Thermodynamical Evaluation on Magnetocaloric Effect of Magnetic Refrigerating Materials Near Room Temperature

The relationship between isothermal magnetic entropy change DELTA S andadiabatic temperature change DELTA T_(ad) was deduced according to the principles of thermodynamics.The MCE and the engineering application were discussed for Gd and several new kinds of magneticrefrigerating materials near room temperature, Gd_5Si_2Ge_2, MnFeP_(0.45)As_(0.55) and LaFe_(11.2)Co_(0.7)Si_(1.1). Isothermal entropy change is proportional to adiabatic temperature change with afactor of T/C (T is temperature, C is heat capacity). When the comparison of magnetacoloric effectis made for two different materials, we should consider isothermal entropy change as well asadiabatic temperature change.

Study on Gd-Al-Dy System Magnetic Refrigeration Materials

d-Al-Dy system materials were prepared by the technique of powder sintering. Twolayers gradient function materials with compositions of (Gd_0.9Dy_0.1)_3Al_2 and Gd_3Al_2 respectively were studied. The results show that the Curie temperature (Tc) of the monolayer material decreases with the increment of Dy content. The Tc values of the twolayer gradient function material agree well with the layer numbers and corresponding to Dy content. For the Tc gradiently changed twolayers Gd-Al-Dy system material, its ΔSm changes smoothly with temperature. Therefore, the magnetic refrigeration is improved.

Magnetocaloric effect of (Gd_(1-x)Nd_x)Co_2 alloys in low magnetic field

The phases and magnetocaloric effect in the alloys （Gd1-xNdx）Co2 with x = 0, 0.1, 0.2, 0.3, and 0.4 were investigated by X-ray diffraction analysis and magnetization measurement. The samples are single phase with a cubic MgCu2-type structure. The To decreases obviously with increasing Nd content from 404 K of the alloy with x = 0 to 272 K of the alloy with x = 0.4; forx = 0.3, the To is 296 K, which is near room temperature. In the samples （Gd1-xNdx）Co2 with x = 0.0, 0.1, 0.2, 0.3, and 0.4, the maximum magnetic entropy change is 1.471, 1.228, 1.280, 1.381 and 1.610 J·kg^-1·K^-1, respectively, in the applied field range of 0-2.0 T. The results of Arrott plots confirmed that the transition type were second order magnetic transition forx = 0, 0.3, and 0.4.

Magnetocaloric effect of (Gd_(1-x)Ce_x)Co_2 compounds in low magnetic fields

The phases in the compounds （Gd1-xCex）Co2 with x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5 were investigated by X-ray diffraction, and the magnetocaloric effect for x = 0-0.4 was studied by magnetization measurements. The samples are almost single phase with a cubic MgCu2-type structure for x = 0-0.5. The magnetization decreases with an increase in Ce content. There is almost no magnetic transition for x = 0.5 at 100-350 K. The Curie temperature （To） of the （Gd1-xCex）Co2compounds with x from 0.1 to 0.4 are 350, 344, 340, and 338 K respectively. The maximum magnetic entropy change is 2.34 J·kg^-1·K^-1 when x = 0.3. The results of Arrott plots show that the magnetic phase transition is second-order magnetic phase transition in these compounds.

Magnetic Entropy Change of (Gd_(1-x)RE_x)_5Si_4(RE=Dy, Ho) Alloys

The magnetic properties, including Curie points, magnetic phases transition and magnetic entropy changes, of （Gd1-xREx）5Sin（RE = Dy, Ho） alloys were systematically studied. The results show that the alloys keep the Sm5Ge4 orthorhombic structures as Gd5Si4, and the Curie points of the alloys almost linearly decrease with increasing content of x, so that the Curie points can be adjusted by adding different concentrations of Dv or Ho in the alloys. The magnetic properties of these alloys obey second order transition. The costs of these alloys are cheaper than that of Gd- Si-Ge alloys because there is not expensive element such as Ge. The large magnetic entropy change at low fields （ 〈 2 T） and wide temperature ranges of these alloys suggest that they are suitable to be the gradient function materials and candidates of magnetic refrigerants at room temperature with low fields.

Magnetic Transition and Magnetic Entropy Change of Gd_5Si_(1.75)Ge_(1.75)Sn_(0.5)

Gd5Si1.75 Ge1.75 Sn0.5 was prepared by arc melting method. The crystal structure and magnetic properties were investigated by XRD and VSM, respectively. The magnetization of the Gd5Si1.75 Ge1.75 Sn0.5 alloy changes abruptly near its corresponding Curie temperature 269 K, possesses a typical first which means that the alloy order phase transition. The Gd5Si1.75Ge1.75 Sn0.5 adopts in Gd5Si2Ge2-type monoclinic structure at room temperature, the maximal magnetic entropy change at a magnetic field change of 1.8 T is as large as 16.7 J·kg^-1·K^-1, exceeding that of Gd about two times and is a little larger than that of Gd5Si2Ge2.

Research Advance on Magnetocaloric Effect of La-Fe-M(Al, Si) Compounds

Recent research progress on magnetocaloric effect of La-Fe-M (M = Al, Si) compounds was presented. La-Fe-M (M = Al, Si) compounds of high Fe content are excellent soft magnetic materials with NaZn13 structure. The Curie temperature of the compounds can be increased by substituting small amount of Co for Si, Al. The La(Fe1-xCoy)(x)Si13-x compounds with an appropriate ratio of Co and Si can produce giant magnetocaloric effect comparable to that for Gd5Si2Ge2 at room temperature. The La (FexSi1-x)(13) doped with H can also produce giant magnetocaloric effect at room temperature, which is much greater than that for Gd. For La (FexSi1-x)(13) compounds with low Si or high Si contents. The nature of phase transition near Curie temperature induced by temperature and magnetic field was described in detail.

Line Faults in Gd_5Si_2Ge_2-Type Phase

Gd5Si2Ge2.2 alloy was synthesized by arcmelting and its phase components, microstructure, and especially the line features were investigated by X- ray diffraction （XRD）, scanning-electron microscope （SEM）, energy-dispersive spectroscopy （EDS）, and transmission-electron microscope （TEM）. Gd5Si2Ge2.2 consists of Gd5Si2Ge2-type and GdGe-type phases and presents eutectic characteristics. There are many regular line features on the Gd5Si2Ge2-type phase according to SEM. EDS shows that the line feature is not the Gd5 （Si,Ge）3-type phase because Gd content decreases at the line features. Two types of line features are found in the fine microstructure of Gd5Si2Ge2-type phase by TEM. Selected area diffraction （SAD） confirms that both line features are not the secondary phase or twins. There is no changes observed in the microstructure of Gd5Si2Ge2 2 from room temperature to 1400 ℃ with in situ high temperature optical microscope, therefore, it is deduced that the line features observed by SEM are formed during the solidification.

Magnetocaloric Properties of (Gd_(1-x)Tb_x)_3Al_2 Compounds Near Room Temperature

Magnetic and thermal properties of the (Gd 1- x Tb x ) 3Al 2 compounds were studied as potential magnetic refrigerant materials which are used in magnetic refrigeration near room temperature at low magnetic field. The compounds (Gd 1- x Tb x ) 3Al 2 with x =0, 0.1, 0.2 and 0 3 exhibit a second order magnetic transition. Curie temperature varies from 255 K for x =0.3 to 280 K for x =0. The maximum of the isothermal magnetic entropy change Δ S increases by substituting Tb element for Gd element. Δ S max =18.9 kJ·m -3 ·K -1 for x =0.1 by changing the magnetic field from 0 to 1 T.

Influence of Sn substitution for Co in RCo_2 (R= Gd,Tb,Dy) alloys on the structure and magnetocaloric effect

The phases and the magnetocaloric effect in the alloys R（Co1-xSnx）2 with X = 0, 0.025, 0.050, 0.075, and 0.100 were investigated by X-ray diffraction analysis and magnetization measurement. The substitution of Sn in RCo2 is limited. The cubic MgCu2-type structure for the alloys of RCo2 was confirmed by X-ray powder diffraction and the remaining alloys mainly consisted of the RCo2 phase, along with some RCo3 and R5Sn3 impurity phases. The impurity phases increase with the increase of Sn content. The Tc of the alloys is not very sensitive to the Sn substitution for Dy（Co1-xSnx）2 and Tb（Co1-xSnx）2, whereas in Gd（Co1-xSnx）2, the Curie temperatures significantly increase. The maximum magnetic entropy changes in the alloys Dy（Co1-xSnx）2 （x = 0, 0.025, 0.050, 0.075） are 5.78, 5.43, 3.88, and 2.98 J·kg^-1·K^-1, respectively, and those in the Tb（Co1-xSnx）2 （x = 0, 0.025） are 3.44, and 2.29 J·kg^-1·K^-1 respectively in the applied field change of 0-2.0 T.

Phase transitions and magnetocaloric effects in intermetallic compounds MnFeX(X=P,As,Si,Ge)

Since the discovery of giant magnetocaloric effect in MnFeP1-x As x compounds,much valuable work has been performed to develop and improve Fe2P-type transition-metal-based magnetic refrigerants.In this article,the recent progress of our studies on fundamental aspects of theoretical considerations and experimental techniques,effects of atomic substitution on the magnetism and magnetocalorics of Fe2P-type intermetallic compounds MnFeX（X=P,As,Ge,Si） is reviewed.Substituting Si（or Ge） for As leads to an As-free new magnetic material MnFeP1-xSi（Ge）x.These new materials show large magnetocaloric effects resembling MnFe（P,As） near room temperature.Some new physical phenomena,such as huge thermal hysteresis and ＇virgin＇ effect,were found in new materials.On the basis of Landau theory,a theoretical model was developed for studying the mechanism of phase transition in these materials.Our studies reveal that MnFe（P,Si） compound is a very promising material for room-temperature magnetic refrigeration and thermo-magnetic power generation.

Phase structure and magnetocaloric effect of (Tb_(1–x)Dy_x)Co_2 alloys

Phase structure and magnetocaloric effect of （Tb1-xDyx）Co2 alloys with x=0, 0.2, 0.4, 0.6, 0.8, and 1.0 were investigated using X-ray diffraction analysis, differential thermal analysis, and magnetization measurement. The samples were single phase with cubic MgCu2- type structure; with the increase of Dy content, Tc decreased from 240 K （TbCo2） to 130 K （DyCo2）, and the maximum magnetic entropy change ｜ △SM,max｜ increased from 3.133 to 8.176 J/kg-K under low magnetic field of 0-2 T. The Arrott plot and the change of ｜△SM,max｜ showed that magnetic phase transition from second order to first order occured with the increase of Dy content between x=-0.6 and 0.8.

Effects of Pr substitution on the hydrogenating process and magnetocaloric properties of La1-xPrxFe11.4Si1.6Hy hydrides

In this paper, we study the effects of Pr substitution on the hydrogenating process and magnetocaloric properties of La（1-x）PrxFe11.4Si1.6Hy hydrides. The powder x-ray diffraction patterns of the La1-xPrxFe11.4Si1.6 and its hydrides show that each of the alloys is crystallized into the single phase of cubic Na Zn13-type structure. There are hydrogen-absorbing plateaus under 0.4938 MPa and 0.4882 MPa in the absorbing curves for the La0.8Pr0.2Fe11.4Si1.6 and La0.6Pr0.4Fe11.4Si1.6 compounds. The releasing processes lag behind the absorbing process, which is obviously different from the coincidence between absorbing and releasing curves of the La Fe11.4Si1.6 compound. The remnant hydrogen content for La0.6Pr0.4Fe11.4Si1.6 is significantly more than that for La0.8Pr0.2Fe11.4Si1.6 after hydrogen desorption, indicating that more substitutions of Pr for La are beneficial to retaining more hydrogen atoms in the alloys. The values of maximum magnetic entropy change are 14.91 J/kg·K and 17.995 J/kg·K for La0.8Pr0.2Fe11.4Si1.6H0.13 and La0.6Pr0.4Fe11.4Si1.6H0.87,respectively.

Magnetic properties and large magnetocaloric effects of GdPd intermetallic compound

With the intention to explore excellent magnetocaloric materials, the intermetallic compound GdPd was synthesized by arc melting and heat treatment. The microstructure, magnetic and magnetocaloric properties of the intermetallic compound of GdPd were investigated by X-ray diffraction（XRD）, scanning electron microscopy（SEM） and the physical property measurement system（PPMS）. A large reversible magnetocaloric effect is observed in GdPd accompanied by a second order magnetic phase transition from paramagnetism to ferromagnetism at ～39 K. The paramagnetic Curie temperature（θp） and the effective magnetic moment（μ（eff））are determined to be 34.7 K and 8.12 μB/Gd,respectively. The maximum entropy change（｜△SM（Max）｜） and the relative cooling power（RCP） under a field change of 5 T are estimated to be 20.14 J/（kg·K） and 433 J/kg, respectively. The giant reversible magnetocaloric effects（both the large△SM and the high RCP） together with the absence of thermal and field hysteresis make the GdPd compound an attractive candidate for low-temperature magnetic refrigeration.

Inhibition of La-Fe-Co-Si compound corrosion in distilled water by sodium molybdate and disodium hydrogen phosphate

A comparative study of Na2MoO4·2H2O and Na2HPO4·12H2O as inhibitors for magnetic refrigeration material La-Fe-Co-Si compound corrosion in distilled water at room temperature was carried out.Moreover,the inhibiting behavior of the mixture of Na2MoO4·2H2O and Na2HPO4·12H2O was investigated.Potentiodynamic polarization curves and electrochemical impedance spectroscopy （EIS） measurements were applied to study the corrosion behavior of the compound in the absence or presence of different concentrations of these inhibitors under the same experimental conditions.The study revealed that the mixture of 3.0×10–3 kg/L Na2MoO4·2H2O and 5.0×10–3 kg/L Na2HPO4·12H2O was the best inhibitor reaching the value of inhibition efficiency （ε%） up to 93.9%.Polarization curves showed that the studied compounds acted as anodic inhibitors.The potential of zero charge （PZC） of La-Fe-Co-Si compound was determined in distilled water in the absence of the studied inhibitors.Corrosion inhibition mechanisms for inhibitors were proposed in this work.

Influence of silicon and carbon elements on formation of 1:13 phase and microstructure in LaFe_(13-y)Si_y compounds

Microstructure dependent on silicon and formation of 1：13 phase in LaFe13-ySiyC0.2 compounds was investigated. C and Si elements played different roles in assisting the formation of 1：13 phase. Si could inhibit the growth of α-Fe. The volume fraction of La-rich phase increased with the increase of Si content in the LaFe13-ySiyC0.2 ingots. When Si content was lower in LaFe13-ySiyC0.2 （S≤1.0）, α-Fe was excess and grew very large in the initial annealing process. As a result, a large amount of α-Fe remained even after a long time annealing process. Carbon doping could accelerate the formation of 1：13 phase in the LaFe13-ySiyC0.2 compounds. The amount of the 1：13 phase reached -90 vol.% in LaFex3_ySiyC02 （y〉1.2） after annealing at 1353 K for only 3 d. After optimized annealing, large magnetic entropy changes were obtained in LaFe13-SiyC0.2 compounds （18.6 and 15 J/（kg.K） in 0-2 T field change fory=1.2, 1.4, respectively）.