scholarly journals Collective electron ferronmagnetism

The essential contribution of Heisenberg to the theory of ferromagnetism was in showing that those effects which had been correlated by means of the formal molecular field hypothesis of Weiss could be interpreted as arising from interchange interaction between electrons in atoms, of the same type as that involved in the formation of homopolar molecules. The Heisenberg method of approach has, however, proved in many ways less convenient in the detailed treatment of ferromagnetism than the method initiated by Bloch for the theory of metallic properties generally, in which possible energy states are derived for electrons treated as waves travelling through the whole crystal. The first approximation in this collective electron treatment is that of free electrons, for which the energy is purely kinetic, the number of states per unit energy range then being proportional to the square root of the energy. The effect of the periodic field of the lattice is to modify the distribution of states, giving rise to a series of energy bands, separate or overlapping. Elaborate calculation is necessary to determine the form of these bands with any precision, though in general near the bottom of a band the energy density of states depends on the energy in the same way as for free electrons, but with a different pro­portionality factor; this holds also near the top of a band, the energy being measured downwards from that limit. The salient characteristics of metals depend on the electrons in unfilled bands. In particular, in the ferro­magnetic metals, iron, cobalt and nickel, the ferromagnetism may be attributed to the electrons in the partially filled band corresponding to the d electron states in the free atoms. The exchange interaction is such that, at low temperatures, instead of the electrons occupying the lowest states in balanced pairs, there is an excess of electrons with spins pointing in one direction, giving rise to a spontaneous magnetization. The decrease of energy due to the exchange effect with increase in the number of excess parallel spins is accompanied by an increase due to the electrons moving to states of higher energy in the band. The equilibrium magnetization depends on the number of electrons, the form of the band, the magnitude of the exchange interaction, and the temperature, and must be calculated on the basis of Fermi-Dirac statistics. The primary purpose in this paper is the determination of the form of the magnetization temperature curves for bands of the standard type and for a range of values of the exchange interaction energy. Before discussing the particular problem more fully, the relation between the present and some of the previous work will be briefly indicated. The advantages of a collective electron treatment for ferromagnetism were pointed out some years ago in a paper (Stoner 1933) in which it was shown that such a treatment enabled an immediate interpretation to be given to the non-integral values of the atomic moments of the ferromagnetic metals, and of the variation of the moment with small additions of non­ferromagnetic metals in alloys. Little was then known about the form of the electronic energy bands in transition metals, and the treatment was necessarily qualitative. Considerably greater precision in formulation became possible on the basis of a suggestion by Mott (1935), having a general justification, on the form of the energy bands in the ferromagnetic metals. In nickel, in particular, it was suggested that a narrow d band was overlapped by a much wider s band, and that the top of the Fermi distri­bution came at a point corresponding to 0·6 electron/atom in the s band, with a deficit of the same number in the d band; this number corresponding to the observed saturation moment of nickel at low temperatures. (It may be noted that “holes” in bands are to a large extent magnetically equi­valent to the same number of electrons in otherwise empty bands, as is more fully discussed elsewhere (Stoner 1936 a ).) This general idea of Mott has been developed successfully in a number of directions (cf. Mott and Jones 1936). A first step in the quantitative treatment of the effect of temperature on the magnetic properties of metals was the determination of the temperature dependence of free electron susceptibility (Stoner 1935, 1936 b ); the results obtained are applicable not only to free electrons but also to electrons in unfilled bands with the same type of energy distri­bution of states. Series expressions were derived appropriate to high and low temperatures, and values for the intermediate temperature range were found by graphical interpolation. In a subsequent discussion on spin paramagnetism in metals (Stoner 1936 a ) a simple method of taking into account the effect of interchange interaction was described, the method being applicable to the determination of the temperature variation of the susceptibility of a ferromagnetic above the Curie point. Shortly after­ wards the treatment was extended to deal with the spontaneous magnetization below the Curie point and the general character of the modifications resulting from the use of Fermi-Dirac, in place of classical, statistics, was determined. It was found, however, that the method previously used, involving series calculations for high and low temperatures, and graphical interpolation, was inadequate to give numerical results of satisfactory precision, the lack of precision being most marked for the temperature range which was often of greatest interest as including the Curie point region. For precise numerical results, an accurate evaluation of a series of the basic Fermi-Dirac functions was indispensable. An extensive table of Fermi-Dirac functions is now available (McDougall and Stoner 1938) and this provides the necessary starting point for much of the computational work involved in the present paper.

1953 ◽  
Vol 49 (1) ◽  
pp. 115-129 ◽  
Author(s):  
A. B. Lidiard

ABSTRACTThe theory of collective electron ferromagnetism given by Stoner applies to a system of electrons in a single energy band; for iron, cobalt and nickel this is identified with the band of states derived from atomic 3d functions. To bring in the generally assumed overlapping of the 3d band by the wide 4s band in these metals, the theory has been extended to take account of the transfer of electrons from 3d to 4s states with change of temperature. A previous calculation of this transfer effect must be regarded as inadequate, for the part played by the exchange energy in determining the distribution of electrons between the two sets of states was omitted. The general equations are derived in § 2 and used as a basis for discussion of the properties of nickel-copper alloys at absolute zero in § 3. In §§4 and 5 numerical results are presented which show the effect of the overlapping 4s band on the magnetic properties of a system such as nickel both above and below its Curie point. Comparison with the measured paramagnetic susceptibility of pure nickel above the Curie point strongly suggests that for this metal the overlapping 4s band has only a minor influence, although in principle the effect could be very large (cf. Fig. 4). This result is not unambiguous, however, because values thus inferred for the two unknown parameters lead to inaccurate predictions below the Curie point. First, the predicted values for the spontaneous magnetization are too small. Secondly, the theory demands that the nickel-copper alloys should only be ferromagnetic below a copper content of about 20 %, whereas experimentally the limit is known to be about 60 %. In conclusion, it is suggested that the implicit assumption of Stoner's theory that the exchange integrals between all pairs of 3d states are equal to one another is a more serious restriction on the theory than the consideration of only a single energy band.


The paper describes the second stage of a project to determine the temperature variation of spontaneous magnetization for various materials. An unequivocal determination of the spontaneous magnetization requires, in addition to magnetic intensities, the measurement of the magnetocaloric effect. Three extrapolation techniques were used to deduce the spontaneous magnetization from the observations, the results being considered with reference to Neel’s theory of ferrimagnetism. Two typical ferrites, manganese ferrite and magnesium zinc ferrite, molecular compositions MnO. Fe 2 O 3 and 1/2MgO. 1/2 ZnO. Fe 2 O 3 respectively were selected for the investigation. Owing to the low conductivity of this class of substances particular care is required in the thermal measurements. The different extrapolation techniques lead to substantially the same values of the spontaneous magnetization. In contrast to the behaviour of the ferromagnetic metals, this agreement is maintained in the Curie point region, the spontaneous magnetization-temperature curves showing a smaller ‘tail’ near the Curie temperature. For both materials the departure of the curve of reduced magnetization against reduced temperature from that predicted by the quantum modification of the Weiss theory is verified by the present work. While the saturation magnetization of the ferrites and the reduced magnetization curve for manganese ferrite are in satisfactory agreement with Neel’s theory, the variation with temperature for the specimen of magnesium zinc ferrite does not correspond to any of the solutions predicted.


An account is given of a determination of the entropy and absolute temperature as a function of ‘magnetic temperature’ (i. e. the reciprocal of susceptibility) for chromium potassium alum in the temperature range 0·007 to 0·1°K. The Curie point, which is characterized by a λ -anomaly in the specific heat, and a maximum in the susceptibility, is found to be at 0·011°K for this substance. The results are discussed in the light of other previously published and contradictory measurements on this substance. A theoretical treatment of the influence of the crystalline electric field on the entropy of magnetization is given in an appendix.


The methods of a previous paper are used to discuss the effect of a magnetic field on the thermoelectric power of a metal containing two overlapping energy bands of normal form. Exact solutions of the transport equation are obtained for the three limiting cases of high temperatures, low temperatures and very strong magnetic fields, and it is shown that the formulae can be generalized to give approximate expressions for all temperatures and all fields. The magnetic change of the thermoelectric power is found to be small at very low and high temperatures, and to pass through a maximum at intermediate temperatures. The transverse galvano- and thermomagnetic effects are also considered, and the formulae which hold for free electrons are generalized so as to be approximately valid for all temperatures. For free electrons, the Hall coefficient remains constant as the temperature decreases, the Righi-Leduc coefficient increases, and the Ettingshausen and Ettingshausen-Nemst coefficients decrease and change sign at very low temperatures. The corresponding formulae for a metal containing two bands are also obtained, and are used to show that the theoretical predictions for free electrons cannot hold for real metals except in special cases. Finally, the two-band model is used to discuss the effect of the magnitude of the magnetic field on the coefficients of the transverse effects.


The spontaneous magnetization is of fundamental importance in the theory of ferromagnetism but only meagre experimental data are at present available. The paper describes the initial stage of a project to determine the temperature variation of spontaneous magnetization for a number of ferromagnetics. It is impossible to deduce the spontaneous magnetization unequivocally over the complete temperature range from purely magnetic measurements so that a determination of the magnetocaloric effect must also be made. An alloy from the system copper-nickel (23.9 atomic % copper, rest nickel) was chosen for the first investigation because the system occupies an important position in the electron theory of ferromagnetism, whilst it also has the additional advantage of freedom from metallurgical complications. The experimental work is in two parts. An apparatus was constructed which enables the temperature rise in the magnetocaloric effect (Δ T ) to be measured accurately over a wider temperature range than hitherto. This incorporates a galvanometer amplifier and the overall sensitivity is 1000 mm/°C. The specific intensity of magnetization (σ) was obtained by using the balance devised by Sucksmith (1939). Both the sets of measurements were made at closely spaced intervals up to the Curie point and, in the case of the magnetocaloric effect, considerably above this. In addition, the susceptibility above the Curie point was measured from 170 to 775° C and was found to obey the Curie-Weiss law x = C /( T — θ) over most of this range with C = 3.90 x 10 -3 and θ = 111° C. The three methods of deducing the spontaneous magnetization from observations are critically discussed in general, and then in relation to the particular results obtained, which are similar to those obtained for other materials except that the dependence of the temperature rise on σ 2 above the Curie point is not linear. This is a new feature which it is considered may have important theoretical consequences. The values of the spontaneous magnetization deduced from purely magnetic measurements are in agreement, but these differ from the values obtained by using the magnetocaloric effect. The spontaneous magnetization-temperature curve deduced from the magnetocaloric effect lies below that obtained from magnetic measurements in the immediate neighbourhood of the Curie point, and is notable for the absence of any ‘ tail '. The departure of the reduced σ against T curve from the law of corresponding states is firmly established by the present work in which the purely magnetic measurements are in fair agreement with earlier investigations.


Author(s):  
A.M. Magerramov ◽  
◽  
N.I. Kurbanova ◽  
M.N. Bayramov ◽  
N.A. Alimirzoyeva ◽  
...  

Using radiothermoluminescence (RTL), the molecular mobility features in the temperature range of 77-300 K were studied for the polypropylene (PP)/ethylene propylene diene elastomer SKEPT-4044 with NiO, Cu2O and Fe3O4 nanoparticles (NPs) based on ABS-acrylonitrile butadiene or SCS-divinyl styrene matrices. It has been shown that the introduction of nanofillers in PP significantly affects the nature and temperature of γ- and β-relaxation processes, while the region of manifestation of the β-process noticeably shifts to the region of low temperatures. Composites with Cu2O NPs have a higher β-transition temperature Tβ than composites with other NPs. It was found that PP/SKEPT-4044 composites with Cu2O NPs with a dispersion of 11-15 nm and acrylonitrile butadiene thermoplastics have optimal frost resistance compared to other compositions.


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