Jpn. J. Appl. Phys. Vol. 40 (2001) pp. 49484951 Part 1, No.

8, August 2001 c 2001 The Japan Society of Applied Physics

Magnetoelectric Properties in Piezoelectric and Magnetostrictive Laminate Composites

Jungho RYU1,2 , Alfredo V zquez C ARAZO1 , Kenji U CHINO1 and Hyoun-Ee K IM2 a
1 International

Center for Actuators and Transducers, Materials Research Laboratory, The Pennsylvania State University, University Park, PA 16802, USA 2 School of Materials Science and Engineering, Seoul National University, Seoul, 151-742, Korea (Received November 15, 2000; accepted for publication May 17, 2001)

Magnetoelectric laminate composites of piezoelectric-magnetostrictive materials were investigated. The composites were prepared by stacking and bonding Pb(Zr, Ti)O3 (PZT) and Terfenol-D disks. Experimental results indicated that the magnetoelectric voltage coefcient, dE/dH, increased with decreasing thickness and increasing piezoelectric voltage constant (g31 ) of the PZT layer. We obtained the highest magnetoelectric voltage coefcient of 4.68 V/cmOe at room temperature for the sample with high g33 PZT of 0.5 mm in thickness. This value is about 36 times higher than the best reported value.
KEYWORDS: magnetoelectric, magnetostrictive, piezoelectric, composites, Terfenol-D, PZT

1. Introduction Magnetoelectric effect is a behavior of a material to generate electric voltage when it is subjected to a magnetic eld. The magnetoelectric effect can be used in various applications such as microwave eld and current measurement.1, 2) Microwave devices and high power electric transmission systems require an accurate measurement of the electromagnetic leak signal generated from these devices, from a viewpoint of human health. Also, a magnetoelectric sensor will be an alternative tool of the Hall sensor for magnetic eld measurement. There are several magnetoelectric single phase materials discovered in the last three decades. Nevertheless, the use of these materials on device applications has not been successful mainly due to one important reason. Most of them have low Neel or Curie temperature below the room temperature, hence they exhibit the magnetoelectric (ME) effect at low temperatures.1, 3) The magnetoelectric coefcient drops to zero as the temperature reaches the transition temperature, making difcult the applications of this single phase magnetoelectric materials for common applications. In order to overcome this problem, ceramic composites can be considered.4) Certainly, ceramic composites exhibiting the magnetoelectric effect in a wide temperature range can be designed.5) The magnetoelectric effect can be factorized perhaps in various ways.4, 5) One way is to use the product property of the piezoelectric and magnetostrictive effects.58) Another way is to use the product property of the pyroelectric and magnetostrictive effects.9) A composite material of magnetostrictive and piezoelectric materials can be explained as follows. When a magnetic eld is applied to the composite, the magnetostrictive material is strained. This strain induces a stress on the piezoelectric, which generates the electric eld. The converse effect is also possible, in which the electric eld applied to the piezoelectric material produces strain, which is transferred as stress to the magnetostrictive material. This causes the change in magnetic permeability of the material. In both case, the product property resulting in such composites is the magnetoelectric effect in which an applied magnetic eld induces an electric eld, and an applied electric eld induces the change in magnetic permeability in the composite. In 1972, Philips developed a magnetoelectric material based on this concept.58) The material was composed of several magnetostrictive ferrites such as CoFe2 O4 and piezoelec-

tric BaTiO3 mixed and sintered together. However, they used unidirectional solidication process of eutectic melts, as a result, the temperature of processing was too high to avoid any chemical reaction of the phases. Therefore, other third phases such as Co2 TiO4 and (BaFe12 O19 ) y (BaCo6 Ti6 O19 )1y were present in their composites.6) These might cause reasonable drop in the piezoelectric or magnetostrictive properties of the component phases. Thus, the magnetoelectric property of their unidirectional composites (dE/dH = 0.13 V/cmOe), though higher than the other sintered particulate composites,6) was not high enough to be cased in practical applications. These problems may be overcome by using a laminar composite type, because no chemical reaction is involved in the fabrication process. Recently, electro-magnetic bending element from Pb(Zr, Ti)O3 (PZT) and Fe-based magnetostrictive thin lm was reported by Shin et al.10) According to their research, magnetostrictive lm was sputtered on the glass plate and bonded with PZT plate. Their structure would be applied to magnetoelectric composites also. However, in applications such as magnetic eld detecting sensor, the level of output electric signals are more important than electromagnetic response. Though their structure seems to be similar to our laminate composites, the structure does not fulll this criterion. The objective of this paper is to investigate the possibility of fabricating magnetoelectric laminate composites suitable for practical magnetic noise sensing applications using PZT and Terfenol-D for piezoelectric and magnetostrictive materials, respectively. The simple fabrication technique of the laminate composite (2-0 composite)3) on a macroscopic scale can have advantages in tailoring design patterns for magnetic noise sensing. 2. Experimental Procedure 2.1 Materials As a magnetostrictive material, a high magnetostrictive property under a relatively low magnetic eld bias is preferred. Since magnetostriction properties are present in most of magnetic materials, there are multiple choices of materials including the ferrites and the ferromagnetic metals. In general, both the magnitude of magnetostriction and the slope of magnetostriction as a function of applied magnetic eld

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should be large, in order to achieve a high value of pseudopiezomagnetic effect in the magnetostrictive material. In the case of laminate composites, highly conductive ferromagnetic materials such as Fe-based magnetostrictive ribbons or lms can be used when the operation frequency is so low that the eddy current loss should remain low. However, the manufacturing cost of Fe-based magnetostrictive ribbons or lms are relatively expensive, and it is difcult to make thick plate or disk, although they have excellent magnetostriction. In this regards, we chose TbDyFe2 (Terfenol-D) magnetostrictive alloy (Etrema Products Inc., IA, USA) for our composites, because of superior magnetostriction (max = 1600 106 ) and coupling factor (k = 0.70),11) as well as easy fabrication of thick disk which can produce the enough stress to generate electric charge from PZT disk. Regarding a piezoelectric material, PZT is one of the most ideal piezoelectric materials for these composites because of their high piezoelectric constants. In order to explore the response of the composites for different piezoelectric materials, three types of PZT powders were tested: APC-841 (American Piezoceramics Inc., PA, USA), APC-840 (American Piezoceramics Inc., PA, USA), and PZT-5A (Morgan Matroc Inc., OH, USA). 2.2 Sample Preparation PZT disks were prepared by the conventional ceramic process. PZT pellets were pressed using cold isostatic pressing at a pressure of 272 MPa for 10 min and sintered at 1200 C for 2 h in atmosphere powder bed. After sintering, pellets were ground and machined to a diameter of 12.7 mm and a different thickness of 0.5, 0.6, and 0.7 mm using an ultrasonic punching machine. Machined PZT disks were electroded by gold sputtering and electrically polarized under the electric eld of 3 kV/mm. Terfenol-D disks were also machined to a dimension of 12.7 1 mm. The thickness of TerfenolD disks was always 1 mm. PZT and Terfenol-D disks were stacked using silver epoxy (E-Solder No. 3021, ACME Division of Allied Products Co., CONN, USA) and cured at 80 C for 4 h for good mechanical coupling. Figure 1(a) shows the schematic structure of a laminar composite sample and (b) is a photograph of the assembled devices. 2.3 Measurements The magnetoelectric voltage coefcient was determined by measuring the electric eld generated across the sample when an a.c. magnetic eld and a d.c. bias were applied to it. The magnetoelectric property was measured in terms of the variation of the coefcient dE/dH as a function of d.c. magnetic bias eld. An electromagnet (GMW 5403 Magnet, Power and Buckley Inc., New Zealand) was used for the bias eld up to 0.45 T (4.5 kOe). The frequency dependence of the magnetoelectric voltage coefcient of composites was determined in the range of 10 Hz to 3 kHz under a 1 kOe d.c. bias. The coefcient was measured directly as response of the sample to an a.c. magnetic input signal at 1 kHz and 2 Oe amplitude (Helmholtz coils were used to give a uniform a.c. eld in the space between the coils) superimposed on the d.c. bias eld, both parallel to the sample axis. A signal generator (33120A, Hewlett Packard Co., USA) was used to drive the Helmotz coils and generate the a.c. magnetic eld. The voltage generated in the piezoelectric layer

was measured under an open circuit condition.12) A differential amplier based on the INA121 FET-input Instrumentation Amplier from Burn-Brown Inc. was used. This amplier is specially designed for high impedance transducers, providing differential input impedance in the order of 1012 G /1pF, which represents almost an ideal open circuit condition.13) The electric circuit of the amplier is shown in Fig. 2. The output signal from the amplier was measured with an oscilloscope (54645A, Hewlett Packard, USA). The output voltage divided by the thickness of the sample and the a.c. magnetic eld gives the magnetoelectric voltage coefcient of the samples.

(a)

Polarization

Shrink

Terfenol-D

PZT

Magnetic Field

(b)

Fig. 1. Magnetoelectric lamina composite using TERFENOL-D and PZT disks. (a) schematic structure, and (b) photograph of the device.

V+

0. 1 F

Over Voltage Protection

+ _
25k

40k

40k

_ +
40k 40k

VIN
Over Voltage Protection

_ +

25k

VOUT

INA121
0. 1 F

1 M

1 M

V-

Fig. 2. Amplier circuit for magnetoelectric voltage measurement.

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Jpn. J. Appl. Phys. Vol. 40 (2001) Pt. 1, No. 8 Table I. Piezoelectric properties of PZT materials used in this study. Materials APC840 PZT-5A APC841 T33 /o 1250 1730 1250 tan (%) 0.4 1.5 0.35 d33 (pC/N) 320 340 275 g33 (mVm/N) 25.6 19.6 22.0

J. RYU et al.

Qm 500 68 1400

kp 0.59 0.57 0.60

3. Results and Discussion The effect of the PZT material on the magnetoelectric effect of the laminate composites was studied on the samples consisting of two Terfenol-D disks and a PZT disk. Table I shows the piezoelectric properties of PZT materials used in this study. Figure 3 shows the magnetostriction response of Terfenol-D disk as a function of applied magnetic eld. The maximum strain of Terfenol-D used in this article was 1250 ppm. Figure 4 shows the magnetoelectric voltage coefcient variation as a function of the d.c. magnetic bias with three different PZT disks. All PZT disks were machined down to the same thickness (0.5 mm) and diameter (12.7 mm). The mag-

2000

Strain (x10 )

-6

1500

1000

netoelectric voltage coefcients of all composites were increased with increasing d.c. bias, and saturated around 4 kOe. Since the sensitivity is mainly determined by the piezoelectric voltage coefcient (g33 ), the composite with APC-840 PZT showed the most superior magnetoelectric property. The maximum magnetoelectric voltage coefcient for this composite was 4.68 V/cmOe under 4.2 kOe d.c. magnetic bias or higher. To use this composites for practical magnetic eld sensing applications, d.c. magnetic bias should be applied into composites. For that, Samarium Cobalt permanent magnet pair can be employed and can be obtained more than 1 kOe of d.c. magnetic bias from them. Figure 5 shows the magnetoelectric voltage coefcients for PZT and Terfenol-D laminate composites measured at 1 kHz of a.c. magnetic eld as functions of d.c. magnetic bias eld and thickness of the APC 840-PZT layer. The magnetoelectric voltage coefcient was found to increase with decreasing thickness of PZT layer. This can be explained by the increase in compressive stress in the PZT layer with decreasing the thickness of PZT. The compressive stress in the PZT layer and the tensile stress in the Terfenol-D layers can be derived from the simple beam theory and plane stress condition, as indicated in eqs. (1) and (2):14)
E 31t =

500
E 31p =

E t E p tp o , (1 )(2E t tt + E p tp ) 2E t E p tt o , (1 )(2E t tt + E p tp )

(1) (2)

0 -2

-1

Magnetic Field (kOe)

Fig. 3. Magnetostriction response of Terfenol-D as a function of applied magnetic eld.

where E, t, o , and are the elastic modulus, thickness, the linear strain of the Terfenol-D layer, and poissons ratio, respectively. The subscript t or p means Terfenol-D or PZT, respectively. As shown in those equations, the compressive stress in the PZT layer is increased with decreasing thickness of PZT layer or increasing thickness of Terfenol-D layer.

5000

dE/dH (mV/Oe cm)

4000

dE/dH (mV/Oe cm)

APC 840 PZT-5A APC 841

5000

4000

3000

3000

2000

2000

1000

1000

0.5 mm PZT(APC840) 0.6 mm PZT(APC840) 0.7 mm PZT(APC840)

0 1000 2000 3000 4000 5000

1000

2000

3000

4000

5000

Magnetic Field (Oe)

Fig. 4. Magnetoelectric voltage coefcient as a function of applied d.c. magnetic bias with various PZT disk (APC 840 for high g33 , PZT-5A for high d33 , APC 841 for high Q m ). At 1 kHz.

Magnetic Field (Oe)

Fig. 5. Magnetoelectric voltage coefcient as a function of applied d.c. magnetic bias with various thickness of PZT layer. At 1 kHz.

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dE/dH (Arb.Unit)

dE/dH

voltage decreases with increasing thickness ratio. Both values saturate above thickness ratio of 10. The value of output voltage is more important than magnetoelectric voltage coefcient for practical sensor applications. Therefore, lower thickness ratio (less then 10) is more suitable, though magnetoelectric voltage coefcient increases with thickness ratio. 4. Conclusion Magnetoelectric laminate composites of PZT and TerfenolD were fabricated for magnetic eld sensing applications. Three different PZT compositions were used to analyze the material property dependence. Several thickness in the piezoelectric layer were also tested for verify the thickness dependence. We obtained the highest magnetoelectric voltage coefcient at 1 kHz of 4.68 V/cmOe at room temperature from the sample with a high g33 PZT with 0.5 mm in thickness, which is about 36 times higher than the best value reported by Philips. The piezoelectric voltage coefcient (g31 ) of the PZT material seems to be the most important factor for obtaining high magnetoelectric voltage coefcients in these PZT/Terfenol-D laminar composites.

dV/dH (Arb. Unit)

dV/dH

Thick PZT
0 5 10 15 20

Thin PZT
25

Thickness Ratio (tt/tp)

Fig. 6. Theoretical expectation of the magnetoelectric voltage coefcient as a function of thickness ratio (tt /tp ) between Terfenol-D and PZT layer.

Since the thickness of the Terfenol-D is xed as 1 mm, with decreasing the PZT layer thickness, the compressive stress in the PZT layer is increased. The output voltage from the composite can be expressed by the following eqs.:
E Vout = 2 g31 tp 31p , E 2 g31 31p Vout dE = = dH Hac tp Hac

(3) (V/cmOe). (4)

Therefore, higher output voltage can be obtained when the compressive stress in the PZT layer is higher, i.e., thinner PZT layer. From these equations, output voltage from the composite is also directly proportional to the piezoelectric voltage constant g31 . Generally in the PZT ceramics, the piezoelectric voltage constant g31 is around 1/3 of g33 . In this regard, the laminate composite made by APC-840 with the highest g33 can show the highest magnetoelectric voltage coefcient, as shown in Fig. 3. Figure 6 shows the theoretical expectation for the magnetoelectric voltage coefcient (dE/dH) and the output volage (dV/dH) as a function of the thickness ratio (tt /tp ) between Terfenol-D and PZT. The magnetoelectric voltage constant increases with increasing thickness ratio (tt /tp ), but output

1) T. H. ODell: Electron. Power 11 (1965) 266. 2) L. P. M. Bracke and R. G. van Vliet: Int. J. Electron. 51 (1981) 255. 3) K. Uchino: Comprehensive Composite Materials (Elsevier, Amsterdam, 2000) Vol. 5, Chap. 5.24, p. 523. 4) R. E. Newnham: Ferroelectrics 68 (1986) 1. 5) V. Suchetelene: Philips Res. Rep. 27 (1972) 28. 6) J. van den Boomgaard and R. A. J. Born: J. Mater. Sci. 13 (1978) 1538. 7) J. van den Boomgaard, A. M. J. G. Van Run and J. Van Suchtelen: Ferroelectrics 10 (1976) 295. 8) J. van den Boomgaard, D. R. Terrell, R. A. J. Born and H. F. J. I. Giller: J. Mater. Sci. 9 (1974) 1705. 9) R. E. Newnham, D. P. Skinner and L. E. Cross: Mater. Res. Bull. 13 (1978) 525. 10) K. H. Shin, M. Inoue and K. I. Arai: IEEE Trans. Magn. 34 (1998) 1324. 11) A. B. Flatau, M. J. Dapino and F. T. Calkins: Comprehensive Composite Materials (Elsevier, Amsterdam, 2000) Vol. 5, Chap. 5.26, p. 563. 12) A. V. Carazo: Ph.D Thesis, Universidad Polit` cnica de Catalunya, e Spain, 2000. 13) Burr-Brown Corporation Datasheet: http://www.burr-brown.com. 14) A. V. Virkar, J. L. Huang and R. A. Cutler: J. Am. Ceram. Soc. 70 (1987) 164.