bands of the IR spectra of the quaternary 50P<sub>2</sub>O<sub>5</sub>-25CaO-(25−x)Na<sub>2</sub>O-xCoO</title></caption><table><tbody><thead><tr><th align="center" valign="middle" >R&#233;gions de fr&#233;quence (cm<sup>−1</sup>)</th><th align="center" valign="middle" >assignements</th><th align="center" valign="middle" >R&#233;ferences</th></tr></thead><tr><td align="center" valign="middle" >490 - 510 777 - 786 880 - 910 1015 1078 - 1093 1280</td><td align="center" valign="middle" >Vibration mode δ<sub>ske</sub> (P-O-P) Vibration mode υ<sub>sym</sub> (P-O-P) in unit Q<sup>1</sup> Vibration mode υ<sub>asym</sub> (P-O-P) in unit Q<sup>1</sup> Vibration mode υ<sub>asym</sub> (P-O-P) in unit Q<sup>0</sup> Vibration mode υ<sub>sym</sub>(PO<sub>2</sub>)/υ<sub>asym</sub> (PO<sub>3</sub>) in units Q<sup>1</sup> + Q<sup>2</sup> Vibration mode υ<sub>asym</sub> (PO<sub>2</sub>) in unit Q<sup>2</sup></td><td align="center" valign="middle" >[<xref ref-type="bibr" rid="scirp.114259-ref3">3</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref4">4</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref5">5</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref6">6</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref14">14</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref19">19</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref20">20</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref21">21</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref22">22</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref23">23</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref14">14</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref18">18</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref19">19</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref20">20</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref5">5</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref18">18</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref19">19</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref5">5</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref23">23</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref27">27</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref20">20</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref3">3</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref4">4</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref5">5</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref19">19</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref26">26</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref27">27</xref>]</td></tr></tbody></table></table-wrap><p>same time, of the vibration band ν<sub>sym</sub> P-O-P, located at 777 cm<sup>−1</sup>, towards the high values and the decrease in the intensity of the vibration band νPO<sub>2</sub>, located at 1280 cm<sup>−1</sup>, added the shift of the vibration band ν<sub>asym</sub> (PO<sub>3</sub>)/ν<sub>sym</sub> (PO<sub>2</sub>) toward low values, confirms the increase in the number of pyrophosphate groups to the detriment of metaphosphate groups, when the CoO content increases in the glass network. As for the vibration bands at approximately 1078-1093 cm<sup>−1</sup> and 1280 cm<sup>−1</sup> are assigned, respectively, to the stretching vibration mode νasym (PO<sub>3</sub>)/ν<sub>sy</sub><sub>m</sub> (PO<sub>2</sub>) attributed of the pyrophosphate groups and to the vibration mode Vasym (PO<sub>2</sub>) attributed to metaphosphate groups (Q<sup>2</sup>) [<xref ref-type="bibr" rid="scirp.114259-ref3">3</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref4">4</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref9">9</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref20">20</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref21">21</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref26">26</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref27">27</xref>]</p></sec><sec id="s3_4"><title>3.4. X-Ray Diffraction and DTA Analysis</title><p>As expected, X-ray diffractions have confirmed the vitreous character of all of the investigated glass samples (see <xref ref-type="fig" rid="fig4">Figure 4</xref>). DTA analysis of the phosphate glass 50P<sub>2</sub>O<sub>5</sub>-25CaO-(25−x)Na<sub>2</sub>O-xCoO (with 0 ≤ x ≤ 25; mol%), shown in <xref ref-type="fig" rid="fig5">Figure 5</xref>, indicates both an increase in the glass transition temperature and the crystallisation temperature versus the CoO content. When the CoO content increases from 0 to 25 mol%, the glass transition temperature (Tg) increases in the 399˚C - 477˚C range, whereas the crystallisation temperature (Tc) increases in the 502˚C - 657˚C range (<xref ref-type="table" rid="table1">Table 1</xref>). The Tc-Tg difference is significant, which explains the high thermal stability [<xref ref-type="bibr" rid="scirp.114259-ref13">13</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref28">28</xref>]. The heat treatments of the S<sub>0</sub>, S<sub>2</sub> and S<sub>4</sub> glasses at 540˚C, 551˚C and 660˚C for 72 h, respectively, give the XRD patterns shown in <xref ref-type="fig" rid="fig6">Figure 6</xref>. These spectra show a structural evolution from orthophosphate (O/P = 4) and olygophosphate phases (3 ≤ O/P ≤ 3.5) to olygophosphate phase with majority of pyrophosphates phases (Q<sup>1</sup>). When the S<sub>0</sub> sample was thermally treated at 540˚C, the amorphous phase partially disappeared and major Ca<sub>3</sub>PO<sub>4</sub> [JCPDS file N˚: 00-009-0340], NaCaPO<sub>4</sub> [JCPDS file N˚: 00-029-1193] and Na<sub>3</sub>PO<sub>4</sub> [JCPDS file N˚: 00-031] occurred in the sample, with minor NaPO<sub>3</sub> [JCPDS file N˚: 00-002-0776], Ca(PO<sub>3</sub>)<sub>2</sub> [JCPDS file N˚: 00-017-0500], CaP<sub>2</sub>O<sub>6</sub> [JCPDS file N˚: 00-015-0204], and Ca<sub>2</sub>P<sub>2</sub>O<sub>7</sub> [JCPDS file N˚: 00-009-0346] phases. When the CaO content increased in the S<sub>2</sub> glass, the heat treatment at 551˚C</p><p>caused the formation of Na<sub>2</sub>P<sub>2</sub>O<sub>7</sub>, [JCPDS file N˚: -], Ca<sub>2</sub>P<sub>2</sub>O<sub>7</sub> [JCPDS file N˚: 00-009-0346] and C<sub>O</sub>P<sub>2</sub>O<sub>7</sub> [JCPDS file N˚00-052-1470] with some traces of metaphosphate and isolated short orthophosphates phases. However, when the CoO content increased to 25 mol%, the heat treatment, at 660˚C, indicated the disappearance of the isolated ortho-phosphate phases, while the CaP<sub>2</sub>O<sub>6</sub> phases [JCPDS file N˚: 01-015-0204], Ca(PO<sub>3</sub>)<sub>2</sub> [JCPDS file N˚: 00-009-0363], Co<sub>2</sub>P<sub>4</sub>O<sub>12</sub> [JCPDS file N˚: 00-040-0068], Co(PO<sub>3</sub>)<sub>2</sub>, [JCPDS file N˚: 00-027-1120], Ca<sub>2</sub>P<sub>2</sub>O<sub>7</sub> [JCPDS file N˚: 00-009-0346], and Co<sub>2</sub>P<sub>2</sub>O<sub>7</sub> [JCPDS file N˚: 00-040-0068] appeared largely in the sample with very high intensities that confirms the results obtained by IR [<xref ref-type="bibr" rid="scirp.114259-ref13">13</xref>].</p></sec><sec id="s3_5"><title>3.5. SEM Micrograph Analysis</title><p>SEM images in <xref ref-type="fig" rid="fig7">Figure 7</xref> illustrate the morphology of the glasses considered in this work. The glass form of S<sub>1</sub> shown in <xref ref-type="fig" rid="fig7">Figure 7</xref>(a), exhibit the presence crystalline phases with different form and size [<xref ref-type="bibr" rid="scirp.114259-ref5">5</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref9">9</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref10">10</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref23">23</xref>]. When the CoO content increases in the glass, the number of crystallites decreases. Hence, SEM analysis confirms a homogenous vitreous phase with feeble crystalline particles in the S<sub>4</sub> sample (<xref ref-type="fig" rid="fig7">Figure 7</xref>(e)) which has the maximum CoO content. Some different crystalline phases were identified by XRD and it seems that a decrease of crystallisation tendency is enhanced and Co(PO<sub>3</sub>)<sub>2</sub>, Ca<sub>2</sub>P<sub>2</sub>O<sub>7</sub> and Co<sub>2</sub>P<sub>2</sub>O<sub>7</sub> phases are crystallized in the last sample (S<sub>4</sub>) [<xref ref-type="bibr" rid="scirp.114259-ref13">13</xref>]. This probably explains the structural change towards more short pyrophosphates at the detriment of shorter isolated</p><p>orthophosphate chains as the CoO content increases in the glass network.</p></sec></sec><sec id="s4"><title>4. Discussion</title><p>The glasses series 50P<sub>2</sub>O<sub>5</sub>-25CaO-(25−x)Na<sub>2</sub>O-xCoO (with 0 ≤ x ≤ 25; mol%), were prepared by direct melting at 1080˚C. The structure and the chemical durability of these glasses have been investigated using various techniques such as density, X-Ray, DTA, diffraction, IR and SEM. The study of the dissolution rate for all the glasses studied indicates an improvement in chemical durability when the CoO content increases to the detriment of Na<sub>2</sub>O. The variation of transition temperature versus CoO content indicates an increase in Tg from 399˚C to 477˚C when the CoO content increases from 0. To 25 mol%, elucidating an improvement in the rigidity of the glass [<xref ref-type="bibr" rid="scirp.114259-ref8">8</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref13">13</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref18">18</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref21">21</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref28">28</xref>].</p><p>The specific mass (Density) of vitrified phosphates is increasing with molar fraction along the series. The covalent radius values of oxygen calculated from Equation (2) indicate that the minimum value r<sub>cal</sub> (O<sup>2−</sup>) is observed for x = 20 mol% and therefore a relatively high reinforcement of the metal-oxygen-phosphorus (Co-O-P) bond [<xref ref-type="bibr" rid="scirp.114259-ref4">4</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref12">12</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref17">17</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref28">28</xref>]. On the other hand, Analysis of infrared spectra indicates that the increase of CoO content to the detriment of Na<sub>2</sub>O, in phosphate glass, leads to the formation of olygophosphate groups (Q<sup>1</sup>-Q<sup>2</sup>) [<xref ref-type="bibr" rid="scirp.114259-ref22">22</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref28">28</xref>] with the majority pyrophosphates at the expense of orthophosphates and metaphosphates and or cyclical metaphosphates groups. X-ray diffraction analysis of glasses, annealed between 502˚C to 663˚C for 72 hours, confirms the evolution, with the increase of CoO content, of crystalline phases towards olygophosphate phase’s rich of pyrophosphates. In fact, when the CoO content exceeds 15 mol%, the orthophosphate phases completely disappear in the vitreous network. Analysis of SEM micrograph indicates the evolution of the structural morphology of the glasses. As the CoO content increases in the glass, the number of crystallites decreases, consequently, SEM micrograph expected in <xref ref-type="fig" rid="fig7">Figure 7</xref>(e) for S<sub>4</sub> sample, having a maximum CoO content, confirms a homogeneous glass phase with low crystalline particles.</p><p>This phenomenon is explained by the fact that Na<sub>2</sub>O (Na<sup>+</sup> alkali ion) is a main modifier oxide which easily depolymerizes the vitreous network by creating increasingly short chains going from ultraphosphate chains to metaphosphate, pyrophosphate and shorter isolated orthophosphate chains [<xref ref-type="bibr" rid="scirp.114259-ref3">3</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref5">5</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref29">29</xref>]. This accentuated depolymerization leads to the formation of a large number of easily hydrated Na-O-P bonds which greatly reduce the chemical durability of the glasses. In addition, the effect of the oxide CaO which depolymerizes the glass from ulra-phosphate towards chains mainly of metaphosphate or cyclic metaphosphate, it can be explained that the increases of CoO to the detriment of Na<sub>2</sub>O has the effect of polymerizing the structure from isolated orthophosphate chains toward the formation of olygophosphates predominately by pyrophosphate chains. This behavior leads to the replacement of hydrated Na-O-P, P-O-P and possibly Ca-O-P bands, by the covalent and resistant Co-O-P bonds.</p><p>Hense, the glasses series studies in the present work can be divided into three categories:</p><p>1) Glasses with a low CoO content (0.5 to 3 mol%) can be applied with a slight improvement in the optical field [<xref ref-type="bibr" rid="scirp.114259-ref19">19</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref30">30</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref31">31</xref>].</p><p>2) Glasses with CoO content between 5 and 15 mol% can be tested successfully in the biomedical field because they can increase the rigidity of the glass and participate in the osteoinduction of bone tissue [<xref ref-type="bibr" rid="scirp.114259-ref14">14</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref15">15</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref18">18</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref31">31</xref>].</p><p>3) Glasses with content between 20 and 25 mole%, can be used, with some improvement, in the electrical conduction range since cobalt can be found under two degrees of oxidation Co<sup>2+</sup> and Co<sup>3+</sup> which ensures the hopping mechanism of the electrons and therefore oxidation reduction phenomenon [<xref ref-type="bibr" rid="scirp.114259-ref21">21</xref>] [<xref ref-type="bibr" rid="scirp.114259-ref32">32</xref>].</p><p>Hence, a better understanding of phosphate glass structure is very relevant to the industry in the development of technical glasses to achieve good performances.</p></sec><sec id="s5"><title>5. Conclusions</title><p>The structure and properties of xCoO-(25−x)Na<sub>2</sub>O-25CaO-50P<sub>2</sub>O<sub>5</sub> phosphate glasses (with 0 ≤ x ≤ 25; mol%) have been investigated in the present paper. Here are some conclusions from this paper:</p><p>1) The structure of the Co-Na-Ca-phosphate samples glasses, predominantly, consists of olygophosphate, Q<sup>2</sup>-Q<sup>1</sup> units, and the CoO leads to the conversion of Q<sup>0</sup> units to Q<sup>1</sup> units.</p><p>2) The glass transition temperature is improved by increasing CoO content in the glass network and leads to the increase of thermal stability.</p><p>3) Increasing the glass transition temperature leads to improved chemical durability.</p><p>4) The SEM Micrograph indicates an obvious decrease in crystallites with the increase in CoO, causing a relatively large equilibrium between the glass bath and the crystallites.</p></sec><sec id="s6"><title>Acknowledgements</title><p>The authors would like to thank the technical analysis and characterization center of Faculty of Sciences, Ain chock, Casablanca, for the help in the realization of this work.</p></sec><sec id="s7"><title>Conflicts of Interest</title><p>The authors declare no conflicts of interest regarding the publication of this paper.</p></sec><sec id="s8"><title>Cite this paper</title><p>Bachachir, B., Er-Rouissi, Y., Makhlouk, R., Harrati, A., El Bouari, A. and Aqdim, S. 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