Materiale nanocristaline obtinute prin mecanosinteza · (mechanical alloying OR mechanical milling...
Transcript of Materiale nanocristaline obtinute prin mecanosinteza · (mechanical alloying OR mechanical milling...
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Materiale nanocristaline obtinute prin Materiale nanocristaline obtinute prin mecanosintezamecanosinteza
Ionel ChicinaşCatedra de Stiinta si Tehnologia Materialelor,
Universitatea Technica din Cluj-Napoca, Romania
Prof. Olivier Isnard, Laboratoire de Cristallographie, CNRS, associé à l’Université J. Fourier, Grenoble, FranceProf. Viorel Pop, Faculty of Physics, Babes-Bolyai University, Cluj-Napoca, Romania Prof. 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, FranceProf. Emil Burzo, Faculty of Physics, Babes-Bolyai University, Cluj-Napoca, Romania
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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
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D1D2
D1B1
B1B2
C1
C2
C3
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Scheme of the morphological transformation of the powder grains induced by milling. D – ductile powder, B – brittle powder, C –composite particles.
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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
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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
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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.
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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.)
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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, presented at ISMANAM 2005, Paris, to be published
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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.
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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
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C. Suryanarayana, E. Ivanovb, V.V. Boldyrev, Mater. Sci. Eng. A304–306 (2001) 151–158
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Scopus - Results TITLE-ABS-KEY(mechanical alloying OR mechanical milling OR Mechanosynthese OR mechanochemistry OR reactive milling OR mechanical activation)
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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
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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)
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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
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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)
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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
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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
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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
I. Chicinaş, O. Isnard, O. Geoffroy, V. Pop, J. Magn. Magn. Mater. 290-291 (2005), 1531-1534 10
15
20
25
30
35
20
40
60
80
100
120
140
0 10 20 30 40 50 60
B=0.1T
µ; Ni3Fe_1_700µ; Ni3Fe_1-5_600µ; Ni3Fe_1-5_700µ; Ni3Fe_1-5_800µ; Ni3Fe_2_700µ; Ni3Fe_3_700
P/f (J/m^3); Ni3Fe_1_700P/f (J/m^3); Ni3Fe_1-5_600P/f (J/m^3); Ni3Fe_1-5_700P/f (J/m^3); Ni3Fe_1-5_800P/f (J/m^3); Ni3Fe_2_700
µ
P/f (
J/m
3 )
f (kHz)
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Cercetari pe plan mondial in domeniul nanomaterialelor 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(sympozion anual: 1994 – Grenoble, …,1997-Barcelona, 1998- Wollongong-Australia, 1999-Dresda, 2001-Michigan, …, 2005 – Paris, 2006 - Varsovia)
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Cercetari pe plan national in domeniul nanomaterialelor produse prin mecanosinteza
• Universitatea Technica din Cluj-Napoca (Catedra de Stiinta si Tehnologia Materialelor: Grup Prof. R.L. Orban si Grup Prof. I. Chicinas):
• Compusi intermetalici/nanocompozite cu propr. mecanice (Prof. R.L. Orban)• Materiale magnetice moi nanocristaline de tip Permalloy si Supermalloy• Nanocompozite magnetice hard/soft (SmCo5/Fe, Sm(CoCu)5/Fe)• 2 teze de doctorat in domeniu MA• 5 doctoranzi cu frecventa in domeniu MA• 1 doctorat in co-tutela in MA (cond. I. Chicinas – UTCN si O. Isnard – Univ. J.
Fourier - Grenoble• Universitatea Babes-Bolyai Cluj-Napoca
• Materiale magnetice moi nanocrystaline de tip Permalloy si Supermalloy• Nanocompozite magnetice hard/soft
• ICPE-CA Bucuresti• Compusi intermetalici si nanocompozitecu propr. mecanice• Materiale stocatoare de hidrogen
• ICEM- Bucuresti• Compusi intermetalici si nanocompozitecu propr. mecanice
• Universitatea din Craiova• Compusi intermetalici si nanocompozite cu propr. mecanice
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Grupul nostru de cercetare in MA, cu colaborare internationala
Universitatea Technica din Cluj-Napoca (Catedra de Stiinta si Tehnologia Materialelor): Prof. Ionel Chicinas
Universitatea Babes-Bolyai, Cluj-Napoca (Facultatea de Fizica): Prof. Viorel Pop
Laboratoire Louis Neel – CNRS Prof. Olivier GeoffroyUniversite Joseph Fourier, Grenoble, Franta: Prof. Dominic Givord
Laboratoire de Cristallographie – CNRSUniversite Joseph Fourier, Grenoble, Franta: Prof. Olivier Isnard
Groupe de Physique des Matériaux, Université de Rouen, Franta: Prof. Jean Marie Le Breton
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Lucrari publicate in domeniul MA de catre grupul nostruIn reviste cotate ISI: 91. I. Chicinaş, V. Pop, O. Isnard, Magnetic properties of Ni3Fe intermetallic compound obtained by
mechanical alloying, Journal of Magnetism and Magnetic Materials, 242-245 (2002), 885-8872. I. Chicinaş, V. Pop, O. Isnard, J.M. Le Breton, J. Juraszek, Synthesis and magnetic properties of
Ni3Fe intermetallic compound obtained by MA, J. Alloys and Comp. 352 (2003), 34-403. V. Pop, O. Isnard, I. Chicinaş, Crystallographic and Magnetic Study of the Nanocrystalline N3Fe
Intermetallic Compound Formation by Mechanical Alloying and Annealing, Journal of Alloys and Compounds, 361 (2003), 144-152
4. I. Chicinaş, V. Pop, O. Isnard, Synthesis of The Supermalloy Powders by Mechanical Alloying, Journal of Materials Science, 39 (2004), 5305-5309
5. O. Isnard, V. Pop, I. Chicinaş, Magnetic and Structural Properties of the Supermalloy Powders Produced by MA and Annealing, J. Magn. Magn. Mater., 290-291 (2005), 1535-1538
6. I. Chicinaş, O. Geoffroy, O. Isnard, V. Pop, Soft magnetic composite based on mechanically alloyed nanocrystalline Ni3Fe phase, J. Magn. Magn. Mater., 290-291 (2005), 1531-1534
7. Z. Sparchez, I. Chicinas, O. Isnard, V. Pop, F. Popa, Mechanical Alloying of Ni3Fe in the Presence of Ni3Fe Nanocrystalline Germs, ISMANAM 2005, Paris, be published in J. Alloys and Comp.
8. V. Pop, O. Isnard, I. Chicinas, D. Givord, J.M. Le Breton, SmCo5/α-Fe Nanocomposite Material Obtained by Mechanical Milling And Annealing, ARM-4, 5-7 Sept. 2005, Constanta, be published inJ. Optoelectronics and Advanced Matterials
9. I. Chicinas, Soft Magnetic Nanocrystalline Powders Produced by Mechanical Alloying TechniquesInvited lecture- ARM-4, 5-7 Sept. 2005, Constanta, be published in J. Optoelectronics and Adv. Materials
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In proceeding conferinta internationala: 8
1. I. Chicinaş, C. Nitray, N. Jumate, The obtaining of the intermetallic compound Ni3Fe by mechanical alloying, in Proc. "2nd Int. Conf. Powder Metall. Romania, RoPM2000, 6-8 July, 2000, Romania, Cluj-Napoca, vol. 2, 637-642
2. I. Chicinaş, V. Pop, O. Isnard, J.M. Le Breton, Synthesis and Magnetic Properties of Ni3Fe Intermetallic Compound Obtained by Mechanical Alloying, Proc. Materiaux 2002 Congrès, Tours, France, 21-25 Oct. 2002, CD
3. Z. Spârchez, I. Chicinaş, Analysis of the Parameters that Influence the Contamination of the Powders Obtained by Mechanical Alloying/Milling, Proc. World Congress on Powder Metall., PM 2004, oct. 2004, Vienna, vol. 1, 213-218
4. I. Chicinaş, O. Isnard, O. Geoffroy, V. Pop, Soft Magnetic Composite Materials Based on the Nanocrystalline Ni3FeIntermetallic Compound, Proc. World Congress on Powder Metallurgy, PM 2004, oct. 2004, Vienna, vol. 4, 623-628
5. F. Popa, O. Isnard, I. Chicinaş, V. Pop, Synthesis of the NiFeCuMo Soft Magnetic Powders by Mechanical Alloying, Proc. 3rd Int. Conf Powder Metall, RoPM 2005, 7-9 July 2005, Sinaia, Romania, vol. 2, 887-894
6. V. Pop, O. Isnard, I. Chicinaş, D. Givord, Nanocomposite SmCo5/α-Fe type magnets prepared by mechanical milling, Proceedings of Euro PM2005 Congress, 2-5 Oct. 2005, Prague, vol. 1, 487-493
7. I. Chicinaş, O. Isnard, V. Pop, Soft Magnetic Powders from Fe-Ni And Fe-Ni-X Systems Produced by Mechanical Alloying Techniques, Proceedings of Euro PM2005 Congress, 2-5 Oct. 2005, Prague, vol.1, 445-450
8. Z. Spârchez, I. Chicinaş, Method for Minimising the Powders Contamination During the Ball Milling ProcessProceedings of Euro PM2005 Congress, 2-5 Oct. 2005, Prague, vol. 2, 99-104
In volum: 21. I. Chicinaş, O. Isnard, V. Pop, J.M. Le Breton, O. Geoffroy, Nanocrystalline Ni3Fe and Supermaloy Powders Obtained
by Mechanical Alloying Techniques and their Applications, in New Trends in Advanced Materials, Ed. by N.M. Avram, V. Pop, R. Tetean, Editura Universităţii de Vest, Timişoara, 2005, ISBN 973-7608-41-0, 29-382. V. Pop, I. Chicinas, Hard and Soft Nanostructured Magnetic Materials Obtained by Mechanical Alloying/Milling, in
New Trends in Advanced Materials, Ed. by N.M. Avram, V. Pop, R. Tetean, Editura Universităţii de Vest, Timişoara, 2005, ISBN 973-7608-41-0, 144-151.
Prezentari orale – 6: ARM 2003 - Constanta, ANM 2003 – Iasi, ARM 2005 - Constanta, ISMANAM 2005 - Paris, RoPM2005 – Sinaia, PM2004 – Praga.
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Rezultate ale cercetarilor proprii in domeniul MA
• Obtinerea si studierea compusului intermetalic nanocristalin Ni3Fe prin MA si MAAC
• Introducerea in premiera a diagramei MAT (milling – annealing –transformation)
• Obtinerea si studierea in premiera a pulberilor nanocristaline de tipul Supermalloy prin MA si MAAC
• Obtinerea de nanocompozite magnetice hard/soft cuplate prin schimb de tipul SmCo5/Fe Slide-urile urmatoare
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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
.)
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I. Chicinas, V. Pop, O. Isnard, J.M. Le Breton and J. Juraszek, J. Alloys and Compounds 352 (2003), p. 34-40
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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, 23
Ni3Fe produced by MAAC
Inginerie si Nanostiinte, Bucuresti, 8 Decembrie 2005, 23
-
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.
Inginerie si Nanostiinte, Bucuresti, 8 Decembrie 2005, 24
-
ARM-4, Constanta, 5 September 2005, 25
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
Inginerie si Nanostiinte, Bucuresti, 8 Decembrie 2005, 25
-
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, 26Inginerie si Nanostiinte, Bucuresti, 8 Decembrie 2005, 26
-
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, 27Inginerie si Nanostiinte, Bucuresti, 8 Decembrie 2005, 27
-
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, 28Inginerie si Nanostiinte, Bucuresti, 8 Decembrie 2005, 28
-
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, 29Inginerie si Nanostiinte, Bucuresti, 8 Decembrie 2005, 29
-
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, 30
V. Pop, O. Isnard and I. Chicinas, J. Alloys and Comp., 361 (2003), p.144-152.
Inginerie si Nanostiinte, Bucuresti, 8 Decembrie 2005, 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 (°)In
tens
ity (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 (°)In
tens
ity (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 milling and annealing at 350 °C for 2 hoursin order to remove second order internal stresses
Supermalloy synthesis by MAAC:• 8 hours milling• different annealing conditions.
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.
Inginerie si Nanostiinte, Bucuresti, 8 Decembrie 2005, 31
-
ARM-4, Constanta, 5 September 2005, 32
O. Isnard, V. Pop, I. Chicinaş, J. Magn. Magn. Mater. 290-291 (2005) 1535
Y. Shen, H.H. Hng, J.T. Oh, J. Alloys Comp. 379 (2003) 266-271.
the mechanical alloying process occurs in two steps
an intermediate amorphous or poorlycrystallined phase, (Ni,Fe)–Mo type.
The high coercivity before 10 h of milling is attributed to strong pinning of domain walls of the interaction domains at the grain boundaries.
Inginerie si Nanostiinte, Bucuresti, 8 Decembrie 2005, 32
-
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, 33Inginerie si Nanostiinte, Bucuresti, 8 Decembrie 2005, 33
-
-100
-50
0
50
100
-3 -2 -1 0 1 2 3
SmCo5+20%Fe
2h MM4h MM6h MM8h MMSmCo
5/2h MM
M (e
mu/
g)
μ0H (T)
Room temperature hysteresis cycles recorded for the SmCo5 +20% Fe composite samples milled from 2 to 8 hours compared to that of the hard phase SmCo5 milled for 2 hours.
Room temperature hysteresis cycles recorded for the SmCo5 +20% Fe composite samples milled 8 hours and annealed compared to that of the hard phase SmCo5 milled for 2 hours
Inginerie si Nanostiinte, Bucuresti, 8 Decembrie 2005, 34
-100
-50
0
50
100
-2 -1.5 -1 -0.5 0 0.5 1 1.5 2
SmCo5 + 20Fe/8h MM
as milled
450oC 0.5h
500oC 1.5h
550oC 1.5h
600oC 0.5h
650oC 0.5hSmCo
5/2h MM
M (e
mu/
g)
H (T)
V. Pop, O. Isnard, I. Chicinas, D. Givord, J.M. Le Breton, J. Optoelectronics and Adv.Matter. (2006) acceptata
SmCo5/α-Fe NANOCOMPOSITE MATERIAL OBTAINED BY MECHANICAL MILLING AND ANNEALING
-
ARM-4, Constanta, 5 September 2005, 35
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
Inginerie si Nanostiinte, Bucuresti, 8 Decembrie 2005, 35
Cercetari pe plan mondial in domeniul nanomaterialelor produse prin mecanosintezaCercetari pe plan national in domeniul nanomaterialelor produse prin mecanosintezaGrupul nostru de cercetare in MA, �cu colaborare internationalaLucrari publicate in domeniul MA de catre grupul nostru Rezultate ale cercetarilor proprii in domeniul MAThe Ni, Fe and Mo maps on starting sample (0 hours milling) and on the 12 hours milled sample. It can observe the chemical hom