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Additive Effects on Tin Electrodepositing in Acid Sulfate Electrolytes2
Additive Effects on Tin Electrodepositing in Acid Sulfate Electrolytes2
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Abstract: Cyanide-free silver electroplating was conducted in thiosulfate baths containing AgNO3 and AgBr major salts, respectively.
The effects of major salt content and current density on surface quality, deposition rate and microhardness of Ag coatings were
investigated. The optimized electroplating parameters were established. The adhesion strength of Ag coating on Cu substrate was
evaluated and the grain size of Ag coating was measured under optimized electroplating parameters. The optimized AgNO3 content is
40 g/L with current density of 0.25 A/dm2. The deposited bright, smooth, and well adhered Ag coating had nanocrystalline grains
with mean size of 35 nm. The optimized AgBr content was 30 g/L with current density of 0.20 A/dm2. The resultant Ag coating had
nanocrystalline grains with mean size of 55 nm. Compared with the bath containing AgBr main salt, the bath containing AgNO3 main
salt had a wider current density range, and corresponding Ag coating had a higher microhardness and a smaller grain size.
Key words: cyanide-free silver electroplating; thiosulfate; current density; bonding strength; grain size
Foundation item: Project (50771042) supported by the National Natural Science Foundation of China; Projects (104100510005; 2009HASTIT023)
supported by the Program for Science and Technology Innovation Talents of Henan Province, China
Corresponding author: Feng-zhang REN; Tel: +86-379-64229405; E-mail: renfz@mail.haust.edu.cn
DOI: 10.1016/S1003-6326(13)62935-0
Feng-zhang REN, et al/Trans. Nonferrous Met. Soc. China 23(2013) 3822í3828 3823
silver electroplating solutions containing uracil, but the electroplating time, and impurities are carried into the
silver plating bath was relatively complex. In 2011, bath by the cathode. Bath composition needs to be
FISHELSON et al [12] prepared silver films from near to checked and adjusted, and impurities need to be removed.
neutral non-cyanide solution. Mirror-quality bright and In this test, when the accumulative electroplating time
white Ag coatings were obtained from proprietary Ag lasted for 20 h, composition check and adjustment were
plating bath. However, they did not mention coatings carried out. It is suitable for keeping the mass ratio of
adhesion strength [9,10,12]. AgNO3:K2S2O5:Na2S2O3 at about 1:1:5. AgNO3 and
Unfortunately, silver deposits obtained using these K2S2O5 should be added at the same time at ratio of 1:1.
non-cyanide electrolytes were of a lesser quality than AgNO3 should not be added in Na2S2O3 solution directly
those obtained with traditional cyanide electrolytes [13]. to avoid precipitation of black Ag2S. Solution pH value
To our knowledge, there is no commercially available of about 5.8 was maintained by adding acetic acid.
non-cyanide silver plating process that meets all desired 2.2.2 AgBr solution system
requirements regarding the solution and the silver deposit Sodium hyposulfite (Na2S2O3) was dissolved in
quality. Thus, cyanide-free silver electroplating needs to distilled water to two thirds of the bath volume. Sodium
be further studied and improved for wider industrial use. sulfite (Na2SO3), ammonium acetate (CH3COONH4),
To further explore the cyanide-free silver plating silver bromide (AgBr) and aminothiourea (CH5N3S)
and optimize the silver plating solution in present work, were sequentially dissolved in the same solution. Finally,
the cyanide-free silver electroplating was conducted in distilled water was added to the solution to top up the
thiosulfate baths containing AgNO3 or AgBr main salts. bath, and the solution pH value was adjusted to about 6.5
The effects of major salt content and current density on by adding acetic acid. The bath also had to be filtered
surface quality, deposition rate and microhardness of Ag periodically (accumulative electroplating time of 20 h) in
coatings were investigated. Electroplating parameters order to remove the impurities carried in by the cathode.
were optimized. The adhesion strength of Ag coating on
Cu substrate was evaluated and the grain size of Ag 2.3 Electroplating process
coating was measured under the optimal process The anode was 99.9% (mass fraction) pure silver
conditions. plate and the cathode was a pre-treated copper sheet.
Electroplating process parameters of AgNO3 and AgBr
2 Experimental
solution systems are listed in Table 1. Coating thickness
2.1 Cathode substrate pre-treatment was controlled by electroplating duration at different
Copper sheets with purity of 99.97%í99.99% (mass current densities.
fraction) and size of 35 mm×25 mm×1.5 mm were used
as cathode substrates. The substrates were mechanically Table 1 Electroplating process parameters of AgNO3 and AgBr
polished, washed from oil in hot aqueous alkali and electroplating solution systems
acetone, and placed into 10% (volume fraction) Parameter AgNO3 system AgBr system
hydrochloric acid solution for 8í10 s for surface ȡ(AgNO3)/(g·Lí1) 30í50 í
í1
activation. The samples were then placed in the galvanic ȡ(AgBr)/(g·L ) í 20í40
bath for electroplating. ȡ(Na2S2O3)/(g·Lí1) 225 200
í1
ȡ(K2S2O5)/(g·L ) 40 í
2.2 Bath preparation and maintenance
ȡ(Na2SO3)/(g·Lí1) í 50
2.2.1 AgNO3 solution system
ȡ(CH3COONH4)/(g·Lí1) 25 40
Sodium hyposulfite (Na2S2O3) was dissolved in
ȡ(CH5N3S)/(g·Lí1) 0.6í0.8 0.2í0.5
distilled water to a third of the bath volume. Silver nitrate
(AgNO3) and potassium metabisulfite (K2S2O5) were pH value 5.5í6.0 6.3í6.8
dissolved in distilled water to a quarter of the bath Current density/(A·dmí2) 0.1í0.3 0.1í0.3
volume, respectively. K2S2O5 solution was poured into
AgNO3 stirred solution to form potassium metabisulfite 2.4 Post-treatment for anti-tarnishing
(Ag2S2O5) turbid solution. The turbid solution was In order to avoid discoloration of the silver coating
slowly added to Na2S2O3 solution to turn it into in air, the following treatments were carried out. Silver
yellowish clear liquid. Appropriate amount of plated part was in turn immersed in concentrated
ammonium acetate (CH3COONH4) was added to the hydrochloric acid (35%í38%) for 30 min, in 60 g/L
solution and left for a short time. Aminothiourea Cr2O3 and 16 g/L NaCl water solution for 8í10 s, in 200
(CH5N3S) was then completely dissolved in the solution. g/L Na2S2O3 water solution for 3í5 s, in 100 g/L NaOH
Finally, distilled water was added to top up the bath. water solution for 5í8 s, and in concentrated
Bath composition changes due to long hydrochloric acid for 10í15 s. Whenever plated part was
3824 Feng-zhang REN, et al/Trans. Nonferrous Met. Soc. China 23(2013) 3822í3828
taken out from a solution, it was immediately washed Ni coatings grains size was measured by means of X-ray
with water. diffraction and metallography with good matching. The
phases and texture of the Ag coatings were analyzed, and
2.5 Coating characterization and microstructure the grain sizes were measured using a BRUKER D8
observations X-ray diffractometer. A Cu target was used with
2.5.1 Microstructure observation and deposition rate corresponding X-ray wave length of 0.154056 nm.
measurement Texture coefficient (C) of a crystalline plane
Surface morphology observation and deposition rate characterizes the degree of the crystal plane preferred
measurements at different current densities of silver orientation. For (hkl) crystal plane, C(hkl) can be written
coating were carried out using scanning electron as [16]
microscopy (SEM, JSMí5610LV). The deposition rate is I ( hkl ) I 0( hkl )
the ratio of the coating thickness and the corresponding C( hkl ) u 100% (1)
n
deposition time. Because of the edge effect, the deposit ¦ I (h k l )
i i i
I 0( hi k i li )
i 1
roughness and the deposition rate at the substrate edges
are larger than those in the centers, thus the surface where I(hkl) and I0(hkl) are the diffraction intensities of (hkl)
morphology observations and the deposition rate crystal plane of the deposited sample and the standard
measurements were performed in the middle of the powder sample, respectively; n is the number of
specimen surface. crystalline planes with relatively high diffraction
2.5.2 Hardness measurements intensity. If C value of every crystalline plane is the same,
The coating hardness was measured using a preferred orientation is not present.
microhardness tester. The load and hold time were 0.49
N and 15 s, respectively. The mean value of hardness 3 Results and discussion
measured from seven micro-areas per sample was taken.
Finite element analysis revealed that the hardness value 3.1 Effect of main salt on silver coating surface
for a thin metal film was not influenced by the substrate
quality
when the indentation depth was smaller than one tenth of
With current densities of 0.25 and 0.20 A/dm2 for
the film thickness [14]. To obtain coating hardness not
AgNO3 and AgBr solution systems, respectively, the
influenced by the substrate, the indentation depth was
effects of main salt contents on surface quality of silver
kept 10 times less than the coating thickness.
coating are listed in Table 2. As shown in Table 2, when
2.5.3 Adhesion strength evaluation
the main salt contents are 40 g/L and 45 g/L for AgNO3
Two methods outlined in the QB/T 3821–1999
Light Industry Standard of the People's Republic of and 30 g/L and 35 g/L for AgBr, respectively, the silver
China were used to evaluate the coating adhesion coatings are bright. Considering surface quality and bath
strength. One method included drawing a 1 mm side cost, 40 g/L AgNO3 for AgNO3 solution system and 30
square on the coating surface using a knife. Whether the g/L AgBr for AgBr solution system should be adopted in
coating flaked off the substrate was used to distinguish the following tests.
between good and bad adhesion. The other method
consisted of bending the sample repeatedly until it broke, Table 2 Effects of main salt content on surface quality of silver
and whether the coating flaked off or crackled was used coating
to characterize the coating adhesion strength. AgNO3 system Surface AgBr system, Surface
2.5.4 Grain size and texture analysis ȡ(AgNO3)/(g·Lí1) quality ȡ(AgBr)/(g·Lí1) quality
The crystallites size perpendicular to the (hkl) 30 Yellow 20 Yellow
crystalline plane can be calculated using the Scherrer 35 Semi-bright 25 Semi-bright
equation D(hkl)=kȜ(ȕcosș)í1. In the equation, k is the 40 Bright 30 Bright
Scherrer constant (k=0.89); D(hkl) is the crystallites size
45 Bright 35 Bright
perpendicular to the crystalline plane (nm); ȕ is the full
Rough, Rough,
width at half maximum of the strongest diffraction 50 40
nigrescent nigrescent
reflection of the (hkl) crystalline plane (rad); ș is the
diffraction angle of the strongest diffraction reflection of
the (hkl) crystalline plane (°); Ȝ is the length of X-ray 3.2 Effect of current density on silver coating surface
wave (nm). quality
Typically electroplated metal coatings are The surface quality of coatings prepared at different
nanocrystalline, so grain size can be measured using the current densities is shown in Table 3. The surface
X-ray diffraction method. In Ref. [15], the electroplated morphologies of coatings prepared at different current
Feng-zhang REN, et al/Trans. Nonferrous Met. Soc. China 23(2013) 3822í3828 3825
densities for two solution systems are shown in Figs. 1 Table 3 Surface quality of coatings prepared at different current
and 2, respectively. In Fig. 1, the surfaces of coatings are densities
flat at different current densities. The surface is slightly Current density/(A·dmí2) AgNO3 system AgBr system
rough at the maximum current density of 0.3 A/dm2 0.10 Yellow Yellow
compared to other current densities. In Fig. 2, the 0.15 Semi-bright Semi-bright
surfaces of coatings are flat at moderate current densities. 0.20 Semi-bright Bright
The surfaces are uneven at the minimum and maximum 0.25 Bright Semi-bright
current density. 0.30 Rough, nigrescent Rough, nigrescent
Fig. 1 Surface morphologies of silver coating prepared at different current densities for AgNO3 solution system: (a) 0.10 A/dm2;
(b) 0.20 A/dmí2; (c) 0.25 A/dmí2; (d) 0.30 A/dmí2
Fig. 2 Surface morphologies of silver coating prepared at different current densities for AgBr solution system: (a) 0.10 A/dm2;
(b) 0.15 A/dm2; (c) 0.20 A/dm2; (d) 0.25 A/dm2
3826 Feng-zhang REN, et al/Trans. Nonferrous Met. Soc. China 23(2013) 3822í3828
The above phenomena can be explained as follows. silver coatings of both systems originally increases and
The deposition rate increases with the current density then decreases, although the hardness does not change
increasing. The increase of current density leads to the much. The coatings at the current density of 0.2 A/dm2
increase of the overpotential, therefore, results in the for both solution systems have a higher hardness because
increase of nucleation rate. When the current density is the coatings surface is relatively even and dense. The
relatively small, the nucleation rate is low. The lower microhardness of the AgNO3 system is lower than that of
nucleation rate provides the crystal nucleus with a larger the AgBr system for the same current density.
space to grow, which results in the formation of an
uneven surface. The increase of nucleation rate with the
current density will make many crystal nuclei grow
synchronously and, therefore, results in the formation of
a flat surface. When the current density is too high,
micro-discharge usually occurs at a sharp angle due to
the lack of discharge metallic ions near the cathode,
which causes larger grains and surface coarsening.
Moreover, from Figs. 1 and 2, it can be seen that the
effects of current density on surface morphology of
coatings for AgBr solution system are more obvious than
that for AgNO3 solution system, which indicates that
adaptable current density range for the AgNO3 solution
system is wider than that for the AgBr solution system.
As shown in Table 3, Figs. 1 and 2, the optimal Fig. 3 Deposition rates at different current densities
current densities for AgNO3 and AgBr solution systems
are 0.25 A/dm2 and 0.20 A/dm2, respectively.
References
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