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  <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.2017.710028</article-id>
      <article-id pub-id-type="publisher-id">AMPC-79678</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>


          Chemical Durability and Structural Properties of Al&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;3&lt;/sub&gt;-CaO-Na&lt;sub&gt;2&lt;/sub&gt;O-P&lt;sub&gt;2&lt;/sub&gt;O&lt;sub&gt;5&lt;/sub&gt; Glasses Studied by IR Spectroscopy, XRD and SEM

        </article-title>
      </title-group>
      <contrib-group>
        <contrib contrib-type="author" xlink:type="simple">
          <name name-style="western">
            <surname>Y.</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>Z.</surname>
            <given-names>Chabbou</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>N.</surname>
            <given-names>Beloued</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>S.</surname>
            <given-names>Aqdim</given-names>
          </name>
          <xref ref-type="aff" rid="aff2">
            <sup>2</sup>
          </xref>
          <xref ref-type="corresp" rid="cor1">
            <sup>*</sup>
          </xref>
        </contrib>
      </contrib-group>
      <aff id="aff2">
        <addr-line>Mineral Chemistry Laboratory, Department of Chemistry, Hassan II University Ain Chock, Faculty of Science, Casablanca, Morocco</addr-line>
      </aff>
      <aff id="aff1">
        <addr-line>Laboratory of Materials Engineering for Environment and Valorization, Hassan II University Ain Chock, Faculty of Sciences, Casa-blanca, Morocco</addr-line>
      </aff>
      <author-notes>
        <corresp id="cor1">
          * E-mail:<email>said_aq@yahoo.fr(SA)</email>;
        </corresp>
      </author-notes>
      <pub-date pub-type="epub">
        <day>18</day>
        <month>10</month>
        <year>2017</year>
      </pub-date>
      <volume>07</volume>
      <issue>10</issue>
      <fpage>353</fpage>
      <lpage>363</lpage>
      <history>
        <date date-type="received">
          <day>7,</day>
          <month>July</month>
          <year>2017</year>
        </date>
        <date date-type="rev-recd">
          <day>15,</day>
          <month>October</month>
          <year>2017</year>
        </date>
        <date date-type="accepted">
          <day>18,</day>
          <month>October</month>
          <year>2017</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>


          Various characterization techniques were used to study the composition of the glass series xAl
          <sub>2</sub>O
          <sub>3</sub>-(40 - x)CaO-10Na
          <sub>2</sub>O-50P
          <sub>2</sub>O
          <sub>5</sub> (with 0 ≤ x ≤ 10) in terms of chemical durability, X-ray diffraction, IR spectroscopy and scanning electron microscopy (SEM). The improved chemical durability was attributed to the replacement of easily hydrated P-O-P bonds by covalent and resistant Ca-O-P and Al-O-P bonds. However, the change in the dissolution rate (D
          <sub>R</sub>) versus time showed a marked decrease in chemical durability with increasing the Al
          <sub>2</sub>O
          <sub>3</sub> content to the detriment of the CaO content. The X-ray diffraction analysis of glasses annealed at 550
          &#176;C and 660
          &#176;C for 48 hours indicated the presence of pyrophosphate phases and predominant metaphosphates or cyclic metaphosphate phases when the Al
          <sub>2</sub>O
          <sub>3</sub> content was ≤7.5 mol%. Nevertheless, both, X-ray diffraction and IR spectroscopy confirmed the structural tendency change from metaphosphate (Q
          <sup>2</sup>) and pyrophosphate structural units (Q
          <sup>1</sup>). Toward short isolated orthophosphate units (Q
          <sup>0</sup>) when the Al
          <sub>2</sub>O
          <sub>3</sub> content above 7.5 mol%. SEM micrographs illustrated that the number of crystallites increased in the glass network when the Al
          <sub>2</sub>O
          <sub>3</sub> content increased at the expense of the CaO content. An increase in the Al
          <sub>2</sub>O
          <sub>3</sub> content to 10 mol% led to the formation of a larger number of crystallites of different sizes, dominated by small crystallite sizes assigned to short isolated orthophosphate groups. This phenomenon led to a decrease in chemical durability and seems to be a favorable factor for the formation of the apatite layers which enclose the glass, in a SBF solution test, able of regenerating bone tissue in biomedical application.

        </p>
      </abstract>
      <kwd-group>
        <kwd>Bioglasses</kwd>
        <kwd> Phosphate Glasses</kwd>
        <kwd> Chemical Durability</kwd>
        <kwd> XRD</kwd>
        <kwd> IR</kwd>
        <kwd> SEM</kwd>
      </kwd-group>
    </article-meta>
  </front>
  <body>
    <sec id="s1">
      <title>1. Introduction</title>
      <p>
        Much research has focused on biomedical glasses and glasses as promising materials for diverse applications [<xref ref-type="bibr" rid="scirp.79678-ref1">1</xref>] - [<xref ref-type="bibr" rid="scirp.79678-ref6">6</xref>] . Phosphate glasses have interesting characteristics and properties such as a low melting point, high thermal expansion coefficient, and bioactivity, including the concept of the degradation of biomaterials, which make them useful as biomaterials. Several studies have shown that single phosphate glasses do not have good chemical stability compared to phosphate glasses with several components and have also demonstrated that the macroscopic properties of phosphate bioglasses can be improved, by making small changes in the molar concentration of the modifying oxides and the intermediate network. The latter make it possible to reinforce the structure of the vitreous network while at the same time releasing an amount of calcium and phosphate, during the attack by an SBF solution, necessary to accelerate the regeneration of damaged tissue and improve chemical resistance [<xref ref-type="bibr" rid="scirp.79678-ref7">7</xref>] . Through the use of phosphorus pentoxide (P<sub>2</sub>O<sub>5</sub>) as the initial network, and sodium oxide (Na<sub>2</sub>O) with calcium oxide (CaO) as network modifiers, followed by adding other oxides (Al<sub>2</sub>O<sub>3</sub>, Fe<sub>2</sub>O<sub>3</sub>, ZnO and TiO<sub>2</sub>), the control of degradation may be achieved. Phosphate bioglasses can react with bone tissue through the formation of a hydroxyapatite layer, which is equivalent to the mineral phase of bone; that will then be involved in the process of bone regeneration via a set of physical and chemical reactions [<xref ref-type="bibr" rid="scirp.79678-ref8">8</xref>] . These surface reactions are also responsible for the degradation of the bioglass after implantation [<xref ref-type="bibr" rid="scirp.79678-ref9">9</xref>] [<xref ref-type="bibr" rid="scirp.79678-ref10">10</xref>] [<xref ref-type="bibr" rid="scirp.79678-ref11">11</xref>] . The aim of the present study was to study the structural changes, chemical resistance modification and properties of bioglasses in the Al<sub>2</sub>O<sub>3</sub>-CaO-NaO-P<sub>2</sub>O<sub>5 </sub>system, focusing particularly on the effect of the addition of CaO and Al<sub>2</sub>O<sub>3</sub> to phosphate oxide glasses for use in the medical field. So the study of series of glasses of composition xAl<sub>2</sub>O<sub>3</sub>-(40-x)CaO-10NaO-50P<sub>2</sub>O<sub>5</sub> (with 0 ≤ x ≤ 10 moles%) indicates that the substitution of CaO by Al<sub>2</sub>O<sub>3</sub> in the glass network entrained a decrease of the chemical durability, and a important change from metaphosphate (Q<sup>2</sup>) and pyrophosphate structural units (Q<sup>1</sup>) toward short isolated orthophosphate units (Q<sup>0</sup>) when the Al<sub>2</sub>O<sub>3</sub> content reached 10 mol%, confirmed by IR spectrum and X-Ray diffraction.
      </p>
    </sec>
    <sec id="s2">
      <title>2. Experimental Procedures</title>
      <p>
        Phosphate glasses were produced by the direct melting of a mixture of (NH<sub>4</sub>)<sub>2</sub>HPO<sub>4</sub>, CaCO<sub>3</sub>, Na<sub>2</sub>O and Al<sub>2</sub>O<sub>3</sub> in suitable proportions. The reagents were ground together and then introduced into a porcelain crucible. Then, they were heated initially to a temperature of 300˚C for 2 hours and then 500˚C for 1 h to complete decomposition. The reaction mixture was then heated at 900˚C for 40 min and finally at 1080˚C for 30 minutes to obtain a homogeneous liquid. This was then poured onto an aluminum plate which had a temperature of 200˚C to avoid thermal shock. This procedure provided pellets 5 - 10 mm in diameter and 1 to 3 mm thick. The prepared samples were attacked with distilled water at 90˚C for 20 days to determine the dissolution rate estimated from the mass loss. IR spectroscopy analysis was done in a frequency range between 400 cm<sup>−1</sup> and 1300 cm<sup>−1</sup> with a resolution of 2 cm<sup>−1</sup> using a Fourier transform Vertex 70 spectrometer and recorded on a DTGS detector (deuterium triglycine sulfate). The samples were ground and mixed with KBr, which is transparent to infrared. The ratio of the material to KBr in the pellets was 10% to 90% by weight. The analysis by X-ray diffraction was used to identify the structure of the glasses annealed at 550˚C and 660˚C for 48 hours. The samples were analyzed by an X’Pert Pro MPD Panalytical diffractometer. The microstructure of the glass samples was characterized using a scanning electron microscope (SEM).
      </p>
    </sec>
    <sec id="s3">
      <title>3. Results</title></sec>
      <sec id="s3_1">
        <title>3.1. Ternary Diagram</title>
        <p>
          As can be seen in the ternary diagram in <xref ref-type="fig" rid="fig1">Figure 1</xref>, the location of the studied glasses indicates that these glasses are theoretically formed of metaphosphate and pyrophosphate groups. The composition of each sample is given in <xref ref-type="table" rid="table1">Table 1</xref>.
        </p>
      </sec>
      <sec id="s3_2">
        <title>3.2. Chemical Durability</title>
        <p>
          The dissolution rate (D<sub>R</sub>) calculated for the series of bioglasses xAl<sub>2</sub>O<sub>3</sub>-(40 - x)CaO-10Na<sub>2</sub>O-50P<sub>2</sub>O<sub>5</sub> (with 0 ≤ x ≤ 10, mol%) is defined as the loss of
        </p>
        <p>
          glass mass after immersion in 100 mL of distilled water at 90˚C for 20 days, and expressed as g∙cm<sup>−2</sup>∙min<sup>−1</sup>. The average dissolution rates, which are shown in <xref ref-type="fig" rid="fig2">Figure 2</xref> and <xref ref-type="table" rid="table2">Table 2</xref>, were measured with respect to the glass surface and the time of exposure. The results show that the chemical durability was improved after increasing the molar percentage of CaO to the detriment of Al<sub>2</sub>O<sub>3</sub> [<xref ref-type="bibr" rid="scirp.79678-ref12">12</xref>] [<xref ref-type="bibr" rid="scirp.79678-ref13">13</xref>] .
        </p>
      </sec>
      <sec id="s3_3">
        <title>3.3. Infrared Spectra</title>
        <p>
          The IR spectra of the glasses xAl<sub>2</sub>O<sub>3</sub>-(40 - x)CaO-10Na<sub>2</sub>O-50P<sub>2</sub>O<sub>5</sub> (with 0 ≤ x ≤ 10) are shown in <xref ref-type="fig" rid="fig3">Figure 3</xref>, and the vibration bands of the assignments are given
        </p>
        <table-wrap id="table1" >
          <label>
            <xref ref-type="table" rid="table1">Table 1</xref>
          </label>
          <caption>
            <title> Glass composition expressed in terms of quaternary systems</title>
          </caption>
        </table-wrap>
      </sec>
    </body>

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