Hysteresis Loop - A plot of magnetizing force versus resultant magnetization (also called a B/H curve) of the material as it is successively

magnetized to saturation, demagnetized, magnetized in the opposite direction and finally remagnetized. With continued recycles, this plot will be a closed loop which completely describes the characteristics of the magnetic material. The size and shape of this "loop" is important for both hard and soft materials. With soft materials, which are generally used in alternating circuits, the area inside this "loop" should be as thin as possible (it is a measure of energy loss). But with hard materials the "fatter" the loop, the stronger the magnet will be. The first quadrant of the loop (that is +X and +Y) is called the magnetization curve. It is of interest because it shows how much magnetizing force must be applied to saturate a magnet. The second quadrant (+X and -Y) is called the Demagnetization Curve. Hysteresis is the dependence of a system not only on its current environment but also on its past environment. This dependence arises because the system can be in more than one internal state. To predict its future development, either its internal state or its history must be known.[1] If a given input alternately increases and decreases, the output tends to form a loop as in the figure. However, loops may also occur because of a dynamic lag between input and output. Often, this effect is also referred to as hysteresis, or rate-dependent hysteresis. This effect disappears as the input changes more slowly, so many experts[who?] do not regard it as true hysteresis. Hysteresis occurs in ferromagnetic materials and ferroelectric materials, as well as in the deformation of some materials (such as rubber bands andshape-memory alloys) in response to a varying force. In natural systems hysteresis is often associated with irreversible thermodynamic change. Many artificial systems are designed to have hysteresis: for example, in thermostats and Schmitt triggers, hysteresis is produced by positive feedback to avoid unwanted rapid switching. Hysteresis has been identified in many other fields, including economics and biology. Hysteresis in materials [edit]Magnetic hysteresis

Theoretical model of magnetization m against magnetic field h. Starting at the origin, the upward curve is the initial magnetization curve. The downward curve after saturation, along with the lower return curve, form the main loop. The intercepts hc and mrs are the coercivity and saturation remanence. When an external magnetic field is applied to a ferromagnet such as iron, the atomic dipoles align themselves with it. Even when the field is removed, part of the alignment will be retained: the material has become magnetized. Once magnetized, the magnet will stay magnetized indefinitely. To demagnetize it requires heat or a magnetic field in the opposite direction. This is the effect that provides the element of memory in a hard disk drive. The relationship between field strength H and magnetization M is not linear in such materials. If a magnet is demagnetized (H=M=0) and the relationship between H and M is plotted for increasing levels of field strength, Mfollows the initial magnetization curve. This curve increases rapidly at first and then approaches an asymptote calledmagnetic saturation. If the magnetic field is now reduced monotonically, M follows a different curve. At zero field strength, the magnetization is offset from the

origin by an amount called the remanence. If the H-M relationship is plotted for all strengths of applied magnetic field the result is a hysteresis loop called the main loop. The width of the middle section is twice the coercivity of the material.[16] A closer look at a magnetization curve generally reveals a series of small, random jumps in magnetization calledBarkhausen jumps. This effect is due to crystallographic defects such as dislocations.[17] Magnetic hysteresis loops are not exclusive to materials with ferromagnetic ordering. Other magnetic orderings, such asspin glass ordering, also exhibit this phenomena.[18] Hysteresis loop of various sized CoSm .0191 Fe 1.981 O 4 at 5K, 5T. The magnetic field is ramped from zero to 50 kOe then to the same magnitude but in a different direction. Once at the magnetization saturation point, where moments align with the direction of the applied field, the reversal of magnetic moments generates a hysteresis. From the different hysteresis loops, there is a direct correlation between size and M s . An increase in size produced higher magnetization saturation points and vice versa for smaller sizes. Coercitivity initially increases with size then decreases with increasing size. This may be attributed to initial coherent rotation of magnetic moments followed by spin canting. 93 As the size of the magnetic nanoparticles is decreased, the anisotropy is decreased. The decrease in anisotropy should decrease the H c but this linear trend was not observed. From the hysteresis loop (Figure 4.7), an initial increase followed by decrease in H c was observed. This initial increase may be due to coherent magnetization while the eventual decrease may be attributed to other surface effects. This type of H c trend was also observed in CoFe 2 O 4 systems synthesized through seed mediated nonhydrolytic process. 21 The saturation magnetization decreased with decrease in size of the nanoparticles and can be attributed to spin-canting where the magnetic disorder of the moment increases when the particle size decreases and the surface to volume ratio increases. 22-24 The observed M s data corresponded well to other reported saturation magnetization trends showing a parallel change in saturation magnetization with change in size 22-26 .

4.4 Conclusions We have shown here a method of modulating the magnetic properties of CoFe 2 O 4 . By doping CoFe 2 O

4 with rare earth metals like samarium, we can alter the blocking temperature and its saturation magnetization as well as its coercitivity through composition and size change. Using different samarium doping percentages, saturation magnetization can be altered by as much as 35.3 emu/g.Oe and the coercitivity can be altered by as much as 4.8 kOe relative to the undoped particle while maintaining similar blocking temperatures. By changing the size of the nanoparticle and maintaining a 94 constant composition, the blocking temperature can be tuned as well. This systematic study proves that the magnetic behavior and intrinsic properties of CoFe 2 O 4 can be tuned by addition of samarium. Fundamentally, the ability to finely tune the magnetic properties is of importance. However, the importance of utilizing these tunable magnetic nanoparticles for developing novel materials with adjustable parameters should not be underestimated. There is ample room to explore the properties of novel materials with magnetically and optically tunable properties for biological and physical applications. 95 Hund's Rule According to Hund's rule, orbitals of the same energy are each filled with one electron before filling any with a second. Also, these first electrons have the same spin. This rule is sometimes called the "bus seating rule". As people load onto a bus, each person takes his own seat, sitting alone. Only after all the seats have been filled will people start doubling up.

M A G OF 3d T R A METALS AND ALLOYS 179 e x c i t a t spin stateo f 22 ' 23

i o n t h e

o f

t h e

l o w

Fe a t o m .

. M o r e p h y s i c a l e x p l a n a t i o n s b a s e d o n t h e b a n d t h e o r y h a v e b e e n d e v e l o p e d b y m a n y t h e o r e t i c i a n s . 24 " 26 ' 17 Ac o m p l i c a t e d p h a s e t r a n s i t i o n inp u r e F e i s a l s o c a u s e d by ac o r r e l a t i o n b e t w e e n m a g n e t i s m and c r y s t a l s t r u c t u r e . Wi t h i n c r e a s i n g t e mp e r a t u r e , p u r e Fe t r a n s f o r m s f r o m bcc to fee at 910C, and then once again f r o m fee to bcc at Zener . C 0 9 3 1 27 p o i n t e d o u t t h a t t h i s p h e n o m e n o n m a y b e e x p l a i n e d b y a s s u m i n g a n a d d i t i o n a l ' m a g n e t i c ' f r e e energy. Since, however, 910C is above the Curie point, this hasn o t h i n g t o d o w i t h m a g n e t i c o r d e r i n g . T h i s p h e n o m e n o n w a s a l s o e x p l a i n e d t h e o r e t i cally int e r m s of ad i s o r d e r e d l o c a l m o m e n t t h e o r y . 28 M a n g a n e s e m e t a l ( M n ) is l o c a t e d n e x t t o Fe i n t h e p e r i o d i c t a b l e , and u n d e r g o e s c o m p l i c a t e d c r y s t a l a n d m a g n e t i c p h a s e t r a n s i t i o n s . B e l o w 705C, it has the a M n s t r u c t u r e wi t h 2 9 a t o ms i n t h e u n i t c e l l . B e l o w 95 K , M n d e v e l o p s a n a n t i f e r r o m a g - n e t i c s t r u c t u r e w i t h f o u r d i f f e r e n t a t o m i c m o m e n t s , 1 . 9 0 , 1 . 7 8 , 0 . 6 0 , and 0 2 . 5 M B , each of w h i c h t a k e s a d i f f e r e n t d i r e c t i o n . 29 W i t h i n c r e a s i n g t e m p e r a t u r e , i t t r a n s f o r m s a t 705Ct o t h e /3-phase w i t h nom a g n e t i c o r d e r i n g , andt h e n t o t h e fee y - p h a s e

at . C 0 1 T h e y p h a s e s i paramagnetic in this t e m p e r a t u r er a n g e . However, this p h a e s c a n b e r e t a i n e d t o l o we r t e mp e r a t u r e s b y a l l o y i n g w i t h C u , a n d i s f o u n d t o e x h i b i t a n t i f e r r o m a g n e t i s m w i t h a m a g n e t i c m o m e n t o f 2.25M B p e r a t o m b e l o w t h e Ne e l p o i n t of 207C. 30 C h r o mi u m (C r ) i s l o c a t e d n e x t t o M n i n t h e p e r i o d i c t a b l e . I t s c r y s t a l s t r u c t u r e i s bcc at all t e m p e r a t u r e s , a n d i t s m a g n e t i s m is c h a r a c t e r i z e d by a spin density w a v e , inw h i c h t h e ma g n i t u d e o f t h e s p i n f o r ms a s p a t i a l wa v e . Th i s i s a k i n d o f a n t i f e r r o ma g - n e t i s m , w i t h N e e l p o i n t 3 1 2 K . T h e m a x i m u m a m p l i t u d e o f t h e w a v e i s 0.50M B a t O K and t h e s p a t i a l p r o p a g a t i o n o f t h e wa v e i s p a r a l l e l t o } 0 1 { with the spin axisp e r p e n d i c u l a r t o t h e p r o p a g a t i o n a b o v e 1 2 2 K a n d p a r a l l e l b e l o w t h i s t e mp e r a t u r e . Th e s p i n d e n s i t y w a v e w a s t r e a t e d t h e o r e t i c a l l y b y Ov e r h a u s e r 31 a n d l a t e r b y L o m e r 32 who t o o k an i n t e r a c t i o n b e t we e n the F e r m i s u r f a c e o f 3 d electrons and h o l e s i n t o c o n s i d e r a t i o n . K a n a m o r i and T e r a o k a 33 proposed an

e n t i r e l y d i f f e r e n t i n t e r p r e t a t i o n o f t h i s p h e n o m e n o n . I n C h a p t e r 6 , w e l e a r n e d t h a t t h e Curie-Weiss l a w h o l d s i n m a n y f e r r o m a g n e t i c m e t a l s anda l l o y s . Its e e m s t h a t t h i s f a c t s u p p o r t s thel o c a l i z e d e l e c t r o n m o d e l , b e c a u s e t h i s l a w wa s d e d u c e d from t h e We i s s t h e o r y wh i c h a s s u me s a fixed magneticm o m e n t p e r a t o m . I t i s k n o w n , h o w e v e r , t h a t t h e r e a r e m a n y f e r r o m a g n e t i c m e t a l s and alloys for w h i c h the effective m a g n e t i c m o m e n t , M eff , and s a t u r a t i o n m o m e n t , M s , a r e n o t consistently described b y t h e s a me J (see (5.30) and 5 ( 3 . 2 . ) Figure 8.17 s h o w s the v a r i a t i o n of P C /P S as a f u n c t i o n of C u r i e p o i n t for v a r i o u s ma g n e t i c m a t e r i a l s , w h e r e P s is gJ, d e d u c e d from M s , and P c is gJ, calculated by u s i n g / d e d u c e d f r o m M

eff . 34 ' 35 I t i s s e e n t h a t f o r f e r r o ma g n e t i c me t a l s wi t h h i g h C u r i e p o i n t s , P C /P S is n e a r l y u n i t y , as expected f r o m the We i s s t h e o r y , wh i l e for m e t a l s wi t h low C u r i e p o i n t s , t h i s r a t i o b e c o me s v e r y l a r g e . Ty p i c a l e x a m p l e s o f t h e l a t t e r c a t e g o r y are ZrZn 2 w i t h M s = 0 1 . 2 M B and 0 f = 2 2 K , andSc 3 In w i t h M s = 0.057M B and 0 f = 7.5 K. T h e s are called w e a k ferromagnets. E v e n in t h e s e we a k f e r r o m a g n e t s , the Curie-Weiss l a w h o l d s . S u c h b e h a v i o r has b e e n e x p l a i n e d by M o r i y a 35 in

t e r m s of spin-fluctuation theory,

M A G N E T I S M OF 3d T R A N S I T I O N METALS AND ALLOYS 179 e x c i t a t i o n o f t h e l o w spin stateo f t h e Fe a t o m . 22 ' 23 . M o r e p h y s i c a l e x p l a n a t i o n s b a s e d o n t h e b a n d t h e o r y h a v e b e e n d e v e l o p e d b y m a n y t h e o r e t i c i a n s . 24 " 26 ' 17 Ac o m p l i c a t e d p h a s e t r a n s i t i o n inp u r e F e i s a l s o c a u s e d by ac o r r e l a t i o n b e t w e e n m a g n e t i s m and c r y s t a l s t r u c t u r e . Wi t h i n c r e a s i n g t e mp e r a t u r e , p u r e Fe t r a n s f o r m s f r o m bcc to fee at 910C, and then once again f r o m fee to bcc at Zener . C 0 9 3 1 27 p o i n t e d o u t t h a t t h i s p h e n o m e n o n m a y b e e x p l a i n e d b y a s s u m i n g a n a d d i t i o n a l ' m a g n e t i c ' f r e e energy. Since, however, 910C is above the Curie point, this hasn o t h i n g t o d o w i t h m a g n e t i c o r d e r i n g . T h i s p h e n o m e n o n w a s a l s o e x p l a i n e d t h e o r e t i cally int e r m s of ad i s o r d e r e d l o c a l m o m e n t t h e o r y . 28 M a n g a n e s e m e t a l ( M n ) is l o c a t e d n e x t t o Fe i n t h e p e r i o d i c t a b l e , and u n d e r g o e s c o m p l i c a t e d c r y s t a l a n d m a g n e t i c p h a s e t r a n s i t i o n s . B e l o w 705C, it has the a M n s t r u c t u r e wi t h 2 9 a t o ms i n t h e u n i t c e l l . B e l o w 95 K , M n d e v e l o p s a n a n t i f e r r o m a g - n e t i c s t r u c t u r e w i t h f o u r d i f f e r e n t a t o m i c m o m e n t s , 1 . 9 0 , 1 . 7 8 , 0 . 6 0 , and 0 2 . 5 M B

, each of w h i c h t a k e s a d i f f e r e n t d i r e c t i o n . 29 W i t h i n c r e a s i n g t e m p e r a t u r e , i t t r a n s f o r m s a t 705Ct o t h e /3-phase w i t h nom a g n e t i c o r d e r i n g , andt h e n t o t h e fee y - p h a s e at . C 0 1 T h e y p h a s e s i paramagnetic in this t e m p e r a t u r er a n g e . However, this p h a e s c a n b e r e t a i n e d t o l o we r t e mp e r a t u r e s b y a l l o y i n g w i t h C u , a n d i s f o u n d t o e x h i b i t a n t i f e r r o m a g n e t i s m w i t h a m a g n e t i c m o m e n t o f 2.25M B p e r a t o m b e l o w t h e Ne e l p o i n t of 207C. 30 C h r o mi u m (C r ) i s l o c a t e d n e x t t o M n i n t h e p e r i o d i c t a b l e . I t s c r y s t a l s t r u c t u r e i s bcc at all t e m p e r a t u r e s , a n d i t s m a g n e t i s m is c h a r a c t e r i z e d by a spin density w a v e , inw h i c h t h e ma g n i t u d e o f t h e s p i n f o r ms a s p a t i a l wa v e . Th i s i s a k i n d o f a n t i f e r r o ma g - n e t i s m , w i t h N e e l p o i n t 3 1 2 K . T h e m a x i m u m a m p l i t u d e o f t h e w a v e i s 0.50M B a t O K and t h e s p a t i a l p r o p a g a t i o n o f t h e wa v e i s p a r a l l e l t o } 0 1 { with the spin axis p e r p e n d i c u l a r t o t h e p r o p a g a t i o n a b o v e 1 2 2 K a n d p a r a l l e l b e l o w t h i s t e mp e r a t u r e . Th e s p i n d e n s i t y w a v e w a s t r e a t e d t h e o r e t i c a l l y b y Ov e r h a u s e r 31 a n d l a t e r b y L o m e r 32

who t o o k an i n t e r a c t i o n b e t we e n the F e r m i s u r f a c e o f 3 d electrons and h o l e s i n t o c o n s i d e r a t i o n . K a n a m o r i and T e r a o k a 33 proposed an e n t i r e l y d i f f e r e n t i n t e r p r e t a t i o n o f t h i s p h e n o m e n o n . I n C h a p t e r 6 , w e l e a r n e d t h a t t h e Curie-Weiss l a w h o l d s i n m a n y f e r r o m a g n e t i c m e t a l s anda l l o y s . Its e e m s t h a t t h i s f a c t s u p p o r t s thel o c a l i z e d e l e c t r o n m o d e l , b e c a u s e t h i s l a w wa s d e d u c e d from t h e We i s s t h e o r y wh i c h a s s u me s a fixed magneticm o m e n t p e r a t o m . I t i s k n o w n , h o w e v e r , t h a t t h e r e a r e m a n y f e r r o m a g n e t i c m e t a l s and alloys for w h i c h the effective m a g n e t i c m o m e n t , M eff , and s a t u r a t i o n m o m e n t , M s , a r e n o t consistently described b y t h e s a me J (see (5.30) and 5 ( 3 . 2 . ) Figure 8.17 s h o w s the v a r i a t i o n of P C /P S as a f u n c t i o n of C u r i e p o i n t for v a r i o u s ma g n e t i c m a t e r i a l s , w h e r e P s is

gJ, d e d u c e d from M s , and P c is gJ, calculated by u s i n g / d e d u c e d f r o m M eff . 34 ' 35 I t i s s e e n t h a t f o r f e r r o ma g n e t i c me t a l s wi t h h i g h C u r i e p o i n t s , P C /P S is n e a r l y u n i t y , as expected f r o m the We i s s t h e o r y , wh i l e for m e t a l s wi t h low C u r i e p o i n t s , t h i s r a t i o b e c o me s v e r y l a r g e . Ty p i c a l e x a m p l e s o f t h e l a t t e r c a t e g o r y are ZrZn 2 w i t h M s = 0 1 . 2 M B and 0 f = 2 2 K , andSc 3 In w i t h M s = 0.057M B and 0 f = 7.5 K. T h e s

are called w e a k ferromagnets. E v e n in t h e s e we a k f e r r o m a g n e t s , the Curie-Weiss l a w h o l d s . S u c h b e h a v i o r has b e e n e x p l a i n e d by M o r i y a 35 in t e r m s of spin-fluctuation theory, M A G N E T I S M OF M E T A L S AND A L L O Y S Fig. 8.17. The ratio P C /P S (see text) of f e r r o m a g n e t i c m e t a l s and alloys as a function of t h e i r C u r i e p o i n t s . ( A f t e r R h o d e s and W o h l f a r t h 34 ) w h i c h t r e a t s theb a n d c a l c u l a t i o n ofm e t a l m a g n e t i s m ate l e v a t e d t e m p e r a t u r e s . Thet h e r m a l l y d i s t u r b e d s p i n s y s t e m c a n b e d e s c r i b e d a s a n a s s e mb l y o f s p i n d e n s i t y wa v e s with d i f f e r e n t w a v e v e c t o r s q. The f e a t u r e of this theory is to take p r o p e r a c c o u n t of thei n t e r a c t i o n b e t w e e n s p i n d e n s i t y w a v e s w i t h d i f f e r e n t m o d e s . Inw e a k f e r r o m a g - n e t i s m , t h e s p i n d e n s i t y w a v e s w i t h large q h a v e m u c h h i g h e r e n e r g i e s , s o t h a t t h e y

Table 8.1. C l a s s i f i c a t i o n of m a g n e t i c m a t e r i a l s by the spin f l u c t u a t i o n c o n c e p t ( a f t e r M o r i y a 36 ). W a v e v e c t o r q Localized ... N o n - l o c a l i z e d Magnetic moment Non-localized ... Localized A m p l i t u d e small (a) (b) (c) M n S i a - M n C e F e 2 C r C r B 2 Fe 3 Pt y - M n MnP CoS 2 Ni C o F e M n P t 3 F e P d 3 s a t u r a t e d (d) (a) N e a r l y f e r r o ma g n e t i c m e t a l s and alloys such asPd, H f Z n 2 , TiBe 2 , YRh 6 B 4) CeSn 3 , Ni-Pt, etc. (b) We a k l y f e r r o m a g n e t i c me t a l s

and alloys such as Sc 3 In, ZrZn 2 , Ni 3 Al, Fe 05 Co 05 Si,L a R h 6 B 4 ,C r R h 3 B 2 , Ni-Pt, etc. (c)Antiferromagnetic metals and alloys such as /3-Mn, V 3 Se 4 , V 3 S 4 ,V 5 Se 8 , etc. (d) Localized magnetic moment system such as i n s u l a t i n g ma g n e t i c c o mp o u n d s , 4/-metals, and H e u s l e r alloys (Pd 2 MnSn etc.).