Technology for Improving Performance of Tin Plating

for Automotive Terminals

Yutaro UEDA＊1・Masahiro TSURU＊1
*1
Copper Rolled Products Plant, Copper Rolled Products Unit, Advanced Materials Business

Abstract process are illustrated in Fig. 1. Reflow tin plating

is a type of plating performed by applying electric
Copper alloy, which has excellent electrical conductivity, tin plating to a copper alloy and then heating and
is widely used for automotive terminals. Since copper melting the plating above the melting point of
alloys are oxidized in the atmosphere, and their oxide tin (hereinafter referred to as "reflow treatment.")
coating acts as electrical resistance, tin plating is applied The reflow tin plating produces an intermetallic
to keep the contact resistance low. This paper explains the compound layer of tin and copper (hereafter referred
characteristics required for the tin plating of automobile to as copper-tin-based intermetallic compound) on
terminals and introduces Kobe Steel's original tin-plated top of the copper alloy and the surface covered with
products with new reflow plating (high thermal resistance tin.
and low friction). The new reflow plating consists of three layers
of nickel, copper-tin-based intermetallic compound,
Introduction and tin on the copper alloy. Fine asperities are given
to the copper alloy surface in advance, and when
Automobiles are equipped with electrical plating is applied in the order of nickel, copper, and
components that consist of, for example, control tin, the plating follows the asperities of the material.
computers, sensors, and actuators, which are After that, the tin melts during the reflow treatment,
connected by wire harnesses. A wire harness is the asperities formed after plating are smoothed,
an assembly consisting of electrical wires and the copper-tin-based intermetallic compound
and connectors, and the terminals built into is exposed on the convex surface. As a result, fine
each connector are one of the essential parts for copper-tin-based intermetallic compounds are
transmitting power and signals. Recently, the dispersed on the tin-plated surface.
electrification of automobiles is accelerating to
realize "CASE," including automatic driving and 1.1 Contact reliability
electric driving. As a result, the number of onboard
electronic devices has increased, and so has the Contact reliability is one of the most important
number of electrical wires and terminals. These characteristics required for terminals, and they are
terminals are generally made of copper alloy, which required to continue transmitting electrical signals
has excellent electrical conductivity; however, and power from the moment of production until
copper alloys oxidize in the atmosphere, and the an automobile's end of life. To this end, the contact
oxide film becomes electrical resistance. Hence, the resistance of the terminal contact point must be kept
common practice is applying a surface treatment low. Contact resistance is expressed by Equation
such as tin plating to maintain the low contact (1) as the sum of film resistance, which is the
electrical resistance (hereinafter referred to as electrical resistance of the film itself, and constriction
"contact resistance") of each contact point, which is
the connection part of the terminal.
This paper explains the characteristics required
for the tin plating of automobile terminals and
introduces Kobe Steel's original tin plating products,
"new reflow plating (heat resistant specifications,
low friction specifications)."

1. Characteristics required for terminal tin plating

The characteristics required for the tin plating of

terminals are described, taking the tin plating used
for the mass-production at Kobe Steel as an example. Fig. 1 Cross section structure of tin plated copper alloys
The cross-sections of copper alloy with reflow tin in plating and reflow processes
plating and new reflow plating in the plating/reflow *IMC: Intermetallic compound layer of tin & copper

57 KOBELCO TECHNOLOGY REVIEW NO. 40 JAN. 2023

resistance due to current concentration:1), 2) requires a heat resistance temperature of 150-160℃.
In addition, due to the electrification of on-vehicle
R = Rf + Rc ………………………………………… (1)
components, the number of terminals per connector
wherein R is the contact resistance (Ω), Rf is the film is increasing, and the dense terminals make heat
resistance (Ω), and Rc is the constriction resistance escape difficult. Therefore, the demand for heat
(Ω). resistance is becoming more stringent.
The film resistance and constriction resistance Fig. 2 illustrates the cross-section of a box
when homogeneous metals make contact are terminal. Terminals include a box-shaped female
expressed by Equation (2): terminal and a plate-shaped male terminal. The
contact resistance is kept low by inserting the male
Rf = ρf d / πa2, Rc = ρ / 2a ………………………… (2)
terminal into the female terminal and applying a
wherein ρf is the film-specific resistance (Ω･m), contact load with the spring of the female terminal.
d is the film thickness (m), ρ is the metal-specific The miniaturization of terminals decreases the
resistance (Ω･m), and a is the contact surface radius contact load of the spring holding down the contact
(m). point. Contact resistance depends on load, and the
According to Equation (2), the film resistance contact resistance tends to increase as the contact
decreases as the film thickness decreases and the load decreases. This is because the contact area
contact area increases, and the constriction resistance decreases as the contact load decreases,5) and the
decreases as the radius of the contact surface oxide film is less likely to be destroyed.
increases; that is, the contact area increases. Gold plating, which has high electrical reliability,
The tin plating applied to the copper alloy is generally used at locations of low contact load,
surface is covered with a thin oxide film. Oxide where the oxide film is less likely to be destroyed,
films have higher electrical resistance than metal but gold plating is very expensive, and there is a
and inhibit electricity transmission; hence, contact need to reduce costs by applying tin plating. In
resistance generally increases when the oxide film addition, electrical reliability is highly required
is formed. However, in the case of tin plating, a thin in high-temperature environments where oxide
hard oxide film (strength: 16.5 GPa)3) is formed on films easily grow. Hence, in areas where the contact
the soft tin (strength: 50-70 MPa).3) As a result, the load is low in a high-temperature environment, it
oxide film cannot follow the deformation of the tin is necessary to improve the contact reliability of tin
caused by sliding when the terminal is inserted and plating.
is broken, making it easy to obtain contact between Fig. 3 shows the contact resistance before
the tins. Therefore, tin plating exhibits low contact heating and after holding at 160℃ for 1,000 h. The
resistance even when an oxide film is formed on its contact resistance was calculated on the basis of
surface. the voltage drop measured by the four-terminal
Tin plating is widely used for the contact points method. A plate-shaped plating specimen and a gold
of terminals because it is a relatively inexpensive wire bent into a U-shaped probe were used for the
metal and provides stable contact reliability thanks measurement. The probe was pressed against the
to the breakage of the oxide film. However, in specimen, and the voltage drop was measured at
recent years, the miniaturization of the terminal has each load in the range of 1 to 5 N while gradually
made it difficult for the oxide film to break, and the increasing the vertical load. The measurements were
mounting environment, with factors such as heat made while sliding in one direction at a speed of
and vibration, has become more severe, making it 1 mm/min. Before heating, all plating specimens
easier for tin plating to cause an increase in contact maintained contact resistance below 1mΩ under the
resistance. Hence, tin plating requires heat resistance load of 1 to 5 N. This is considered to be because
to withstand high-temperature environments and the tin oxide film had been destroyed by the sliding.
fretting wear resistance to endure vibration and After holding for 1,000 h, the contact resistance
temperature changes. of the reflow tin plating increased significantly,
exceeding 5 mΩ at load 3 N. On the other hand, with
1.2 Heat resistance

The primary heat source in an automobile is the

heat-generating engine, and the engine room tends
to be hotter than the car interior.4) The engine room
reaches a maximum temperature of 120℃ under
a scorching sun,4) and the accelerated life testing Fig. 2 Schematic image of cross section of terminal

KOBELCO TECHNOLOGY REVIEW NO. 40 JAN. 2023 58

 the new reflow plating, the contact resistance was resistant copper oxide on the surface layer and
less than 1 mΩ at a load of 3 N and above, showing the contact resistance. It is also presumed that the
almost no increase, and maintaining 5 mΩ or less lower the load, the more difficult it is for oxide to
even at a load of 1 N. be removed by sliding, which further increases the
Fig. 4 shows the results of cross-sectional SEM contact resistance.
observation of tin plating after holding at 160℃ In the case of the new reflow plating, Cu6Sn5
for 1,000 h and the construction of the oxide film and a certain amount of tin is retained even after
in the surface layer. In the reflow tin plating, tin holding for 1,000 h. Unlike the reflow tin plating,
disappears, and a copper-tin-based intermetallic no thick copper oxide is formed. Therefore, it is
compound, Cu 3 Sn (ε phase), is formed. It is presumed that the oxide has been easily removed
considered that the exposure to a high-temperature by sliding to maintain the low contact resistance. Tin
environment has promoted the mutual diffusion of and Cu6Sn5 are maintained because the underlying
copper and tin in the material, forming a primary nickel plating suppresses the diffusion of copper
copper-tin-based intermetallic compound, Cu6Sn5 from the base material, making it difficult for copper
(η phase), depleting tin, and further diffusion has oxide to form.
resulted in the formation of Cu3Sn (ε phase).6) In It should be noted, however, that when tin
addition, a thick layer of Cu2O is formed on the plating is directly applied to the nickel plating, an
surface of the reflow tin plating. The specific intermetallic compound of nickel and tin is formed,
electrical resistance of copper oxide (CuO: 106- reaching up to the plating surface due to mutual
10 7Ω･m, Cu 2O: 10Ω･m) 7) is higher than that of diffusion of nickel and tin in a high-temperature
tin oxide (SnO2: 4 × 10-4Ω･m)7) and is considered environment, resulting in the formation of nickel
to affect the contact resistance significantly. It is oxide with high resistivity (NiO: 4 × 1011 Ω・m)7)
presumed that the formation of Cu3Sn with a high on the surface. As a result, the contact resistance
copper content increased the thickness of the highly increases. 8) Therefore, it is necessary to form

Fig. 3 Relationship between contact load and contact resistance before and after 160℃×1,000 h annealing

Fig. 4 Cross sectional SEM images and composition of oxide films of tin plating after 160℃×1,000 h annealing

59 KOBELCO TECHNOLOGY REVIEW NO. 40 JAN. 2023

the 3-layer structure with a copper-tin-based
intermetallic compound between the nickel and tin
layers to suppress the diffusion.
The above facts show that it is essential to
maintain tin and Cu6Sn5 to suppress the increase in
contact resistance at high temperatures. To that end,
it is effective to increase the thickness of the tin or
use a 3-layer plating structure with a nickel layer, as
in the case of the new reflow plating.1)

1.3 Fretting wear resistance

Fretting wear is a phenomenon in which

slight rubbing occurring between the contact
points of terminals causes wear of the plating at Fig. 5 Fretting test system
the contact points. Once fretting wear occurs, the
contact resistance may increase as the wear debris
of tin accumulates and oxidizes between the
contact points. Fretting wear has been said to be
attributable to contact point displacement caused
by vibration during engine drive and automobile
running, and thermal expansion and contraction
due to, for example, temperature changes in the
surrounding environment and heat generated by
energization.1), 6) As the miniaturization of terminals
progresses, the contact load at the contact points
decreases, making the contact points more prone
to displacement due to vibration and impact that
hitherto have not been a problem, increasing the
importance of fretting wear resistance. Fig. 6 Changes of contact resistance of reflow tin plating
with different contact load
Fig. 5 shows a schematic diagram of the fretting
wear test, and Fig. 6 shows the contact resistance
behavior during the fretting wear test at loads of fretting wear, the lower the load, the easier it is
3 N and 5 N for reflow tin plating. For the load for the wear debris to accumulate, which tends to
of 3 N, a peak of contact resistance (first peak) is increase the first peak value of the contact resistance.
observed around 40 to 80 cycles, but this is Therefore, plating is required to suppress the first
different for the load of 5 N. In the fretting wear of peak of contact resistance at a low load. The first
tin plating, the wear debris of tin is generated by peak of contact resistance is due to the accumulation
sliding, and, although some of the wear debris is and oxidation of tin wear debris, and in order
discharged outside, the rest accumulates between to lower the first peak of contact resistance, the
the contact points. The accumulated wear debris of generation and accumulation of wear debris must be
tin oxidizes, increasing the contact resistance.1) After suppressed. To this end, it is effective to reduce the
that, when wear progresses as far as the copper- thickness of tin plating, which is the source of wear
tin-based intermetallic compound, more wear debris, or to suppress tin wear.
debris is discharged than is generated, decreasing Fig. 7 shows the relationship between the tin
the wear debris accumulated at the contact points plating thickness of new reflow plating and
and decreasing the contact resistance (first peak). reflow tin plating at the load of 3 N and the first
Further sliding causes wear to progress, exposing peak contact resistance in fretting wear. Here, the
the copper alloy base material, and finally contact tin plating thickness is the average thickness of
resistance increases due to the wear and oxidation the tin layer only, excluding the copper-tin-based
of the base material. 1) The first peak of contact intermetallic compound. For either type of plating,
resistance observed at the load of 3 N is considered reducing the tin thickness lowers the first peak.
to be caused by the small contact load weakening The reason for this is considered to be the decrease
the force to discharge the wear debris to the outside, in the amount of tin wear debris generated. When
making it easy to accumulate. Thus, in the case of homogeneous metals are rubbed against each other,

KOBELCO TECHNOLOGY REVIEW NO. 40 JAN. 2023 60

 wherein F is the friction force (N), W is load (N) in
the direction normal to the plate thickness, A is the
contact area (m2), s is the shear strength of adhered
part (N/mm2), p is the plastic flow pressure (N /mm2)
= hardness of the material (N/mm2).
The plastic flow pressure is the pressure at
which the entire interior close to the surface near the
contact part undergoes plastic deformation when
the contact load is increased and corresponds to the
hardness of the material.1) According to Equation
(3), the coefficient of friction can be reduced by
lowering the shear strength of the adhered part and/
or increasing the plastic flow pressure.
Fig. 7 Relationship between tin plating thickness and 1st Fig. 8 is a schematic diagram of the method for
peak of contact resistance
measuring the coefficient of friction. The coefficient
of friction was measured following the Japan Copper
adhesion generally tends to occur, making the wear and Brass Association technical standard JCBA
severe (adhesive wear).9) Thus, the primary cause of T311:2002. A plate-shaped test piece (Flat) and a
wear between two layers of tin plating is regarded as test piece with a hemispherical protrusion with
adhesive wear. The new reflow plating exposes the a radius of curvature of 1.0 mm (Emboss) were
copper-tin intermetallic compound on the surface to brought into contact, and the coefficient of friction
suppress the adhesive wear of tin. At around 0.7 μm was calculated from the friction force when a load of
tin thickness in Fig. 7, the new reflow plating has a 3 N was applied in the normal direction of the plate
lower first peak than the reflow tin plating. This is surface.
considered to be attributable to the effect, described Fig. 9 shows the relationship between tin
above, of suppressing the adhesive wear of tin. thickness and coefficient of friction for new reflow

1.4 Terminal insertability

In recent years, the number of terminals per

connector has increased, and the connector insertion
force has increased accordingly. Since the work
of inserting connectors is done manually, there is
a move to tighten the insertion force standard to
reduce the burden on workers, and reducing the
insertion force of the connector is considered to
become even more critical in the future. Since the
friction force of the tin plating affects the insertion
force of the connector, a reduction in the coefficient
Fig. 8 Friction coefficient measurement system
of friction is required for the tin plating.
Friction force is expressed as the sum of a force
component required to separate the adhered parts
(adhesive friction), a force component due to a hard
surface digging into a soft surface (friction due to
digging), and a component based on the energy loss
caused by the difference in deformation force when
pushing and pulling the material (elastic hysteresis
loss).1) In general, the difference in hardness of two
layers of tin plating has little effect on the friction
between them, the friction caused by digging is
slight, and the adhesive friction becomes dominant.
Therefore, the coefficient of friction is given by
Equation (3):9)
Fig. 9 Relationship between tin plating thickness and
μ = F/W = As/Ap = s/p…………………………… (3) friction coefficient

61 KOBELCO TECHNOLOGY REVIEW NO. 40 JAN. 2023

plating and reflow tin plating. For both cases of tin plating by having a three-layered structure and
plating, the thinner the tin layer, the lower the finely dispersed copper-tin-based intermetallic
coefficient of friction becomes. Thinning the tin compound on the surface of the tin plating, and it
layer makes the plating more susceptible to the has been adopted for automobile terminals.
rigid base material, increasing the apparent However, with the recent changes in
hardness and decreasing the coefficient of friction by automobiles, the characteristics required for tin
suppressing the adhesive wear of the tin. Also, the plating used for automobile terminals are becoming
new reflow plating results in a coefficient of friction more stringent. Kobe Steel has developed a new
lower than that of the reflow tin plating. The new reflow plating with heat-resistant specifications
reflow plating has a copper-tin-based intermetallic and low friction specifications as new variations
compound exposed on the surface, and the hard in response to the increasing demand for heat
copper-tin-based intermetallic compound increases resistance and terminal insertability.
the apparent plating hardness and suppresses the
adhesive friction of the tin, which is considered to 2.2 New reflow plating (heat resistant specifications)
have reduced the coefficient of friction.
For improved heat resistance, the new reflow
2. Introduction to new reflow plating (heat resistant plating (heat resistant specifications) has a greater
specifications, low friction specifications) thickness of tin than the standard new reflow
plating.
The following introduces a new reflow plating Fig.11 shows the contact resistance at a vertical
(heat resistant specifications) that has improved heat load of 1 to 5 N when held at 160℃ for 1,000 h
resistance by varying the tin thickness compared and 5,000 h. The contact resistance after 5,000 h of
with the standard new reflow plating and a new reflow tin plating is higher than after 1,000 h. This
reflow plating (low friction specification), especially is presumed to be due to the thick growth of copper
with improved terminal insertability.

2.1 Developmental approach to tin plating for

terminals

Fig.10 shows the positioning of tin plating for

terminals with respect to terminal insertability and
heat resistance. As mentioned above, increasing the
tin thickness improves the heat resistance, but on the
other hand, the terminal insertability and the fretting
wear resistance characteristics decline. Therefore,
it is difficult to achieve both by controlling the tin
plating thickness alone. The new reflow plating
simultaneously achieves various characteristics that Fig.10 Positioning of friction coefficient and thermal
were difficult to attain with conventional reflow resistance of tin plating for terminals

Fig.11 Relationship between contact load and contact resistance before and after 160℃×1,000 h and 5,000 h annealing

KOBELCO TECHNOLOGY REVIEW NO. 40 JAN. 2023 62

 oxide. On the other hand, the new reflow plating friction is equivalent to that of the reflow tin plating.
(heat resistant specifications) maintains a contact The new reflow plating (heat resistant
resistance of 1 mΩ or less at load 1 N even after 5,000 specifications) is suitable for applications requiring
hours and is more heat resistant than the new reflow improved heat resistance and maintenance
plating. This is considered to be because thicker tin of terminal insertability in high-temperature
maintained the tin and Cu6Sn5 for a longer period environments.
than the new reflow plating did, suppressing the
generation of copper oxide. 2.3 New reflow plating (Low friction specifications)
Fig.12 shows the relationship between the square
root of the tin plating holding time at 160℃ and The new reflow plating (low friction
the thickness of the copper-tin-based intermetallic specifications) has reduced tin thickness in
compound. The linear approximation of the plots comparison with the standard new reflow plating
has been extrapolated to obtain the growth rate for improved terminal insertability.
of the copper-tin-based intermetallic compound. Fig.14 shows the coefficient of friction of tin
As mentioned above, increasing the tin thickness plating. The bar graph represents the average value
effectively improves the heat resistance. Therefore, of ten measurements, and the error bar indicates the
the change in the time required for the tin to maximum and minimum values. The new reflow
disappear when the tin thickness is increased from plating (low friction specifications) exhibits a lower
1 μm to 1.5 μm has been calculated from the linear coefficient of friction than the standard new reflow
approximation of the growth rate of the copper- plating and is more consistent with less variability.
tin-based intermetallic compound. As a result, it Fig.15 shows the behavior of the friction force of
was found that the reflow tin plating increases the tin plating. Several small peaks are observed with
disappearance time of tin by approximately 40 the reflow tin plating and new reflow plating, but
hours, whereas the new reflow plating significantly few peaks are observed with new reflow plating
lengthens it to approximately 2,900 hours. Therefore, (low friction specifications). As mentioned above, tin
increasing the tin thickness of the new reflow plating plating results mainly in adhesive friction. Adhesive
is more effective in improving the heat resistance. friction is a phenomenon of repeated sticking and
Fig.13 shows the coefficient of friction for the
reflow tin plating and new reflow plating (heat
resistant specifications). As mentioned above, the
coefficient of friction increases as the tin plating
thickness increases. The new reflow plating (heat
resistant specifications) shows a coefficient of
friction similar to that of the reflow tin plating,
despite the thicker tin. The new reflow plating
has the advantage of a coefficient of friction lower
than that of the reflow tin plating. Hence, the new
reflow plating (heat resistant specifications) has set
the tin thicker than in the new reflow plating by
determining the extent to which the coefficient of
Fig.13 Friction coefficient of tin plating

Fig.12 Growth of intermetallic compound layer at 160℃ Fig.14 Friction coefficient of tin plating

63 KOBELCO TECHNOLOGY REVIEW NO. 40 JAN. 2023

 Fig.15 Change of friction force of tin plating Fig.17 Relationship between contact load and contact
resistance before and after 160℃×1,000 h annealing

Conclusions

The new reflow plating is a type of plating with

improved heat resistance, fretting wear resistance,
and terminal insertability compared with the
conventional reflow tin plating and its use in tin
plating for automobile terminals is spreading. Kobe
Steel has added heat resistant specifications and low
friction specifications as new variations of the new
reflow plating. Utilizing these, the company will
strive to propose tin plating suitable for the usage
environment.
Fig.16 Changes of contact resistance of reflow plating
References

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reflow plating but is more heat resistant than the
reflow tin plating. This is because the three-layered
structure suppresses the diffusion of copper.
The new reflow plating (low friction
specifications) is suitable for applications with
exceptionally high insertion force specifications and
where fretting wear resistance is required.

KOBELCO TECHNOLOGY REVIEW NO. 40 JAN. 2023 64