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
Workshop “Clumagin”, Iasi, aprilie 2007, 2
Workshop “Clumagin”, Iasi, aprilie 2007, 3
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
Workshop “Clumagin”, Iasi, aprilie 2007, 4
ARM-4, Constanta, 5 September 2005, 5
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.)
Workshop “Clumagin”, Iasi, aprilie 2007, 5
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.
ARM-4, Constanta, 5 September 2005, 7
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
Workshop “Clumagin”, Iasi, aprilie 2007, 7
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.
Workshop “Clumagin”, Iasi, aprilie 2007, 8
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
Workshop “Clumagin”, Iasi, aprilie 2007, 9
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
Rezultate cautare in baza de date Scopus pentru:
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)
Workshop “Clumagin”, Iasi, aprilie 2007, 11
1980 1985 1990 1995 2000 20050
100
200
300
400
500
600
700
800Dinamica domeniului mecano-sinteza
Rezultate cautare in baza de date Scopus pentru:
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)
Workshop “Clumagin”, Iasi, aprilie 2007, 12
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
ARM-4, Constanta, 5 September 2005, 13
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
Workshop “Clumagin”, Iasi, aprilie 2007, 13
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
Workshop “Clumagin”, Iasi, aprilie 2007, 14
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)
Workshop “Clumagin”, Iasi, aprilie 2007, 15
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
Workshop “Clumagin”, Iasi, aprilie 2007, 16
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)
Workshop “Clumagin”, Iasi, aprilie 2007, 17
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
Workshop “Clumagin”, Iasi, aprilie 2007, 18
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
Workshop “Clumagin”, Iasi, aprilie 2007, 19
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
.)
Workshop “Clumagin”, Iasi, aprilie 2007, 20
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
.)
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 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
.)
2 theta (degrees)88 90 92 94 9
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
.)
2 theta (degrees)88 90 92 94 9
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
8 8 9 0 9 2 9 4 9
Inte
nsity
(a.u
.)
2 theta (degrees)88 90 92 94 9
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
.)
2 theta (degrees)88 90 92 94 9
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
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
ARM-4, Constanta, 5 September 2005, 21
Ni3Fe produced by MAAC
Workshop “Clumagin”, Iasi, aprilie 2007, 21
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
V. Pop, O. Isnard and I. Chicinas, J. Alloys and Comp., 361 (2003), p.144-152.
Workshop “Clumagin”, Iasi, aprilie 2007, 22
ARM-4, Constanta, 5 September 2005, 23
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
Workshop “Clumagin”, Iasi, aprilie 2007, 23
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 %
milling time (hours)
annealed
V. Pop, O. Isnard and I. Chicinas, J. Alloys and Comp., 361 (2003), p.144-152.
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
V. Pop, O. Isnard and I. Chicinas, J. Alloys and Comp., 361 (2003), p.144-152.
Ni3Fe produced by MAAC
Influence of the milling and annealing conditions on the Ms
ARM-4, Constanta, 5 September 2005, 25Workshop “Clumagin”, Iasi, aprilie 2007, 25
0.00
0.50
1.00
1.50
2.00
0 2 4 6 8 10 12
(Mt-M
0)/M
0 (%
)
annealing time (hours)
milled 4 h
milled 6 h
milled 8 h
T = 330 °C
Ni3Fe produced by MAAC
Influence of the milling and annealing conditions on the Ms
V. Pop, O. Isnard and I. Chicinas, J. Alloys and Comp., 361 (2003), p.144-152.
ARM-4, Constanta, 5 September 2005, 26Workshop “Clumagin”, Iasi, aprilie 2007, 26
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 (%
)
milling time (hours)
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
ARM-4, Constanta, 5 September 2005, 27Workshop “Clumagin”, Iasi, aprilie 2007, 27
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)
annealing time (hours)
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)
annealing time (hours)
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
ARM-4, Constanta, 5 September 2005, 28
V. Pop, O. Isnard and I. Chicinas, J. Alloys and Comp., 361 (2003), p.144-152.
Workshop “Clumagin”, Iasi, aprilie 2007, 28
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%)
Workshop “Clumagin”, Iasi, aprilie 2007, 29
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
Workshop “Clumagin”, Iasi, aprilie 2007, 30
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
Workshop “Clumagin”, Iasi, aprilie 2007, 31
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
Workshop “Clumagin”, Iasi, aprilie 2007, 32
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
Workshop “Clumagin”, Iasi, aprilie 2007, 33
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
Workshop “Clumagin”, Iasi, aprilie 2007, 34
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
Alliage 77Ni14Fe5Cu4Mo % massique
Température en K
F. Popa, O. Isnard, I. Chicinas, V. Pop, J. Magn. Magn. Mater., (2007), sub tipar
Workshop “Clumagin”, Iasi, aprilie 2007, 35
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)
Alliage 77Ni14Fe5Cu4Mo % massique
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
Workshop “Clumagin”, Iasi, aprilie 2007, 36
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
ARM-4, Constanta, 5 September 2005, 37Workshop “Clumagin”, Iasi, aprilie 2007, 37
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)
Workshop “Clumagin”, Iasi, aprilie 2007, 40
ARM-4, Constanta, 5 September 2005, 41
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
Workshop “Clumagin”, Iasi, aprilie 2007, 41
MULTUMESC !MULTUMESC !
Workshop “Clumagin”, Iasi, aprilie 2007, 42
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 !
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