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Electroforming of TiB2 Reinforced Copper Matrix

Electrode for EDM
a a a a a
L. Li , X. T. Wei , G. M. Zheng , L. Y. Li & C. S. Dai
a
School of Mechanical Engineering, Shandong University of Technology, Zibo, China
Accepted author version posted online: 24 Jul 2015.

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To cite this article: L. Li, X. T. Wei, G. M. Zheng, L. Y. Li & C. S. Dai (2015): Electroforming of TiB2 Reinforced Copper Matrix
Electrode for EDM, Materials and Manufacturing Processes, DOI: 10.1080/10426914.2015.1070418

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 Electroforming of TiB2 reinforced copper matrix electrode for EDM

L. Li1, X. T. Wei1, G. M. Zheng1, L. Y. Li1, C. S. Dai1

1
School of Mechanical Engineering, Shandong University of Technology, Zibo, China

Corresponding author: E-mail: sdutlili@163.com; sdutwd@163.com

Abstract

TiB2 particles reinforced copper matrix composite is electroformed in copper sulfate on

stainless steel plate. The impact of the particle content in electroforming solution on the
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surface morphology, hardness and electrical conductivity of the electroformed composite

are studied, and the influence of electroforming current density on the effective content of

particles in the composite is also analyzed. The results show that when the content of

particles in electroforming solution is 25g/L, the current density is 4A/dm2, particles in

the electroformed composite are well-distributed, and the average grain diameter can be

reduced to 20μm. The microhardness of Cu/TiB2 composite reinforced by particles with

diameter of 3μm is 25% higher than that of electroformed copper, and its conductivity

remains 86% of the copper.

KEYWORDS: Electroforming, TiB2, Electrode, Composite

INTRODUCTION

Electrical discharge machining (EDM) is based on the electrical corrosion of a pulsed

spark discharge between the tool and the workpiece to corrode excess metal, so as to

achieve the predetermined machining requirements on the size, shape and surface quality

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 of the components (1, 2). It is suitable for machining of the materials with high hardness

and brittleness (3, 4). The property of electrode material is an important factors affecting

the quality of electrical discharge machining (5, 6). Red copper, with a good conductivity,

is a common material used as EDM electrode (7). While it has a low melting point; using

high current for processing will increase the electrode erosion loss, and thusly decreases

the machining precision of the workpiece. In order to reduce the electrode loss and

improve the hardness of copper electrode, we can change the forming method and tissue

components of material. Such as powder metallurgy method, self propagating synthesis,

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mechanical alloying and casting (8, 9). At present, most studies adopt the method of

mixing two or three kinds of powder for sintering molding to prepare EDM electrode to

improve the machining precision (10, 11). TiB2 ceramic particle, whose conductivity is

close the same excellent electrical conductivity as copper matrix (12, 13). Qiu adopted

the method of self-propagating high-temperature synthesis to prepare Cu/ TiB2, its

relative EDM erosion rate is far lower than that of the copper electrode (14). Because the

dispersion coefficient of TiB2 is very low and the thermal expansion shows anisotropy in

the sintering process, which make the densification process is restricted, the

electroforming method is based on dissolution of the anode and deposition of the cathode

in solution, it is a method which can replicate the cathode morphology accurately in room

temperature (15). Composite reinforced with well-distributed particles can be obtained

when particles is fully decentralized in the solution by stirring, avoiding the thermal

expansion of particles and the matrix material. Firstly this paper adopts orthogonal test to

optimize the electroforming parameters, then uses the best experimental scheme to

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 conduct single factor experiment and analyzes the impact of particle content on surface

morphology, hardness and electrical conductivity.

MATERIALS AND METHODS

Phosphorus copper plate with dimension of 60mm × 35mm ×10mm is used as the anode

and stainless steel plate is used as the cathode in the electroforming process. The stainless

steel plate is polished with sandpaper (600#~1500#), unoiled(Na3 PO4 70g/L、Na2CO3

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50g/L, NaOH 10g/L), pickled (5%HNO3) and inactivated (25% HNO3 ) before

electroforming. The basic electroforming solution is mainly composed of 200g/L copper

sulfate, 10g/L sulfuric acid, and 130mg/L sodium chloride. The electroforming stirring

speed is 60~100r/min and the current density is 2~8A/dm2 . TiB2 is chosen as the

reinforced phase for copper matrix composite, its thermal physical properties are shown

in Table 1. TiB2 with three different average particle diameters produced by Shandong

Telongji Ceramic Factory are chosen in this experiment.

Volume fraction is adopted to represent the content of TiB 2 particles in the composite

electroforming deposit. Firstly, take 2g electroformed composite and weigh out the exact

value of WC, then, dissolve Cu/ TiB2 composite with 20% dilute nitric acid solution and

filter the solution after it dissolves completely, separate TiB2 precipitates and dry off,

finally, weigh out the value of W P. The volume fraction is calculated with Formula (1):

W m
V (1)
p W( m p )

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 In Formula (1), m and p refer to the density of Cu (8.9 g/cm3) and the density of TiB2

(4.5g/cm3) respectively.

Scanning electron microscope (Sirion 200, FEI Company, Holland) is used to observe the

surface morphologies, and the sample is intercepted, grinded, polished and etched to

make metallographic sample whose microscopic structure is observed with microscope

(Axio Lab.A1, Zeiss Company, German). Copper phase and the second phase of particles

are analyzed by Axio Images software and the average grain diameter is measured with
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intersection point method. The microhardness is measured with microhardness meter

(FM800, Future Tech Company, Japan). Every sample is tested for 10 times with the

loading force of 50gf and loading time of 15 seconds and the average value is taken.

Electrical conductivity is measured using RTS-8 four-point probe meter produced by

Shanghai Electronic Instrument Company.

Orthogonal factors table L9(34) shown in Table 2 is used to analyze the influence of four

parameters of temperature, current density, particle diameter and the additive amount on

the surface roughness.

RESULTS AND DISCUSSIONS

According to results of analysis of variance, the influential degree sequences of four

factors on the surface roughness are particle diameter, current density, temperature, and

effective particle content. The optimum experimental parameters are the current density

of 4A/dm2, temperature of 30℃, the particle diameter of 3μm, and effective content in

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 the electroforming solution of 25 g/L. The minimum surface roughness Ra of the

composite gained in this condition is 1.859 μm.

The influence of current density on TiB2 particles in the electroformed composite is

shown in Figure 1, the particle diameter in the composite is 3μm and the effective content

is 25g/L.

The particle content in the electroformed composite increases with the increase in current
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density before the current density reaches to 4A/dm 2. According to the two step

adsorption mechanism, particles which have adsorbed copper ions move towards the

cathode under the function of electric field force. When the particles reach to the cathode,

strong adsorption is formed due to the enhanced electrostatic attraction, and the increase

in current density can enhance the over potential in the cathode and accelerate the strong

adsorbing process (10). In addition, the metal deposition rate increases linearly with the

increase of current density, so the speed of particles entering into the electroforming

deposit become faster, eventually, the content of particles buried in the electroforming

deposit increases with the increase of current density. When the current density increases

to 5A/dm2, TiB2 particles distribute uniformly on the surface, whose conductivity is

lower than that of the copper, decrease the area of the cathode, leading the actual current

density increase further and the electrodeposition rate surpasses the embedding rate of

TiB2, then resulting that there is insufficient contact time for particles to be wrapped by

copper ions, and even particles which do not deposit into the matrix are taken back to the

electroforming solution under the function of stirring. So when the current density

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 reaches to 5A/dm2 , the content of TiB2 particles in the electroformed composite declines.

The maximum content of TiB2 in Cu/TiB2 composite can reach to 14.3% at the condition

of current density of 4 A/dm2.

As shown in Figure 2, the electroforming current density is 4A/dm2. The more the

effective amount of particles in suspension in the electroforming solution, the larger the

chance that particles reach to the cathode surface is. Experimental results show that when

the effective particle content in the electroforming solution reaches to 25g/L, the
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maximum particle content in the electroforming deposit can reach to 14.3%, with the

continuous increase of the effective particle content in the electroforming solution, the

actual particle content in the electroforming deposit does not increase continuously,

instead, it stays at a stable value. This may be caused by the influence of many factors on

the electrodeposited coating, when the particle content in the electroforming solution

reaches to a certain value, an excess of particles will cover on the surface of the cathode,

which increase the concentration polarization. In addition, particles in the electroforming

solution strike the surface of the cathode due to the function of stirring, particles which

have deposited on the electroformed deposit are taken back to the electroforming

solution, thus, the deposition of particles decreases. Therefore, the suitable additive

amount of particles is 25g/L.

Figure 3 shows the distribution of particles (with additive amounts 15g/L and 25g/L

respectively) in the electroforming solution, black ones are TiB 2 particles whose

diameters are 3μm. TiB2 particles are basically well-distributed when the effective

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 concentration in the electroforming solution is 15g/L and 25g/L, and there is no large

agglomeration. Particles connect closely with the copper matrix without cracks and pores.

Compared with the situation where the particle content is 25g/L, there is less embedded

particles in the electroformed composite when the particle content is 15g/L, leading to the

significant decline in the reinforcement of particles. Considering the comprehensive

performance of the composite, the effective particle concentration in the electroforming

solution is 25g/L.
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Figure 4 shows the surface topographies of copper and Cu/TiB 2 composite reinforced by

TiB2 with diameter of 3μm. The current density is 4A/dm2 and the effective concentration

of particles is 25g/L. It can be seen from Fig. 4 (a) that there are many greatly different

cell-like substances on the surface of the copper deposition, and there are cracks on the

micro surface. Fig. 4 (b) shows that cell-like substances on the surface of the composite

which has been added TiB2 particles are relatively small and uniform, the surface is

smooth with good compactness. The reason is that TiB2 particles co-deposit with ions at

the cathode in the electroforming solution under the drive of stirring and disperse in the

copper matrix, producing dispersion force and reducing the interfacial tension of crystal

nucleus, thus the critical nucleation radius has been decreased and more crystal nucleuses

have been formed. In addition, metal copper ions can deposit directly with TiB2 particles

as the base point, which can hinder the growth of copper crystal grains effectively, so the

grains of Cu/TiB2 composite are fine and uniform without cracks, holes and other defects.

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 Figure 5 is the metallographic microscope of copper and Cu-TiB2 composite obtained

under the electroforming current density of 4A/dm2. The effective TiB2 content is 25g/L

and the average diameter of TiB2 is 3μm. The SEM of Cu/TiB2 composite clearly shows

that there is no crack on the bonding interface between TiB 2 particles and copper. The

average crystal grain diameter of electroformed composite is 20μm, while that of Cu is

50μm. The reason for the microstructure refinement is the increase in the cathode

overpotential. The electroforming current density determines the overpotential of metal

deposition, adding TiB2 particles increases the local current density in cathode and the
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overpotential also increases, which makes the nucleation rate of crystal grains greater

than their growth rate, leading to the refinement of crystal grains.

Figure 6 shows the Vickers hardness and the electrical resistivity of copper and Cu/TiB2

composite obtained under the electroforming current density of 4A/dm 2.

Copper matrix and TiB2 particles are different in their thermal conductivities, dislocation

and accumulation will occur around TiB2 particles, leading to an obvious increase in the

hardness of the composite. Results show that with the increase of TiB2 content, the

microhardness of composite increases, the hardness of Cu/TiB2 composite with 14.2%

TiB2 content is 18% higher than that of electroformed copper. According to the

explanation about the relationship between the hardness and crystal grains of composite

in Hall-petch principle, if the electroforming grains reinforce, the hardness of copper

matrix composite increase obviously. On one hand, it is because that the solid particles

have relatively high hardness and they are well-distributed on the copper grain

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 boundaries, on the other hand, it is because that TiB 2 particles are disperse, leading to the

refinement of grains and reducing the porosity.

The electrical resistivity increases with the increase of the effective TiB2 content in the

composite as shown in Fig. 6. Compared with the resistivity of electroformed copper,

when the content of TiB2 in the deposited composite reaches to the highest degree of

14.3%, the resistivity increases to 2.0μΩ·cm. The density of TiB2 is 4.52 g/cm3, which is

less than that of copper (8.9 g/cm3), when its volume fraction is large in copper matrix, it
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is not conducive to the formation of three-dimensional network structure of copper

matrix, leading to the increase in the conductivity of composite. The electrodeposition

process realizes the co-deposition of copper ions and particles, which avoids the serious

separation between the second phase and the matrix. The band theory of solid believes

that, in the ideal crystal, crystal lattice is arrayed periodically; conduction electrons can

move freely in the crystal, when the periodicity of the crystal lattice is destroyed, lattice

distortion will occur, the crystal lattice destroyed becomes the scattering source of

conduction electrons, thus the resistance of electron movement generates. When TiB2

particles participate in the co-deposition, with the increase of particle content in the

electroforming deposit, the lattice distortion of the matrix metal increases, at the same

time, the co-deposition of TiB2 particles causes the grain refinement of matrix metal, all

of these have increased the resistivity of the electroformed composite. Compared with the

pure copper, when the TiB2 content reaches to 14.3%, the conductivity of the

electroformed composite is about 86% of that for elementary copper, which is still higher

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 than that of most metals and various copper alloys, this further proves the good

combination between particles and matrix metal.

CONCLUSIONS

 The content of TiB2 particles deposited in the composite can reach to 14.3% under

the current density of 4 A/dm2 and the effective TiB2 content of 25g/L in the

electroforming solution.

 The surface of Cu/TiB2 composite is fine and dense. The minimum average grain
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diameter can decrease to 20μm, which is 60% lower than that of electroformed copper.

 Compared with the hardness of elementary copper, that of Cu/TiB 2 composite has

increased by 18%.

 The conductivity of reinforced copper matrix composite with a TiB 2 particle

content of 14.3% is 86% of that for elementary copper, and the composite still maintain a

good conductivity.

ACKNOWLEDGEMENT

The authors would like to thank the National Natural Science Foundation of China

(#51105235) and the Taishan Scholar Program for support the research.

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 Table 1. Thermo physical properties of TiB 2

melting density thermal conductivity electrical thermal expansion micro

point (g/cm3) (W/m·K) resistivity coefficient hardness

(℃ ) (Ω·m) (m/m·K) (GPa)

2980 4.52 25 14.4 10-8 14.4 10-8 34

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 Table 2. Factors and level

Level factors

diameter of temperatu current addition of

TiB2 re density TiB2

(µm) (℃) (A/dm2) (g/L)

1 3 30 3 15

2 7 40 4 25
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3 10 50 5 35

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 Figure 1. Influence of current density on TiB2 content.
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 Figure 2. Influence of addition amount of TiB2 particles in Cu/TiB2 composite.
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 Figure 3. SEM images of TiB2 particles distribution in Cu-TiB2 compositions.
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 Figure 4. SEM images of the surfaces of (a) copper and (b) Cu/TiB 2 composities.
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 Figure 5. SEM images of the surfaces of (a) copper and (b) Cu/TiB 2 composities.
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 Figure 6. Microhardness and electrical resistivity of composite with different TiB 2

content.
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