Industrial developmentof materials forsustainable development(magnets + magneto-caloric materials) M. Katter

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1 Industrial developmentof materials forsustainable development(magnets + magneto-caloric materials) M. Katter

2 PowderMetallurgy the industrialproduction route forhighly efficient magnetic parts M. Katter

3 magnetic materials Rapid Solidification Rolling Process Powder Route Saturation magnetization J S [ T ] 2,5 2,0 1,5 1,0 0,5 0 nanocrystalline Amorphous Co based Fe-Ni (medium) FeSiAl FeNi 80% (Permalloys) Fe, FeSi Fe-Co Soft ferrites FeNi(Co)AlTi La-Fe-Si CoercivityH C [A/cm] Ductile magnets CoFeV CuNiFe FeCrCo Sm-Co MnAlC AlNiCo PtC o Hard ferrites NdFeB sintered 0, ,5 2,0 1,5 1,0 RE bonded 0,5 0 Remanence B R [ T ] soft magnetic semi hard magnetic hard magnetic Industrial Rare-EarthPermanent Magnets and theirapplications Seite 3

4 worldwide outputof industrial permanent magnets output Nd-Fe-B sintered in 1000 t Nd-Fe-B sintered; 34 Nd-Fe-B bonded; 4 SmCo; Hard ferrite bonded; 156 Alnico; total output in t Y. Luo (2005, 2008) Hard ferrite sintered; year China Japan USA Europe Total Industrial Rare-EarthPermanent Magnets and theirapplications Seite 4

5 Powder Metallurgical (PM) Processing of Rare Earth Magnets Vacuum Induction Alloying and Casting Crushing (HD) Milling Aligning H P isostatic pressing Pressing: CIP (RIP, PLP) - AP - TP diepressing Industrial Rare-EarthPermanent Magnets and theirapplications Seite 5

6 Powder Metallurgical (PM) Processing of Rare Earth Magnets P Isostatic pressing Pressing: CIP - AP - TP diepressing Sintering and Annealing Machining and Surface Finishing Magnetizing Industrial Rare-EarthPermanent Magnets and theirapplications Seite 6

7 Energy Density Records for Nd-Fe-B Magnets Neomax kj/m MGOe B r = T VAC VAC S. Hirosawa 2005 F. Kunuyoshi 2003 W. Rodewald 2002 Y. Kaneko 2000 Industrial Rare-EarthPermanent Magnets and theirapplications Seite 7

8 High Dy-contentfor high application temperatures remanence B r at 20 C (T) T a < 50 C, MRI, VCM 1.30 T a > 150 C, motors, generators, HEV increasing Dy content coercivity H cj at 20 C (koe) Industrial Rare-EarthPermanent Magnets and theirapplications Seite 8

Coercivity HcJ (ka/m) Coercivity of Nd 14.3 Fe 78.9 TM 1.

6 (TM = Co, Cu, Al, Ga) for various grain sizes 1250

9 Coercivity HcJ (ka/m) Coercivity of Nd 14.3 Fe 78.9 TM 1.2 B 5.6 (TM = Co, Cu, Al, Ga) for various grain sizes y = 2177,6x -0, K. Üstüner, Intermag C Average Grain Size according to ASTM E112 (µm) Industrial Rare-EarthPermanent Magnets and theirapplications Seite 9

10 segmented magnets produced by glue-coating technique for reduction of application temperature to save Dy Industrial Rare-EarthPermanent Magnets and theirapplications Seite 10

11 applications of Nd-Fe-B magnetes servo motor linear motor mini motor hybrid electric vehicle Wind power Industrial Rare-EarthPermanent Magnets and theirapplications Seite 11

12 Conclusion I t of RE-Fe-B magnets produced in industrialre-fe-b magnets available up to 53 MGOe (laboratory 59.6 MGOe) - Dy, Tb, Co, Cu, Ga, fine grainsize and Dy-diffusion improve temperature and/or corrosion stability - powder metallurgy offers economic shaping possibilities - segmented magnets reduce temperature and help to save Dy - since 2004 motors and generators are Nr. 1 application ahead of VCM Industrial Rare-EarthPermanent Magnets and theirapplications Seite 12

000 t/a 3-15kW: automotive A/C, A/C for whole houses (60M/a) 450.000 t/a world production in 2008: ca. 60.

13 Nd-Fe-B magnets for magnetic refrigeration Cooling power demand of Nd-Fe-B (1.5 kg/kw) <0.5kW refrigeration at private houses (95M/a) t/a 1-3kW : display cabinets, single room air conditioning (37M/a) t/a 3-15kW: automotive A/C, A/C for whole houses (60M/a) t/a world production in 2008: ca t 2005 Prototypes 2006 Prototype 2007 clients developments Cooltech Applications (2008) Industrial Rare-EarthPermanent Magnets and theirapplications Seite 13

14 magnetocaloric materials Specific etropy density ( S/l/ H) expensive, limited temperature range poisonous GdSiGe MnFePAs MnAs target operating range LaMnO3 Gd poisonous LaFeSi ( ) small effect most promising at the moment: La-Fe-Si Cooltech Applications (2008) Industrial Rare-EarthPermanent Magnets and theirapplications Seite 14

15 conventional preparationof La(Fe,Si) 13 -casting -anneal, e.g C/140 h -optionally load with hydrogen long annealing times, with hydrogen only powder S. Fujieda et al F.X. Hu et al (with Co) D S m (J/kg K) melt spinning -short anneal, e.g C/2 h only flakes or powder, no shaped parts for heat exchangers O. Gutfleisch et al S. Hirosawa et al y = La(Fe 0.88 Si 0.12 ) 13 H y T (K) Industrial Rare-EarthPermanent Magnets and theirapplications Seite 15

16 Designs for active magnetic regenerators large pressure drops in powder beds? J.A. Barclay and S. Sarangi 1984 in A.M. Tishin and Y.I. Spichkin 2003 Industrial Rare-EarthPermanent Magnets and theirapplications Seite 16

17 Powder Metallurgical (PM) Processing of La-Fe-Si Vacuum Induction Alloying and Casting Crushing Milling Blending elemental powders P isostatic pressing Pressing: CIP - die diepressing Industrial Rare-EarthPermanent Magnets and theirapplications Seite 17

18 Powder Metallurgical (PM) Processing of La-Fe-Si P Isostatic pressing Pressing: CIP - die diepressing Reactive Sintering Machining and Surface Finishing Industrial Rare-EarthPermanent Magnets and theirapplications Seite 18

19 sintered La(Fe Co x Si ) 13 -DSm (J/kgK) 10,00 8,00 6,00 4,00 2,00 0,00 H = 16 koe x = x = x = x = x = x = x = Gd -30,0-20,0-10,0 0,0 10,0 20,0 30,0 40,0 50,0 60,0 70,0 80,0 T ( C) several kg blocks 23x19x12 mm produced on labscale for prototyping Katter (2008) Industrial Rare-EarthPermanent Magnets and theirapplications Seite 19

20 thermal expansionof sintered La-Fe-Co-Si 0,00-0,05-0,10 La(Fe 0,865 Co 0,05 Si 0,085 ) 13 TD process Thermallyinduced Decrepitation (HD would do the same) thermal expansion Dl/l (%) -0,15-0,20-0,25-0,30-0,35 difficult to machine La(Fe 0,803 Co 0,112 Si 0,085 ) 13-0,40-0,45-0,50 tensile stress => cracks temperature T ( C) Buschow (1984) Industrial Rare-EarthPermanent Magnets and theirapplications Seite 20

21 effect of sintering temperature for LaFe10.91Co1.10Si0.99 1/13 αfe Industrial Rare-Earth Permanent Magnets and their Applications Seite 21

Decomposition of LaFe 10.91 Co 1.10 Si 0.

22 Decomposition of LaFe Co 1.10 Si 0.99 at 850 C αfe 1080 C 1/1/1 850 C 1/13 αfe + La/Si-rich phases? Industrial Rare-EarthPermanent Magnets and theirapplications Seite 22

23 Thermally induced Decomposition of the 1/13 phase αfe Gehalt content a-fe [%] (%) 80,0% 70,0% 60,0% 50,0% 40,0% 30,0% 20,0% La(Fe 1-x Co x Si ) 13 TD process no decrepitation! MPS/1037 x=0.050 x=0.058 x=0.065 x=0.075 x=0.087 x=0.099 MPS/1038 MPS/1039 MPS/1040 MPS/1042 MPS/ ,0% 0,0% annealing Homogenisierungstemperatur temperature ( C) [ C] Industrial Rare-EarthPermanent Magnets and theirapplications Seite 23

24 mechanical properties of sintered a) LaFe Co 0.68 Si 1.11, b) LaFe Co 0.98 Si 1.07 and c) LaFe Co 1.42 Si bending strength (N/ mm 2 ) a) b) c) 1073 K / 6h 1313 K / 4h 0 Industrial Rare-EarthPermanent Magnets and theirapplications Seite 24

25 Thermally induceddecomposition and Recombination (TDR) process 0,20 0,10 0,00 good MFP-1056, machinability T C = -14 C magnetocaloric passive state a-fe = 71 % strain [%] -0,10-0,20 reversible conversion -0,30-0,40-0, ,0 200 temperature [ C] magnetocaloric active state a-fe = < 2% good magnetocaloric properties -DSm (J/kgK) 10,0 8,0 6,0 4,0 0, temperature T (K) Hmax (koe) 4,0 8,0 12,0 16,0 Industrial Rare-EarthPermanent Magnets and theirapplications Seite 25

26 Conclusions II -La(Fe,Co,Si) 13 sucessfully prepared by powder metallurgy -TDR process developed for machining of thin plates or complex shaped parts -thin plates (ca. 0.5 mm) available for prototyping 50 mm -T C tailorable between -20 and +80 C, Industrial Rare-EarthPermanent Magnets and theirapplications Seite 26

Maximum Energy Products (MGOe) 10 Maximum Energy Products (kj/m ) 3

60 Maximum Energy Products (MGOe) 480 400 320 240 160 80 0 50 40 30 20 10 0 Maximum Energy Products (kj/m ) 3 Guiding principles which led to the new magnets: Old Transition New Guiding principle Alnico