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Materials Science and Engineering C 36 (2014) 329335

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Materials Science and Engineering C


journal homepage: www.elsevier.com/locate/msec

Precipitation of phase and hardening in dental-casting


Ag20Pd12Au14.5Cu alloys subjected to aging treatments
Yonghwan Kim a, Mitsuo Niinomi a,, Junko Hieda a, Masaaki Nakai a, Ken Cho a, Hisao Fukui b
a
Department of Biomaterials Science, Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan
b
Department of Dental Materials Science, School of Dentistry, Aichi-Gakuin University, Nagoya 464-0045, Japan

a r t i c l e i n f o a b s t r a c t

Article history: The age-hardening behavior of the dental-casting Ag20Pd12Au14.5Cu alloy subjected to aging treatment at
Received 10 May 2013 around 673 K is well known, and this hardening has been widely employed in various applications. To date,
Received in revised form 18 November 2013 the age-hardening of this alloy has been explained to attribute to the precipitation of a phase, which is a B2-
Accepted 14 December 2013
type ordered CuPd phase or PdCuxZn1 x phase. In this study, results obtained from microstructural observations
Available online 19 December 2013
using a transmission electron microscopy and a scanning transmission electron microscopy revealed that a ne
Keywords:
L10-type ordered phase precipitated in the matrix and a coarse-structure region (consisting of Ag- and Cu-rich
Dental-casting Ag20Pd12Au14.5Cu alloy regions) appeared after aging treatment at 673 K and contributed to increase in hardness. The microstructure of
Aging treatment the coarse phase, which existed before aging treatment, did not change by aging treatment. Thus, it is conclud-
Precipitation hardening ed that the ne phase precipitated by aging treatment contributed more to increase in hardness than the
L10-type ordered phase coarse-structure region and coarse phase.
2013 Elsevier B.V. All rights reserved.

1. Introduction () [15]. To date, our research group has claried that in comparison
with the coarse phase, the ne phase precipitated by high-
AgPdAuCu alloys, substitute materials for high-cost Au alloys, are temperature solution treatment may contribute more to the unique
well-known dental materials for prosthetic restoration because these hardening of the Ag20Pd12Au14.5Cu alloy [11]. It has been consid-
alloys have good formability, good mechanical properties, and good cor- ered that precipitation of the phase signicantly contributes to the
rosion resistance [18]. It is essential that these alloys have good me- hardening of the Ag20Pd12Au14.5Cu alloy. In addition, it has been
chanical properties because they are prone to high occlusal forces reported that in the Ag25Pd25Au10Cu alloya type of AgPdAuCu
during their function. The conventional hardening method for AgPd alloys phases precipitate by aging treatment [16]. Therefore, it is
AuCu alloys is aging treatment around 673 K. The Ag20Pd12Au necessary to consider the contribution of the phase to the hardening
14.5Cu alloy exhibits age-hardening [9] and this hardening has been ex- of the Ag20Pd12Au14.5Cu alloy subjected to aging treatment. The
plained by the precipitation of CsCl(B2)-type ordered CuPd phases () aim of this study was to clarify the relationship between the microstruc-
[10]. The investigation of the microstructure and mechanical strength ture and hardening of the Ag20Pd12Au14.5Cu alloy subjected to
of the Ag20Pd12Au14.5Cu alloy has revealed that the phase, aging treatment. Ag20Pd12Au14.5Cu alloys are used as dental cast-
which is known to induce precipitation hardening upon aging treat- ing alloys for dental restorations (crown and inlay). This type of applica-
ment, is coarse and the microstructure of this phase hardly changes by tions requires the mechanical strength because high occlusal forces are
heat treatment [11]. Moreover, it has been reported that the phase applied during eating. On the other hands, this type of alloys is expen-
may not be a CuPd ordered phase but a PdCuxZn1 x phase [4,12]. It sive because they consist of precious metals. The hardness is related
has been mentioned that Zn grows as a primary crystal in this phase to the tensile strength, the stiffness, and the wear resistance and can
by bonding to Pd and reduces hardening [12]. The Ag20Pd12Au be measured using small size of specimens. Therefore, the hardness
14.5Cu alloy exhibits a unique hardening behavior in addition to the was measured for evaluation of mechanical properties in this study.
conventional age-hardening behavior. This unique hardening behavior
is demonstrated through the enhancement in the mechanical strength 2. Materials and methods
of the alloy by high-temperature solution treatment without any
aging treatment [13,14]. This unique hardening behavior has been ex- 2.1. Materials and heat treatment processes
plained to be attributed to the precipitation of L10-type ordered phases
The materials used in this study were commercial dental Ag20Pd
Corresponding author at: Institute for Materials Research, Tohoku University, 2-1-1
12Au14.5Cu alloys (Ishifuku Kinpara S12, Ishifuku Metal Industry Co.,
Katahira, Aoba-ku, Sendai 980-8577, Japan. Tel.: +81 22 215 2425; fax: +81 22 215 2553. Ltd.) fabricated by a wrought process (hereafter referred to as S12).
E-mail address: niinomi@imr.tohoku.ac.jp (M. Niinomi). Their chemical composition was 51%Ag20%Pd12%Au14.5%Cu2.5%

0928-4931/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.msec.2013.12.020
330 Y. Kim et al. / Materials Science and Engineering C 36 (2014) 329335

others (Zn, Ir, In) (mass%). The dimensions of S12 were 12.0 mm 300, FEI) equipped with a high-angle annular dark-eld (HAADF) detec-
6.0 mm 1.0 mm. In order to investigate the age-hardening behavior tor at an acceleration voltage of 300 kV. The elemental distributions in
of S12, aging treatments at various temperatures were carried out as STAT673 were analyzed using an energy-dispersive X-ray spectrosco-
schematically shown in Fig. 1(a). Seven S12 were subjected to solution py (EDX) detector installed in the STEM.
treatment (ST) at 1023 K for 3.6 ks in vacuum of about 1 Pa and were
then quenched in cold water (hereafter referred to as ST1023). More- 2.3. Mechanical evaluation
over, each ST1023 was subjected to aging treatments (AT) at each tem-
perature of 573, 623, 673, 723, 773, 823 and 873 K for 1.8 ks in vacuum The hardness measurements were performed on each mirror-
of about 1 Pa and was then quenched in cold water (hereafter referred polished specimen using a Vickers microhardness tester (Shimadzu mi-
to as STAT573, STAT623, STAT673, STAT723, STAT773, STAT823, crohardness tester HMV-1ADW, Shimadzu Corp.) with a load of 4.9 N
STAT873). In order to observe the changes in the microstructure of and a holding time of 15 s. Each specimen was tested 10 times and
STAT673, which exhibits an age-hardening behavior, further solu- the average value of these iterations was used as the hardness of the
tion treatment was carried out at 1023 K for 3.6 ks in a vacuum of specimen. Vickers hardness (Hv) was considered as the average hard-
about 1 Pa, followed by quenching in cold water (hereafter referred ness of 3 specimens. Furthermore, data of Vickers hardness was statisti-
to as STATST1023), as schematically shown in Fig. 1(b). cally analyzed by one-way ANOVA.

2.2. Microstructural observations 3. Results and discussion

ST1023, STAT573, STAT623, STAT673, STAT723, STAT773, ST The Vickers hardness of ST1023, STAT573, STAT623, STAT673,
AT823, STAT873, and STATST1023 were wet-polished using emery STAT723, STAT773, STAT823, and STAT873 are shown in Fig. 2.
papers of up to 4000 grit, and were then mirror-polished using an alu- The error bars are calculated using standard deviation. The Vickers
mina suspension. Commercial alumina suspensions with a diameter of hardness of ST1023 was found to be about 170.1 Hv. Moreover, it in-
1 m and 0.05 m (Baikalox, Baikowski) were used to mirror-polished creased with increasing AT temperature and showed the maximum
specimens. X-ray diffraction (XRD) analysis of these alloys was carried value of about 283.4 Hv for STAT673. Vickers hardness then decreased
out using a diffractometer (D8 DISCOVER, Bruker) (operating at 40 kV with increasing AT temperature.
and 40 mA) to identify the constitutional phases. A transmission elec- Fig. 3 shows the compositional phases of ST1023, STAT573, ST
tron microscope (JEM-2000EXII, JEOL) was used at an acceleration volt- AT623, STAT673, STAT723, STAT773, STAT823, and STAT873 as
age of 200 kV for observing the microstructures of the alloys. For this, determined from their XRD proles. It appears that the peak intensity
ST1023, STAT673, and STAT-ST1023 were cut into 2.0 mm and positions of the phase, which is known to induce age-hardening
2.0 mm 1.0 mm pieces by diamond saw. These specimens were [10], hardly changed by aging treatment. In STAT673, the (110) peak
ground to a thickness of 50 m by using emery papers of up to of the phase appeared at around 3132 (Fig. 3(b)). It is assumed
4000 grit, and were then mirror-polished using an alumina suspension. that the precipitation of the second phase like the phase contributed
The specimens were thinned to 10 m in thickness by dimple grinder. more to the increase in hardness than that of the phase, the composi-
After that, the specimens were thinned until a hole was made by ion tion and microstructure of which did not change by aging treatment.
milling. In addition, the microstructure of STAT673 was observed Fig. 4 shows the changes in the hardness of ST1023, STAT673, and
using a scanning transmission electron microscope (STEM) (TITAN80- STATST1023. The hardness of age-hardened STAT673 decreased by

ST
a 1023 K / 3.6 ks in vacuum AT
1.8 ks in vacuum
873 K STAT873
823 K STAT823
773 K STAT773
723 K STAT723
673 K STAT673
WQ
623 K STAT623
573 K STAT573
S12 WQ

ST1023
b ST ST
1023 K / 3.6 ks in vacuum 1023 K / 3.6 ks in vacuum

AT
673 K / 1.8 ks in vacuum
WQ
WQ
S12 WQ

STAT673 STATST1023
ST1023

Fig. 1. Schematic drawings of heat treatments: (a) aging treatments at temperatures in the range of 573873 K, and (b) aging treatment and subsequent solution treatments. ST: solution
treatment followed by water quenching (WQ), AT: aging treatment followed by WQ.
Y. Kim et al. / Materials Science and Engineering C 36 (2014) 329335 331

p < 0.05 p < 0.05

300
300

250
250

Vickers hardness (HV0.5)


Vickers hardness (HV0.5)

200 200

150 150

100
100

50
50
0
ST ST ST
10 -A -
0 23 T6
73 ST AT-
10
73

23

73

23

73

23
23

73
23
T5

T6

T6

T7

T7

T8
10

T8
ST

-A

-A

-A

-A

-A

-A

-A
ST

ST

ST

ST

ST

ST

ST

Fig. 4. Vickers hardness of ST1023, STAT673, and STATST1023.


Fig. 2. Vickers hardness behaviors of Ag20Pd12Au14.5Cu alloy subjected to solution
treatment (ST1023) and aging treatments at various temperatures (STAT573, ST
AT623, STAT673, STAT723, STAT773, STAT823, and STAT873). hardness increase [5,11]. The round-structure region shown in Fig. 6
was claried to be a coarse B2-type ordered phase (Fig. 7(e)(g)),
subsequent solution treatment at 1023 K for 3.6 ks and became nearly similar to the phase in ST1023 (Fig. 5(e)(h)). The coarse-structure
equal to that of ST1023. This hardness change suggests that AT or subse- region was further observed for detailed microstructure analysis. Fig. 8
quent ST caused signicant microstructural change. shows a bright-eld TEM image, dark-eld TEM image, SADP, and key
TEM observations (Fig. 5) showed that ST1023 consisted of a matrix diagram of the coarse-structure region. The dark-eld TEM image
() with an fcc crystal structure (Fig. 5(a)(d)) and a precipitate () (Fig. 8(d)) was taken using the inside (220) diffraction spot of SADP
with a B2-type ordered crystal structure (Fig. 5(e)(h)). The phase shown in Fig. 8(b). The bright region in this image was a phase with
was coarse (a few hundred nanometers in diameter) and was sparsely an fcc crystal structure having a long lattice parameter. The dark-eld
distributed. Therefore, the contribution of the coarse phase toward TEM image shown in Fig. 8(e) was taken using the outside (220) diffrac-
hardening would be small, and as a result, ST1023 showed low tion spot of SADP shown in Fig. 8(b). Again, the bright region in this
hardness. image was a phase with an fcc crystal structure having a short lattice pa-
A bright-eld TEM image of STAT673 shown in Fig. 6 indicates that rameter. Thus, the coarse-structure region of STAT673 shown in Fig. 6
its microstructure changed signicantly by aging treatment. STAT673 corresponded to two phases with the same fcc crystal structure but with
consisted of different regions with ne, round, and coarse different lattice parameters. The results of elemental mapping analysis
structures. Fig. 7(a)(d) show a bright-eld TEM image, selected-area of the coarse-structure region of STAT673 (Fig. 9) suggest that this re-
diffraction pattern (SADP), and key diagram corresponding to the gion was rich in both Ag and Cu. The shape and distribution of the Ag-
ne-structure region shown in Fig. 6. A ne lath-shaped precipitate and Cu-rich regions appeared similar to those shown in the dark-eld
existed in the matrix. The SADP and key diagram indicate that this TEM images in Fig. 8(d) and (e), respectively.
ne lath-shaped precipitate was phase, which also precipitated by TEM observations shown in Fig. 10 indicate that STATST1023
high-temperature solution treatment and contributed signicantly to consisted of a matrix () with an fcc crystal structure (Fig. 10(a)(d))

a b
2(220)
2(111)

2(200)
1(200)

2(222)
(100)


1(111)

1(220)

2(311)

1(311)
(111)

(200)
(110)

(211)

ST-AT873

ST-AT873
ST-AT823

Intensity (counts)

ST-AT823
Intensity (counts)

ST-AT773

ST-AT773
ST-AT723

ST-AT723 ' ST-AT673

ST-AT673
ST-AT623
ST-AT623

ST-AT573
ST-AT573

ST1023
ST1023
25 30 35 40 45 50 55 60 65 70 75 80 85 90 29 30 31 32 33
Diffraction angle, 2/deg. Diffraction angle, 2/deg.

Fig. 3. (a) XRD proles of Ag20Pd12Au14.5Cu alloy subjected to solution treatment (ST1023) and aging treatments at various temperatures (STAT573, STAT623, STAT673, ST
AT723, STAT773, STAT823, and STAT873), and (b) their enlarged XRD proles for 2 = 2933.
332 Y. Kim et al. / Materials Science and Engineering C 36 (2014) 329335

a b c d

200 220

000 020

500 nm 50 nm

e f g h
002 012 022

001 011 021

000 010 020

50 nm 100 nm

Fig. 5. TEM observation results for ST1023: (a) and (e) bright-eld images; (b) and (f) enlarged bright-eld images of encircled regions in (a) and (e); (c) and (d) selected area diffraction
pattern (SADP) corresponding to encircled region in (a) and its key diagram; and (g) and (h) SADP corresponding to encircled region in (e) and its key diagram. Beam direction is parallel
to [001] plane of matrix.

and a precipitate () with a B2-type ordered crystal structure by water quenching and that this phase contributed signicantly to in-
(Fig. 10(e)(h)). However, unlike STAT673, STATST1023 did not crease in mechanical strength [5,10,11]. Although the ne phase in
show a coarse-structure region and a phase; moreover, the micro- STAT673 precipitated during heat treatment that is different from
structure of STATST1023 was similar to that of ST1023. the high-temperature solution treatment, the microstructure of the
The hardness of the alloys changed signicantly with their micro- phase precipitated in STAT673 was similar to that of the phase ob-
structure (p b 0.05). The hardness of STAT673 consisting of ne- and tained by high-temperature solution treatment. Generally, the effect of
coarse-structure regions was higher than that of ST1023 (p b 0.05). ne phase on the increase in hardness was much stronger than that of
Moreover, the hardness of STATST1023 without any ne- or coarse- a coarse phase. Therefore, it is considered that the precipitation of the
structure regions was lower than that of STAT673 (p b 0.05). The mi- ne phase by aging treatment contributed more to hardness increase
crostructure of the phase did not change by aging treatment. This ob- than the coarse-structure region, which precipitated by aging treat-
servation indicated that the ne- and coarse-structure regions were ment, and the coarse phase, whose microstructure did not change
related to increase in hardness than the coarse phase. The ne- by aging treatment. It is supposed that the amount and the size of
structure region was the phase precipitated in the matrix. It has phase precipitated in the alloys subjected to aging treatment inuenced
been reported that in Ag20Pd14.5Cu12Au alloys, the ne phase on the increased amount of hardness. In addition, Ohta et al. reported
densely precipitated by high-temperature solution treatment followed that the decrease in hardness of the aged AgPdAuCu alloys at higher

fine structure region

coarse structure region


round shape
structure region

Fig. 6. Bright-eld TEM image of STAT673.


Y. Kim et al. / Materials Science and Engineering C 36 (2014) 329335 333

002N 1 022N1
a b c d
202N 2
020fcc 200N2 201N2 220P
020P 220fcc
001N1 021N 1
110P

002N 2
000 001N2 020
N1
200P
200fcc

: matrix (, fcc) : phase (L10)

fine structure

e f g
002 012 022

001 011 021

000 010 020

round shape
structure
Fig. 7. TEM observation results for STAT673 showing ne- and round-structure regions: (a) and (e) bright-eld images; (b) enlarged bright-eld image of encircled region in (a); (c) and
(d) SADP corresponding to ne-structure region in (a) and its key diagram; and (f) and (g) SADP corresponding to round-structure region in (e) and its key diagram. Beam direction is
parallel to [001] plane of matrix.

a b c

d e

Fig. 8. TEM observation results for STAT673 coarse-structure region: (a) bright-eld image; (b) SADP and (c) its key diagram; (d) enlarged dark-eld image of (220) diffraction spot
(lower circle in (b)); and (e) enlarged dark-eld image of (220) diffraction spot (upper circle in (b)). Beam direction is parallel to [001] plane of matrix.
334 Y. Kim et al. / Materials Science and Engineering C 36 (2014) 329335

a b

Ag-K Pd-K Cu-K Au-L Zn-K


c

Fig. 9. STEM observation results for STAT673 showing coarse-structure region: (a) bright-eld image, (b) STEM-HAADF image, and (c) elemental mapping analyses of squared region in
(b).

aging temperature was caused by precipitation of nodule in grain Acknowledgments


boundaries [16].
The authors are very grateful to Ishifuku Metal Industry Co., Ltd. for
4. Conclusions their support in this study. This study was nancially supported in
part by the Grant-in-aid for Scientic Research from the Japan Society
It is concluded that the ne phase precipitated by aging treatment for the Promotion of Science (#21360332), the Global COE program
contributed more to hardness increase than the coarse-structure region Materials Integration International Center of Education and Research,
and coarse phase. Moreover, the contribution of this phase was Tohoku University, Ministry of Education, Culture, Sports, Science and
similar to the phase precipitated by high-temperature solution Technology (MEXT) of Japan, Tohoku Leading Women's Jump Up
treatment. Project of Tohoku University, and the inter-university cooperative

a b c d

200 220

000 020

500 nm 100 nm

e f g h
002 012 022

001 011 021

000 010 020

500 nm 100 nm

Fig. 10. TEM observation results for STATST1023: (a) and (e) bright-eld images; (b) and (f) enlarged bright-eld images of encircled region in (a) and (e); (c) and (d) SADP corre-
sponding to encircled region in (a) and its key diagram; and (g) and (h) SADP corresponding to encircled region in (e) and its key diagram. Beam direction is parallel to [001] direction
of matrix.
Y. Kim et al. / Materials Science and Engineering C 36 (2014) 329335 335

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