effect of hsmf on electrodeposited ni-fe membrane-- crystal morphology and magnetism performance...
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Effect of HSMF on Electrodeposited Ni-Fe Membrane-- Crystal Morphology and
Magnetism Performance
Yunbo Zhong, Yanling Wen, Zhongming Ren, Kang Deng, Kuangdi Xu
Shanghai Key Laboratory of Modern Metallurgy & Material Processing, Shanghai University
2nd Sino-German Workshop on EPM, October, 16-19, 2005, Dresden, Germany
Outline Motivation; Experimental Apparatus; Results and Discussion; Conclusion and Outlook; Acknowledgement;
Influence on electron transfer kinetics ?
Influence on mass transportMHD effect
Influence on Surface Diffusion 、 Necleation 、Crystal Growth?
1.MotivationElectro-Crystallization in HSMF
H2OMe2+
MetalMembrane
E0
ChargeTransfer
SurfaceDiffusionNucleation
CrystalGrowth
Bulk Solution
BoundaryLayer
2
02BUM
2
02BU Ls
M
Variation of Free Energy in the process of Electro-deposition of NiFe membrane
The χ data is very lacking, and the magnetism of ions in solution are not very clear
Ni2+ : Paramagnetism ;
Fe2+ : Diamagnetism;
Ni atom: Paramagnetism;
Fe atom: Paramagnetism;
Ni Crystal: Ferromagnetism;
Fe Crystal: Ferromagnetism;
PID TemperatureController
B
I
B I⊥
B
I
B//I
Magnetic Field Center
Nitrogen
Thermocouple
Water-cooling Pipe
Supercon-ductive Coil
HeaterElectrolyte
Heat Insulator
Quartz Pipe
Electrode
B
+ -
Fix Block
2.Experimental Equipment
Nickel Plate
Copper Foil
0
1
2
3
4
5
6
7
8
9
10
11
-20 -15 -10 -5 0 5 10 15 20
Distance to Magnetic Field Center, z /cm
MFD
, B/T
- 500
- 400
- 300
- 200
- 100
0
100
200
300
400
500
- 20 - 15 - 10 - 5 0 5 10 15 20
Di stance to Magneti c Fi el d Center, Z/ cm
BdB/
dz,T2/m
Distribution of MFD in High Static Magnetic Field
Homogeneous MF Upper Gradient MF
Lower Gradient MF
Effect of HSMF on electrodeposited Ni-Fe membrane When I⊥B
B
IMagnetic Field
Center
Ni2+: 1.2mol/l;
Fe2+: 0.07mol/l
pH=3.5;
J=4.0A/dm2
3.Results and Discussion
Surface SEM pictures of NiFe membrane electrodeposited in various magnetic fields(J=4A/dm2)
0T 4T 6T
8T 10T 12T
Across-section SEM pictures of NiFe membrane electrodeposited in various magnetic fields(J=4A/dm2)
( -electrodeposit growth direction )
0T 4T 6T
8T 12T10T
B
XRD patterns of the NiFe membranes
electrodeposited in different magnetic flux density
Intensity ratio of three main peaks: I(111):I(200):I
(220)=
( 0T)100:54.3:4.3; (04T)100:24.7:6.2; (06T)100:26.9:6.4; (08T)100:28.8:7.1; (10T)100:28.2:8.4; (12T)100:19.1:6.6
(111)
(200)
(220)
(111)
(200)(220)
M - Crystal orientation coefficient ;I(hkl) - Measured value of the (hkl) plane diffraction peaks ;I0(hkl) - Standard value of the (hkl) plane diffraction
peaks in PDF card ;
Crystal Orientation Discussion
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
0 2 4 6 8 10 12 14
Magnetic Flux Density/T
Ori
enta
tion
Coe
ffic
ient
(111)
(200)
(220)
Effect of MFD on Crystal Orientation Coefficient
EDS analysis of the samples electrodeposited in different magnetic fields
(Fe wt%= 0T-12.71%; 6T-14.99%; 10T-23.32%; 12T-26.10%.)
0T 6T
10T 12T
The relation between saturation magnetization
of the samples and preparation magnetic flux density
40
50
60
70
80
90
100
110
120
0 2 4 6 8 10 12 14
B/T
Ms/
emu/
g
Effect of magnetic field on electrodeposited Ni-Fe membrane
When B//I
B
I
B//I
Magnetic Field Center
SEM pictures of the surface of NiFe membrane
electrodeposited in parallel magnetic fields(J=4A/dm2)
0T 4T 6T
8T 10T 12T
6T0T
SEM pictures of the across-section of NiFe membrane electrodeposited in parallel magnetic fields (J=4A/dm2)
10T 12T
4T
8T
BJ
XRD patterns of the NiFe membranes
electrodeposited in different static magnetic fields
(Strength ratio of three main peaks : I(111):I(200):I(220)= (0T)100:41.1:4.5; (6T)100:25.8:6.6; (10T)100:27.2:7.6; (12T)100:26.1:7.4)
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
0 2 4 6 8 10 12 14
Magnetic Flux Density/T
Orie
ntat
ion
Coe
ffic
ient (111)
(200)
(220)
Analysis of crystal orientation coefficient of the samples
EDS analysis of the samples
electrodeposited in different magnetic fields
(Fe wt%= 0T-14.13%; 6T-14.12%; 10T-15.17%; 12T-14.47%.)
0T 6T
10T 12T
The relation between saturation magnetization intensity
of the samples and preparation magnetic field
Effect of magnetic field on electrodeposited Ni-Fe membrane When
B//I Without Bubble Agitation and at Room Temperature
B
I
B//I
Magnetic Field Center
0T
10T
Electro-depostion of NiFe Membrane in Gradient Magnetic Field (B//I)
+400T2/m 0 -400T2/m
J=0.3A/cm2
Room Temperature, No Agitation
Magnetic Field Gradient
Element Wt % At%
+400T2/mFeK 38.37 39.56
NiK 61.63 60.44
0T2/mFeK 22.84 23.73
NiK 77.16 76.27
+400T2/mFeK 29.39 30.44
NiK 70.61 69.56
(a) 0T (b) B1(B1≠0T) B2(B2≥10T)
Hydration Ions Metal atom
Metal Crystal
Sphere Crystal nucleus
FL
IBFE
Outer Helmholtz area
Bulk solution
Trajectory of Ions
Boundary LayerTrajectory of Ions
Sketch Map of Nucleation and Crystal Growth when B⊥I
In Homogeneous Magnetic Field
Discussion
Initial velocity (v0)
BubbleDirection of electric field (I)
Direction of magnetic field (B)
Cathode
Anode
Sketch Map of Nucleation and and Crystal Growth when B//I
In Homogeneous Magnetic Field
Magnetic field
Migration of atoms in Horizontal direction
B
I
B//I
B
J
Sketch Map of Nucleation and and Crystal Growth when B//I and in Gradient Magnetic Field
Room Temperature, No Agitation
Interpret for the Composition-Change of Electrodeposited Ni-Fe Membrane in HSMF
B
I
B//I
BdB/dzFe2+ Rich
Fe2+ Rich
Stable area
B
I
I
B J⊥
Agitation
Homo. MF
B//J
Agitation
Homo. MF
B//J
No Agitation
Gradient MF
z
4.Elementary Conclusions
In HSMF, Strengthened MHD effect can influence the crystal morphology of electrodeposited NiFe membrane remarkably, so do the mass transfer process;
Both perpendicular and parallel magnetic field can make the crystal (111) plane orientation reinforced;
The ion concentration in electrolyte would be changed due to different magnetism property of ions in gradient HSMF, which would effect the composition of deposit;
The superimposition of HSMF would affect the nucleation of electro-crystallization process;
The saturation magnetization of Ni-Fe membrane was determined mainly by the concentration of iron.
Outlook
There are a lot of questions need to be made clear: Will HSMF change the electron transfer process? Simulation on the nucleation of crystal when electro-
deposition in HSMF; The magnetic susceptibility (x) Value of ions in electrolyte; Can we control the structure even the property of membrane? …………To answer those questions, maybe we can collaboration with
Germany Part and Chinese Part!
5.Acknowledgement
This work was financial supported by Shanghai Scientific & Technological Committee (Key Project No. 03JC14029);
Thankful to Sino-German Center for Research Promotion to Support this Workshop;
Thankful to Dr. Gerbeth for well organization!
Thank you
for your attentions!
Effect of magnetic field on electrodeposited Ni-Fe membrane
When I⊥B
B
IMagnetic Field
Center
Ni2+: 1.2mol/l;
Fe2+: 0.07mol/l
pH=3.5;
J=4.0A/dm2
SEM pictures of the surface of NiFe membrane electrodeposited without magnetic field
(J= a-1A/dm2; b-2A/dm2; c-3A/dm2; d-4A/dm2; e-6A/dm2)
a b c
d e
a b c
d e
FSEM pictures of the across-section of NiFe membrane
electrodeposited without magnetic field
(J= a-1A/dm2; b-2A/dm2; c-4A/dm2; d-5A/dm2; e-6A/dm2)
Fig.17-a SEM pictures of the surface of NiFe membrane
electrodeposited in 10T static magnetic field
(J= a-1A/dm2; b-2A/dm2; c-3A/dm2; d-4A/dm2; e-5A/dm2; f-6A/dm2)
a b c
d e f
a b
c d
SEM pictures of the across-section of NiFe membrane
electrodeposited in 10T static magnetic field
(J= a-2A/dm2; b-3A/dm2; c-4A/dm2; d-6A/dm2)