TW381067B - Method for producing low-temperature firing piezoelectric ceramics - Google Patents

Description

V. Description of the invention (l) A7 B7 Background of the invention · PbZr03-PbTi〇3 (PZT) as the main component of the piezoelectric excellent piezoelectric properties, as early as the 1950s, it has been widely used parts, loudspeakers, ultrasound Ceramics such as vibrators, buzzers, piezoelectric delay lines, and other electrical-mechanical energy conversion elements have PZT piezoelectrics used for igniter filters and piezoelectrics. At this high temperature, the burn-in and microstructure components are miniaturized. The development method of electrical materials is firstly sintered with ceramics up to 100 μm. From tens to hundreds of ceramics, it has a high ratio of oxidation resistance and can be used at, for example, commonly used temperature ceramics. The sintering temperature must reach 1 The junction between 2 0 0 ° C and 1 350 ° C will cause severe volatilization of lead oxide, making piezoelectric control of the material difficult, and causing environmental pollution. In addition, with the development trend of low operating voltage g, multilayer components have been It is one of the mainstreams. Taking laminated piezoelectric actuators as an example, the manufacturing method uses doctor blade to make a porcelain slice with a thickness of 10. After coating the electrodes, it is then hot-pressed and stacked together. To obtain a large amount of displacement, the layer to be stacked In the meantime, the cost of the internal electrode being fabricated by the actuator is the same as the above example, and the electrode material used in the multilayer component is capable of co-firing at high temperatures. Platinum, palladium, silver and other precious metals such as palladium-silver alloys are required. As the content increases, the electrode material increases, and the relative cost also rises. Among them, p |} / Ag = 30/70 .-------- <-装 ------ Order- -----: Grade (please read the notes on the back before filling this page) The temperature printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs can be used below 1 150 t, as for the pure silver glue below 96 ° C, Therefore, how to reduce the sintered stratospheric piezoelectric actuator of piezoelectric ceramics is one of the important keys. In short, the development of piezoelectric ceramics below ° c can not only reduce energy loss and environmental pollution, but also change the inner M pole used for multilayer piezoelectric element co-firing to silver-based electrode materials, which greatly reduces the production cost . The sintering temperature becomes low-temperature sintering at a temperature of 960 ° C. (960) The reduction of the possible size of the paper is applicable to Chinese national standards (CNS> A4 specifications (210 X 297 mm). A7 B7 V. Description of the invention (In the high-voltage electrical strain constant ( d33) and electromechanical coupling coefficient material development 'PbZr03-PbTib3 binary system piezoelectric material requires high Kp, but the sintering temperature is often as high as 1250 ° C, the sintering temperature of the material is reduced, and high d33 and high Kp (K p Although the piezoelectric material can reach high d33, high; in order to make the piezoelectric good piezoelectric properties, one or two relaxation ferroelectric materials (Relaxor Ferroe 1 ec tr ics) such as Pb can be added to the composition adjustment. (Ni1 / 3Nb 3) 03 (PNN)

Pb (Zni, 3N.b2 / 3) 〇3 (PZN) spear mouth Pb (Mgi / 3Nb2 / 3) 〇3 (.) MN), and its components are taken near the so-called MPB (Morphotropic Ph, also near That is, Tetrahedral and Rhombohedral two-phase ase Boundary) coexist region to obtain higher d33 and Kp 値. In 1977, Bunno and others in Japan proposed the ternary phase diagram of PNN-PZ-PT. In 1981, the Sony Gazette PNN-PZN-PZ-PT quaternary piezoelectric ceramics was sintered at oxygen ° C ~ 1 200 and obtained Good piezoelectric characteristics; ^ US Pat. No. 4,765,9 19 describes in detail P203-PZ-PT piezoelectric ceramics such as Bi203 and Nb205, and the required sintering temperature is 1 200 ° C ~ 1 300 ° C; In the Kitamura atmosphere of the company, various properties of Sb203 can be added to Tomita and others in 1988. In the United States in 1989: HI I n IK ^ ^^^ 1 nm ^ i 11 ^ 11 n ^ i 1 -OJ (Please read the notes on the back before filling in this page.) Printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs, Japan, 1980

Choi et al. Reported that PMN-PT piezoelectric ceramics were sintered at 1 250 ° C, with a d33 値 of up to 669 pC / N: the lowest commercial sintering temperature currently known is not used by Tohoku Metals Corporation to make laminated piezoelectric actuators. The sintering temperature of the PNN-PZ-PT ternary series piezoelectric ceramics with f-number N-1 0 can reach 1100 ° C. Researches on using sintering aids to reduce the sintering temperature of piezoelectric ceramics. As early as 1979, Schulze et al. Of the United States proposed that adding a large amount of Pb5Ge3Ou (up to 30% by weight) in PZT ceramics can bring the sintering temperature to 1000 °. Below C, but the piezoelectric properties are significantly reduced due to the high amount of addition 2 The paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 0 X 297 mm) V. Description of the invention (3) + NaF) makes PZT Dielectric constant

Takahashi added 5 ~ 1 5mol% (2PbF sintering temperature from 1 2 0 ° C to 8 0 0 ° C in PZT, but the material (ε ^) 'mechanical coupling coefficient (kr) and mechanical quality coefficient (Qm) The addition of an amount in the U.S. patent makes the PZT ceramics decline. In 1980, the sintered capacitor industry of BaTi, 03 followed the properties of (fie02, Si02, etc. compounds, CdO, CuO, and so on. Therefore, it is not a sintering aid, Increase and decrease significantly: 1 98 1 Witter and Buchan No. 4, 2 83, 2 8 8 pointed out that the addition of 0.25 ~ 6wt% V205 can reduce the sintering temperature to 960 ° C, but its piezoelectric characteristics will follow the initial generation of BaTi03. The low-temperature sintering technology has matured, and the temperature has dropped from more than 1300 ° C to 1100 ° C. The multilayer ceramics have developed vigorously. The sintering aid used in it is B203 glass former as the main body (GlassFormer) to synthesize low-melting and energy. The PbO and BaO entering the perovskite structure have a good piezoelectricity to reduce the doping temperature to 900 transducers and filter materials. In addition, the formation of B2O3 glass reduces 03, Si02,

ZnO 'Bi203 and other modifications! j (Modifier) is used to adjust the material for low-temperature sintering of piezoelectric materials. Mostly, glass powder is used. For example, SY Cheng and others at Chenggong University in 1986. Li2C03, Na2C03, and B203 are added to PZT doped with Nb205. It is a sintering aid, but its sintering temperature can only be reduced to 1070 ° C. In 1989, Guizhi Lun and others in China added 1 ~ 5wt% of B203-Bi203-Cd0 to PZT material doped with manganese, which effectively reduced the sintering temperature from 1250 ° C to 96 ° C, and maintained the characteristics. In addition, They also used Pb0-Si02 as a sintering aid for the firing of PNN-PZ-PT ternary piezoelectric ceramics with manganese and cadmium. C 'Guizhi Lun et al's research purpose was to develop the high Qm required for the controller , High-κρ, low-temperature sintered piezoelectric materials Wu Lang of Gong University et al. Reported in 1 993 that the sintering temperature of pbO-piezoelectric materials was used. All the above studies were added with B%. V. Description of the invention (4) kl B7 G eCh The glass-forming agent is added to increase the melting point of the piezoelectric material in the low-burning and low-burning agent, but the small ionic radius prevents the glass phase from remaining on the grain boundary, which can adversely affect the material. The invention refers to the need for low temperature sintering of high d33 and high Kp piezoelectric ceramics. PXN-PbZr03-PbTi03 piezoelectric ceramics, where PXN =: PNN, PZN or PMN 'are added without the aid of glass-based agents such as 8203, Ge02, and Si02. The sintering agent enables high-d33 and high-KP piezoelectric ceramics to be sintered below 960 ° C. The gas properties can be used to reduce lead pollution and reduce the mechanical properties of the dissolution of the internal electrode agent of the laminated piezoelectric element and reduce the dissolution into the perovskite crystals, and can reduce the cost when maintaining a good electrical component. (Please read the notes on the back before filling out this page)

Illustration of the relationship between sintering density and sintering temperature of B1 — ^ 0.40PNN-0.23PZ-0.37PT ^ 1. Figure 2 shows the relationship between d33 'Kp and sintering temperature of 0.40PNN-0.23PZ-0.37PT with 1 added. Detailed description of the present invention In the preparation of piezoelectric materials, the present invention uses PbO 3wt% burning aid 3wt% burning aid

NiO, ZnO, -1 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

MgO, Nb205, Ti〇2, Zr〇2 are used as raw materials, according to the measurement ratio of PXN-IfbZr03-PbTiO, where PXN = PNN, PZN or PMN, and then wet-milled with Zr〇2 balls and mixed. 850 ° C ~ 6 hours to synthesize perovskite structure; does not contain B203, G glass forming agent, low temperature sintering aid, its composition is or PbO)-z (CuO or ZnO), where x + y + z = powder required for weighing ~ 900 calcined 3 e02, Si02, etc. xCd0-y (Bi203, 0.40 $ x 4) This paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) Department t

A Standard Employee Consumption Cooperation Du printed A7 B7 V. Description of the invention (5) S 0.80, 0.20S 0.50, 〇 $ 〇0.20, weighed in proportion, wet-milled and mixed, at 5 00 ° C ~ 70, ° C Calcination for 3 ~ 6 small days: f 'Subsequently take 1 ~ 5wt% of the burning aid and piezoelectric powder, mix them together with Zr〇2 ball mill, dry and add 1 ~ 2wt% PVA for granulation, and pass through the sieve〗 i Be pressed into a 15 mm φ xl.5mm1 'wafer; the wafer is placed in a crucible and sealed and sintered. It can also be opened in a high temperature furnace. The sintering temperature is 8 50 ° C ~ 1 000 ° C. The sintering time is 3 to 6 hours; the sintered test piece is ground to a thickness of about 1 mm, polished with 3um Al203 powder, and coated with silver glue on both sides as the electrode. In Silicon oil at about 100 ° C, an electric field of about 20 to 3 Ok V / cm is applied for 5 to 10 minutes for polarization; the polarized test piece is left at room temperature for 24 hours, and the measurement frequency is 1 KHz. ε 3 3 and tan 6 値 'piezoelectric parameters are measured using the IRE Standards test gauge | Fan, using the HP4194 impedance analyzer to measure the resonance frequency and anti-communication of the test piece Frequency, thereby obtaining the material Kp, Qm, as to pressure of the material strain constant d33 meter the amount of available places. Example: According to the measurement ratio of 0.40PNN-0.23PZ-0.37PT, 1 weigh the appropriate amount of PbO, NiO, Nb205, Ti〇2, Zr〇2 powder, and then grind for 16 hours. After drying, forging at 85 0 t Burn for 3 hours to synthesize the perovskite structure. The composition of the sintering aid is 0-50CdO-0.45Bi203-0.05CuO, weighed according to luxury j, mixed by wet milling for 16 hours, and calcined at 600 ° C for 3 hours. 1 ~ 3 wt% of burn aid with 0.40PNN-0.23PZ-0.37PT powder as main component, --- Wet mill with Zr02 ball for 20 hours, dry, granulate, and shape at 850. . ～ 100 ° C sintering time is 3 ~ 6 hours. After the sintered test piece has undergone 硏 | _ 5 丨 1, the size of the double-sided coated paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) .. .......... Please read the back of the clothes order first and then fill out this page. V. Description of the invention (6) ΑΊ B7 With silver glue as the electrode, polarization conditions 90 ° C, 20kV | / cm, 6 minutes; The polarized test piece was left at room temperature for 24 hours, and then subjected to various electrical tests. Table 1 is 0.40PNN-0.23PZ- 0.37PT without adding a combustion aid. The ψ properties of the powder were measured after sintering the powder at ^ 1 05 0 ° C ~ 1? 0 0 t for 3 hours (the theoretical density of sintering), with the composition at 1 2 0 0. (3 1.8%, tL = density needs to be above 1 1 50 ° c to reach 7.9g / cm3 (96% due to low piezoelectric and dielectric parameters at this temperature, this 4 163 sintering can obtain the best characteristics : Ε 3: 610pC / N, kp = 0.69. Figure 1 shows 0.40PNN-0.23PZ-0.37PT with the addition of tai 1 wt% sintering agent 0.50CdO-0.45Bi2〇3-〇〇5CuO, and its sintering temperature needs 2 950 ° C, dense

The density can reach more than 7.9g / cm3, and the added amount can be increased to 2 ~ ° C to obtain good density. Figure 2 shows 0.40PNN wt% with lwt% burning aid at 900.

0.23PZ-0.37PT need to be at 1000 ° C to get higher d33 and Kp 者, if the amount is 2wt% C, please read the precautions on the back before filling this page}-= &amp; Ministry of Economic Affairs The quasi-station employee consumer cooperative has good piezoelectric characteristics (d Kpg 0.63) printed at 900 ° C to 100 ° C, but when the amount is increased to 3wt%, the material slightly decreases. Table 2 shows the properties of 0.4 0PNN-0 electric ceramics with 2wt% sintering aid at 850 ° C ~ 1000 ° C for 3 ~ 6 hours. Among them, it is sintered at 850 ° C for 3 hours, and the density is 7 Even if the junction time is extended to 6 hours, the piezoelectric and dielectric parameters obtained after the junction temperature rises to 9 0 ° C, the sintering time is 3 or 6 hours, and the obtained piezoelectric characteristics are equivalent to those of 95 0 ° C, 1 000 ° C. It shows the alignment of this material. The piezoelectric coefficient of P, 3 ^ 540pC / N &gt; obtained over a wide temperature range will be 3PZ-0.37PT. The measured material is 9g / cm3, but the firing is still low; and Burning L. 3 3 Sintering temperature insensitivity ta η 5, d 3 3 and 6 This paper size is applicable to China National Standards (CNS) A4 specifications (2 丨 OX297 mm) Ministry t Central Standards Bureau staff printing A7 B7 V. Description of the invention (7) Kp changes and the chemical conversion is small. In the open-type sintering test without PbO atmosphere compensation, the dielectric and piezoelectric characteristics obtained after sintering at 900 ° C for <hours are comparable to those with PbO atmosphere compensation. Therefore, Cd〇_Bi2〇3_ CuO was added after Sintering at low temperature can greatly reduce the volatilization of PbO and reduce possible environmental pollution. When the sintering temperature drops to 900 ° C, the internal electrode used to make the multilayer piezoelectric element can be replaced with silver electrode instead of expensive platinum or palladium. Can significantly reduce the cost of manufacturing components. In addition, the test piece sintered at 900 t was thinned to 25 // m, and g Dengming had good mechanical strength. 7 This paper size applies to the Chinese national standard (CNS> A4 size (210X297mm) Please read the Φ item on the back and fill in this page to order A7 B7 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Form of Invention (8) 1. · 0.40PNN-0.23PZ-0.37PT sintering without the addition of a combustion aid j • All properties of the constitution Tsint Time P (g / cm3) ^ 33 tan 5 (%) ^ 33 Kp Qm 1050 ° C 3h 7.61 2993 2.07 506 0.589 70 1100 ° C 3h 7.80 3149 1.86 533 0.624 74 1150 ° C 3h 7.90 3502 1.84 555 0.654 70 1200 ° C 3h 7.96 4163 1.80 610 0.696 63 Table 2: 0.40 PNN-0.23PZ of Timlikou 2wt% burn aid All characteristics of -0.37PT sintered body Tsint Time p (g / cm3) ε 33 tan δ (%) d33 Kp Qm 85〇t: 3h 7.93 3430 2.50 475 0.569 67 850 ° C 6h 7.98 3688 2.16 527 0.590 62 900 ° C 3h 7.95 3987 2.05 540 0.635 65 900 ° C 6h 7.96 3756 2.10 555 0.648 63 900 ... * 6h 8.00 3860 2.09 545 0.640 63 950¾ 3h 8.02 3860 2.09 550 0.645 62 1000 ° C 3h 8.00 3915 1.95 560 0.650 65 A open sintering 8 -------- 1 Install 丨 _ ^-. 丨 -Order ------ (Please read the Precautions to fill out this page) This paper scale applicable Chinese National Standard (CNS) A4 size (210X297 mm>

Claims (1)

The method is based on the composition of Nil / 3Nb2 / 3) 03, high kp 値 piezoelectric ceramic degree reduced to 96 (TC is determined by g sintering aids) [Cd0-y (Bi203 or p.20 ^ y ^ 0.50 »(Nij / 3Nb2 / 3) 〇3 -ft% sintering aid below ° C and maintaining 1. A local d; j3 値 piezoelectric ceramic low temperature sintering method, using this PXN- PbZr〇3- PbTi03 (where ρχΝ = pb (Pb (Zn! / 3Nb2 / 3) 〇3 or Pb (Mg 丨 / 3Nb2 / 3) 〇3) series of high d33 porcelain 'can be sintered at a specific temperature by adding a specific amount of sintering aid, and can maintain Excellent electrical properties such as piezoelectricity and dielectric. This glass forming agent contains B203, Ge02, and Si02. Its composition is PbO) -z (CuO or ZnO) 'where x + y + z = ι 〇〇〇〇〇〇〇〇〇〇〇 0〇, 0SzS0.20, the required amount of addition is 1 ~ 5 wt%. 2. According to the method of the scope of the first patent application, applied to 0.40Pt 0.23PbZr03-0.37PbTi03 piezoelectric material After adding 2 ~ 3 0.50CdO-0_45Bi203-0.05CuO, the sintering temperature can be reduced to 96. Good piezoelectric characteristics. (Please read the precautions on the back before filling this page) ♦ 1T Central Ministry of Economic Affairs Industrial and consumer cooperatives printed on paper Like quasi (CNS) A4 size (210X297 mm) The method is based on the composition of Nil / 3Nb2 / 3) 03, high kp 値 piezoelectric ceramic degree reduced to 96 (TC is determined by g sintering aids) [Cd0-y (Bi203 or p.20 ^ y ^ 0.50 »(Nij / 3Nb2 / 3) 〇3 -ft% sintering aid below ° C and maintaining 1. A local d; j3 値 piezoelectric ceramic low temperature sintering method, using this PXN- PbZr〇3- PbTi03 (where ρχΝ = pb (Pb (Zn! / 3Nb2 / 3) 〇3 or Pb (Mg 丨 / 3Nb2 / 3) 〇3) series of high d33 porcelain 'can be sintered at a specific temperature by adding a specific amount of sintering aid, and can maintain Excellent electrical properties such as piezoelectricity and dielectric. This glass forming agent contains B203, Ge02, and Si02. Its composition is PbO) -z (CuO or ZnO) 'where x + y + z = ι 〇〇〇〇〇〇〇〇〇〇〇 0〇, 0SzS0.20, the required amount of addition is 1 ~ 5 wt%. 2. According to the method of the scope of the first patent application, applied to 0.40Pt 0.23PbZr03-0.37PbTi03 piezoelectric material After adding 2 ~ 3 0.50CdO-0_45Bi203-0.05CuO, the sintering temperature can be reduced to 96. Good piezoelectric characteristics. (Please read the precautions on the back before filling this page) ♦ 1T Central Ministry of Economic Affairs Industrial and consumer cooperatives printed on paper Like quasi (CNS) A4 size (210X297 mm)