Materiale nanocristaline magnetice moi obtinute prin ... · (mechanical alloying OR mechanical...

Workshop “Clumagin”, Iasi, aprilie 2007, 1

MaterialeMateriale nanocristalinenanocristaline magneticemagnetice moimoiobtinuteobtinute prinprin mecanosintezamecanosinteza

Ionel ChicinaşCatedra de Stiinta si Tehnologia Materialelor,

Universitatea Technica din Cluj-Napoca, Romania

Prof. Viorel Pop, Faculty of Physics, Babes-Bolyai University, Cluj-Napoca, RomaniaProf. Olivier Isnard, Laboratoire de Cristallographie, CNRS, associé à l’Université J. Fourier, Grenoble, FranceProf. Jean Marie Le Breton, Groupe de Physique des Matériaux, UMR CNRS 6634, Universitéde Rouen, FranceProf. Zeno Sparchez, Department of Materials Science and Technology, Technical University of Cluj-Napoca, RomaniaProf. Olivier Geoffroy, Laboratoire Louis Neel, CNRS, associé à l’Université J. Fourier, Grenoble, France

Mechanical alloying (MA)involves the synthesis of materials by high-energy milling

Ω

Disc

Vialω

Mechanical milling (MM) refers to the process of milling pure metals or compounds whithout solid state reaction

Ω » ω → shock mode process (SMP)

Ω « ω → friction mode process (FMP)

R. Hamzaoui, O. Elkedim, E. Gaffet, Mater. Sci. Eng. A 381 (2004) 363-371

Mechanical routes for producing nanocristalline powders



D1D2

D1B1

B1B2

C1

C2

C3

Scheme of the morphological transformation of the powder grains induced by milling. D – ductile powder, B – brittle powder, C –composite particles.

ARM-4, Constanta, 5 September 2005, 4

A BA Bn mEn

ergi

a lib

eă

Aliaj amorf

Amestec al componenţilor A şi B

Compus intermetalic cristalin

1

2

3

H.K.D.H. Bhadeshia, Mater. Sci. Techn. 16 (2000) 1404-14011

C.C. Koch, J.D. WhittenbergerIntermetallics, 4 (1996) 339



Reactive milling (RM)Mechanochemistry (MC)

(dry or wet MM)

The MC consists of:

a. reduction of the grain size below a certain value

b. the subsequent chemical reaction towardsthe equilibrium phase composition underthe milling conditions.

MO + R → M + RO(se aplica pentru oxizi, cloruri, sulfuri, etc.)


MAAC MAAC – can reduce the synthesis time!

Mechanical Alloying and Annealing Combining (MAAC) -What is this technique?

MA

Generally, synthesis of new material by MA needs a long time

What's happening if we STOP the milling process before the mechanical alloying finishing and then we make an annealing?

It is `possible to improve (finishing) the solid state reaction of compound/alloy forming!

Annealing the mixture milled

I. Chicinas, V. Pop, O. Isnard, J.M. Le Breton, J. Juraszek, J. Alloys and Comp. 352 (2003), 34-40V. Pop, O. Isnard and I. Chicinas, J. Alloys and Comp., 361 (2003), p.144-152.


80

20

40

60

0

100

τ0 τ1 τ3τ2 τ4time

germi-nation development

Saturation/finishinginitiation

20%Ni3Fe+80%(3Ni+Fe)

80

20

40

60

0

100

Ni 3F

e pe

rcen

tage

τ0 τ1 τ3τ2 τ4time

development Saturation/finishinginitiation

3Ni+Fe

20%Ni3Fe+

Mechanical Alloying in the Presence of Nanocrystalline Germs of the same Product

nm BAnBmA =+ nmnm BABAxnBmAx =⋅++⋅− )()1(

Z. Sparchez, I. Chicinas, O. Isnard, V. Pop, F. Popa, J. Alloys and Compounds, 434–435 (2007) 485–488


Aplicatii ale metodelor de aliere mecanica

•superaliaje cu dispersie de oxizi cu proprietăţi foarte bune la temperaturi ridicate (ODS Superalloys);

•structuri/microstructuri de neechilibru (inclusiv aliaje amorfe), pornind de la compuşi intermetalici cristalini;

•compuşi intermetalici cu structură nanocristalină/amorfă şi cu punct de fuziune ridicat, dificil de preparat prin tehnici convenţionale;

•soluţii solide terminale realizate prin extinderea domeniului de solubilitate, prevăzut de diagrama de echilibru fazic;

•soluţii solide şi faze amorfe în sisteme de aliaje cu miscibilitate nulă în stare solidă, foarte dificil de obţinut prin metode de răcire rapidă;

•faze cristaline metastabile;

•quasicristale;

•materiale compozite cu structură ierarhizată.


Comparatie intre solubilitatea de echilibru si solubilitatea extinsa prin MAa diferitelor elemente in Cu

C. Suryanarayana, E. Ivanovb, V.V. Boldyrev, Mater. Sci. Eng. A304–306 (2001) 151–158


Scopus - Results TITLE-ABS-KEY(mechanical alloying OR mechanical milling OR Mechanosynthese OR mechanochemistry OR reactive milling OR mechanical activation)

Inginerie si Nanostiinte, Bucuresti, 8 Decembrie 2005, 10

1970 1975 1980 1985 1990 1995 2000 20050

500

1000

1500

2000Dinamica domeniului mecano-sinteza

Rezultate cautare in baza de date Scopus pentru:

nr a

rtico

le/c

iclu

ciclu de 3 ani

MA-MM-RM-3ani

1970 1975 1980 1985 1990 1995 2000 20050

200

400

600

800

Dinamica domeniului mecano-sinteza


nr. a

rtico

le/a

n

anul

MA-MM-RM

Dinamica domeniului MA: 1967-2005:Baza de date SCOPUS: 7694 articole, 1375 patente, 6896 ref. web

Scopus - Results TITLE-ABS-KEY(mechanical alloying OR mechanical milling OR Mechanosynthese OR mechanochemistry OR reactive milling OR mechanical activation)

Scopus - Results (TITLE-ABS-KEY(mechanical alloying OR mechanical milling OR Mechanosynthese OR mechanochemistry OR reactive milling OR mechanical activation) AND (magnetic)


1980 1985 1990 1995 2000 20050

100

200

300

400

500

600

700

800Dinamica domeniului mecano-sinteza


nr. a

rtico

le/a

n

anul

MA-MM-RM MA+Magn

Scopus - Results TITLE-ABS-KEY(nanostructured OR nanocrystalline OR nanosized)

Scopus - Results TITLE-ABS-KEY(mechanical alloying OR mechanical milling OR Mechanosynthese OR mechanochemistry ORreactive milling OR mechanical activation)


1985 1990 1995 2000 20050

2000

4000

6000

8000

10000

12000 Dinamica domeniilor "nanomateriale" si "mecano-sinteza"

nr lu

crar

i/an

anul

MA-MM-RM nanomateriale


1. FAPASField activated pressure assisted sintering.Compared to a classical sintering process under pressure, a currentis applied in order to assist the sintering.A current exhibiting a high intensity (up to 8,000 A) under low voltage (10 V) is applied.

2. Spark plasma sinteringA process leading to bulk materials by a sintering step using pulse electric discharge.Due to the high intensity of the current, plasma may occur between the various powder grains.

Methods to produce nanocrystalline compacts from the nanocrystalline powders


3. Soft magnetic nanocrystalline composites

Ni3Fe

polymer layer

+polymer

dissolvingNi3Fenano

covered powder (1, 1.5, 2, 3 wt%)

Die pressed (600 - 800 MPa )

Polymerisation(60 min., 180 oC)

Composites Production


Cercetari pe plan mondial in domeniulnanomaterialelor produse prin mecanosinteza

• Centre puternice de cercetare: – Rusia (Moscova, Novosibirsk), – Franta (Belfort, Grenoble), – SUA (Michigan, Los Alamos, North Carolina), – Germania (Braunschweig, Drezda, Stuttgart), – Japonia (Senday, Kyoto),– Anglia (Cambridge), – Spania (Madrid, Barcelona), – Brazilia (Sao Paolo) , etc.

• Conferinte dedicate: – INCOME – Int. Conf. Mechanochemistry and Mechanical Alloying

(conf cu perioada de 3 ani: 2003 – Braunschweig, 2006 – Novosibirsk)

– ISMANAM – Int. Symp. Metastable and Nano Materials (partial)(sympozion anual: 1994 – Grenoble, …,1997-Barcelona, 1998- Wollongong-Australia, 1999-Dresda, 2001-Michigan, …, 2005 – Paris, 2006 - Varsovia)


Soft magnetic nanostructures

Small ferromagnetic crystallites coupled by exchange interaction

Local anisotropy Model D< Lex

Local anisotropies are randomly averagedout by exchange interactions → there is not any anistropy net effect on the magnetisation process

Low coercivity and high permeability

63

41 DAM

KpMKpH

SStc

StcC ≈

><=

6410

32

0

2/1 D

KAMp

KMp StSti ⋅

⋅≈=

μμμ μμ

G. Herzer, Mater. Sc. & Eng. , A133 (1991), 1-5 & Physica Scripta, T49 (1993), 307-314


Mechanical routes used for producing SMA

MA MAAC Two-step MA MAACwith inoculated germsMC*

MM of oxides blend

reduction of oxides

alloying by heat treatment

obtaining nanocrystallinealloy by MA

obtaining nanocrystalline alloy by MM

*X.Y. Qin, S.H. Cheong, J.S. Lee, Mater. Sci. Eng., A 363 (2003) 62

Soft Magnetic Nanocrystalline Powders

Raw materials used – generaly elemental powdersMilling equipment used - generaly planetary ball millBall/powder mass ratio : very different (from 5:1 to 30:1)


Why Ni-Fe and Ni-Fe-X(-Y) systems?

Polycrystalline Ni-Fe and Ni-Fe-X alloys have very good SMP

Why mechanical alloying techniques?

Nanocrystalline materials have very good SMP

It is possible to combine the properties of Ni-Fe and Ni-Fe-X systems with the properties of nanocrystalline state


Pulberi nanocristaline magnetic moi din sistemul Fe-Ni

0 10 20 30 40 50 60 70 80 90 100

200

800

600

400

γ-fcc

α-b

cc

Ni3Fe

Fe NiAtomic percent Nickel

Tem

pera

ture

(°C

) bcc+

fcc

bcc

bcc+

fcc

bct fcc

40%

[86,

99]

50%

[86,

96,

100

]

60%

[86]

70%

[86]

80%

[86,

115

]

90%

[86]

[106, 107

, 96, 104,

112, 101

, 103, 114

]

38%

[86]

36%

[86]

34%

[86]

32%

[86]

30%

[86,

100]

28%

[86]

26%

[86]

22%

[86]

11.1

1% [8

4]

20%

[96,

86]

14.4

% [9

4]

9.09

% [8

4]7.

69%

[84]

10% [86]

24.1% [9

7]

75%

bcc+

fcc

bct[

97] b

ct

bct+

fcc

[98]

19.2

% [9

3, 9

7]

9.6% [93]

24%

[86]

29% [97,

98]

33.9% [9

7, 98]

35% [96,

99]

bcc+

fcc

[99,

100

]

bcc+

fcc

[99]

27,5% [9

9]25% [99]

22.5% [9

9]

85%

[93]

0 10 20 30 40 50 60 70 80 90 1000 10 20 30 40 50 60 70 80 90 100

200

800

600

400

γ-fcc

α-b

cc

Ni3Fe

Fe NiAtomic percent Nickel

Tem

pera

ture

(°C

) bcc+

fcc

bcc

bcc+

fcc

bct fcc

40%

[86,

99]

50%

[86,

96,

100

]

60%

[86]

70%

[86]

80%

[86,

115

]

90%

[86]

[106, 107

, 96, 104,

112, 101

, 103, 114

]

38%

[86]

36%

[86]

34%

[86]

32%

[86]

30%

[86,

100]

28%

[86]

26%

[86]

22%

[86]

11.1

1% [8

4]

20%

[96,

86]

14.4

% [9

4]

9.09

% [8

4]7.

69%

[84]

10% [86]

24.1% [9

7]

75%

bcc+

fcc

bct[

97] b

ct

bct+

fcc

[98]

19.2

% [9

3, 9

7]

9.6% [93]

24%

[86]

29% [97,

98]

33.9% [9

7, 98]

35% [96,

99]

bcc+

fcc

[99,

100

]

bcc+

fcc

[99]

27,5% [9

9]25% [99]

22.5% [9

9]

85%

[93]

V. Pop, I. Chicinaş, Rocam 2006, J. Optoelectron. Adv. Mater. (2007), sub recenzie


Ni3Fe

ss1h1h+330°C/1h2h2h+ 330°C/1h3h3h+330°C/1h

4h4h+330°C/1h6h6h+330°C/1h

8h8h+330°C/1h10h10h+330°C/1h12h12h+330°C/1h

Inte

nsité

(uni

t. ar

b.)

2 theta (degrés)36 40 50 60 70 80 9040 50 60 70 80 90

2 θ (°)

Inte

nsity

(a.u

.)

Fe Fe

Ni3Fe

Ni

peaks shift to LOWER 2θ angles

peaks shift to HIGHER 2θ angles

broadening of the diffraction peaks

•Ni3Fe phase formation•the first order internal stresses

relaxion of the first order internal stresses

the second order internal stresses

I. Chicinas et al. J. Alloys and Compounds 352 (2003), p. 34-40.

Improve the solid state reaction

Relax the internal stresses

Annealing effectNi

Inte

nsité

(u.a

.)

2 t h e t a8 9 . 2 9 0 9 1 9 2 9 3 9 4 9 5

1h1h+ 330°C/1h2h2h+ 330°C/1h3h3h+ 330°C/1h4h4h+ 330°C/1h6h6h+ 330°C/1h8h8h+ 330°C/1h10h10h+ 330°C/1h12h12h+ 330°C/1hss

90 91 92 93 94 95

2 θ (°)

Inte

nsity

(a.u

.)


I. Chicinas, V. Pop, O. Isnard, J.M. Le Breton and J. Juraszek, J. Alloys and Compounds 352 (2003), p. 34-40

88 90 92 94 9

Inte

nsity

(a.u

.)

2 theta (degrees)88 90 92 94 9

Ni3Fe Ni

88 89 90 91 92 93 94 952 θ (°)

1 h2 h3 h4 h6 h8 h

10 h12 h14 h16 h20 h24 h

as milled

1 h2 h3 h4 h6 h8 h

10 h12 h

+300°C/30min

1 h2 h3 h4 h6 h8 h

10 h12 h14 h16 h20 h24 h

+330°C/1h

1 h2 h3 h4 h6 h8 h

10 h12 h

+330°C/3h

+330°C/8h

1 h2 h3 h4 h6 h8 h

10 h12 h

+330°C/12h

ss

Inte

nsity

(a.u

.)

88 90 92 94 9

Inte

nsity

(a.u

.)


Ni3Fe Ni

88 89 90 91 92 93 94 952 θ (°)

1 h2 h3 h4 h6 h8 h

10 h12 h14 h16 h20 h24 h

as milled

1 h2 h3 h4 h6 h8 h

10 h12 h14 h16 h20 h24 h

as milled

1 h2 h3 h4 h6 h8 h

10 h12 h

+300°C/30min

1 h2 h3 h4 h6 h8 h

10 h12 h

+300°C/30min

1 h2 h3 h4 h6 h8 h

10 h12 h14 h16 h20 h24 h

+330°C/1h

1 h2 h3 h4 h6 h8 h

10 h12 h14 h16 h20 h24 h

+330°C/1h

1 h2 h3 h4 h6 h8 h

10 h12 h

+330°C/3h

1 h2 h3 h4 h6 h8 h

10 h12 h

+330°C/3h

+330°C/8h

1 h2 h3 h4 h6 h8 h

10 h12 h

+330°C/12h

+330°C/8h

1 h2 h3 h4 h6 h8 h

10 h12 h

+330°C/12h

ss

Inte

nsity

(a.u

.)

(311)

One annealing time Different milling time

V. Pop, O. Isnard and I. Chicinas, J. Alloys and Comp., 361 (2003), p.144-152.

8 8 9 0 9 2 9 4 9

Inte

nsity

(a.u

.)


88 8 9 9 0 9 1 9 2 9 3 9 4 9 52 θ (°)

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 1 h

ss

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 2 h

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 3 h

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 4 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 6 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 8 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 1 0 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 1 2 h

0 h1 h m illed 1 4 h0 h1 h m illed 1 6 h0 h1 h m illed 2 0 h

0 h1 h m illed 2 4 h

N i3F e N i

Inte

nsity

(a.u

.)

8 8 9 0 9 2 9 4 9

Inte

nsity

(a.u

.)


88 8 9 9 0 9 1 9 2 9 3 9 4 9 52 θ (°)

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 1 h

ss

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 2 h

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 3 h

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 4 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 6 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 8 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 1 0 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 1 2 h



8 8 9 0 9 2 9 4 9

Inte

nsity

(a.u

.)


88 8 9 9 0 9 1 9 2 9 3 9 4 9 52 θ (°)

8 8 9 0 9 2 9 4 9

Inte

nsity

(a.u

.)


88 8 9 9 0 9 1 9 2 9 3 9 4 9 52 θ (°)

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 1 h

ss

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 2 h

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 3 h

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 4 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 6 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 8 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 1 0 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 1 2 h



0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 1 h

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 1 h

ss

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 2 h

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 2 h

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 3 h

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 3 h

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 4 h

0 h0 .5 h

1 h2 h3 h

1 2 h

m illed 4 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 6 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 6 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 8 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 8 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 1 0 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 1 0 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 1 2 h

0 h0 .5 h

1 h2 h3 h8 h

m illed 1 2 h

0 h1 h m illed 1 4 h0 h1 h m illed 1 4 h0 h1 h m illed 1 6 h0 h1 h m illed 1 6 h0 h1 h m illed 2 0 h0 h1 h m illed 2 0 h

0 h1 h m illed 2 4 h0 h1 h m illed 2 4 h

N i3F e N iN i3F e N i

Inte

nsity

(a.u

.)

One milling timeDifferent annealing time


Ni3Fe produced by MAAC


2 θ (°)

8 9 0 9 2 9 4

Inte

nsity

(a.u

.)

2 t h e t a ( d e g r e e s )8 8 9 0 9 2 9 4 9

Inte

nsity

(a.u

.)

88 89 90 91 92 93 94 95

ss

0 h

0.5 h1 h2 h

3 h12 h

milled 1 h

0 h0.5 h

1 h2 h3 h

12 h

milled 4 h

0 h0.5 h

1 h2 h3 h8 h

milled 6 h

2 θ (°)

8 9 0 9 2 9 4

Inte

nsity

(a.u

.)

2 t h e t a ( d e g r e e s )8 8 9 0 9 2 9 4 9

Inte

nsity

(a.u

.)

88 89 90 91 92 93 94 95

ss

0 h

0.5 h1 h2 h

3 h12 h

milled 1 h

0 h0.5 h

1 h2 h3 h

12 h

milled 4 h

0 h0.5 h

1 h2 h3 h8 h

milled 6 h

0 h

0.5 h1 h2 h

3 h12 h

milled 1 h

0 h

0.5 h1 h2 h

3 h12 h

milled 1 h

0 h0.5 h

1 h2 h3 h

12 h

milled 4 h

0 h0.5 h

1 h2 h3 h

12 h

milled 4 h

0 h0.5 h

1 h2 h3 h8 h

milled 6 h

0 h0.5 h

1 h2 h3 h8 h

milled 6 h

(311)

θβλ

cos21 ⋅

⋅= kd

21β - FWHM

d = 12 nm - 52 h milling22 nm - 24 h milling




0

0.3

0.6

0.9

1.2

0 100 200 300 400 500 600 700 800

ss12 h

M2

(a.u

.)

T(oC)

TC(Ni)

TC(Ni

3Fe)

TC(Fe)

I. Chicinas, V. Pop and O. Isnard, J. Magn. Magn. Mater. 242-245 (2002) p. 885-887


3.8

3.9

4.0

4.1

4.2

4.3

4.4

4.5

0 10 20 30 40 50 60

4 K295 K

Ms (

µ B/f.

u.)

Tem ps de broyage (h)

recuit

3.8

4

4.2

4.4

4.6

4.8

0 5 10 15 20 25

not annealed300°C/30min330°C/1h330°C/3h330°C/8-12h

Ms (

µ Bf.u

.)

milling time (hours)

T = 4 K

T = 300 K

*H. Hasegawa, J. Kanamori, J. Phys. Soc. Jap. 33 (1972) 1599

Fe1-xNixin the reach nickel region*

x MFe and MNi=ct.

MNi-Fe when Ni3Fe %


annealed


I. Chicinas, V. Pop and O. Isnard, J. Magn. Magn. Mater. 242-245 (2002) p. 885-887

ARM-4, Constanta, 5 September 2005, 24Workshop “Clumagin”, Iasi, aprilie 2007, 24

3.8

3.9

4.0

4.1

4.2

4.3

4.4

0 0.5 1 1.5 2 2.5 3 3.5

M (µ

B/f.

u.)

annealing time (hours)

T = 300 K

ss 1 h

2 h

3 h

4 h

6 h

8 hx 10 ho 12 h

4.0

4.1

4.2

4.3

4.4

4.5

4.6

4.7

0 0.5 1 1.5 2 2.5 3 3.5

M (µ

B/f.

u.)

annealing time(hours)

T = 4 K

ss

1 h

2 h

3 h

4 h

6 h

8 hx 10 ho 12 h



Influence of the milling and annealing conditions on the Ms


0.00

0.50

1.00

1.50

2.00

0 2 4 6 8 10 12

(Mt-M

0)/M

0 (%

)


milled 4 h

milled 6 h

milled 8 h

T = 330 °C


Influence of the milling and annealing conditions on the Ms



0

20

40

60

80

100

0 10 20 30 40 50 60In

tens

ité M

ossb

auer

(%)

Temps de broyage (h)

Ni3Fe

α-FeMös

sbau

erin

tens

ity (%

)


0h

3h

4h

8h

10h

12h

Velocity ( mm / s )

0-10 +10

0.96

1.00

Absorption ( %

)

0.96

1.00

Absorption ( %

)

0.97

1.00

Absorption ( %

) 0.98

1.00

Absorption ( %

)

0.99

1.00

Absorption ( %

)

0.98

1.00

Absorption ( %

)

16h

24h

40h

48h

52h

52hannealed

Velocity ( mm / s )

0-10 +10

0.99

1.00

Absorption ( %

)

0.99

1.00

Absorption ( %

)

0.98

1.00

Absorption ( %

) 0.98

1.00

Absorption ( %

)

0.98

1.00

Absorption ( %

)

0.98

1.00

Absorption ( %

)

Speed (mm/s)-10 0 +10

Speed (mm/s)-10 0 +10

Abs

orpt

ion

(%)

Abs

orpt

ion

(%)

Mössbauer spectrometryNi3Fe powders

I. Chicinas, V. Pop, O. Isnard, J.M. Le Breton and J. Juraszek, J. Alloys and Compounds 352 (2003), p. 34-40


0.0

2.0

4.0

6.0

8.0

10.0

12.0

0 0.5 1 1.5 2 2.5 3

mill

ing

time

(hou

rs)


0.0

2.0

4.0

6.0

8.0

10.0

12.0

0 0.5 1 1.5 2 2.5 3

mill

ing

time

(hou

rs)


Ni Fe3

M = const.s

Ni+Fe+Ni Fe (Ni-Fe) 3

330 C o

T >330 C1 o

T >T2 1

Milling – Annealing - Transformation (MAT) diagram

Mechanical Alloying and Annealing Combining technique




Elaboration dans un broyeur planétaire sous atmosphère inerte Ar de 2 jusqu’à 40h de broyage

16h12h10h

8h7h6h4h

Superm.ss

Inte

nsity

(a.u

.)

N iFeM o

Superm.

M o(110)

36 40 50 60 70 80 9040 50 60 70 80 90

2 Theta (°)

16h12h10h

8h7h6h4h

Superm.ss

Inte

nsity

(a.u

.)

N iFeM o

Superm.

M o(110)

36 40 50 60 70 80 9040 50 60 70 80 90

2 Theta (°)Disparition progressive des pics de Bragg de :=> Fe après 4 heures=> Mo après 12 heures

Supermalloy (79Ni16Fe5Mo wt%)


Supermalloy (79Ni16Fe5Mo wt%)Diffraction de rayons X

ss

2h MA4h MA6h MA8h MA12h MA

16h MA20h MA

24h MA

28h MA32h MA36h MA40h MA

39 40 41 42 43 44 45 46 47 2 theta (°)

Inte

nsita

te(u

.a.)

NiSupermalloy

ss

2h MA4h MA6h MA8h MA12h MA

16h MA20h MA

24h MA

28h MA32h MA36h MA40h MA

39 40 41 42 43 44 45 46 47 2 theta (°)

Inte

nsita

te(u

.a.)

NiSupermalloy

Formation de supermalloy⇒décalage vers les petits angles

⇒Élargissement des pics de Bragg car la taille de cristallites diminue + tensions du second ordre

Tensions internes => décalage vers les petits angles

Jusqu’à 12 heures incorporation de Mo dans l’alliage NiFe


350 °C/4h

350 °C/2h

350 °C/1h

350 °C/30 min

ss

as milled

Ni3Fe

800

700

600

500

400

300

200

100

040 50 60 70 80 90 100 110

2 Theta (°)

Inte

nsity

(a.u

.)

350 °C/4h

350 °C/2h

350 °C/1h

350 °C/30 min

ss

as milled

Ni3Fe

800

700

600

500

400

300

200

100

040 50 60 70 80 90 100 110

2 Theta (°)

350 °C/4h

350 °C/2h

350 °C/1h

350 °C/30 min

ss

as milled

Ni3Fe

800

700

600

500

400

300

200

100

0

350 °C/4h

350 °C/2h

350 °C/1h

350 °C/30 min

ss

as milled

Ni3Fe

350 °C/4h

350 °C/2h

350 °C/1h

350 °C/30 min

ss

as milled

Ni3Fe

350 °C/4h

350 °C/2h

350 °C/1h

350 °C/30 min

ss

as milled

Ni3Fe

350 °C/4h

350 °C/2h

350 °C/1h

350 °C/30 min

ss

as milled

Ni3Fe

800

700

600

500

400

300

200

100

040 50 60 70 80 90 100 110

2 Theta (°)

Inte

nsity

(a.u

.)

350 °C/4h

350 °C/2h

350 °C/1h

350 °C/30 min

as milled

Ni3Fe

ss

40 50 60 70 80 90 100

2 Theta (°)

800

700

600

500

400

300

200

100

0

Inte

nsity

(a.u

.) 350 °C/4h

350 °C/2h

350 °C/1h

350 °C/30 min

as milled

Ni3Fe

ss

40 50 60 70 80 90 100

2 Theta (°)

800

700

600

500

400

300

200

100

0

350 °C/4h

350 °C/2h

350 °C/1h

350 °C/30 min

as milled

Ni3Fe

ss

40 50 60 70 80 90 100

2 Theta (°)

350 °C/4h

350 °C/2h

350 °C/1h

350 °C/30 min

as milled

Ni3Fe

ss

40 50 60 70 80 90 100

2 Theta (°)

350 °C/4h

350 °C/2h

350 °C/1h

350 °C/30 min

as milled

Ni3Fe

ss

350 °C/4h

350 °C/2h

350 °C/1h

350 °C/30 min

as milled

Ni3Fe

ss

350 °C/4h

350 °C/2h

350 °C/1h

350 °C/30 min

as milled

Ni3Fe

ss

40 50 60 70 80 90 100

2 Theta (°)

800

700

600

500

400

300

200

100

0

Inte

nsity

(a.u

.)

8 hours milling 6 hours milling

θβλ

cos21 ⋅

⋅= kd

21β - FWHM

d = 11 nm - 16 h broyage et recuit à 350 °C 2 heurespour éliminer les tensions internes

Supermalloy synthèse par broyage et recuit :• 6 et 8 heures de mécanosynthèse• différentes conditions de recuit

I. Chicinas, O. Isnard, V. Pop, J. Mater. Sci. 39 (2004), p. 5305-5308 O. Isnard, V. Pop, I. Chicinaş, J. Magn. Magn. Mater. 290-291 (2005), p. 1535-1538.

MoMoDisparition de Mo après recuit Mo subsiste après recuit


80

81

82

83

84

85

0 1 2 3 4 5Annealing time (h)

12h MA

16h MA

Effet bénéfique du traitement thermique

76

80

84

88

92

96

100

104

0 2 4 6 8 10

µ0H (T)

12h MA

12h MA350°C/4h

ss

24h MA

24h MA350°C/4h

40h MA

40h MA350°C/4h

Supermalloy (79Ni16Fe5Mo wt%) Mesures magnétiques

Conforte les résultats obtenus par diffractions de rayons X


Elaboration dans un broyeur planétaire sous atmosphère inerte Arde 2 jusqu’à 32 h de broyage

Alliage 77Ni14Fe5Cu4Mo % massique

ss

2h

4h

6h8h

10h12h16h20h24h28h32h

39 40 41 42 43 44 45 462 theta (°)

Inte

nsita

te(u

.a.)

Mo(110)

Cu(111)

NiFeCuMoNi

(111)

NiFeCuMotopit

ss

2h

4h

6h8h

10h12h16h20h24h28h32h

39 40 41 42 43 44 45 462 theta (°)

Inte

nsita

te(u

.a.)

Mo(110)

Cu(111)

NiFeCuMoNi

(111)

NiFeCuMotopit

Disparition progressive des pics de Bragg de :=> Fe après 4 heures de broyage=> Cu après 6 heures=> Mo après 12 heures


ss

2h MA350°C/4h

4h MA

350°C/4h

6h MA350°C/4h

8h MA350°C/4h

Mo(110)

Cu(111)

Cu(200)

Mo(200)

Fe(200)

Ni(111) Ni(200)

NiFeCuMo NiFeCuMo

38 40 45 50 55 60 652 theta (°)

Inte

nsita

te(u

.a.)

ss

2h MA350°C/4h

4h MA

350°C/4h

6h MA350°C/4h

8h MA350°C/4h

Mo(110)

Cu(111)

Cu(200)

Mo(200)

Fe(200)

Ni(111) Ni(200)

NiFeCuMo NiFeCuMo

38 40 45 50 55 60 652 theta (°)

Inte

nsita

te(u

.a.)

Réaction à l’état solide

Effet bénéfique du traitement thermique à 350°C


300 500 700 900 1100Temperature (K)

TC

Ni

TC

NiFeCuMoT

C Fe

Temperature (K)M

² (a.

u.) 10 h

4h

ss

AB

300 500 700 900 1100Temperature (K)

TC

Ni

TC

NiFeCuMoT

C Fe

Temperature (K)M

² (a.

u.)

300 500 700 900 1100Temperature (K)

TC

Ni

TC

NiFeCuMoT

C Fe

Temperature (K)M

² (a.

u.) 10 h

4h

ss

AB

Analyse thermomagnétique

4h : -Chauffage changement de penteau point A correspond à Tc de NiFeCuMo obtenu par broyage

-Formation progressive de l’alliagepar chauffage (région B) Large domaine de composition

-Refroidisement une seule Tc détectéealliage formé dans le volume

10h : seule la Tc de l’alliage est observéele traitement thermique homogénéise

SS : Mélange de départ Tc de Ni et Fe


Température en K

F. Popa, O. Isnard, I. Chicinas, V. Pop, J. Magn. Magn. Mater., (2007), sub tipar


70

75

80

85

90

0 2 4 6 8 10

µ0H (T)

8h MA

8h MA 350°C/4h

24h MAss

24h MA350°C/4h

24h MA350°C/4h

4 K

300 K

70

72

74

76

78

80

82

84

0 5 10 15 20 25 30 35

MATT @ 350 °C/4h

Timp de macinare (h)


Temps de broyage (heure)

Aim

anta

tion

(µB/

f.u.)

Aim

anta

tion

(µB/

f.u.)

Effet bénéfique du traitement thermique à 350°C

2 étapes dans la mécanosynthèse : similitude avec le supermalloy


The Ni, Fe and Mo maps on starting sample (0 hours milling) and on the 12 hours milled sample. It can observe the chemical

homogeneity of the Supermalloy powders obtained by mechanical alloying and the particles morphology, too.

Ni particles Fe particles Mo particles


Ni-Fe (3:1) mixture – after 1 h of milling

Ni3Fe Supermalloy

4 h milling

Soft magnetic nanocrystalline composites

Ni3Fe

polymer layer

+polymer

dissolvingNi3Fenano

covered powder (1, 1.5, 2, 3 wt%)

Die pressed (600 - 800 MPa )

Polymerisation(60 min., 180 oC)

Composites Production

I. Chicinaş, O. Isnard, O. Geoffroy, V. Pop, J. Magn. Magn. Mater. 290-291 (2005), 1531-1534 I. Chicinaş, O. Isnard, O. Geoffroy, V. Pop, J. Magn. Magn. Mater. 310 (2007), 2474-2476

16

18

20

22

24

26

28

30

0

100

200

300

400

500

600

0 20 40 60 80 100

µ; Ni3Fe; B=0.05 Tµ; NiFe; B=0.05 Tµ; Ni3Fe; B=0.1Tµ; NiFe; B=0.1Tµ; Ni3Fe; B=0.2Tµ; NiFe; B=0.2T

P/f; Ni3Fe; B=0.05 TP/f; NiFe; B=0.05 TP/f; Ni3Fe; B=0.1 TP/f; NiFe; B=0.1 TP/f; Ni3Fe; B=0.2 TP/f; NiFe; B=0.2 T

µ

P/f (

J/m

3 )

f (kHz)



Conclussions

The possibility of producing chemical transformations through mechanical energy has been extensively demonstrated in metallic as well as in oxide systems

The nanocrystalline/nanosized/nanocomposite powders obtained by different mechanical routes exhibit very interesting properties, some from them different from those of bulk materials


MULTUMESC !MULTUMESC !


Cercetari pe plan mondial in domeniul nanomaterialelor produse prin mecanosintezaElaboration dans un broyeur planétaire sous atmosphère inerte Ar de 2 jusqu’à 40h de broyageSupermalloy (79Ni16Fe5Mo wt%)�Diffraction de rayons XElaboration dans un broyeur planétaire sous atmosphère inerte Ar de 2 jusqu’à 32 h de broyageThe Ni, Fe and Mo maps on starting sample (0 hours milling) and on the 12 hours milled sample. It can observe the chemical homMULTUMESC !

Materiale nanocristaline magnetice moi obtinute prin ... · (mechanical alloying OR mechanical...

Documents

Transcript of Materiale nanocristaline magnetice moi obtinute prin ... · (mechanical alloying OR mechanical...