Materials Letters 59 (2005) 920 – 924 www.elsevier.

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Role of nanoparticle in PNN-PZT/Ag nanocomposite
Hoon-Taek Chunga,*, Deuk-Soo Cheongb, Chang-Sam Kimb
a

Department of Ceramic Engineering, Dongshin University, 252 Daeho-dong, Naju, Chonnam 520-714, Republic of Korea b Division of Materials, Korea Institute of Science and Technology, P.O.Box 131, Cheongryang, Seoul, Republic of Korea Received 20 October 2003; accepted 15 January 2004 Available online 23 December 2004

Abstract In the present work, we studied the role of nanoparticles in ferroelectric/silver composites, in which silver is the secondary particle. The ferroelectric system that we adapted was PNN-PZT. To make the PNN-PZT/silver nanocomposite, we hot-pressed the composite at 850 8C/2 h. A nanocomposite could be obtained with b0.5 vol.% of silver. We found that silver nanoparticles more effectively relieved the internal stresses than microparticles, which affected lattice parameter and transition temperature of the nanocomposites. D 2004 Elsevier B.V. All rights reserved.
Keywords: Nanocomposite; Nanoparticle; Ferroelectric; Residual stress; Hot pressing

1. Introduction Recently, nanocomposites have emerged as a new means of improving materials properties. In a nanocomposite, the secondary particles dispersed in the matrix are nanometersized. Niihara and co-workers [1–6] have reported the improved properties of many ceramic nanocomposites, such as Al2O3/SiC, Si3N4/SiC, Al2O3/W, Al2O3/Ni, ZrO2/Ni, and MgO/Ni. These nanocomposites all exhibit superior mechanical properties. Cheong and co-workers [7,8] also have reported a new route to the in situ fabrication of Si3N4/ SiC nanocomposites of which the fracture strength at room temperature (~1 GPa) was maintained up to 1400 8C in the sample that contained SiC particles (30 nm in size). This significant improvement of the high-temperature strength was attributed to inhibition of grain-boundary sliding and cavity formation, primarily by intergranular SiC particles bonded directly to the matrix grains. Thus, nanoparticles have been shown to very effectively improve mechanical properties of structural ceramics. Few studies have reported on electroceramics/metal nanocomposite, and it is not yet clear how nanoparticles affect the properties of ceramic nanocomposites. Hwang et
* Corresponding author. Tel.: +82 61 330 3183; fax: +82 61 330 2909. E-mail address: htchung@dsu.ac.kr (H.-T. Chung). 0167-577X/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2004.01.042

al. [9,10] studied ferroelectric(PZT)/Ag composites and found that silver particles relieve the internal stress induced by phase transformation, possibly a reason for the increased Curie temperature with increased silver content. However, in that case, the silver particles were micrometer-sized. Nanometer-sized silver particles are very difficult to achieve in a ceramics/silver composite system because the melting temperature of silver is lower than that of ceramics. The goal of the present research was to produce nanometer-sized silver particles in a ferroelectric matrix and study the particular effects of the silver particles. Thus, we used a hot-press sintering method to make silver nanometer-sized particles. The matrix used in this study was PNN-PZT, and microstructure and dielectric properties of the composite were studied.

2. Experimental procedure The PNN-PZT composition used in the present experiments was Pb0.98Cd0.02 (Ni1/3Nb2/3)0.15(Zr0.3Ti0.7)0.85O3. The experimental procedure used to make PNN-PZT/silver composite is shown in Fig. 1. All of the constituent metal oxide powders were mixed by ball-milling in ethanol with zirconia media for 15 h. The mixed slurry was dried and calcined in a covered alumina crucible at 850 8C for 3 h. We

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Ag solution
(AgNO3 and H2O) pH adjustment By NH4OH

PNN-PZT Powder

Ag complex

Mixing

Electroless Plating Reducing Agent: Formalin (HCHO) At 80 °C/10hr

Washing with water Drying Calcination of PNNPZT/Ag Composite powder Hot Pressed at 850 °C/2hr

were increased to N5 vol.%, silver particles grew at a hotpressing temperature as low as 850 8C (Fig. 3(b) and (c)). Fig. 4 shows TEM micrographs of the 0.5 vol.% silver sample. The bright-field image (Fig. 4(a)) does not clearly indicate silver particles in the sample. Fig. 4(b) is the diffraction pattern obtained around the same area shown in Fig. 4(a). Most of the diffraction spots are from PNN-PZT and small spots around silver 100 ring are marked by arrow. Using the arrow-marked silver spots, we obtained the darkfield image (Fig. 4(c)), which clearly shows 20–50 nm silver particles within the grain boundary junctions and inside the grains. Therefore, PNN-PZT/Ag nanocomposites with a silver content of 0.5 vol.% can be fabricated by hot pressing at 850 8C for 2 h. Fig. 5(a) and (b) are the XRD patterns obtained from hotpressed disc samples and powder samples, respectively. In this case, the powder samples were prepared by crushing the

Fig. 1. Flow chart of experimental procedure.

used electroless-plating method to produce nanometer-sized silver particles, and the volume percents of silver used in making PNN-PZT/Ag composite were 0.5%, 5%, and 10%. Hot-pressing was conducted below the melting temperature of silver, at 850 8C/2 h in air atmosphere by using an alumina mold. Microstructural analysis was conducted by transmission electron microscopy (TEM) and optical microscopy. X-ray diffractometry (XRD) was used for phase analysis and lattice parameter measurement. Gain-phase analyzer was used to analyze dielectric properties.

3. Results and discussion Fig. 2 shows the TEM micrographs of the PNN-PZT/Ag powders before sintering. Fig. 2(a) is a bright-field image, which shows nanometer-sized particles around the micrometer-sized particles. Diffraction pattern of the silver powders (Fig. 2(b)) shows ring patterns. The dark-field image from the silver 100 ring (Fig. 2(c)) clearly shows silver particle that measures ~20 nm. Therefore, the nanometer-sized silver particles were homogeneously dispersed around the micrometer-sized PNN-PZT particles. Fig. 3 shows optical-micrographs obtained by polishing the hot-pressed samples with various silver contents. No chemical or thermal etching was used, to avoid shape changes and reaction of silver particles. In the sample with 0.5 vol.% of silver, no silver particles were observed by optical microscopy, as shown in Fig. 3(a). As the silver contents

Fig. 2. TEM micrographs of dried powders: (a) bright-field image, (b) diffraction pattern, and (c) dark-field image.

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measured the lattice parameters perpendicular to the compressive stress. The lattice parameters decreased after annealing because the compressive stresses were relieved by annealing. The interesting result is that the dependences of lattice parameter on the silver content differed for the two samples, hot-pressed and annealed. In the hot-pressed samples, the lattice parameter decreased for up to 5 vol.% of silver and then increased. This decrease might be caused by the stress relaxation of the silver particles [9]. In particular, this decrease of the lattice parameter was steeper for up to 0.5 vol.% of silver when silver particles were nanometer-sized, as discussed earlier in this paper. Therefore, it can be said that nanometer-sized silver particles relieved the internal stress more effectively than micrometer-sized particles. When the silver content was increased to 10 vol.%, the lattice parameter increased again. There is no clear explanation for this change, and further study is needed to

Fig. 3. Optical micrographs(X200) (a) 0.5 vol.% silver, (b) 5 vol.% silver, and (c) 10 vol.% silver.

hot-pressed disc samples, and then annealed at 400 8C for 20 min to relieve the stress developed during hot pressing. The PNN-PZT used in this experiment was tetragonal phase, and no second phase was found. The lattice parameters calculated for the disc and powder samples are given in Fig. 6. As shown, the lattice parameters of the disc samples were larger than those of the powders, independent of the c- or a-axis. The mold used for hotpressing was alumina, which has a larger thermal expansion coefficient than PNN-PZT ceramics. Therefore, compressive stresses were applied to the PNN-PZT samples along their diameters during cooling, and remained in the sample even after the mold was separated. This compressive stress is the reason that the lattice parameters increased because we

Fig. 4. TEM micrographs of hot-pressed disc samples: (a) bright-field image, (b) diffraction pattern, and (c) dark-field image.

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(a)
Ag (111) peak 10 vol%

2.0x10

4

Measured at 100 kHz
Monolithic Ag 0.5vol% Ag 5vol% Ag 10vol%

Intensity (a. b.)

1.5x10 Ag 5 vol%

4

εr
1.0x10
4

Ag 0.5 vol%
(001) (100) (101)

5.0x10
(002) (200) (102)
(112) (211)

3

(111)

Monolithic 10

(220)

0.0 70

0

50

100 150 200 250 300 350 400 450 500

20

30

40

50

60

Temperature (°C)
Fig. 7. Dependence of dielectric constant on temperature for various silver contents.

(b)
Ag (111) peak Ag 10 vol%

Ag 5 vol%

Ag 0.5 vol%
(101) (110)

Mono. 10

20

30

40

50

60

70

80


Fig. 5. XRD patterns: (a) hot-pressed disc samples, and (b) annealed powder samples.

explain it. In the annealed samples, the lattice parameter decreased slightly as the silver content decreased, especially along the c-axis. However, a steeper decrease of the lattice parameter was also observed in 0.5-vol.%-silver sample,
4.040 4.035 Hot pressed disc c Annealed powder c 4.14 4.13

which implies that the stresses induced by phase transition were largely relieved by the silver nanoparticles. This result, we think, suggests that nanometer-sized silver particles relieve stress more effectively. Fig. 7 shows the temperature dependence of the relative dielectric constant for monolithic PNN-PZT and PNN-PZT/ Ag composite. As shown, dielectric constants at room temperature increased with silver content. Transition temperature has been reported to increase proportionally with the silver content in ferroelectric/silver composite, because silver relieves the internal stress induced during phase transition. However, in this experiment, the internal stresses were induced mainly by the hot-pressing process. Therefore, the situation was different from that of previous reports. Fig. 8 shows the dependence of transition temperature on the silver contents. No proportional change in the transition temperature with silver content is indicated. On the contrary, the transition temperature shows a tendency very similar to that of the lattice parameter variation with silver contents (Fig. 6). Therefore, stress relaxation affects the lattice parameter, and lattice parameters, in turn, affect the transition temperatures. The transition temperature increases

Intensity (a. u.)

(002) (200)

(102) (201)

(112) (211)

(001) (100)

(111)

(220)

(221)

(103) (310)

355
Lattice Parameter c (Å)

Lattice Parameter c (Å)

4.030 4.025

4.12 4.11

Curie Temperature (°C)

350

1KHz 10KHz 100KHz 1000KHz

4.020 4.015 4.010 4.005 Hot pressed disc a Annealed powder a 4.10 4.09 4.08 0 1 2 3 4 5 6 7 8 9 10

345

340

Ag content (vol%)
Fig. 6. Dependence of lattice parameter on silver content for hot-pressed and annealed powder samples.

0

2

4 6 Ag Content (vol%)

8

10

Fig. 8. Dependence of Curie temperature on silver content.

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as the lattice parameters increase and decreases as the lattice parameters decrease.

References
[1] K. Niihara, J. Ceram. Soc. Jpn. 99 (10) (1991) 974. [2] T. Ohji, A. Nakahira, T. Hirano, K. Niihara, J. Am. Ceram. Soc. 77 (12) (1994) 3259. [3] T. Hirano, K. Niihara, Mater. Lett. 22 (5-6) (1995) 249. [4] T. Sekino, Ji-Hun Yu, Yong-Ho Choa, Lee Jai-Sung, K. Niihara, J. Ceram. Soc. Jpn. 108 (6) (2000) 541. [5] T. Nakayama, Y.H. Choa, T. Sekino, K. Niihara, J. Ceram. Soc. Jpn. 108 (9) (2000) 781. [6] T. Sekino, T. Nakajima, S. Ueda, K. Niihara, J. Am. Ceram. Soc. 80 (5) (1997) 1139. [7] C.S. Kim, Y.S. Oh, W.S. Cho, D.S. Lim, D.S. Cheong, J. Alloys Compd. 274 (1998) 229. [8] D.S. Cheong, K.T. Hwang, C.S. Kim, J. Am. Ceram. Soc. 82 (4) (1999) 981. [9] H.J. Hwang, T. Nagai, T. Ohji, M. Sando, M. Toriyama, K. Niihara, J. Am. Ceram. Soc. 81 (3) (1998) 709. [10] H. Hyuga, Y. Hayashi, T. Sekino, K. Niihara, Nanostruct. Mater. 9 (1997) 547.

4. Conclusions PNN-PZT/Ag nanocomposites with nanometer-sized silver particles have been successfully synthesized by hot pressing at 850 8C for 2 h. Nanometer-sized silver particles in the nanocomposites apparently relieve residual stress much more effectively than micrometer-sized particles. The relaxation of the residual stresses affects the lattice parameters and transition temperatures of the nanocomposites.

Acknowledgement This work was supported by Korea Research Foundation Grant (KRF-2000-041-E00543).