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J. Mater. Sci. Technol., 2010, 26(5), 429-432.

Direct Electrodeposition of Cu-Ni-W Alloys for the Liners for Shaped Charges
Hanwei He and Shouya Jia
State Key Lab of Powder Metallurgy, Central South University, Changsha 410083, China
[Manuscript received March 20, 2009, in revised form June 21, 2009]

The Cu-Ni-W alloys for the liners for shaped charges were successfully prepared by direct current (DC) electrodeposition. The inuence of cathode current density on morphology, microstructure and composition of the Cu-Ni-W alloys was investigated by means of scanning electron microscopy (SEM), X-ray diraction (XRD) and energy dispersive spectrometry (EDS). With the increasing of current density, the copper content reduces gradually and the nickel and tungsten content increase; the crystallite size is decreased. When the current density is 15 A/dm2 the tungsten content reaches 12.96 wt pct, and the crystallite size is submicron degree. The Cu-Ni-W alloy is face-centered cubic (fcc) solid solution. All of the Cu-Ni-W alloys take on (220) texture. KEY WORDS: Electrodeposition; Cu-Ni-W alloy; Cathode current density

1. Introduction The shaped charges are widely applied in the modern ammunition and certain industries, e.g. oil, mining, geology, etc. In many applications it is desirable for the jet to penetrate the target material to a depth as great as possible. A still further method for maximizing penetration depth is to change the liner material used for the shaped charge liner. In the past the liners for shaped charges have typically been composed primarily of wrought copper[1] , but it is known that other materials exhibit benets in certain applications. Because of its high density, high sound velocity and high ductility[2] , the tungsten will be a type of shaped charge liner materials. It has been suggested in U.S. Patent[3] that if the grain size of a high percentage tungsten liner is less than 1 micron the jet so produced has properties at least comparable to that derived from a depleted Uranium (DU) liner. Tungsten is therefore one of the few readily available materials that may provide a serious alternative to DU. Usually liners for shaped charges have been formed
Corresponding author. Prof., Ph.D.; Tel.: +86 731 8836264/8836311; Fax: +86 731 8710855; E-mail address: hehanwei@163.com (H.W. He).

from various materials by forming the materials into powders and then pressing the powdered materials into the desired liner shape[46] . Liners comprising compressed powdered materials are very fragile and therefore tend to disintegrate into very small pieces when the shaped charge assembly is actuated. However, liners formed from pressed powdered materials, either sintered or unsintered, tend to be either porous or hydroscopic, or both, and therefore do not provide adequate protection for the explosive material comprising the shaped charge. However, these methods do not allow fabricating of the liners with required dimensional accuracy. Electroforming (electrodeposition) technique is of great interest for industrial usage. It is a straightforward process for the shaped charges with low cost and easy control. The electroforming technique has been used for fabricating copper and nickel liners of shaped charges[79] . Fan et al.[10] regarded that the grain size of electroformed copper liners of shaped charges was ner than that of the spin-formed copper liners of shaped charges. Investigation by Fan et al.[11] indicate that by controlling the parameters of electroforming technology, e.g. the current density, the value of pH, the rotation velocity of the substrate, etc, it makes the materials possible to have character-

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H.W. He et al.: J. Mater. Sci. Technol., 2010, 26(5), 429432

istic microstructures, controlled grain size and shape, ultra-ne and homogenous grain and controlled grain orientation of growth direction. The electrodeposition of pure tungsten from aqueous solutions has been unsuccessful, and it can be codeposited with an iron group metal. The induced codeposition of tungsten with nickel has been investigated[1214] . Ni-Cu is a regular system[15,16] . So far no literature data are available for this Cu-NiW alloy system by direct current (DC) electrodeposition. The aim of this study was to prepare the CuNi-W alloy for the liners for shaped charges by direct current (DC) electrodeposition. The eect of cathode current density on morphology, texture, structure and content of these alloys was investigated. 2. Experimental The alloys were plated onto copper sheet serving as cathodes with a dimension of 20 mm20 mm1 mm. Platinum sheets were used as anodes. Pretreatment of the working surface before plating process included degreasing in organic solvent, water rinsing, acid pickling and chemical polishing in acid solution. Electrodeposition of CuNi-W alloys were plated from a bath containing nickel sulphate (NiSO4 7H2 O) 0.05 mol/L, sodium tungstate (Na2 WO4 2H2 O) 0.15 mol/L, copper sulphate (CuSO4 5H2 O) 0.005 mol/L, sodium citrate (Na3 C6 H5 O7 2H2 O) 0.2 mol/L and organic additives such as saccharin (SAC), all reagents of analytical grade. All solutions were freshly prepared with puried water. The bath was maintained at pH 6.5+0.1 adjusted by 0.1 mol H2 SO4 , temperature 55+1 C and current density ranging from 5 to 15 A/dm2 , and the plating time was 30 min during which the bath was agitated. The contents of Cu, Ni and W of the electrodeposits were analyzed via an KYKY-2800LV Energy Dispersive Spectrometer (EDS). The structural characterization was performed by using an X-ray diraction spectrometer (D/AX 2550, Japan). The morphology of the surface of the alloys was observed via a scanning electron microscope (SEM, KYKY-2800LV). 3. Results and Discussion Figure 1 shows the mass contents of Cu, Ni and W of alloy electrodeposited on the various cathode current densities. As can be seen, the nickel weight percent (Ni%) in the deposits increases signicantly as cathode current density increases. This observation indicates that the Cu content is more than the Ni content in the alloy at low current densities and the alloy consists of Cu, Ni and W at moderate current densities and the Ni Content is more than the Cu content conversely at high current densities. The dependence of the composition of the Cu-Ni alloy on the applied potential has also been reported earlier by

80
Cu Ni W

70

Cu,Ni,W content / wt pct

60

50

40

30

20

10

0 4 6 8 10 12
2

14

16

Current density / (A/dm )

Fig. 1 Relationship between cathode current density and the Cu, Ni and W content of the electrodeposits

Bennett et al.[16] . They have conrmed that, at low applied potentials, the more noble copper is deposited easily, but when the potential is set at a value corresponding to nickel, both metals will be deposited at rates limited by their relative concentrations, resulting in a structure of unalloyed copper alternating with nickel having low copper content. Tungsten cannot be produced by electrodeposition lonely from aqueous solutions, unless in conjunction with deposition of nickel. So the W content of the electrodeposits increases slightly as the content of Ni increases. Figure 2 shows SEM micrographs of the Cu-NiW alloy electrodeposited on various cathode current densities. The deposition is uniform throughout and exhibits a cauliower-like appearance at low current densities, a pyramid-like appearance at moderate current densities, and a ridge-like appearance at high current densities. The decrease in grain size with increase in current density is clearly evident. According to the Butler-Volmer equation, overpotential increases as cathode current density increases, accordingly, can promote the nucleation rate. When the nucleation rate exceeds the growth rate of crystal, the grains of coatings become ne. Figure 3 illustrates the XRD patterns of the CuNi-W alloy electrodeposited on various cathode current density . All the composite coatings exhibit single phase of Cu matrix with face-centered cubic (fcc) crystal structure (PDF number:04-0836) and peaks corresponding to Ni phase is not found in the spectra indicating that crystal lattice in Cu matrix perhaps has been replaced by Ni and W partly and formed solid solution. A shift is observed in the diraction angle towards lower angles as the nickel and tungsten content of the alloy is increased. To substantiate this, the lattice constant (a) of the Cu-Ni-W alloy lms is determined using the fcc Cu-Ni diraction angle and the Bragg s equation[17] . The lattice constant (a) of all the Cu-Ni-W alloys is larger than the lattice constant (a0 ) of the pure Cu. The atomic radius of W (0.202 nm) and Ni (0.162 nm) is larger than that of

H.W. He et al.: J. Mater. Sci. Technol., 2010, 26(5), 429432

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Fig. 2 SEM micrographs of Cu-Ni-W alloys the electrodeposited in dierent current density: (a) 5 A/dm2 , (b) 7.5 A/dm2 , (c) 10 A/dm2 , (d) 12.5 A/dm2

(111)

d=15 A/dm

(2

00)

(22 ) (311)

2.5 (a )

Texture coefficient (X random)

(b) 2.0 (c) (d ) (e )

d=12.5 A/dm
Intensity / a.u.

1.5

d=10 A/dm

1.0

d=7.5 A/dm

0.5

d=5 A/dm 30

0.0

40

50
2

60

70

80

90

(111)

(200)

(220)

(311)

/ deg.

Plane

Fig. 3 XRD patterns of Cu-Ni-W alloys electrodeposited at dierent current density

Fig. 4 Texture coecients for Cu-Ni-W alloys in dierent current density: (a) 5 A/dm2 , (b) 7.5 A/dm2 , (c) 10 A/dm2 , (d) 12.5 A/dm2 , (e) 15 A/dm2

Cu (0.128 nm)[18] , which cannot enter into the Cu crystal lattice space. Only a Cu-Ni-W solid solution alloy can be produced, which do not change crystal lattice type, but can change the lattice constant. If atomic radius of the solute atom (W, Ni) is larger than the solvent atom (Cu), the lattice constant of solid solution increases. The average grain size of the Cu-Ni-W alloy calculated using Scherrer formula was in the range of 0.2 to 1 m; the higher the current density, the lower is the crystallite size, in accordance with Fig. 2. When the current density is 12.5 A/dm2 , the average grain size is only 0.2 m. Figure 4 shows texture coecients for the Cu-Ni-

W alloys. The texture coecients, T Chkl are calculated from X-ray patterns using Eq. (1): T Chkl =
1 n

I(hkl) /I0(hkl) [I(hkl) /I0(hkl) ]

(1)

In this equation I(hkl) is the integrated peak intensity of (hkl) plane obtained from X-ray patterns. I0(hkl) is the corresponding integrated peak intensity of (hkl) plane in Cu powder as a polycrystalline texture free sample. n is the number of Cu peaks in X-ray diffraction which is 4. As seen all of the Cu-Ni-W alloys take on (220) texture, the texture coecients change slightly upon cathode current density.

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H.W. He et al.: J. Mater. Sci. Technol., 2010, 26(5), 429432

The direct deposition technique is used to prepare the Cu-Ni-W alloys. The surface appearance of the Cu-Ni-W alloy is uniform and compact, showing a nickel metallic luster. The grain sizes of the Cu-Ni-W alloy are submicron degree observed by scanning electron microscopy. The Cu-Ni-W alloy is face-centered cubic (fcc) solid solution as proven by X-ray diraction. The nickel weight percent (Ni%) in the deposits increases signicantly as cathode current density increases; the W content of the electrodeposits increases slightly.
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