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Review Jurnal dan Soal-soal Proses Manufaktur dan

Pemilihan Material

Danurwendho Fikri Hekmatsyar (1406571533)


Tasya Masyeba (1406569453)

Teknik Perkapalan
Departemen Teknik Mesin FTUI
Universitas Indonesia

M.Duet al./ Applied Surface Science342(2015)6975

70

1. Keadaan seperti apa untuk mendapatkan substitional dan interstitial solid solutions?
Substitutional Solid Solutions. Jika ukuran dari atom terlarut mirip dengan atom
pelarut, atom terlarut dapat menggantikan atom pelarut dan membentuk substitutional
solid solution. Contohnya kuningan, perpaduan antara seng dengan tembaga, dimana
seng (atom terlarut) dimasukkan kedalam kisi tembaga (pelarut atom). Sifat kuningan
dapat diubah dengan cara mengendalikan jumlah seng yang ada pada tembaga. 2
kondisi yang diperlukan untuk membentuk substitutional solid solution adalah:
a. 2 logam harus mempunyai struktur Kristal yang sama
b. Perbedaan jari-jari atom kedua logam harus kurang dari 15%
Interstitial Solid Solutions. Jika ukuran atom terlarut jauh lebih kecil daripada atom
pelarut, setiap atom terlarut dapat menempati posisi interstitial. Misalnya proses yang
membentuk interstitial solid solution. 2 kondisi yang diperlukan untuk membentuk
interstitial solid solutions:
a. Atom pelarut harus memiliki lebih dari 1 elektron valensi
b. Jari-jari atom terlarut harus kurang dari 59% ukuran jari-jari atom pelarut
2. Jelaskan ciri utama dari diagram fase.
Ciri utama dari diagram fase ada 2, yaitu phase boundaries dan triple point.
a. Phase boundaries, atau garis kesetimbangan adalah batas-batas yang
menunjukkan kondisi dimana 2 fase materi dapat berdampingan pada suatu
kesetimbangan.
b. Triple point adalah titik pada diagram fase dimana garis kesetimbangan
berpotongan. Titik dimana 3 materi yang berbeda (padat, cair, dan gas) dapat
berdampingan.
3. Apa syarat equilibrium dan konstitusional yang diterapkan pada diagram fase, apa
indikasinya? Diagram fase yang juga disebut sebagai kesetimbangan atau diagram
konstitusional menunjukkan hubungan antara suhu, komposisi, dan fase-fase dalam
sistem kesetimbangan. Equilibrum berarti keadaan sistem tidak berbeda dengan
waktu. Kata Konstitusi menunjukkan hubungan antara struktur, komposisi, dan paduan.
4. Apa yang dimaksud dengan pemampatan? Kenapa pengendapan ini penting?
Heat treatment ini adalah teknik dimana partikel-partikel kecil dari fase yang berbeda
yang disebut dengan endapan merata dalam sebuah matriks fase. Dalam proses ini,
paduan dipanaskan ke suhu menengah kemudian ditahan disana untuk jangka waktu
dimana curah hujan berlangsung. Atom tembaga berdifusi lalu nukleasi dan bergabung
dengan atom aluminium. Proses ini menghasilkan fase teta yang membentuk endapan
submicroscopic. Struktur ini menjadi lebih kuat. Peningkatan kekuatan ini disebabkan
oleh peningkatan restitensi pada daerah endapan.
5. Jelaskan karakteristik dari ferit, austenite, sementit.
Ferite
Alpha ferit adalah larutan padat dari besi kubik yang memiliki kelarutan padat
maksimum 0,022% C pada suhu 727 C. Delta ferit adalah bentuk lain yang akan stabil
pada suhu yang sangat tinggi. Ferit relative lunak dan ulet. Bersifat magnetic pada
suhu ruangan sampai 768 C.

M.Duet al./ Applied Surface Science342(2015)6975

71

Austenite
Struktur ini memiliki kelarutan padat hingga 2,11% C pada suhu 1148 C. Karena
struktur fcc memiliki posisi yang lebih interstisial, kelarutan padat austenite mengenai
2 hal yang besarnya lebih tinggi daripada ferit, dan atom karbon ada pada posisi
interstisial. Ini lebih padat daripada ferit dan struktur fcc fase tunggal akan ulet pada
suhu tinggi yang mengakibatkan memiliki kemampuan untuk membentuk yang baik.
Cementite
Sementit adalah senyawa inter-metalik yang sangat keras dan rapuh dan memiliki
pengaruh yang signifikan pada sifat-sifat baja. Sementit yang 100% besi karbida (Fe 3C)
6. Apa tujuan dari proses annealing?
Annealing adalah istilah umum yang digunakan untuk menggambarkan pemulihan dari
hasil heat and cold treatment yang dikembalikan lagi ke bentuk aslinya. Misalnya,
untuk meningkatkan daktilitas, mengurangi kekerasan dan kekuatan, atau mengubah
struktur mikronya. Proses ini digunakan untuk meringankan tegangan sisa dalam
manufaktur serta meningkatkan machinability dan stabilitas dimensi.
7. Jelaskan engineering significance dari keberadaan eutectic point pada fase diagram.
Eutectic point menyesuaikan dengan komposisi paduan yang memiliki suhu leleh
terendah pada sistem. Suhu leleh terendah jika dikatikan dengan eutectic point
misalnya, membantu untuk mengendalikan kerusakan thermal seperti pada soldering.
8. Biasanya baja tidak digunakan saat kondisi baja tersebut dalam keadaan quenched.
Mengapa?
Kekerasan dari penguatan martensit sebagai fungsi tempering time 1080 steel
didinginkan sampai 65 HRC. Kekerasan berkurang karena partikel karbid membesar
karena itu meningkatkan jarak interpartikel membuat ferit menjadi lebih halus.
9. Jelaskan karakteristik dari alloy, pearlite, austenite, martensite dan cementite.
Alloy
Alloy terdiri dari 2 atau lebih elemen, setidaknya 1 elemennya adalah logam. Alloy
dapat menjadi solusi padat dan memungkinkan untuk membentuk senyawa
intermetalik.
Pearlite
Apabila ferit dan sementit lamellae dalam struktur pearlite pada baja eutectoid tipis
dan dikemas dalam keadaan tertutup, mikrostrukturnya disebut perlit halus. Jika tebal
dan banyak ruangan disebut perlit kasar. Perbedaan dari keduanya bergantung pada
tingkat pendinginan. Jika laju pendinginan cepat maka perlit halus dapat diproduksi,
jika laju pendinginan lambat maka, perlit kasar diproduksi.
Austenite
Struktur ini memiliki kelarutan padat hingga 2,11% C pada suhu 1148 C. Karena
struktur fcc memiliki posisi yang lebih interstisial, kelarutan padat austenite mengenai
2 hal yang besarnya lebih tinggi daripada ferit, dan atom karbon ada pada posisi
interstisial. Ini lebih padat daripada ferit dan struktur fcc fase tunggal akan ulet pada
suhu tinggi yang mengakibatkan memiliki kemampuan untuk membentuk yang baik.

72

M.Duet al./ Applied Surface Science342(2015)69 75

Martensite
Martensit tidak memiliki banyak sistem yang keliru seperti struktur bcc dan sangat
keras juga rapuh. Tidak memiliki ketangguhan dan penggunaan yang terbatas.
Transformasi martensit terjadi karena melibatkan diri, bukan proses difusi, namun
mekanisme yang keliru yang merupakan fenomena yang bergantung pada waktu dan
juga transformasi lainnya.
Cementite
Sementit adalah senyawa inter-metalik yang sangat keras dan rapuh dan memiliki
pengaruh yang signifikan pada sifat-sifat baja. Sementit yang 100% besi karbida
(Fe3C).
10.Mengapa dari semua elemen, karbon sangat efektif dalam meningkatkan kekuatan
besi?
Karbon yang sedikit dapat larut secara interstisial dalam besi bcc, jumlah karbon dapat
memengaruhi sifat mekanik dari ferit secara signifikan. Karbon memiliki jari-jari atom
yaitu sekitar 57% dari atom besi, sehingga menempati posisi interstisial pada sel besi.
Namun, karena radiusnya lebih besar daripada lubang terbesar antara atom Fe, hal ini
dapat mengganggu pergerakan yang menyebabkan strain hardening. Ukuran dari atom
karbon memungkinkan untuk memiliki kelarutan yang tinggi pada fcc saat temperature
tinggi besi (austenite). Pada suhu rendak, strukturnya bcc dan memiliki kelarutan yang
rendah dari atom karbon. Pada pendinginan, struktur austenitic bertransformasi
menjadi martensit tetragonal yang menghasilkan distorsi tinggi pada kisi Kristal.
Karena lebih tinggi, peningkatan kekuatannya lebih tinggi daripada ditambahkan
dengan elemen lain.
11.Jenis baja yang digunakan untuk pipa menggunakan standar AISI 1040 dan baja untuk
senar atau kawat musik adalah 1085. Berdasarkan aplikasinya, jelaskan alasan dari
perbedaan persentase karbon.
AISI-SAE 1085 steel adalah contoh besi karbon dengan karbon sebanyak 0,85%.
Contoh dari besi tipe ini adalah senar piano. Senar piano memiliki strktur perlit dan
kekuatan yang besar dari proses cold working pada proses produksi. Sementara AISISAE 1040 steel digunakan sebagai gear dan shaft.

M.Duet al./ Applied Surface Science342(2015)6975

Depositing and alloying on the inner surface of Gasar Cupores by


annealing treatment

platingand

Ming Dua, Hua-wei Zhanga,b, Yan-xiang Lia,b,, Yuan Liua,b, Xiang Chena,b, Yun Hea
a

School ofMaterials Science andEngineering, Tsinghua University,Beijing,PRChina b Key


Laboratoryfor Advanced Materials ProcessingTechnology,MOE,PRChina

ar ti cl e

in fo

Article history:
Received31December2014
Receivedinrevised form2March 2015
Accepted 8March 2015
Available online14March 2015

a bs tr ac t
Depositing and alloying on the inner surface of Gasar Cu pores were realized by plating Zn and subsequent annealing treatment.
Influences of cathode current and plating time on alloy layer thickness at different positions along the pore axial direction were
investigated. The obtained results showed that alloy layers with different thickness were formed on the overall inner surface of
pores. Phaseconstitution of alloy layerswasdetermined byenergydispersiveX-rayanalysisandthephasediagramof CuZn.It was

Keywords:

measured from field emission scanning electron microscopy images, the relationship between phase
Gasar Cu thickness and annealing time was obtained.
Plating
Annealing
Surface alloying

2015ElsevierB.V.Allrightsreserved.

1.Introduction
A type of porous metal with long cylindrical pores aligned in one direction
was fabricated by unidirectional solidification process under a pressurized gas
(such as hydrogen), which was addressed as Gasar or lotus-type porous metal
[1,2]. Owing to the existence of directional pores, these materials possess not
only conventional properties caused by the porosity, such as lightweight and
high specific surface area, but also unique properties originating from the
oriented pores, such as supplying channels for mass transport and anisotropic
mechanicalproperties[35].Thus,suchaligned porousmetalsareconsideredto
be one of the most promising candidates for heat-sinks, filters and biomaterials
[68]. So far, a number of metals [2,911], nonmetals [12] and alloys [1316]
have been successfully employed to fabricate Gasar structures. Among these,
Cuisthemostintensivelyresearched material. Also, researcheshaveprovedthat
Gasar Cu hasanadvantage for heatdissipationdue toits orientedporesproviding
flowing channels and the intrinsic superior heat conductivity [6,1719], but the
inherent poor strength restricts its practical applications in other fields [20,21].
In some cases for overcoming the drawback, depositing a coating with higher
strengthisanappropriatechoice.

Corresponding authors at: School of Materials Science and Engineering, Tsinghua University,
Beijing,PRChina.Tel.: +861062773268; fax:+861062773268.
E-mail addresses: huawei.zhang@gmail.com(H.-w.Zhang), yanxiang@tsinghua.edu.cn (Y.-x.
Li).

H. Du et al. [22] reported that Gasar Cu could be plated with a Ni coating on the
inner surface of Gasar pores, and the compressive strength and hardness of the
Gasar Cu substrate were improved. However, the improving effect was limited
by the poor adhesion strength between the Ni coating and the Cu substrate.
Furthermore, T. Aoki et al. [23] reported the fabrication of Gasar brass by
combining plating or vapor deposition of Zn on Gasar Cu substrate with
annealing treatment. The resulting Gasar brass could possess higher strength
and wear resistance than Gasar Cu substrate. Therefore, it is believed that alloy
layers with high mechanical properties obtained by a combined process of
depositing and annealing have an added advantage in improving the strength of
GasarCusubstrateduetoreinforced interfacialbonding.
Except for improving mechanical properties, alloy layers formed on the
surface of metals can also be used as a precursor to prepare nanoporous films
(NPF) by subsequent dealloying [24]. This kind of porous material has many
potential applications due to their high surface area [2529]. The general
procedure for fabricating the NPF included three steps: depositing a less noble
metal on a noble metal substrate, annealing treatment for surface alloying, and
chemical or electrochemical dealloying for fabricating NPF of the noble metal.
If the dealloying process is conducted on Gasar Cu coated with suitable alloy
layers, a nanoporous Cu film (NPCF) will be prepared on the inner surface of
Gasar pores. Comparedwith the authors previous works [30,31] about the route
tofabricate bulkbimodal porous CubydealloyingGasar CuMnalloy,this route
will produce a new kind of bimodal porous structure composed of oriented
Gasarporeswithrandomnanoporouslayer ontheirinnersurface.

73

74

M.Duet al./ Applied Surface Science342(2015)69 75

foundthatthegenerating sequenceof alloyphaseswas

http://dx.doi.org/10.1016/j.apsusc.2015.03.039
Elsevier B.V.Allrightsreserved.

0169-4332/

2015

Based on the above discussion, it can be seen that a suitable alloy layer can
improve the strength and hardness of Gasar Cu substrate as well as serve as a
precursor for preparing a new kind of bimodal porous Cu. CuZn alloy is a potential
reinforcing coating for improving the strength of Gasar Cu substrate due to its higher
strength and hardness than those of pure Cu [23]. In addition, it is also a proper
precursor for fabricating nanoporous Cu by selective dissolution of the less noble
element Zn because of the difference of standard electrode potential between Cu and
Zn [32,33]. Therefore, CuZn alloy layer is an adequate choice. In our previous
study,we have reported thatathin(about1.5m)CuZnalloylayercouldbe fabricated
on the inner surface of Gasar pores uniformly by the electroless plating and
subsequent annealing treatment [34]. Here, our aim is to fabricate a relatively thick
CuZn alloy layers on the inner surface of Gasar pores by plating with
electromagnetic stirring and annealing treatment, control the layers phase
constitution, and further investigate their morphology, thickness and phase
constitution.
2.

Experimentalprocedure
2.1. Specimenpreparation

.Basedonthethicknessof eachphase

Gasar Cu samples with average pore diameter of 460 m, porosity of 36%, were
employed as the substrate. Prior to plating, samples were cut into half-cubic
specimens with 10 mm (width) 10 mm (length) 5 mm (height, in pore direction)
by an electric spark wire-cutting machine. In order to remove grease and surface
oxide, specimens were first immersed in acetone for 10 min, and then were
degreased in 1 mol/L dilute hydrochloric acid (HCl) for 5 min with ultrasonic
washing. After rinsing with deionized water, specimens were ultrasonically cleaned
withabsolute ethanolfor 10s thendriedwithArflowfor thenextoperation.
2.2. PlatingZn
PlatingZnwas conductedatroom temperature ina bath, using pure Zn plate asthe
anode and Gasar Cu as the cathode. The distance between the anode and the cathode
was about 20 mm, and the pore direction was perpendicular to the Zn plate. The
plating solution (100 mL) consisted of sodium hydroxide (NaOH) 2.5 mol/L, zinc
oxide (ZnO) 0.125 mol/L, and 2 vol.% plating additive. In order to guarantee enough
plating solution flow through Gasar pores and bubbles discharge rapidly during the
plating process, electromagnetic stirring was explored throughout the process.

M.Duet al./ Applied Surface Science342(2015)6975

Halfway through the plating time, Gasar Cu specimens were turned round to assure
the uniformityofplatingthicknessalongthespecimen height.
2.3. Annealingandcharacterization
The as-plated specimens were annealed to transform Zn coatings into CuZn
alloy layers in Ar atmosphere. The annealing treatment was conducted at the
temperature of 473 K and 683 K for different times to get alloy layers with different
thickness and phase constitution, respectively. The cross section at different sample
heights was observed. In order to observe the phase boundary clearly, a solution
containing 5 g ferric chloride (FeCl3), 11.94 mol/L HCl (20 mL) and 80 mL distilled
water was employed to corrode the cross section of Gasar Cu specimens coated with
alloy layers for 10 s. Phase constitution of the alloy layer was justified by comparing
the energy dispersive X-ray detector (EDX, Oxford INCA) results and the phase
diagram of CuZn. The growth rate constants of Zn in Cu substrate, and phases of ,
and were calculated from their respective thickness measured from field emission
scanning electron microscopy (FESEM, Zeiss MERLIN-VP-COMPACT) images.
The error barsrepresentedstandarddeviations.Specimensof S1S20

75

where H is Zn coating thickness; K is thickness coefficient; Dk is current density;


k is cathode current efficiency; t is plating time. As can be seen from Eq. (1), the
depositing rate of Zn is affected by Dk which is proportional to the cathode
current. For plating Zn on Gasar Cu surface, with a large cathode current, the
depositing rate at the pore openings becomes so fast that a mass of Zn is deposited
in a short time, and this will restrain the flow of plating solution throughout
elongated pores and consequently terminate the plating process in the depth of
pores. This is why the alloy layer thickness does not increase but decreases when
the cathode current exceeds 0.6 A, asshown in Fig. 2. Another fact observedfrom
Fig. 2 is that the increasing rate of plating thickness becomes to slow down when
the cathode current reaches up to 0.4 A. That is, the plating rate begins to be
affected by Gasar pores after this point. It is believed therefore, for depositing Zn
coatings on the inner surface of pores under the current experimental conditions,
theoptimal currentvalue locatesaround0.4A.

Table 1
Specimensused in the work.
Specimens

Cathode
current(A)

S1

S2
S3
S4
S5
S6
S7
S8
S9
S10
S11
S12
S13
S14
S15
S16
S17
S18
S19
S20

0.4
0.2
0.4
0.6
0.8
1
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4
0.4

Plating
time (min)

Annealing
temperature (C)

15
15
15
15
15
15
5
10
15
20
15
15
15
15
15
15
15
15
5

410
410
410
410
410
410
410
410
410
410
410
410
200
200
200
200
200
410

Annealing
time ( h )

6
6
6
6
6
4
4
4
4
1 / 12
0.5
2
1 / 12
1/6
1/3
1
2
5.9

usedinthisworkatdifferentexperimentalconditionswere shown inTable1.


3.Resultsanddiscussion
Fig. 1(a) shows the outer appearance of Gasar Cu experienced ordered steps
of plating and annealing treatment, which has changed from representative red
color of Cu to Znsgray and then to CuZn alloy yellow.Moreover,it can be seen
that the appearance of the inner surface of Gasar Cu pores has also changed into
CuZnalloy,whichmeansthatthe alloyingprocesshasoccurred there. Fig.1(b)
shows a FESEM image of cross section of S3. It can be seen that the alloy layer
distributeduniformlyonthe inner surface of pores.
Fig. 2 shows the alloy layer thickness of S3S7 as a function of cathode
current at the distance of 0.5 mm from the pore openings. It can be seen that the
alloy layer thickness increases first and then decreases with the current increase.
Under the same annealing conditions, the variation of alloylayer thickness canbe
ascribed to the changing of Zn coating thickness. Therefore, the key point is to
analyze the influence of cathode current on Zn coating thickness. With regard to
plating on flat surface, plating thickness can be calculated by traditional
FaradaysLaw[35]:
H=KDK tK

(1)

Fig. 1. Outer surface appearance of S1, S2 and S3, and the inner surface appearance of pores on the
longitudinal section of S3 (a); a FESEM image of S3 on the cross section at the distance of 0.5 mm
fromGasarporeopenings (b).

Fig. 3 shows the alloylayer thickness of S8S11with different plating time as


a function of the sample height (0.5 mm, 1.5 mm and 2.5 mm) along the pore axial
direction (Fig. 3a); at different sample height as a function of the plating time (5
min, 10 min, 15 min and 20 min) (Fig. 3b). It can be seen from Fig. 3(a), that the
alloylayer

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M.Duet al./ Applied Surface Science342(2015)69 75

of pores. Second, the plating process at the shallow position of pores consumes part
of Zn2+ leading to the diminishing concentration of

Fig. 2. Variation of alloy layer thickness of S3S7 with the cathode current increase at the sample height
of0.5 mmalongtheporeaxialdirection.

thicknessdecreasesas the specimenheight increases.The vary


ing trendcanbe ascribedto two aspects.First,the shieldingeffect
causedby Gasarporesgivesrisetoa reduced potentialin the depth

L =D t

solution along the pore axial direction. Fig. 3(b) shows the variation of alloy layer
thickness withplatingtime.Itcanbe observed thatthe alloylayer thicknessincreases
continuously with plating time increase at the same position of pores. This indicates
that the deposition of Zn coatings at the position near to the pore openings does not
affect the plating process in the depth of pores under the moderate depositing rate
during the plating time range. Another fact observed from Fig. 3(b) is that the alloy
layer thickness shows a discrepancy along the pore axial direction because of the
shielding effect and the diminishing concentration of the solution, but the difference
is small. It is supposed therefore, that the alloy layer thickness is nearly well
distributed along the pore axial direction. Thus, the alloylayer located at the distance
of 0.5 mm from the pore openings can be taken for representative to analysis related
performances of alloylayersonthe overallinnersurface of pores inthefollowing.
Fig. 4 shows the alloy layer thickness of S4, S10 and S13S15 as a function of
annealing time at the sample height of 0.5 mm. As can be seen from Fig. 4(a), the alloy
layer thickness raises with the annealing time increase. The relationship between
phasethickness andannealingtime canbeexpressedasbelow[36]:

(2)

M.Duet al./ Applied Surface Science342(2015)6975

77

Fig. 3.Alloy layer thickness of S8S11 with different plating time asa function of the sample height along the pore axial direction (0.5 mm, 1.5 mm and 2.5 mm) (a); at different sample height as a function of plating time
(5min,10min,15min,20min) ( b ).
Fig.4.Variationofmeasuredalloylayer thicknessofS4,S10and S13S14withannealingtime increase atthesample height of0.5mm(a); anditsfittingcurve ( b ).

D= D

(3)

where L is phase thickness; D is growth rate constant; t is annealing time; D0 is


frequency factor; Q is diffusion activation energy; R is gas constant; T is annealing
temperature. During the diffusion process, Cu atoms are more supplied from the
interface between Zn and Cu because the diffusion coefficient of Cu in Zn is much
larger than that of Zn in Cu. For example, when the temperature is 473 K, the
diffusion coefficientof ZninCu is 8.21027 m2/s, and that of Cu in

And EDX results of points 1 and 2 shown in Fig. 5 are given in Tables 2 and 3,
respectively. From FESEM images, it can be seen that the alloy layer is made up
of two phases showing layered distribution. By the way, phase constitution of
alloy layers distributed on the cross section of Gasar pores cannot be justified
using the conventional X-ray diffraction analysis because of the thin alloy layer
andthe existence of pores. Here, in order todetermine phase constitution of alloy
layers, the method of comparing the EDX result with the phase diagram of Cu
Zn (Fig. 6) [38] is employed. Based on this, phase constitution of alloy layers can
beconfirmedtobe and
Table 3
EDXresults andphase constitutionofpoints1and 2showninFig.5( b ).

Zn is 3.01018 m2/s [37]. Therefore, the increment of alloy layer

thickness is controlled by the diffusion of Zn in Cu. Based on Eq. (2), DZn in Cu can be
calculated from data shown in Fig. 4(a), and the fitting result is shown in Fig. 4(b). It
can be seen that the alloy layer thickness is of linear relationship with t0.5, and D is
equal

Point

Element

Weightpercentage

Cu
Zn

55
45

Cu
Zn

62
38

Phas
e

Fig.6.Phase diagramofCuZn.

Zn in Cu

to 0.056m/s1/2 at the temperature of 683K. Owing to the low

DZn in Cu, the alloy layer thickness can be supposed to be constant for the sake of
analyzingeachphasegrowthconstant.
Fig. 5shows FESEM imagesof crosssectionsof poresof S12(a); S13(b);S4(c) at
the distanceof0.5mmfromthepore openings.
Table 2
EDXresults andphase constitutionofpoints1and 2showninFig.5( a ).
Point

Elements

Weightpercentage

Cu
Zn

39
61

Cu
Zn

51
49

Phas
e

(Fig. 5a), and (Fig. 5b and c) along the outside-in direction. Therefore, it can be
concluded that the generating sequence of phases is
during the
annealing treatment, whichis consistent with results obtainedfromstudies about
diffusion couple of Cu and Zn [39]. As shown in Fig. 5(b), phase begins to occur
when the annealing time is over 0.5 h. And then, the thickness of phase increases
with annealing time increase. Similarly with discussion about Zn diffusing in
Cu, the relationship between phase thickness and plating time can also be
describedbytheEq.(2).Fig.7 shows the fitting curve of phase thickness with
t0.5. The fitting

Fig.5.FESEMimagesofcrosssectionsofS12(a); S13 (b);S4(c) atthedistance of0.5mmfromthe pore openings.

78

M.Duet al./ Applied Surface Science342(2015)69 75

(5)

7885
= 4. 7 10 exp
t
T
4

slope (D) is 0.08m/s0.5. According to the reference [37], the Q/R of


It has been reported that D is equal to 1.88.4m/s0.5 [37],
is 20457K1,thus,the calculatedD is 8.51011 m/s0.5 when
0

Tis683K.Therefore,Eq.(3)canbetransformedintoasbelow:
L

(4)

thus,the Zncoatingwithmicrometer-scale thicknesswill be transformed to phase in a


short time when the annealing temperature is 683 K. Obviously, it is impossible to
calculate growth rate constant with the changing of phase thickness under the
annealing treatment conditions. Therefore, the annealing temperature is reduced to
evaluate theconstant.
Fig. 8 shows the FESEM image of the cross section of S18 at the distance of 0.5
mm from the pore openings. It can be seen that except for phase and pure Zn, no other
phase is detected. The phase constitution can be confirmed by Table 4 which gives
EDX results at points 1 and 2 in Fig. 8. Therefore, 473 K is a preferable temperature to
calculate the D0 of phase with the same method like that of phase. Fig. 9 shows the
phase thickness of S15S19 as a function of t0.5. The fitting slope (D) is 0.15m/s 0.5.
The ref-

erential value of Q/Ris4580K1 [37].Sothecalculationof D is


0

2.4103 m/s0.5. Thus, Eq. (3) can be expressed as:

L =2.

(6)

4580
t
4 10 exp
T
3

Fig.7.Fittingcurve for phasethicknesstot0.5.

Fig. 10 shows the relationship between phase thickness and annealing time
according to Eqs. (4)(6) at the temperature of 683 K. Observed results have proved
that the generating sequence of CuZn alloy phases is
. It is supposed that
the alloy phase is formed one after the other. Therefore, the transferring end of the
prior phaseisthe startof the followingphase.Ascanbe seen
Table 4
Point

Element

Weight percentage

Cu
Zn

1
99

Cu
36
Zn
64
EDXresults andphase constitutionofpoints1and 2showninFig.8.
2

Fig. 8. FESEM image of alloy layer of S18 on the cross section at the distance of 0.5 mm from the pore
openings.

As can be seen from Fig. 5(a), the phase is formed when annealing time is only 5
min. In addition, it can be seen from Fig. 5 that the phase is a transient phase in this
system. Therefore, the growth rate constant of the phase is difficult to be calculated
using the phase thickness as a function of annealing time. However, it still can be
reckoned by means of the thickness obtained at the annealing time of 5 min.
According to the reference [37], the Q/R of phase is 7885 K1, so, the calculation of
D is 4.7104 m/s0.5.
0

Thus,Eq.(3)canbe expressedas:

Phas
e
Zn

M.Duet al./ Applied Surface Science342(2015)6975

Fig.9.Fittingcurve for phase thicknesstot0.5.

from Fig. 5, the sum of each phase thickness is kept at about 20 m, because the low
diffusion coefficient of Zn in Cu results in the little change of alloy layer thickness
under different annealing time. Therefore, taken the diffusion distance of 20 m for
example,the full formationtime of , and phasesis about 46s(a),32.5min (b) and18
h(c),whichhasbeenmarkedinFig.10respectively.
In order to justify these equations further,an average 12 m thickness Zn coating is
fabricated at cathode current of 0.4 A and plating time of 5 min. It can be reckoned that
the coating will be fully transformed into phase at a total time of about 5.9 h with an
annealing temperature of 683 K. Fig. 11 shows the FESEM image of alloy layer of
S20 at the sample height of 0.5 mm with the established annealing plan, and the EDX
resultisgiveninTable5.Itcanbe

seen that the alloy layer is made up of a single phase, which can be confirmed to be
phase considering with the EDX result shown in Table 5. Therefore, Equations
gotten from phase thickness as a function of annealing time is believable. Thus,
via adjustingthe plating
Table 5
EDXresults andphase constitutionofthe point 1showninFig.11.
Point

Elements

Weight percentage

Cu
Zn

65
35

Fig. 11. FESEM image of alloy layer of S20 at the sample height of 0.5 mm, and Cu and Zn elements
distributingalongthe pore radialdirection.

Fig.10.Relationshipbetween phasethicknessandannealingtime, (a);

(b); ( c ).

Phas
e

79

80

M.Duet al./ Applied Surface Science342(2015)69 75

andannealing technologicalparameters, alloylayers with controllable thickness


and phase constitution can be prepared on the inner surface of Gasar Cu pores. In
addition, from the measurement of element line scanning, the alloy layer
thickness can be confirmed to be about 11 m, which is very close to the original
average Zn coating thickness. This manifests that the diffusion scope is mainly
determined bythe Zn coating thickness owing to the slow diffusion coefficient of
ZninCu.
4.Conclusions
1.

A combined process of plating Zn with electromagnetic stirring and


subsequent annealing treatment is appropriate for alloying the inner surface
ofGasar Cupores.
Alloy layer thickness increases first and then decreases with the cathode
current increase. This is attributed to that abundant of Zn deposited at the pore
openings resulting from high cathode current restrains the plating process in
thedepthofpores.
The generating sequence of CuZn alloyphases is
. The growth rate
constants of each phase can be calculated via the measured data of phase
thicknessatdifferentannealing times.

2.

3.

4.

Alloy layers with controllable thickness and phase constitution can be


fabricated by tailoring the plating layer thickness and annealing treatment
parameters.
Acknowledgements
This work was supported by National Natural Science Foundations (Nos.
51371104 and 51101092) and International Science and Technology
CooperationProgramofChina (No.2013 DFR 50330).
References

[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]

V.I.Shapovalov,Method for Manufacturing PorousArticles, US5181549, 199301-26.


S. Yamamura, H. Shiota, K. Murakami, H. Nakajima, Evaluation of porosity in porous copper
fabricated by unidirectional solidification under pressurized hydrogen, Mater. Sci. Eng. A 318
(2001)137143.
H. Nakajima, Fabrication, properties and application of porous metals with directional pores,
Prog.Mater.Sci.52(2007) 10911173.
V.Shapovalov,L. Boyko, Gasar a new class of porous materials, Adv.Eng. Mater.6 (2004) 407
410.
H. Nakajima, T. Ikeda, S.K. Hyun, Fabrication of lotus-type porous metals and their physical
properties, Adv.Eng.Mater.6(2004) 377384.
H.W.Zhang, L.T.Chen, Y.Liu, Y.X. Li, Experimental studyon heat transfer performance of lotustype porouscopper heat sink,Int.J.Heat MassTransfer56 (2013) 172180.
X.N. Gu, W.R. Zhou, Y.F. Zheng, Y. Liu, Y.X. Li, Degradation and cytotoxicity of lotus-type
porous pure magnesium as potential tissue engineering scaffold material, Mater. Lett. 64 (2010)
18711874.
Theoreticalstudyon fluid resistance in poresofGasar metal porousfilter material, in:Y.J. Li, X.C.
Liu, Y.J. Ding, ICECE (Eds.), Proceedings of the 2010 Conference on Electrical and Control
Engineering(ICECE 2010), Wuhan,2010, pp.57625764.
Y. Liu, Y.X. Li, J. Wan, H.W. Zhang, Evaluation of porosity in lotus-type porous magnesium
fabricated by metal/gas eutectic unidirectional solidification, Mater. Sci. Eng. A 402 (2005) 47
54.
H.W.Zhang,Y.X.Li,Y.Liu,Fabricationporousaluminumwith directionalsolidification ofAlH
system,Acta Metall.Sin.43(2007)1116(in Chinese).
H.W. Zhang, Y.X. Li, Y. Liu, The critical processing conditions for directional solidification of
solid/gaseutectics, ActaMetall. Sin.43(2007) 589594(in Chinese).
Q.Q. Yang, Y. Liu, Y.X. Li, Pore structure of unidirectional solidified porous silicon, Trans.
Nonferrous Met.Soc.China 24(2014)35173523.
G.R. Jiang, Y.X. Li, Y. Liu, Experimental study on the pore structure of directionally solidified
porousCuMnalloy,Metall.Mater.Trans.A 41(2010) 34053411.
T.Ide, M.Tane,S.K. Hyun, H.Nakajima, Fabrication of lotus-type porous Ni3Al with and without
boron, Mater.Trans.47(2006)21162119.
T. Ikeda, T. Aoki, H. Nakajima, Fabrication of lotus-type porous stainless steel by continuous
zonemeltingtechniqueand mechanicalproperty,Metall. Mater. Trans.A 36A(2005)7786.
F.Yang, M. Tane, J.P.Lin, Y.H. Song, H. Nakajima, Pore formation and compressive deformation
inporousTiAlNballoys containingdirectionalpores, Mater. Des.49(2013)755760.

[17] H. Du, D.Z. Lu, J.Z. Qi, Y.F. Shen, L.S. Yin, Y. Wang, Z.G. Zheng, T.Y. Xiong, Heat dissipation
performance of porous copper with elongated cylindrical pores, J. Mater.Sci. Technol. 30 (2014)
934938.
[18] Y. Liu, H.F. Chen, H.W. Zhang, Y.X. Li, Heat transfer performance of lotus-type porous copper
heat sinkwith liquidGaInSncoolant,Int.J.HeatMassTransfer 80(2015) 05613.
[19] L.T. Chen, H.W.Zhang, Y.Liu, Y.X. Li, Experimental research on heat transfer performances of
directionally solidified porous copper heat sink, Acta Metall. Sin. 48 (2012) 329333 (in
Chinese).
[20] S.K. Hyun, H. Nakajima, Anisotropic compressive properties of porous copper produced by
unidirectionalsolidification, Mater.Sci.Eng.A 340(2003) 258264.
[21] X.H. Liu, H.Y.Huang, J.X. Xie, Effect of strain rate on the compressive deformation behaviors of
lotus-type porouscopper,Int.J.Min.Met.Mater.21(2014) 687695.
[22] H. Du, G.H. Song, H. Nakajima, Y.H. Zhao, J.Q. Xiao, T.Y. Xiong, Study on lotustype porous
copper electroplated with a Ni coating on inner surface of pores, Appl. Surf. Sci. 264 (2013) 772
778.
[23] T. Aoki, T. Ikeda, H. Nakajima, Fabrication of lotus-type porous brass by zinc diffusion into
porouscopper,Mater.Trans.44(2003) 8993.
[24] M. Stratmann, M. Rohwerder, Materials science a pore view of corrosion, Nature 410 (2001)
420423.
[25] H.J. Qiu, F.X. Zou, Fabrication of stratified nanoporous gold for enhanced biosensing, Biosens.
Bioelectron. 35(2012)349354.
[26] Y.Yu, L. Gu,X.Y.Lang,C.B.Zhu,T.Fujita,M.W.Chen,J. Maier,Li storage in 3D nanoporous Ausupported nanocrystalline tin,Adv.Mater.23(2011) 24432447.
[27] S.H. Yoo, L. Liu, S.H. Cho, S. Park, Platinum-coated porous gold nanorods in methanol
electrooxidation: dependence of catalytic activity on ligament size, Chem. Asian J. 7 (2012)
29372941.
[28] S.C. Zhang, Y.L. Xing, T. Jiang, Z.J. Du, F. Li, L. He, W.B. Liu, A three-dimensional tin-coated
nanoporous copperfor lithium-ion batteryanodes,J.Power Sources 196(2011)69156919.
[29] H. Jeong, J. Kim, Fabrication of nanoporous Au films with ultra-high surface area for sensitive
electrochemical detection ofglucoseinthepresenceofCl,Appl. Surf.Sci.297(2014)8488.
[30] X.M. Zhang, Y.X. Li, H.W. Zhang, Y. Liu, Fabrication of a three-dimensional bimodal porous
metal,Mater.Lett.106(2013) 417420.
[31] X.M. Zhang, Y.X. Li, Y.Liu, H.W.Zhang, Fabrication of a bimodal micronanoporous metal bythe
Gasar anddealloyingprocesses, Mater.Lett.92(2013) 448451.
[32] F.L. Jia, C.F. Yu, K.J. Deng, L.Z. Zhang, Nanoporous metal (Cu, Ag, Au) films with high surface
area: general fabrication and preliminary electrochemical performance, J. Phys. Chem. C 11
(2007) 84248431.
[33] Y.W. Lin, C.C. Tai, I. Sun, Electrochemical preparation of porous copper surfaces in zinc
chloride-1-ethyl-3-methyl imidazolium chloride ionic liquid electrochemical/chemical
depositionand etching,J.Electrochem. Soc.154(2007) 316321.
[34] M.Du,H.W.Zhang, Y.X. Li, Inner surface alloyingon poresofLotus-type porous copper through
electroless plating with supersonic vibration and annealing treatment, Surf. Coat. Technol. 261
(2015) 16.
[35] R.Z.Liu,ModernElectroplatingHandbook, ChemicalIndustryPress,Beijing, 2010.
[36] S.K. Pabi, B.S. Murty, Mechanism of mechanical alloying in NiAl and CuZn systems, Mater.
Sci.Eng.A 214(1996) 146152.
[37] C.J. Smithells, Smithells Metals Reference Book, 7th edition, ButterworthHeinemann, Boston,
1992.
[38] H.Baker,AlloyPhaseDiagrams, ASM InternationalMaterials Park,OH,2006.
[39] D.G. Li, Q. Wang, G.J. Li, Diffusion layer growth at Zn/Cu interface under uniform and gradient
high magnetic fields,Mater.Sci.Eng.A 495(2008) 244248.

M.Duet al./ Applied Surface Science342(2015)6975

81

Reviewer
: Danurwendho Fikri Hekmatsyar (1406571533) & Tasya Masyeba (1406569453)
Judul
: Depositing and alloying on the inner surface of Gasar Cu pores byplating and
annealing treatment
Sumber
: Science Direct, Elsevier, Applied Surface Science
Penulis
: Ming Du, Hua-Wei Zhang

Introduction
Beberapa metal, nonmetal, dan alloy sudah berhasil dijadikan bahan untuk fabrikasi
Gasar Structure. Diantara itu, bahan Gasar Cu memiliki keuntungan pada heat dissipation
karena pori yang dapat diisi dan intrinsik superior konduktivitas panas, tetapi lemah dalam
aplikasi di beberapa aspek. fabrikasi Gasar kuningan dengan menggabungkan penyepuhan
atau Vapor deposition dari Zn pada substrat Gasar Cu dengan annealing treatment. Yang
dihasilkan Gasar kuningan bisa memiliki kekuatan yang lebih tinggi dan ketahanan aus dari
Gasar Cu substrat. Oleh karena itu, diyakini bahwa lapisan paduan dengan sifat mekanik yang
tinggi diperoleh dengan proses gabungan dan annealing memiliki keuntungan tambahan
dalam meningkatkan kekuatan substrat Gasar Cu karena diperkuat ikatan antar muka.
Prosedur umum untuk fabrikasi NPF mencakup tiga langkah: menyetorkan logam yang kurang
mulia pada substrat logam mulia, annealing treatment untuk paduan permukaan, dan kimia
atau dealloying elektrokimia untuk fabrikasi NPF dari logam mulia.

Experimental Prosedure
1. Specimen Preparation
Sample Gasar Cu oleh percikan listrik mesin pemotong kawat. Dalam rangka
untuk menghilangkan grease dan permukaan oksida.
2. Plating Zn
Plating Zn dilakukan pada suhu kamar, menggunakan plat Zn murni sebagai
anoda dan Gasar Cu sebagai katoda. Larutan Plating (100 ml) terdiri dari natrium
hidroksida (NaOH) 2,5 mol / L, seng oksida (ZnO) 0,125 mol / L, dan 2 vol.%
Plating aditif. Untuk menjamin aliran larutan plating cukup melalui pori-pori Gasar
dan keluarnya gelembung cepat selama proses plating
3. Annealing and characterization
Phase Constitution lapisan paduan dibenarkan dengan membandingkan dispersi
hasil energi X-ray detector (EDX, Oxford INCA) dan diagram fase Cu-Zn. Konstanta
laju pertumbuhan Zn di Cu substrat, dan fase , dan dihitung dari ketebalan
masing-masing diukur dari emisi scanning gambar mikroskop elektron (FESEM,
Zeiss MERLIN-VP-COMPACT).

Results and Discussion

82

M.Duet al./ Applied Surface Science342(2015)69 75

Gambar 1 (a) menunjukkan penampilan luar Gasar Cu mengalami langkah-langkah dari


plating dan annealing treatment, yang telah berubah dari warna merah dari Cu Zn abu-abu
dan kemudian ke Cu-Zn alloy kuning. Selain itu, dapat dilihat bahwa penampilan permukaan
dalam dari Gasar Cu pori-pori juga telah berubah menjadi Cu-Zn alloy, yang berarti bahwa
proses paduan telah terjadi di sana. Gambar 1 (b) menunjukkan gambar FESEM dari
penampang S3. Hal ini dapat dilihat bahwa lapisan paduan didistribusikan merata pada
permukaan bagian dalam dari pori-pori. Dalam kondisi annealing yang sama, variasi
ketebalan lapisan paduan dapat berasal perubahan ketebalan lapisan Zn. Oleh karena itu,
kuncinya adalah untuk menganalisis pengaruh katoda saat ini pada ketebalan lapisan Zn.
Berkenaan dengan plating pada permukaan datar, ketebalan plating dapat dihitung dengan
hukum Faraday

Hubungan antara ketebalan fase dan waktu annealing dapat dinyatakan sebagai berikut

M.Duet al./ Applied Surface Science342(2015)6975

Dari gambar FESEM, dapat dilihat bahwa lapisan paduan terdiri dari dua fase
menunjukkan distribusi berlapis. Phase Constitution lapisan paduan didistribusikan pada
penampang Gasar pori-pori tidak dapat dibenarkan menggunakan analisis difraksi sinar-X
konvensional karena lapisan paduan tipis dan adanya pori-pori. Di sini, dalam rangka untuk
menentukan konstitusi fase lapisan paduan, digunakan metode membandingkan hasil EDX
dengan diagram fase Cu-Zn (Gbr. 6).

Berdasarkan ini, konstitusi fase lapisan paduan dapat dikonfirmasi untuk menjadi dan
(Gambar. 5a), dan (Gambar. 5b dan c) sepanjang arah luar-dalam. Oleh karena itu,

83

84

M.Duet al./ Applied Surface Science342(2015)69 75

dapat disimpulkan bahwa urutan menghasilkan fase yang selama annealing


treatment, yang konsisten dengan hasil yang diperoleh dari studi tentang pasangan difusi Cu
dan Zn. Seperti yang ditunjukkan pada Gambar. 5 (b), Fase mulai terjadi ketika waktu
annealing lebih 0,5 jam. Dan kemudian, ketebalan meningkat fase dengan peningkatan
waktu annealing. Seperti dapat dilihat dari Gambar. 5 (a), fase terbentuk ketika anil waktu
hanya 5 menit. Selain itu, dapat dilihat dari Gambar. 5 bahwa fase adalah fase transien
dalam sistem ini. Lapisan Zn dengan ketebalan skala mikrometer akan berubah bentuk untuk
fase dalam waktu singkat ketika suhu annealing 683 K. Jelas, tidak mungkin untuk
menghitung tingkat pertumbuhan konstan dengan perubahan ketebalan fase dalam kondisi
annealing treatment. Oleh karena itu, suhu annealing direduksi untuk evaluasi konstan.
hubungan antara ketebalan fase dan waktu annealing menurut Pers. (4)-(6) pada suhu 683 K.
Diamati telah membuktikan bahwa urutan pembangkit fase paduan Cu-Zn adalah .
Hal ini diduga bahwa fase paduan dibentuk satu demi satu. Oleh karena itu, akhir
mentransfer dari fase sebelumnya adalah awal dari fase berikut.

Conclusion

M.Duet al./ Applied Surface Science342(2015)6975

85

Urutan menghasilkan fase paduan Cu-Zn adalah konstanta yang pada setiap
perubahan fase mengalami titik eutectic . Laju pertumbuhan setiap fase dapat dihitung
melalui data yang diukur ketebalan fase pada waktu annealing yang berbeda.
lapisan Alloy dengan ketebalan dan Phase Constitution dapat dibuat dengan
menyesuaikan ketebalan lapisan plating dan parameter annealing treatment
ketebalan dari lapisan paduan pertama meningkat lalu akan menurun seiring dengan
peningkatan katoda