<?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">MSA</journal-id><journal-title-group><journal-title>Materials Sciences and Applications</journal-title></journal-title-group><issn pub-type="epub">2153-117X</issn><publisher><publisher-name>Scientific Research Publishing</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="doi">10.4236/msa.2014.512086</article-id><article-id pub-id-type="publisher-id">MSA-50672</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></subj-group></article-categories><title-group><article-title>
 
 
  Critical Parameters and Magnetocaloric Effect of the La&lt;sub&gt;5/8&lt;/sub&gt;Ca&lt;sub&gt;3/8&lt;/sub&gt;Mn&lt;sub&gt;0.9750&lt;/sub&gt;Pd&lt;sub&gt;0.025O3&lt;/sub&gt; Compound
 
</article-title></title-group><contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>.</surname><given-names>V. Bau</given-names></name><xref ref-type="aff" rid="aff1"><sup>1</sup></xref><xref ref-type="corresp" rid="cor1"><sup>*</sup></xref></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>N.</surname><given-names>M. An</given-names></name><xref ref-type="aff" rid="aff1"><sup>1</sup></xref></contrib></contrib-group><aff id="aff1"><addr-line>Hong Duc University, Thanh Hoa, Vietnam</addr-line></aff><author-notes><corresp id="cor1">* E-mail:<email>levietbau@yahoo.com(.VB)</email>;</corresp></author-notes><pub-date pub-type="epub"><day>21</day><month>10</month><year>2014</year></pub-date><volume>05</volume><issue>12</issue><fpage>857</fpage><lpage>862</lpage><history><date date-type="received"><day>10</day>	<month>June</month>	<year>2014</year></date><date date-type="rev-recd"><day>15</day>	<month>August</month>	<year>2014</year>	</date><date date-type="accepted"><day>8</day>	<month>September</month>	<year>2014</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 La
  <sub>5/8</sub>Ca
  <sub>3/8</sub>Mn
  <sub>0.9750</sub>Pd
  <sub>0.025O3</sub> compound was studied using DC magnetization measurements. The data were analyzed in the paramagnetic-ferromagnetic phase transition region by the Arrott plot method. The results show the Curie temperature 
  T
  <sub>C</sub> ~ 247.8 K and the critical exponents of 
  b 
  = 0.48633, 
  g
   = 1.18623 and 
  d 
  = 3.431682. The values of the critical exponents are between the mean-field theory and 3D Ising model. The magnetocaloric value is ~5 J/kgK, extracted from the M(H) curves.
 
</p></abstract><kwd-group><kwd>Magnetocaloric</kwd><kwd> Critical Parameters</kwd><kwd> Perovskite</kwd></kwd-group></article-meta></front><body><sec id="s1"><title>1. Introduction</title><p>Above the Curie temperature T<sub>C</sub>, colossal magnetoresistance (CMR) perovskite manganites behave paramagnetic insulating state. As the temperature is decreased below T<sub>C</sub>, they become ferromagnetic metals. It is shown that the ferromagnetic clusters are formed and extracted as decreasing temperature below T<sub>C</sub>. The existence of ferromagnetic clusters above T<sub>C</sub> [<xref ref-type="bibr" rid="scirp.50672-ref1">1</xref>] as well as inhomogeneity and phase separation [<xref ref-type="bibr" rid="scirp.50672-ref2">2</xref>] suggests that ferro-magnetic long-range order may be established by percolation of ferromagnetic regions as the temperature is lowered. Such magnetic inhomogeneities in the spin systems may be a result in a reduced local effective topological dimensionality [<xref ref-type="bibr" rid="scirp.50672-ref3">3</xref>] , thereby leading to different critical behaviors. Hence, the critical properties of the paramagnetic-fer- romagnetic (PM-FM) phase transitions in manganites pose an important fundamental problem. On the other hand, the vast variability of competing mechanisms, which may inﬂuence the magnetic ordering, may also yield other types of paramagnetic-ferromagnetic transitions for different systems in this class of materials. Experimental studies [<xref ref-type="bibr" rid="scirp.50672-ref4">4</xref>] -[<xref ref-type="bibr" rid="scirp.50672-ref6">6</xref>] of critical behavior of manganites near the PM-FM phase transition by using a variety of techniques have yielded a wide range of values for the critical exponent of b. The values range from about 0.3 - 0.5, which embrace mean-field (b = 0.5), three-dimensional (3D) isotropic nearest-neighbor Heisenberg (b = 0.365) and 3D Ising (b = 0.325) estimates. Static dc-magnetization measurements [<xref ref-type="bibr" rid="scirp.50672-ref4">4</xref>] -[<xref ref-type="bibr" rid="scirp.50672-ref7">7</xref>] , in addition to b, also yield the critical parameters g and d for initial susceptibility c(T) and critical isotherm M(T, H), respectively. However, they may fail to determine a unique universality class for the phase transition of these manganites. The very low values of b = 0.095 for LaMnO<sub>3</sub> [<xref ref-type="bibr" rid="scirp.50672-ref5">5</xref>] and 0.147 for La<sub>0.7</sub>Ca<sub>0.3</sub>MnO<sub>3</sub> [<xref ref-type="bibr" rid="scirp.50672-ref6">6</xref>] obtained from static magnetization measurements suggest that the PM-FM transition in these compounds is first-order transition. Further, a first-order PM-FM phase transition has been reported [<xref ref-type="bibr" rid="scirp.50672-ref8">8</xref>] for La<sub>0.7</sub>Ca<sub>0.3</sub>MnO<sub>3</sub> based on the sign of the slope of the isotherm plots, (H/M)<sup>1/</sup><sup>g</sup> vs. M<sup>1/</sup><sup>b</sup> (g = 1 and b = 0.5 or g = 1.336 and b = 0.365). Interestingly, a continuous transition has been reported [<xref ref-type="bibr" rid="scirp.50672-ref7">7</xref>] for La<sub>0.8</sub>Ca<sub>0.2</sub>MnO<sub>3</sub>. Recently, a critical point has been identified [<xref ref-type="bibr" rid="scirp.50672-ref9">9</xref>] in the La<sub>1-x</sub>Ca<sub>x</sub>MnO<sub>3</sub> phase diagram at x = 0.4, thus marking a boundary between first- and second-order phase transitions. La<sub>0.7</sub>Sr<sub>0.3</sub>MnO<sub>3</sub>, a typical perovskite, has generated much interest in recent work. It has a ferromagnetic transition near 360 K [<xref ref-type="bibr" rid="scirp.50672-ref10">10</xref>] , which is the highest T<sub>C</sub> among perovskite manganites having the same Mn<sup>3+</sup>/Mn<sup>4+</sup> ratio of 7/3. The critical parameters of maganites materials have been reported in a number of publications. It is interesting that the temperature can be shifted to room temperature for applications.</p><p>According to the Curie-Weiss law for ferromagnetism, the large magnetic entropy change, ΔS<sub>M(T,H)</sub>, is expected at the Curie temperature T<sub>C</sub> and has high values for materials having large effective magnetic moment [<xref ref-type="bibr" rid="scirp.50672-ref11">11</xref>] . Since 1996, there have been numerous reports of exceptionally large magnetocaloric effects in perovskite manganese oxides [<xref ref-type="bibr" rid="scirp.50672-ref12">12</xref>] -[<xref ref-type="bibr" rid="scirp.50672-ref16">16</xref>] . In this paper, we report the critical parameters b, g and d determined from the Arrott plots, Arrott plots modified and magnetocaloric effects of the La<sub>5/8</sub>Ca<sub>3/8</sub>Mn<sub>0.975</sub>Pd<sub>0.025</sub>O<sub>3</sub> compound by analyzing the magnetization curves.</p></sec><sec id="s2"><title>2. Experiments</title><p>The sample was fabricated by the sol-gel method. The original chemical substance are La(NO<sub>3</sub>)<sub>2</sub>, Ca(NO<sub>3</sub>)<sub>2</sub>, Mn(NO<sub>3</sub>)<sub>2</sub> and PdCl<sub>2</sub> with the pure of more than 99.99%. The sample had been heated at 980˚C for 3 hours. After that it had been sintered at 1050˚C for 4 hours in air. Sample was checked and confirmed by X-ray diffraction. The results show that the sample was quality with structure of orthorhombic. The magnetic measurements were carried out on the PPMS-6000.</p></sec><sec id="s3"><title>3. Results and Discussion</title><p><xref ref-type="fig" rid="fig1">Figure 1</xref> shows the temperature dependence of magnetisation of the sample measured in the applied field of 100 Oe using zero field cooled and field cooled mode. The ferro-paramagnetic transition temperature is T<sub>C</sub> = 252.7 K, defined from derivative the M(T) curve as temperature. The sample behaves the second-order-phase transition. It also behaves a large of the range of temperature. This is a typical behavior of the samples fabricated by sol-gel</p><fig id="fig1"  position="float"><label><xref ref-type="fig" rid="fig1">Figure 1</xref></label><caption><title> The temperature dependence of the magnetisation of the La<sub>5/8</sub>Ca<sub>3/8</sub>Mn<sub>0.975</sub>Pd<sub>0.025</sub>O<sub>3</sub> sample</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/3-7701088x5.png"/></fig><p>method. The range of the wide of transition as well the difference between the zero-field cooled and filed cooled in the range of low temperature does not seems to reflect the chemical disorder but seems due to the disorder in magnetism. It may be in a result of phase separation phenomenal [<xref ref-type="bibr" rid="scirp.50672-ref15">15</xref>] .</p><p><xref ref-type="fig" rid="fig2">Figure 2</xref> shows the magnetic field dependence of magnetization at different temperatures. It can be seen that at low temperatures, far from T<sub>C</sub>, the value of magnetisation of the sample is not saturated. To understand clearly the interaction between the samples, we have built the Arrot plots. The transition temperature, of cause, is not shown from the shape of the curves event thought near the phase transition. So we have had to build the Arot plots modified by using the critical exponents.</p><p>In the range of the ferro-paramagnetic transition temperature, the scaling law was used for the saturate magnetisation and susceptibility and given by [<xref ref-type="bibr" rid="scirp.50672-ref16">16</xref>] [<xref ref-type="bibr" rid="scirp.50672-ref17">17</xref>] . The critical parameters β and γ, are inferred by using</p><p><inline-formula><inline-graphic xlink:href="http://html.scirp.org/file/3-7701088x6.png" xlink:type="simple"/></inline-formula>in the temperatures of T &lt; T<sub>C</sub>. The susceptibility is defined by the equation <inline-formula><inline-graphic xlink:href="http://html.scirp.org/file/3-7701088x7.png" xlink:type="simple"/></inline-formula> in</p><p>the range of temperatures T &gt; T<sub>C</sub>. At the ferro-magnetic transition temperature, the applied field dependence of</p><p>the susceptibility is given by<inline-formula><inline-graphic xlink:href="http://html.scirp.org/file/3-7701088x8.png" xlink:type="simple"/></inline-formula>, where the critical parameter δ = 1 + γ/β. The value of δ can be found</p><p>from the log(M) curves versus log(H) at T<sub>C</sub>. By the extrapolating the Arot plots, we have gained the saturate magnetisasion and susceptibility as shown in the <xref ref-type="fig" rid="fig3">Figure 3</xref>. The critical parameters of the sample are defined of b = 0.48633, g = 1.1826 and δ = 3.431682. This implies that both mean-field and Heisenberg model are not applied for those samples. As mentioned above, the samples are complicated phase in physic so this term can be</p><fig id="fig2"  position="float"><label><xref ref-type="fig" rid="fig2">Figure 2</xref></label><caption><title> The isotherm curves of the La<sub>5/8</sub>Ca<sub>3/8</sub>Mn<sub>0.975 </sub>Pd<sub>0.025</sub>O<sub>3</sub> sample at different temperatures</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/3-7701088x9.png"/></fig><fig id="fig3"  position="float"><label><xref ref-type="fig" rid="fig3">Figure 3</xref></label><caption><title> The temperature dependence of the saturate magnetisation and susceptibility of the La<sub>5/8</sub>Ca<sub>3/8</sub>Mn<sub>0.975 </sub>Pd<sub>0.025</sub>O<sub>3</sub> sample</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/3-7701088x10.png"/></fig><p>explained by a point of view of phase separation. The critical parameters defined are between the mean-filed and Heisenberg model. This suggests that the sample seems not to be single phase but at least two phases, which should obey mean-field and Heisenberg model.</p><p>The thermo-magnetisation measurements show the transition temperature T<sub>C</sub> = 252.7 K. However, it is relative based on the derivative of the curve M(T) as T. This value was defined at the peak of the derivative curve. At this temperature, the variety of magnetisation as temperature is the strongest. Base on the obtained results, we have calculated and defined the ferro-magnetic transition temperature of the sample T<sub>C</sub> = 247.79 K. This is mean value after calculating both temperature regions above and below T<sub>C</sub>. It is much different to the value defined by the magnetisation curve. However, this value is more exactly because it is defined in the region of phase transition. It behaves the nature of the transition process in the sample.</p><p>The Arot plots modified were built using the critical parameters. The result is shown in the <xref ref-type="fig" rid="fig4">Figure 4</xref>. The Arot plots modified show the difference above the shape of the between two regions, above and below T<sub>C</sub>, which was defined to be T<sub>C</sub> = 247.79 K by analyzing the data of saturate magnetisation and susceptibility. This shows that there is a strongest change of magnetic order of the sample at 247.9 K.</p><p>The magnetocaloric phenomena was investigated using the applied field dependence of the magnerisation, M(H), at different temperatures. The result is displayed in the <xref ref-type="fig" rid="fig5">Figure 5</xref>. The magnetocaloric curves calculated for the applied fields of 0.5 T up to 6.0 T. As can be seen from <xref ref-type="fig" rid="fig5">Figure 5</xref>, the peaks of those curves shift to the higher temperature in higher applied field. In the low field, magnetocaloric shift to the ferro-paramagnetic transition temperature, T<sub>C</sub> = 247.79 K. This can be understood that the magnetocaloric phenomenon is strongest at</p><fig id="fig4"  position="float"><label><xref ref-type="fig" rid="fig4">Figure 4</xref></label><caption><title> The Arrot modified of La<sub>5/8</sub>Ca<sub>3/8</sub>Mn<sub>0.975</sub>Pd<sub>0.025</sub>O<sub>3</sub></title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/3-7701088x11.png"/></fig><fig id="fig5"  position="float"><label><xref ref-type="fig" rid="fig5">Figure 5</xref></label><caption><title> The CME in the La<sub>5/8</sub>Ca<sub>3/8</sub>Mn<sub>0.975</sub>Pd<sub>0.025</sub>O<sub>3</sub> sample in the difference applied fields</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/3-7701088x12.png"/></fig><p>the phase transition temperature related to the applied field for the thermo-magnetisation measurements. The shifting of the peaks due to the transition phase temperature is shifted to higher in high applied field. Approximate of 5 J/Kg∙K is the maximum value of magnetocaloric gained in the applied field of 6 T. Despite of small but it is close to room temperature. It is interesting that the magnetocaloric phenomenon broad over temperature region. It reduces sharply as increasing temperature higher T<sub>C</sub> whereas it reduces more slowly in the temperature lowers T<sub>C</sub>. This can be explained that in the temperature higher T<sub>C</sub>, the materials is paramagnetic and it is ferromagnetic in the lowers T<sub>C</sub>.</p><p>Phase separation of the materials can affect the positive effects at T<sub>C</sub> such as magnetoresistance or magnetocaloric. For the magnetoresistance, phase separation plays a role in the temperature region. It enhances the low- field magnetoresistance especially in low temperatures, far from T<sub>C</sub>. However, the magnetocaloric is not enhanced in low temperatures. This is a challenge for application.</p></sec><sec id="s4"><title>4. Conclusion</title><p>The critical parameters have been studied. The results show b = 0.48633, g = 1.1826 and δ = 3.431682. This means that the transition model of the sample is between the mean-field and the Heisenberg mode. The thermomagnetic properties were investigated. The results show that Pd substituted for Mn in the materials reduces the ferro-paramagnetic transition temperature as well as magnetocaloric. However, the region of temperature having magnetocaloric is broadened to the lower transition temperature.</p></sec><sec id="s5"><title>Acknowledgements</title><p>This work was supported by the National Foundation for Science &amp; Technology Developments (NAFOSTED), Vietnam, project code: 103.02-2010.28. 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