Materiale nanocristaline obtinute prin mecanosinteza · Comparatie intre solubilitatea de echilibru si solubilitatea extinsa prin MA a diferitelor elemente in Cu C. Suryanarayana,

Inginerie si Nanostiinte, Bucuresti, 8 Decembrie 2005, 1

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

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


ARM-4, Constanta, 5 September 2005, 3

D1

D2

D1

B1

B1

B2

C1

C2

C3


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


A BA Bn m

Ener

gia

libeă

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


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.



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.)



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


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


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)


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

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)


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)


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


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


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


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.


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


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, 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



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)/M0 (%

)


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




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.



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.


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


-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


-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


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


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