Fe 2 MgO 3 O Fe Mg

SPS SPS SPS

SPS

1.

1.1.

1.

(Spark Plasma Sintering : SPS)

1),2)

MA

Ni-Cu-Zn MA

SPS

3)

Ni-Cu-Zn

SPS SPS

2.

2.2.

2.

2.12.12.1

2.1

Table 1Table 1Table 1Table 1 SPS MA MA

99.91 % 275.9 µm Ni-Cu

matrix

4 30 Ferrite

12 MGFR 14 MGFR 18 MGFR

10 Ferrite

Pure Al 34 MGFR

38 MGFR 32 MGFR

52 MGFR

8 2 4 8 2 8 compound

58 MGFR

Designation Material (mass%) MA time (h)

54 MGFR 50 Ferrite

2 4

-Zn ( (Fe2O3)49.41

(ZnO)32.09(NiO)12.71(CuO)5.79

4.3 µm) Table 1Table 1Table 1Table 1

( CH3(CH2)16COOH)

0.75 g MA

MA Fig.

Fig. Fig.

Fig. 1111 SPS

50 mm 20.1 mm 40 mm

20 mm 20 mm

MA 5 g

Fig. 1 Fig. 1 Fig. 1 Fig. 1

473 K

SPS 2.2

2.22.2

2.2

SPS

1 kg

20 7

5

SPS X

Table 1 Table 1 Table 1

Table 1 Designation, starting compositions Designation, starting compositions Designation, starting compositions Designation, starting compositions and mechanical alloying time of test and mechanical alloying time of test and mechanical alloying time of test and mechanical alloying time of test materials.

materials.

materials.

materials.

Properties of Magnesium Based Composites Exhibiting Magnetism by Spark Plasma Sintering.

Sho AOKI, Hiroki MATSUSHIMA, Kiyozumi NIIZUMA and Masahiro KUBOTA

−日本大学生産工学部第42回学術講演会（2009-12-5）−

― 105 ― 1-30

Starting powders Mechanical alloying (MA)

MA powders

Spark Plasma Sintering (SPS)

SPS materials

MA time : 2,4,8 h

Temp : 673 K~873 K Holding time : 1 h Pressure : 49 MPa Heating rate : 1.67 K/s

40 kV 60 mA CuKα

1.66×10^-2 °/s 2θ 20° 80°

SPS ( )

(Vibrating Sample Magnetometet : VSM)

6×4×1 mm 800 kA/m

SPS SPS

(

3 g 20 ml

20 ml 2 ml)

3.

3.3.

3.

Fig. 2 Fig. 2Fig. 2

Fig. 2 SPS

14

MGFR SPS

673 K SPS

Ni-Cu-Zn Mg

MgO α-Fe

773 K 873 K SPS

Mg MgO α-Fe Mg2Ni Fe3C

MgO MgO Ni-Cu-Zn

MgO Fe2O3

1mol

Fig. 3 Fig. 3 Fig. 3 Fig. 3

MgO Fe2O3

●

●

●

●

●●

●●

●

●●

●

●

●

●

●

●●

●●

●

●●

●●●●● ●●●● ■■■■

▲▲

▲▲

■■■

■

■

■■

■

●

●

●

●

●

●●

●

◆◆

◆◆

◆

◆

◆

◆

●

●

●

● MgMgMgMg

▲

▲

▲

▲ FeFeFeFe

■■

■■:MgO:MgO:MgO:MgO

◆

◆

◆

◆ MgMgMgMg2222NiNiNiNi

★★

★★ FeFeFeFe3333CCCC

▼

▼

▼

▼ NiNiNiNi----CuCuCuCu----Zn FerriteZn FerriteZn FerriteZn Ferrite

Intensity(arb. units)Intensity(arb. units)Intensity(arb. units)Intensity(arb. units)

Diffraction angle, 2 Diffraction angle, 2 Diffraction angle, 2 Diffraction angle, 2θθθθ deg) deg) deg) deg)

MgMg

MgMg----10mass%Ferrite10mass%Ferrite10mass%Ferrite10mass%Ferrite SPS materials SPS materials SPS materials SPS materials fabricated from MA4h powder fabricated from MA4h powder fabricated from MA4h powder fabricated from MA4h powder

(a)(a)(a) (a) (c) (c) (c) (c)(b) (b) (b)(b)

(a) powder (a) powder(a) powder (a) powder (b) (b) (b) (b) 673 K673 K673 K673 K (c) (c) (c) (c) 773 K773 K773 K773 K (d) (d)(d) (d)873 K873 K873 K873 K

(d) (d)(d) (d)

▼▼▼

▼ ▼▼▼▼ ■■■■ ▲▲▲▲ ▼▼▼▼ ●●●●

●

●

●

●

●●

●●

●

●●

● ●●●●

■■■

■ ■■■■

●

●

●

● ●

●●

●

★

★

★

★ ★★★★ ★★★★ ★★★★ ★★★★

★★

★★

★

★

★

★

-1.0 -0.8 -0.6 -0.4 -0.2 0.0

1000 1100 500 600 700 800 900

400 300 Standard free energy of formation, ⊿G / MJ/molO

Temperature, T / K

1/3 Fe₂O₃ MgO

Fe 2 MgO 3 O Fe Mg

3 +

→ +

Ni-Cu-Zn Fe2O3

MgO α-Fe 773 K

873 K α-Fe

Fe3C Fig. 4

Fig. 4Fig. 4

Fig. 4 MA SPS

12 MGFR 673 K

SPS 65.0 HV

673 K

84.8%

773 K 873

K Ni-Cu-Zn

(MgO α-Fe Mg2Ni Fe3C) Fig. 3 The standard free energies of Fig. 3 The standard free energies of Fig. 3 The standard free energies of Fig. 3 The standard free energies of formation of the relevant oxides as a formation of the relevant oxides as a formation of the relevant oxides as a formation of the relevant oxides as a function of temperature.

function of temperature.function of temperature.

function of temperature.

Fig. 2 Fig. 2 Fig. 2

Fig. 2 XXXX----rrrray diffraction patterns of ay diffraction patterns of ay diffraction patterns of ay diffraction patterns of SPS SPS SPS SPS materials fabricated

materials fabricatedmaterials fabricated

materials fabricated from 14 MGFR from 14 MGFR from 14 MGFR from 14 MGFR powder.

powder.powder.

powder.

Fig. 1 Process chart for fabricating test Fig. 1 Process chart for fabricating test Fig. 1 Process chart for fabricating test Fig. 1 Process chart for fabricating test materials.

materials.materials.

materials.

― 106 ―

14 MGFR 18 MGFR

773 K SPS

154.7 HV 198.0 HV 873 K

135.8 HV 175.8 HV 773 K

Fig. 2 Fig. 2 Fig. 2 Fig. 2 X MgO

MgO Fe3C Mg2Ni

Fe3C 1200 HV⁴⁾

873 K

773 K MA

MA 2

4 8 h 96.6 HV 154.7 HV

198.0 HV MA

50 HV MA

MA SPS 773 K

Fig. 5 Fig. 5Fig. 5

Fig. 5 MA SPS

MA 673

K SPS

1.0×10^-5 Wbm/kg MA (0.65×10^-5 Wbm/kg) 2

MA α-Fe

α-Fe 2.73×10^-4

Wbm/kg Ni-Cu-Zn

Fe2O3 50 %

Mg-10 mass% Ferrite 5 % Fe2O3

Fe2O3 α-Fe

69.94 % Mg-10 mass%

Ferrite 3.5 % α-Fe α-Fe

3.5 % 0.95×10^-5 Wbm/kg SPS

0 60 80 100 120 140 160 180 200 220

Sintering temperature, T / K

Mg-10mass% Ferrite SPS materials

(99.2)

(93.9) (97.7)

(78.2) (94.8)

(82.7)

(93.6)

873 773

673 (84.8)

(89.3)

Pressure 49 MPa constant

Vickers hardness, HV 1

MA2h MA4h MA8h

( ) Relative density,

0.0 0.2 0.4 0.6 0.8 1.0

0 10 20 30 40 50 60

873 773

673

Coercive force, Hc / kA/m

Coercivity

Magnetization

Magnetization, Ms / ×10-5Wbm/kg

Sintering temperature, T / K MA2h MA4h MA8h Mg-10mass% Ferrite SPS materials

MA2h MA4h MA8h

0.95×10^-5 Wbm/kg Ni-Cu-Zn Fe2O3 α-Fe

MA SPS Fig.

Fig.

Fig.

Fig. 2222 X Ni-Cu-Zn

Fe3C

Fe3C α

-Fe Fe3C

MA SPS

α-Fe Fe3C Fig. 5

Fig. 5 Fig. 5

Fig. 5 Change in the Change in the Change in the magneChange in the magnemagnemagnetizationtizationtization and tization and and and coercive force for the SPS materials coercive force for the SPS materials coercive force for the SPS materials coercive force for the SPS materials fabricat

fabricatfabricat

fabricatededed from edfrom from 12 MGFR, 14 MGFR and 18 from 12 MGFR, 14 MGFR and 18 12 MGFR, 14 MGFR and 18 12 MGFR, 14 MGFR and 18 MGFRMGFRMGFR

MGFR powderpowderpowders.powders.s.s.

Fig. 4 Fig. 4 Fig. 4

Fig. 4 Change in the hardnessChange in the hardnessChange in the hardnessChange in the hardness together together together together with relative density

with relative densitywith relative density

with relative density for the SPS materials for the SPS materials for the SPS materials for the SPS materials fabricat

fabricatfabricat

fabricatededed from edfrom from 12 MGFR, 14 MGFR and 18 from 12 MGFR, 14 MGFR and 18 12 MGFR, 14 MGFR and 18 12 MGFR, 14 MGFR and 18 MGFR

MGFR MGFR

MGFR powderpowderpowderssss.... powder

― 107 ―

Fig. 6 Fig. 6Fig. 6

Fig. 6 14 MGFR

(a) 673 K (b) 883 K (c) 873 K SPS

Fe3C

Fe3C

Mg MA

Fe3C Fe3C

673 K 10~30 µm

773 K 10~60 µm

873 K 20~100 µm

873K SPS

Fe3C

10μ (a)

10μ (b)

4.4.4.

4.

Ni-Cu-Zn MA

SPS SPS

1) 673 K SPS

MgO α-Fe

773 K 873 K

SPS MgO α-Fe

Mg2Ni Fe3C

2) MA 8 h 773

K

Fe3C

198.0 HV

3) 673 K SPS

Ni-Cu-Zn Fe2O3

α-Fe

MA 2

773 K 873 K

Fe3C α-Fe

SPS 4) SPS

α-Fe

5) Fe3C

SPS 873 K 773 K

6) Ni-Cu-Zn

673 K

4

1) ―

(SPS) , SPS pp.1-4.

2) 30 (1993)

pp.790-802 3)

116

(2009) pp.103-104

4) http://www.tobu.or.jp/yasashii/book/gj0 6.htm

10μ (c)

Fig.

Fig.

Fig.

Fig. 6666 Optical micrographs of the SPS Optical micrographs of the SPS Optical micrographs of the SPS Optical micrographs of the SPS materials

materials materials

materials fabricated from 14 MGFR powderfabricated from 14 MGFR powderfabricated from 14 MGFR powder fabricated from 14 MGFR powder at different temperatures of (a) 673 K, at different temperatures of (a) 673 K, at different temperatures of (a) 673 K, at different temperatures of (a) 673 K, (b) (b) (b) (b) 773 K and (c) 873 K.

773 K and (c) 873 K.

773 K and (c) 873 K.

773 K and (c) 873 K.

― 108 ―