Maximum magnetic entropy change modulated toward room temperature in perovskite manganites La0.7−xNdx(Ca,Sr)0.3MnO3

With Nd³⁺ doping and Ca²⁺, Sr²⁺ modulating in the sol–gel technique, a series of polycrystalline perovskite samples La_0.7?xNd_x(Ca,Sr)_0.3MnO₃ (x = 0, 0.05, 0.1, 0.15, 0.20, 0.25) was prepared, their maximum magnetic entropy changes were tuned to room temperature (ΔS_H = ?1.47 J/kg K at 298 k for La_0.45Nd_0.25(Ca,Sr)_0.3MnO₃), an enhancement of the maximum magnetic entropy change (ΔS_H = ?1.89 J/kg K at 315 k) and its refrigerant capacity (about 45.3 J/kg) had also been obtained under 9 kOe magnetic field variation for La_0.55Nd_0.15(Ca,Sr)_0.3MnO₃ contrast to La_0.7(Ca,Sr)_0.3MnO₃.     

Giant magnetic refrigerant capacity in Ho3Al2 compound

Magnetic properties and magnetocaloric effects (MCEs) of the intermetallic Ho₃Al₂ compound are investigated by magnetization and heat capacity measurements. Two successive magnetic transitions, a spin-reorientation (SR) transition at T_SR=31 K followed by a ferromagnetic (FM) to paramagnetic (PM) transition at T_C=40 K, are observed. Both magnetic transitions contribute to the MCE and result in a large magnetic entropy change (ΔS_M) in a wide temperature range. The maximum values of ?ΔS_M and adiabatic temperature change (ΔT_ad) reach 18.7 J/kg K and 4.8 K for the field changes of 0–5 T, respectively. In particular, a giant value of refrigerant capacity (RC) is estimated to be 704 J/kg for a field change of 5 T, which is much higher than those of many potential refrigerant materials with similar transition temperatures.     

A comparative study of the magnetocaloric effect in Gd3Co and Gd3Ni

Magnetic and magnetocaloric properties of polycrystalline samples of Gd₃Co and Gd₃Ni have been studied. Both these compounds are antiferromagnets and undergo metamagnetic transitions in the antiferromagnetic phase. The Neel temperatures are found to be 128 and 99 K, respectively for Gd₃Co and Gd₃Ni. Though both these compounds have the same crystal structure, their magnetic structures seem to be different. It is found that Gd₃Ni possesses larger magnetic anisotropy compared to Gd₃Co. The maximum values of isothermal magnetic entropy change are 11 and 18.5 J Kg⁻¹ K⁻¹ for Gd₃Co and Gd₃Ni respectively, while their refrigerant capacities are 2.6 J cm⁻³ for both of them. Magnetic entropy change in the paramagnetic region shows a quadratic dependence on the magnetic field in the case of Gd₃Ni, indicating the presence of spin fluctuations above the Neel temperature.     

Magnetic properties and magnetocaloric effects in Gd1−xHoxNiIn intermetallic compounds

Magnetic properties and magnetocaloric effects (MCEs) of the intermetallic Gd_1?xHo_xNiIn (x=0?1) compounds have been evaluated by magnetization and heat capacity measurements. The Curie temperature T_C can be tuned from near 100 K to 20 K by substituting Ho for Gd atoms. In addition, all the compounds with Ho atoms undergo two successive magnetic transitions with the decrease of temperature: a paramagnetic (PM) to ferromagnetic (FM) transition around T_C and a spin-reorientation (SR) transition around 7?9 K. It is found that both transitions contribute to the magnetic entropy change (ΔS_M). For a field change of 5 T, the maximum values of ?ΔS_M for Gd_0.4Ho_0.6NiIn are 6 J/kg K at T_t=9 K and 10 J/kg K at T_C=52 K, respectively. These two ?ΔS_M peaks overlap partly and result in a wide working temperature range of MCE, and thus leading to the largest RC value of 443 J/kg in the Gd_1?xHo_xNiIn system.     

Giant magneto-caloric effect around room temperature at moderate low field variation in La0.7(Ca1−xSrx)0.3MnO3 perovskites

Among the perovskite manganites, a series of La_1?xCa_xMnO₃ has the largest magneto-caloric effect (MCE) (|ΔS_m|_max=3.2–6.7 J/kg K at ΔH=13.5 kOe), but the Curie temperatures, T_C, are quite low (165–270 K). The system of LaSrMnO₃ has quite high T_C but its MCE is not so large. The manganites La_0.7(Ca_1?xSr_x)_0.3MnO₃ (x=0, 0.05, 0.10, 0.15, 0.20, 0.25) have been prepared by solid state reaction technique with an expectation of large MCE at room temperature region. The samples are of single phase with orthorhombic structure. The lattice parameters as well as the volume of unit cell are continuously increased with the increase of x due to large Sr²⁺ ions substituted for smaller Ca²⁺ ions. The field-cooled (FC) and zero-field-cooled (ZFC) thermomagnetic measurements at low field and low temperatures indicate that there is a spin-glass like (or cluster glass) state occurred. The Curie temperature T_C increases continuously from 258 K (for x=0) to 293 K (for x=0.25). A large MCE of 5 J/kg K has been observed around 293 K at the magnetic field change ΔH=13.5 kOe for the sample x=0.25. The studied samples can be considered as giant magneto-caloric materials, which is an excellent candidate for magnetic refrigeration at room temperature region.     

Antiferromagnetic phase transition in garnet-type AgCa2Mn2V3O12 and NaPb2Mn2V3O12

Ferrimagnetism has been extensively studied in garnets, whereas it is rare to find the antiferromagnet. Present work will demonstrate antiferromagnetism in the two Mn–V-garnets. Antiferromagnetic phase transition in AgCa₂Mn₂V₃O₁₂ and NaPb₂Mn₂V₃O₁₂ has been found, where the magnetic Mn²⁺ ions locate only on octahedral A site. The heat capacity shows sharp peak due to antiferromagnetic order with the Néel temperature T_N=23.8 K for AgCa₂Mn₂V₃O₁₂ and T_N=14.2 K for NaPb₂Mn₂V₃O₁₂. The magnetic entropy change over a temperature range 0–50 K is 13.9 J K^?1 mol-Mn²⁺-ions^?1 for AgCa₂Mn₂V₃O₁₂ and 13.6 J K^?1 mol-Mn²⁺-ions^?1 for NaPb₂Mn₂V₃O₁₂, which are in good agreement with calculated value of Mn²⁺ ion with spin S=5/2. The magnetic susceptibility shows the Curie–Weiss behavior over the range 29–350 K. The effective magnetic moment μ_eff and the Weiss constant θ are μ_eff=6.20 μ_B Mn²⁺-ion^?1 and θ=?34.1 K (antiferromagnetic sign) for AgCa₂Mn₂V₃O₁₂ and μ_eff=6.02 μ_B Mn²⁺-ion^?1 and θ=?20.8 K for NaPb₂Mn₂V₃O₁₂.     

Anisotropic properties of rare-earth dibismites

We report measurements of magnetic, thermal and transport properties of single crystals of rare-earth dibismites RBi₂ (R=La–Nd, Sm), grown via self-flux method. All compounds are good metals, and those with magnetic ions order antiferromagnetically at low temperatures. Ce, Pr and Sm members of the series show single magnetic transition whereas NdBi₂ most likely exhibits two magnetic transitions. Significant magnetic anisotropy and a series of metamagnetic transitions in fields up to 55 kG are found in PrBi₂. Ordering temperatures range from 3 K to just above 16 K and they scale well with the de Gennes factor.     

The effect of chemical pressure in rutheno-cuprates

We have studied the effect of negative chemical pressure in the RuGd_1.5(Ce_0.5?xPr_x)Sr₂Cu₂O_10?δ with Pr content of 0.0 ? x ? 0.2. This is also investigated using the bond length results obtained from the Rietveld refinement analysis. The c parameter and cell volume increase with x for 0.0 ? x ? 0.15. The width of the resistivity transition also increases with Pr concentration, indicating higher inhomogeneity and oxygen deficiency. The difference in the ionic valences of Pr^3+,4+ and Ce⁴⁺ causing different hole doping, the difference in the ionic radii, and oxygen stoichiometry affect the superconducting transition. The magnetoresistance shows a cusp around 135 K which lies between the antiferromagnetic and ferromagnetic transition temperatures, which is probably due to the presence of a spin glass region. There exist two magnetic transition temperatures for 0.0 ? x ? 0.2 which respectively change from T_M = 155 K to 144 K and from T_irr = 115 K to 70 K. The magnetization versus applied magnetic field isotherms at 77 K and 300 K show that the remanent magnetization and coercivity are lower for samples with higher Pr content.     

Structural and magnetic ordering in La0.6Ca0.4MnO3

The structural and magnetic ordering in La_0.6Ca_0.4MnO₃ has been studied by neutron powder diffraction as a function of temperature between 15 and 300 K. The para-ferromagnetic transition at T∼250 K is accompanied by significant structural distortions in the form of octahedral Mn–O₆ rotations. At 15 K, the total refined ferromagnetic moment on the Mn site was obtained as 3.1 μ_B, in reasonable agreement with the total expected average moment of mixed Mn³⁺/Mn⁴⁺ matrix.     

Magnetic properties of rare-earth transition metal aluminides R6T4Al43 with Ho6Mo4Al43-type structure

The magnetic properties of 53 aluminium-rich intermetallic compounds R₆T₄Al₄₃ with R=rare-earth elements and T=Ti, V, Nb, Ta, Cr, Mo, W were investigated using polycrystalline samples and a SQUID magnetometer in the temperature range from 2 to 300 K with magnetic flux densities up to 5.5 T. The yttrium and lutetium compounds are Pauli paramagnetic, indicating that the transition metal atoms do not carry magnetic moments. The samarium compounds show van Vleck behavior and antiferromagnetic order with Néel temperatures of less than 12 K. Of these Sm₆Ti₄Al₄₃ becomes metamagnetic. The ytterbium compounds show a mixed or intermediate valent behavior and no magnetic order down to 2 K. All other compounds obey the Curie–Weiss law above 30 K. Their effective magnetic moments correspond to the theoretical moments of the rare-earth ions. They show ferromagnetic or metamagnetic behavior with ordering temperatures all below 20 K. The magnetization curves of most compounds (recorded up to 5.5 T) reach about 50% of the theoretical magnetization already at 0.5 T. The gadolinium compounds are exceptional in that they reach at 0.5 T only about 10% of their theoretical magnetization. The crystal structures of the isotypic compounds Yb₆V₄Al₄₃ and Yb₆Ta₄Al₄₃ were refined from single-crystal X-ray data.     

Electrical,magnetic and magnetocaloric properties of polycrystalline Pr0.63A0.07Sr0.3MnO3 (A=Pr,Sm and Bi)

We studied the effects of the partial substitution (10%) of praseodymium by samarium and bismuth, on the structural, magnetic, magnetocaloric and electrical properties of the Pr_0.63A_0.07Sr_0.3MnO₃ (A=Pr, Sm and Bi) manganites prepared using the solid state reaction. Refinement of the X-ray diffraction patterns shows that all our samples are single phase and crystallize in the orthorhombic structure with Pnma space group. Magnetic studies indicate that all the samples exhibit a ferromagnetic–paramagnetic transition with increasing temperature. Curie temperature T_C decreases by substitution. M(H) curves indicate the presence of some antiferromagnetic domains in the substituted samples testifying the phase-separated nature of these samples. The magnetic entropy curves –ΔS(T) show a maximum in vicinity of T_C. Important values of maximum of −ΔS are recorded for our compounds. For the parent compound, we found 4.59 J/kg K for an applied magnetic field of 2 T at T_C=266 K which raises the possibility of using this compound as a magnetic refrigerant. The temperature dependence of the electrical resistivity ρ(T) indicates that all compounds exhibit a metal-insulator transition with increasing temperature. Electrical study suggests the presence of a correlation between electrical and magnetic properties.     

Magnetic phase transitions in the Nd(Mn0.9Me0.1)O3 (Me=Al, Fe, Cr, Zn) perovskites

It is shown that perovskite NdMnO₃ is a weak ferromagnet with an anomalous magnetization behavior due to Nd sublattice contribution. Ferromagnetic component drastically increases whereas T_N slightly decreases when a part of manganese ions is replaced with Cr, Al, Fe, Zn. It is suggested that the Mn³⁺–O–Mn³⁺ superexchange interaction changes a sign in the microdomains enriched with Me=Cr, Al, Fe, Zn ions due to removing static Jahn–Teller distortions. All these substituted perovskites show a sharp drop of the magnetization as temperature decreases. A large temperature hysteresis indicates first-order phase transition. Below this transition neodymium magnetic moments orient opposite to a moment of manganese magnetic sublattice. It is supposed that this phase transition results from a change of the ground state of Nd ions.     

Magnetic entropy change in perovskite manganites La0.65Nd0.05Ca0.3Mn0.9B0.1O3 (B=Mn,Cr, Fe)

We have investigated the effect of B-site dopant on magnetic entropy change in perovskite manganite samples of La_0.65Nd_0.05Ca_0.3MnO₃, La_0.65Nd_0.05Ca_0.3Mn_0.9Cr_0.1O₃, and La_0.65Nd_0.05Ca_0.3Mn_0.9Fe_0.1O₃ prepared by sol–gel technique. The maximum ΔS_H is in the order of −1.68 J/kg K and peaks at Curie temperature for La_0.65Nd_0.05Ca_0.3MnO₃ upon 10 kOe applied field change. For the sample with B-site dopant, a decrement of the maximum magnetic entropy change has been observed.     

Low-temperature investigations of the open-framework material HfMgMo3O12

The A₂Mo₃O₁₂ family, where A³⁺ is a large trivalent cation, can show interesting thermal properties such as negative thermal expansion. One member of this family, HfMgMo₃O₁₂, where the two A³⁺ cations have been replaced by Hf⁴⁺ and Mg²⁺, has been shown to have a low positive coefficient of thermal expansion above room temperature. This property makes HfMgMo₃O₁₂ an attractive candidate as a component for solid solutions with near-zero thermal expansion. However, its properties below room temperature were unexplored. In this work we report the phase transition from orthorhombic Pnma to monoclinic P2₁/a at T～175 K with an enthalpy change of 0.27 kJ mol^?1. Relaxation calorimetry, from 5 K to 300 K, show only the small anomaly associated with this transition. The thermal conductivity, determined from 2 K to 300 K, was low, but not as low as some other materials exhibiting negative thermal expansion. Analysis of the low-temperature heat capacity indicates the presence of low-energy phonon modes in HfMgMo₃O₁₂, consistent with the low thermal conductivity. The upper bound of the Young's modulus, estimated from the effective Debye temperature derived from the low-temperature heat capacity, is 20 GPa, a relatively low value due to the flexibility of the framework structure.     

Enhanced magnetocaloric effect in a Co-doped Heusler Mn50Ni37Co3In10 unidirectional crystal

A high-pressure optical zone-melting technique was employed to grow a Mn-rich Heusler Mn₅₀Ni₃₇Co₃In₁₀ unidirectional crystal in the present study. It was found that the Co-doped Mn₅₀Ni₃₇Co₃In₁₀ unidirectional crystal showed a low magnetic hysteretic loss and a widened working temperature interval in the vicinity of the martensitic transformation. The inverse magnetic entropy change (∆S_M) reached 7.84 Jkg⁻¹K⁻¹ around 237.5 K under a magnetic field change of 30 kOe, and the corresponding effective refrigeration capacity (RC_eff) was about 127.2 Jkg⁻¹. The experimental results demonstrated a high potential to develop high-performance Mn-rich Heusler Mn–Ni–In magnetocaloric materials by means of Co doping in combination with the high-pressure optical zone-melting fabrication technique.     

Synthesis and near-infrared luminescence properties of LaOCl:Nd3+/Yb3+

Near-infrared emitting phosphors LaOCl:Nd³⁺/Yb³⁺ were prepared by the solid-state method, and their structures and luminescent properties were investigated by using X-ray diffraction and photoluminescence analysis, respectively. The studies shows that tetragonal LaOCl:Nd³⁺/Yb³⁺ can be synthesized by the solid-state reaction at 600 °C for 3 h. Upon 353 nm UV excitation, LaOCl:Nd³⁺/Yb³⁺ sample shows strong near-infrared emission lines in the region of 1060–1150 nm (corresponding to ⁴F_3/2 → ⁴I_J′ transition of Nd³⁺, J′ = 9/2, 11/2, 13/2, 15/2) and 980–1050 nm (corresponding to ²F_5/2 → ²F_7/2 transition of Yb³⁺). The decreasing emission intensity of Nd³⁺ with increasing doping concentration of Yb³⁺ proved the energy transfer in LaOCl:Nd³⁺/Yb³⁺. The possible near-infrared emission and energy transfer mechanism between Nd³⁺ and Yb³⁺, as well as the energy transfer efficiency of LaOCl:Nd³⁺/Yb³⁺ were discussed.     

Magnetocaloric effect in antiferromagnetic Dy3Co compound

Magnetic properties and magnetocaloric effects (MCEs) of the Dy₃Co compound are studied. Two successive magnetic transitions: the antiferromagnetic (AFM)-to-AFM transition at T _AF =29 K and the AFM-to-paramagnetic (PM) transition with increasing temperature at the Néel temperature T _N =44 K are observed. Dy₃Co undergoes a field-induced metamagnetic transition from the AFM to the ferromagnetic (FM) state below T _N , giving rise to a large MCE. The maximal value of magnetic entropy change ΔS _m is −13.9 J/kg K with a refrigerant capacity (RC) of 498 J/kg around T _N for a field change of 0–5 T. A sign change of MCE in Dy₃Co with magnetic field and temperature is observed near the critical field where the metamagnetic transition occurs.     

White LED based on nano-YAG:Ce3+/YAG:Ce3+,Gd3+ hybrid phosphors

Nano-YAG:Ce³⁺ and YAG:Ce³⁺,Gd³⁺ phosphors were synthesized by glycothermal method. The X-ray diffraction (XRD) measurements showed that the samples can be well-crystallized at 600 °C. The transition electron microscope (TEM) showed that the particles have sizes mostly in the range between 35 and 100 nm. The YAG:Ce nano-phosphor had a wide emission band ranging from blue to yellow peaking at 532 nm, due to the transition from the lowest 5d band to ²F_7/2, ²F_5/2 states of the Ce³⁺ ion. Red-shift of emission peak wavelength from 532 nm to 568 nm has been achieved as doping Gd³⁺ ions into the YAG:Ce³⁺ to substitute some Y³⁺ ions. White LEDs were fabricated by combining GaN (460 nm) chip with the YAG:Ce³⁺ and YAG:Ce³⁺,Gd³⁺. Color rendering index of the white LED as a function of the ratios of theses two kinds of phosphors was studied. As the ratio of YAG:Ce³⁺,Gd³⁺ phosphor increased, the color rendering index of the LED improved significantly under the forward bias of 20 mA. As the ratio of YAG:Ce³⁺ and YAG:Ce³⁺,Gd³⁺ was 11:9, the white LED had a color rendering index, CIE chromaticity coordinates and color temperature T_c of 85, (0.3116, 0.3202) and 6564 K, respectively.