Microstructures and Oxide Scale of Melted Mark on Copper Wire Solidified under

Various Cooling Conditions and Subsequent Heat Exposure

Suphattra Sachana, Kohei Morishita and Hirofumi Miyahara

Reprinted frOnl

MIATERIALS TRANSACT10NS,VOL.64 NO.9,SEPTEIMIBER,2023

THE JAPAN INSTITUTE OF ⅣIETALS AND「 燿ATERIALS

l-14-32,Ichibancho,Aoba― ku,Sendai 980‐ 8544,Japan
Materials Transactions, Vol. 64, No. 9 (2023) pp.2296 to 2301
@2023 Japan Foundry Engineering Society

Microstructures and Oxide Scale of Melted Mark on Copper Wire Solidified under
Various Cooling Conditions and Subsequent Heat Exposure
Suphaffra Sachana*1, Kohei Morishita and Hirofumi Miyahara*2
Department oJ Materials, Faculty oJ Engineering, Kyushu University, Fukuoka Bl9-0395, Japan

A primary melted mark (PMM) on copper wire has been expected to identify the fire origin. However, the solidification microstructure
under various cooling conditions has not been extensively studied. In this research, the effects ofcooling conditions on PMM microstructure
before and after heat treatment were investigated. The results represent dendrite growth direction to the surface ofthe melted mark with copper
dendrites surrounded by (Cu*Cu2O) eutectic struchrre for air and water-cooling specimens. Moreover, the melted mark cooled in the air has
more than twice of secondary dendrite arm spacing (SDAS) than the water-cooling sample in the case of pre-heat treatment. After heat treatment
and cooled down in the fumace, aiq and water: the dendritic structure disappears and Cu2O precipitates on the copper matrix. The smaller
crystallite size and oxide layer cracking could be found in a higher cooling rate case. Therefore, by connecting thermal history with solidification
structure and surface oxidation morphology, the change in microstructures and physical parameters of PMM could be expected to be helpful for
fi re investigation . ldoi: I O.2320 / matertrans. F-M2023 8061

(Received November 29,2022; Accepted March29,2023; Published August 25,2023)

Kelnoords: copper alloys, dendrite growth, oxidation mechanism, surfbce morphology, fre investigdtion

1. Introduction
Copper wire with oxygen between 0.01 and
generally contained has been extensively used for electrical
applications because of its excellent electrical conductiv-
ity.',2) Ho*e,rer, the solidification structure of melted marks
on copper wire generated by arcing of electrical current in a
fire accident is still insufficient to describe the fire behavior
in order to determine the origin of the fire accident. The
critical evidence used to identifl, the cause of the fire for
the fire investigator is the "melted mark" on the copper wire
that is not bumed and is left behind at the fire scene.3)
Generally, various melted marks are found in the fire site;
primary melted mark (PMM), secondary melted mark
(SMM), and fire melted mark (FMM). PMM is an electrical
melted mark caused the fire, generated before the fire. SMM
is an electrical melted mark created after a fire by the buming
of PVC insulation.H) pVttvt is a thermal damage caused by
fire melting. Lee et al.a'1) reported that PMM is generated
in an atmosphere at or near room temperature and rapidly
cooled, whereas SMM is generated in the high temperature
of the fire atmosphere. Therefore, the cooling rate of PMM
should be much higher than SMM. As a result, they proposed
thatit is possible to distinguish between PMM and SMM
by measuring the oxygen concentration and dendrite arm
spacing of melted marks on copper wire. The solidification
of PMM due to cooling type effects both pre- and post-heat
treatment by observing the microstructure, dendrite growth
0.05Vo direction, and investigating the cooling condition effects on
oxygen concentration for the melted mark. Each micro-
strucfure was evaluated from a metallurgical point of view for
the judgment of fire cases.
2. Experimental Procedure
Commercial pure copper wires with a diameter of 2.6 mm
and a length of 25 mm were used in this study. For arc
simulation, an arc welding machine has been used to melt the
copper wire without PVC insulation. The distance befween
two electrodes was fixed at one centimeter, and a voltage of
100 Volt was applied to all samples. The copper wire was
rapidly melted and suddenly solidified in air (A) and water
(W) (Fig. l(a)). These two PMMs were examined for the pre-
heat treatment condition. To simulate the fire environment
and investigate post-treatment characteristics, the thermo-
couple was set under the copper wire at 2 mm from the end of
the copper wire. PMMs solidified in the air were annealed in
(a) (b)
Melting point
I
OC

structure of melted marks on copper simulated by short-

Ｏ ｏ ヽＬ

circuiting in the atmosphere was continuously discussed 1000 'C.10 min

by Liu et al.8) They presented that the Cu-dendrites and
＾
ｏ一●一

(Cu*Cu2O) eutectic structure under the cuprous oxide

“一ｏＱ´

(Cu2O) surface layer is the fingerprint of PMM.

こ ０い

However, the solidification microstrucfure and post-heat

treatment characteristics of PMM under different cooling
conditions have not been extensively studied. Therefore, the
objective of this study is to explore the characteristic features WA WA F

Time, t/min
*lGraduate Student, Kyushu University
*2Corresponding author, E-mail: miyahara.hirofumi.683 @m.kyushu-u. Fig. I Schematic diagram of various cooling types for melted mark on
acjp copper wire: (a) solidification process, and (b) heat treatment process.
 Microstructures and Oxidc Scale of Melted Mark on Copper Wire Solidified under Various Cooling Conditions and Subsequent Heat Exposure 2297

the fumace at 1000'C for 10 min, and finally cooled down to
room temperature through various cooling types (Fumace,
Air, and Water), as shown in Fig. 1(b).
The microstructure in the longitudinal section was then
observed by first grinding with SiC paper from #500 to
#4000 and secondly minor-polishing by 0. I um of diamond
paste. Before microstructural observation with an optical
microscope, the aqueous ferric chloride (l20ml distilled
water, 30ml hydrochloric acid, and 10g ferric chloride)
was used to etch the surface of the melted marks for a few
minutes.ell) The phase identification of the oxide layer for
heat treatment specimens was done by X-ray diffraction
(Rigaku, RINT-2100), under 40kY l4rnA with CuKcv
radiation of wavelength 2:0. l540nm. Data were taken in
the range 20 of 20 to 80 degrees with increments of 0.02
degrees. The surface morphology and chemical composition
of the heat treatment specimens were observed by SEM
(Hitachi, SU3500) attached EDS.
3. Results and Discussions
3.1 Dendrite growth
This section describes the influence of cooling rate on
dendrite growth in the melted marks of the copper wire
before heat treatment. The micrographs in the longitudinal
section of the melted marks on the copper wire solidified in
air and water are illustrated in Figs. 2(a)-(d) and Figs. 2(e)-
(h), respectively. Both specimens represent the microstructure
of the non-melting region that is different from the melting
region with a distinct boundary at the left side. The grain
boundaries and annealing twins are observed at the non-
melting zone, while the melting zone is a dendritic structure.
Moreover, gas porosities are observed only in the melting
zone; it was thought that gas porosities were formed during
the solidification process in which oxygen and hydrogen have
been dissolved into liquid copper by air or water.
The dendrites begin to grow at an interface between the
non-melting and melting regions, as shown in Figs. 2(b) and
2(f). lt means that during solidification when the liquid
copper temperature is lower than the melting point of
1083'C,12'13) the copper grains are nucleated at the solid-
liquid interface of the copper wire like an epitaxial growth.
Then these grow towards the interface into the surface of
the melted mark to form columnar crystals, as shown in
Figs. 2(b)-(d) for air-cooling and Figs. 2(f) (h) for water
cooling. Clear dendrite growth is observed throughout the
specimens, but the size of dendrite is relatively smaller at the
surface of melted mark of both cooling conditions. Although

a e

500 pm 500 μin

(b

50 pn 50 μnl

5()μ lll 50 μrn 50 μrn

Fig. 2 The longitudinal section of melted mark solidified: (af{d) in air, and (ef{h) by water where (b), (f ) at close to non-melting zone,
(c), (g) in the middle, and (d), (h) at close to surface of melted mark.
2298 S. Sachana, K. Morishita and H. Miyahara
the dendrite growth direction for the water-cooling specimen
should be growing from the surface to inside the melted
mark, the liquid copper rapidly solidifies, and the dendrites
quickly grow to the surface. It is because the heat transfer
occurs along the long solid copper wire and the melted
mark has a minimal volume. Therefore, the dendrite growth
direction from the non-melting region to the surface of the
melted mark in the direction opposite the heat flow becomes
the predominant growth direction for both cooling types. In
addition, the growth direction of dendrites for the air-cooling
specimen is consistent with short-circuiting in the ll0 Volt
experiment of copper wire at an ambient atmosphere
described by Liu et al.8'ta\
3.2 Solidification microstructure characterizatron
Figure 3 shows the typical microstructures of the melted
mark in air and water cooling. The microstructure in most
regions of both specimens comprised primary copper
dendrites in a bright region surrounded by a copper-oxygen
eutectic structure in a dark region. It can be described
according to the Cu-O phase diagram.2) When the liquid
copper temperature is lower than 1083'C, the copper atoms
firstly crystallize on the non-melting zones. They solidif, into
primary copper dendrites and grow rapidly from the interface
to the surface of the melted mark to form columnar dendrites
along the preferred crystallographic direction. During dendrite
growth, the oxygen atoms are piled-up from the dendrite tips
into the liquid and progressively create richer solutions to
form eutectic composition solutions. When the temperature
is below the eutectic temperature (1065"C), the liquid of
eutectic composition solidifies into a (Cu*Cu2O) eutectic
structure. Therefore, the final microstructure of the melted
mark on copper wire under both cooling types has two
constituents of primary copper dendrites and (Cu*Cu2O)
eutectic structure. Although the constituents in the micro-
structure of air- and water-cooling specimens are similar, there
50 μn■
(b)
Fig. 3 Microstructures of the melted marks solidified: (a) in air, (b) by
water.
is a noticeable difference in dendrite arm spacing. The second-
ary dendrite arm spacing (SDAS) near the surface of the air-
and water-cooling specimens are 12.0 pm and 4.7 pm, respec-
tively. The water-cooling specimen has the SDAS less than
the air-cooling specimen because of the faster cooling rate in
the water. When the cooling rate is high, the size of diffusion
field around the dendrite in the liquid phase reduces, resulting
in smaller SDAS in the water-cooling specimen. Therefore,
the difference in SDAS befween high and low cooling rates
can describe the fire behaviors after short-circuiting.
3.3 Oxygen concentration
From the solidification process of the Cu-Cu2O binary
alloy, when the oxygen concentration in the liquid phase is
0.39 mass%o or less, copper is solidified first, and solidification
continues while increasing the oxygen concentration in the
liquid phase. When the oxygen concentration in the remaining
liquid phase portion reaches 0.39massVo, the solidification
is complete, and a eutectic structure is formed. As a result,
the oxygen concentration in the Cu primary dendrite part is
0.08 massTo, while it is 0.39 massTo in the eutectic structure.T)
Accordingly, the oxygen concentration can be calculated
from the area ratio method by the following eq. (l)
O (massTo) : 0.39 x (A - Ao)/A (l)
where O (massTo) is the oxygen concentration in mass
percent, A is the total area, and Ap is the copper dendrite
area. According to Fig. 4, the oxygen concentration of both
cooling types is highest when far from the non-melting
region, which is located close to the surface of the melted
mark, and decreases with distance from the surface. It was
considered that the liquid copper absorbed oxygen from
the air into the surface during melting. Then, the oxygen
concentration decreased with an increasing diffusion distance
from the surface of the melted mark.8'15) The oxygen
concentration distribution can be described according to the
Cu-O phase diagram. When the copper, which has an oxygen
content of less than 0.39mass% is melted and solidified, the
solidification proceeds with an increasing oxygen content
in the liquid phase. This oxygen is rejected by dendrite tips
■
１
︵Ｓ ∽∽“日 ︶ Ｃ Ｏ事 ● ヨ ００ＣＯＯ Ｃ Ｏｍ、Ｘ Ｏ
● Air
０ｌ
２
１
■ Watcr
■
ｏ
１
０．
０
０
0 500 1000 1500 2000 2500
Distancc■ om non―mcltinノ mclting intcrね cc,D/μ m
Fig. 4 The relationship between oxygen concentration and distance to
surface for air and water-cooling melted marks.
 Microstructures and Oxide Scale of Melted Mark on Copper Wire Solidified under Various Cooling Conditions and Subsequent Heat Exposure 2299
growing from the non-melting/melting interface to the
surface. When the oxygen content in the liquid phase reaches
0.39 massTo. The eutectic structure is formed, and the
solidification is complete at the surface of the melted mark.
As a result, locations close to the surface region could
demonstrate the highest oxygen concentration. Furthermore,
the oxygen concentration between air and water specimens is
difficult to distinguish because of the temperature fluctuation.
The small difference in melting temperature and time during
melting by arc-welding machine was thought to have a a larger grain as a well-known ripening phenomenon.l6) At
significant effect on the absorbed oxygen content of both
cooling types. As a result, it was claimed that it is nearly the
same for air and water-cooling samples. Lee et al.1\ reported
that oxygen concentration has an impact on SDAS. A higher
oxygen concentration and faster cooling rate for water-
cooling specimens leads to smaller SDAS. Thus, the
estimation of oxygen concentration from the area ratio
method should be evaluated near the surface to understand
the solidification behavior and lead to an explanation of fire
behaviors I'or fire investigation.
3.4 Post-heat treatment microstructure characterization
An optical microscope was used to examine the micro-
structures of heat treatment as shown in Fig. l(b) specimens.
Figure 5 depicts the microstructures of the melted mark
before heat treatment (a) and after heat treatment with furnace
sg
bl
‐
.r
3,
50 pm
n;r
r!,
, t
I年 、重
・ ●
・ .ヽ I● ヽ
50 pm
Fig.5 Themicrostrucruresofmeltedmark:(a)beioreheattreatment,(b)-(e)afterheattreatmentthencooledin:
(e) water.
cooling (b), (c), air cooling (d), and water cooling (e). A
significant change in microstructure is clearly observed after
annealing. Namely, the microstructure before heat treatment
comprises the primary copper dendrites in a bright region and
the (Cu*Cu2O) eutectic phase (Fig. 5(a)) as described in
section 3.2. After heat treatment, the dendrites disappear
entirely (Figs. 5(b)-(e)). This is because the copper dendrites
in the same crystal orientation have to reduce their interfacial
energy by dissolving and merging together to finally become
the same time, the eutectic structure is changed into Cu2O
particles precipitated on the Cu matrix all over the surface. ln
Fig. 6, the distribution of individual elements at center of
the melting region of the annealed specimen of Fig. 5(b) was
determined by EDS analysis. The obtained images show that
copper is uniformly distributed on the surface while the black
point is enriched by oxygen. The oxygen-rich point was
identified by EDS as precipitated Cu2O. According to the
Cu O phase diagram,2)when the copper-oxygen is reheated
below the eutectic temperature at CufCu2O phase region, the
diffusion rate of Cu2O is extremely fast resulting in the precip-
itation of Cu2O over the entire copper matrix.lT) Furthermore,
we reported the presence of Cu2O precipitates in the micro-
structure of real-world flre samples after exposure to flre.18)
The microstructure of annealed specimens cooled under
various cooing rates is not significantly different. The most
500 μrn
t, I
:,t t
:*
50 pm
(c)fumace,(d)air,and
2300 S. Sachana, K. Morishita and H. Miyahara

(1 l)

２ １ Ａ
０︶
(200ヽ
｀
(311ヽ
(110) ￨ 1 Water ズ2η

．
●．“ヽヽ ぃ
20 pm 20 μln

、一一
∽口〇一α Ｈ
Cu
EDS Quantitative Resu:ts Air
E■ emMDnt iFtt Att
C)K 9.37 29.■ 0
CuL 90.63 70.90

20 μ 1
l■
I Fu-u..
^

20 30 40 50 60 70 80
Fig. 6 EDS mapping of composition of annealed specimen. 2θ (° )

Fig. 8 X-ray diffraction pattems of copper oxide on melted mark of copper

constituent microstructure consists of Cu2O particles
precipitated on a copper matrix as noticed in the small black
points (Figs. 5(c)-(e)). The large black points are gas
porosities generated during the melting process before heat
treatment. The different colors in the bright and dark regions
in the air- and water-cooled specimens display the difference
in crystal orientation for each grain. The dendritic structure
cannot be observed for annealed specimens.
3.5 Surface morphology after heat treatment
Heat treatment of melted marks on the copper wire was
conducted at 1000'C for lOmin and cooled in the furnace,
air. and water to simulate the fire environments. The surface
morphologies for each cooling condition were investigated
by SEM, as shown in Fig. 7. The oxide layer on the outer
surface of the melted mark of the water-cooling specimen in
Fig. 7(c) was almost completely cracked. In contrast, fumace
and air-cooling specimens partially delaminated, as illustrated
in Figs. 7(a) and 7(b). It can be described in terms of the
difference in thermal expansion. As the oxide layer forms
during heat treatment at high temperatures, strain-free oxide
growth is assumed because of high diffusivity and high
500 μrn
wire after heat treatment for different cooling conditions.
atomic mobility. When the heat treatment is complete, the
strain is introduced into the copper and copper oxide layer as
the specimen cools down. Suppose the cooling rate of the
water-cooling specimen is too high. In that case, the ability
of the crystallites to reanange themselves cannot handle this
strain, increasing the possibility of cracking of the oxide layer
leaving the outer surface of the melted mark.le)
3.6 Phase identification of the oxide layer
The XRD pattems of the copper oxide layer prepared
under heat treatment at I 000'C for l0 mins and cooled down
in the furnace, air and, water are demonstrated in Fig. 8. The
peak positions at 20 values of 29.42, 36.29, 42.16, 61.2'7,
73.40, and 77.27 degrees correspond to the (ll0), (lll),
(200), (220), (3ll), and (220) planes of Cu2O. These peaks
are in good agreement with Cu2O powder from JCPDS file
no. 00-002-1067 confirming the presence of Cu2O for all
cooling types. The oxidation can be explained as copper
atoms reacting with oxygen atoms to form Cu2O, refened by
the following reaction:
2Cu * I l2O2 --> Cu262o) Q)
At high heat treatment temperatures, the more reaction
between copper and oxygen is produced, and the Cu2O grows
predominant with increasing Cu2O layer thickness. More-
over, the broadened peaks in the XRD pattems have been
used to estimate the crystallite size of Cu2O by using the
Debye-Scherrer formula2 I 23)

D : 0.9) / frcos9 (3)

where D is crystallite diameter size, ) is the wavelength of

the x-ray (0.1541nm), p is FWHM (Full width at half
maximum) and 0 is the diffraction angle. The crystallite sizes
of all specimens were determined from the broadened major
500 pm
peak located at 20:36.29. The relationship between
5里
堕二 1
crystallite size and cooling rate is revealed in a logarithmic
plot in Fig. 9. The temperature and time were measured by
Fig.7 Surface morphology taken by SEM on melted marks cooled: (a) in
fumace, (b) in air, (c) by water. Figure (d) shows part of a crack in the a thermocouple to calculate the cooling rate. The average
oxide layer of Fig. (c). cooling rates were calculated in the temperature range from
 Microstructures and Oxide Scale of Melted Mark on Copper Wire Solidified under Various Cooling Conditions and Subsequent Heat Exposure 2301

５
(1) The dendrite growth direction from the non-meting
region to the surface of the melted mark is the dominant
５

growth direction, and the microstructure consists of

Cu dendrites surrounded by (Cu+CuzO) eutectic
口︼ｇ ヽ︵﹃

structure for both cooling types.

４

(2) Quantitatively, smaller SDAS for water cooling is

＾
ＯＮ 一∽ ０↓¨〓 “一∽ヽ﹄︵

obtained, which is an indicator of the cooling rate in

４

the real-world fire case, whereas oxygen concentration

is nearly the same.
４

(3) The dendritic structure disappears on the microstructure

４

after heat treatment and Cu2O precipitates on the copper

︺

matrix.
４

(4) After heat treatment, a higher cooling rate in water

results in oxide layer cracking and smaller Cu2O
４

crystallite size.
0.01 0.t I l0 100 1000
Cooling rate, R/Ks-r Acknowledgments
Fig. 9 The plot of cooling rate versus Cu2O crystallite size.
This work was supported by the Royal Thai Govemment
scholarship.
1000'C to 400"C. Cu2O with a size of about 50nm is
obtained after cooling in the fumace at a slow cooling rate. REFERENCES
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