DIELECTRIC CERAMIC MATERIAL

Abstract: A dielectric ceramic material used as a protective coating or a substrate material of a magnetic head for video tape recorders and microfloppy disks. The dielectric ceramic material of the invention has a basic composition expressed by [(Ca 1-3/2y Bi y )O] 100-x (TiO₂) x wherein x ranges from 40 to 80 mol %, y ranges from 0.005 to 0.6 mol ratio, and/or ZnO is added to the basic composition in an amount of 0.5 to 7.0 parts per 100 by weight. With this composition, a dielectric ceramic material is obtained having fewer pores and a high density, and this is accomplished by an ordinary baking method. Further, the coefficient of thermal expansion can be varied depending upon the amount of Bi substitution.

Description: DESCRIPTION TITLE OF THE INVENTION DIELECTRIC CERAMIC MATERIAL TECHNICAL FIELD The present invention relates to a dielectric ceramic material and more particularly to a dielectric ceramic material of CaO-TiO2 type exhibiting optimum characteristics as a guard member, a substrate member and so on for a magnetic transducer head used in, for example, a video tape recorder, a floppy disk drive and so on. BACKGROUND ART Generally, in a magnetic transducer head used in a video tape recorder, a micro-floppy disk. drive and so on, a non-magnetic guard member is disposed to grip a magnetic gap so as to form a part of its contact surface for a magnetic recording medium. The prior art guard member having CaO and TiO2 as its main composition uses oxides of Aç, Si, Ca, Mc, Sn, Zr, Ba, Sr and so on as an additive in order to reduce the pores thereof. However, the firing temperature of the guard member is high in general and the pores can not be reduced so much. Therefore, there may occur such phenomenon that magnetic powders adhere to the pore or that chipping of the guard member causes change on the magnetic transducer head of magnetic recording medium such as a magnetic sheet. Further, in order to reduce the pores, HIP (hot isostatic press) treatment and hot press treatment, etc. have to be carried out, increasing the manufacturing cost of the dielectric ceramic material. In addition, a difference between thermal expansion coefficients of the guard member and a magnetic core member causes the guard member to be cracked or peeled off upon bonding. In view of the above mentioned aspects, the present invention is to provide a dielectric ceramic material which can be made high in density by the normal firing without special treatment and which can present a desired thermal expansion coefficient. DISCLOSURE OF INVENTION The present invention relates to a dielectric ceramic material which is made by such a manner that in a fundamental composition expressed by { (Cal¯3/2 Bi) } 100-x (TiO2)x where x is selected in a range from 40 to 85 mol %, y is selected in a range from 0.005 to 0.6 molar ratio and/or 0.5 to 7;0 parts by-weight of ZnO are added to 100 parts by weight of the above mentioned fundamental composition and then the mixture is fired. Where such a case that ZnO is added to the fundamental composition, the above substituting amount y of Bi includes zero. That is, in this case, the dielectric ceramic material is made such that to the main composition of CaO and TiO2, part of its Ca substituted with Bi, ZnO is added thereto or both of them are added thereto. According to this invention, a dielectric ceramic material which is less in pore and high in density can be obtained by the normal firing method. Also, the thermal expansion coefficient thereof can be varied by the substituted amount of Bi. BEST MODE FOR CARRYING OUT THE INVENTION Examples of this invention will be described hereinafter. In the present examples, TiC2, CaC03, Bi2O3 and ZnO, which would become components, were mixed in a ball mill by the wet mixing method. After the mixture being dried, the product was pulverized and calcined at a temperature between 7500C and 9000C. Thereafter, the powders pulverized were molded under a pressure ranging from 1.0 to 2.0t/cm2 and then fired, thus a dielectric ceramic material being formed. The firing was carried out in the oxigen atmosphere at a temperature between 12000C and 13500C. Various characteristics of the resultant samples (dielectric ceramic materials) are indicated on respective tables. On each table, the thermal expansion coefficient was measured at a temperature between 500C and 400 C. The pore rank was determined as follows. Rank 3 indicates that the diameter of pore lies in a range from about 5 to 10um; rank 4 indicates that the diameter of pore lies in a range from about 3 to 5m; and rank 5 indicates that the diameter of pore is equal to or smaller than 3ism. The above mentioned firing temperature is only an example and can be varied within a range of about 1000C relative to such firing temperature. Example 1 1.0 part by weight of ZnO was added to 100 parts by weight of a mixture of 55 mol % of TiO2 and 45 mol % of (Cal 3/2v Bi )O and a substituting amount y of Bi was varied y from 0 to 0.6, thus to make samples 1 to 12. Various characteristics, such as density (g/cm3), pore rank and thermal expansion coefficient (x 10 7 1/or) of the respective samples are indicated on a table 1. From the table 1, it will be noted that as the substituting amount of Bi was increased, the firing temperature was lowered and the thermal expansion coefficient was varied from 120 x 10 7 1/,C to 80 x 10 7 l/oC. Example 2 The adding amount of ZnO to 100 parts by weight of a mixture of 55 mol % of TiO2 and 45 mol % of (Cag.97 Bio 02) 0 was varied from 0 to 7 parts by weight, thus respective samples 13 to 18 being made. The various characteristics of the respective samples are indicated on a table 2. From table 2, it will be clear that even when the adding amount of ZnO was varied, the thermal expansion coefficient was not varied substantally. It should be noted that when the adding amount of ZnO exceeded 7 parts by weight, the bending strength and so on were lowered. Example 3 1.0 part by weight of ZnO was added to 100 parts by weight of a mixture of x mol % of TiO2 and (100-x) mol % of (CaO 925 Bio 05) 0 and the x mol % of TiO2 was varied from 55 to 85, thus respective samples 19 to 23 being made. The various characteristics of the respective samples are indicated on a table 3. From the table 3, it will be apparent that as the x mol % of TiO2 was increased, the thermal expansion coefficient a was lowered and that the pore rank was not changed at all. Example 4 3.0 parts by weight of ZnO was added to 100 parts by weight of a mixture of x mol % of TiO2 and (100-x) mol % of (CaO 97 Bio 02) O and the mol % of TiO2 was varied from 40 to 70, thus respective samples 24 to 27 being made. The various characteristics of the respective samples are indicated on a table 4. Example 5 1.0 part by weight of ZnO was added to 100 parts by weight of a mixture of x mol % of TiO2 and (100-x) mol % of (Ca0 7 Bio 2) and the x mol 8 of T102 was varied in a range from 50 to 75, thus respective samples 28 to 31 being made. The various characteristics of the respective samples are indicated on a table 5. From the tables 4 and 5, it should be noted that the examples 4 and 5 both had the same tendency as the example 3. Example 6 1.0 part by weight of ZnO was added to 100 parts by weight of a mixture of 70 mol % of TiO2 and 30 mol % of (Cal 3J2 Bi ) 0 and the substituting amount y of Bi was y varied from 0.05 to 0.3, thus respective samples 32 to 35 being made. The various characteristics of these samples are indicated on a table 6. Example 7 1.0 part by weight of ZnO was added to 100 parts by weight of a mixture of 80 mol % of TiO2 and 20 mol % of (Cal 3/2v Bi ) 0 and the substituting amount y of Bi was y varied from 0 to 0.05, thus respective samples 36 to 38 being made. The various characteristics of the respective samples are indicated on a table 7. TABLE 1 EMI6.1 Sample <SEP> mol <SEP> % <SEP> Substituting <SEP> Adding <SEP> amount <SEP> Firing <SEP> Density <SEP> Pore <SEP> Thermel <tb> of <SEP> amount <SEP> y <SEP> of <SEP> (parts <SEP> by <SEP> temper- <SEP> (g/cm3) <SEP> rank <SEP> expansion <tb> <SEP> TiO2 <SEP> Bi2O3 <SEP> weight) <SEP> ature <SEP> coeffi <tb> of <SEP> ZnO <SEP> C <SEP> cient <SEP> &alpha; <tb> <SEP> (x <SEP> 10-7 <SEP> 1/ C <tb> --------------------------------------------------------------------------------- No. <SEP> 1 <SEP> 55 <SEP> 0 <SEP> 1.0 <SEP> 1350 <SEP> 4.01 <SEP> 3 <SEP> 126 <tb> No. <SEP> 2 <SEP> 55 <SEP> 0.005 <SEP> 1.0 <SEP> 1350 <SEP> 4.04 <SEP> 5 <SEP> 117 <tb> No. <SEP> 3 <SEP> 55 <SEP> 0.01 <SEP> 1.0 <SEP> 1350 <SEP> 4.06 <SEP> 5 <tb> No. <SEP> 4 <SEP> 55 <SEP> 0.02 <SEP> 1.0 <SEP> 1350 <SEP> 4.12 <SEP> 5 <SEP> 111 <tb> No. <SEP> 5 <SEP> 55 <SEP> 0.03 <SEP> 1.0 <SEP> 1350 <SEP> 4.14 <SEP> 5 <SEP> 117 <tb> No. <SEP> 6 <SEP> 55 <SEP> 0.05 <SEP> 1.0 <SEP> 1350 <SEP> 4.21 <SEP> 5 <SEP> 111 <tb> No. <SEP> 7 <SEP> 55 <SEP> 0.07 <SEP> 1.0 <SEP> 1300 <SEP> 4.29 <SEP> 5 <SEP> 113 <tb> No. <SEP> 8 <SEP> 55 <SEP> 0.1 <SEP> 1.0 <SEP> 1300 <SEP> 4.40 <SEP> 5 <SEP> 109 <tb> No. <SEP> 9 <SEP> 55 <SEP> 0.2 <SEP> 1.0 <SEP> 1250 <SEP> 4.76 <SEP> 5 <SEP> 107 <tb> No.10 <SEP> 55 <SEP> 0.3 <SEP> 1.0 <SEP> 1250 <SEP> 5.08 <SEP> 5 <SEP> 90 <tb> No.11 <SEP> 55 <SEP> 0.4 <SEP> 1.0 <SEP> 1250 <SEP> 5.44 <SEP> 4 <SEP> 90 <tb> No.12 <SEP> 55 <SEP> 0.6 <SEP> 1.0 <SEP> 1250 <SEP> 6.18 <SEP> 4 <SEP> 80 <tb> -------------------------------------------------------------------------------- TABLE 2 EMI6.2 Sample <SEP> mol <SEP> % <SEP> 'substituting <SEP> Ad lng <SEP> amount <SEP> Firing <SEP> Density <SEP> Pore <SEP> Thermal <tb> of <SEP> amount <SEP> y <SEP> of <SEP> (parts <SEP> by <SEP> temper- <SEP> (g/cm3) <SEP> rank <SEP> coeffi- <SEP> expansion <tb> TiO2 <SEP> Bi2O3 <SEP> weight) <SEP> ature <SEP> cient <SEP> &alpha; ; <tb> of <SEP> ZnO <SEP> C <SEP> (x <SEP> 10-7 <SEP> 1/ C <tb> <SEP> --------------------------------------------------------------------------------- <tb> No.13 <SEP> 55 <SEP> 0.02 <SEP> 0 <SEP> 1350 <SEP> 3.82 <SEP> 3 <SEP> 111 <tb> No.14 <SEP> 55 <SEP> 0.02 <SEP> - <SEP> 0.5 <SEP> 1350 <SEP> 4.0 <SEP> 5 <SEP> 113 <tb> No.15 <SEP> 55 <SEP> 0.02 <SEP> 1.0 <SEP> 1350 <SEP> 4.12 <SEP> 5 <SEP> 111 <tb> No.16 <SEP> 55 <SEP> 0.02 <SEP> 3.0 <SEP> 1350 <SEP> 4.12 <SEP> 5 <SEP> 111 <tb> No.17 <SEP> 55 <SEP> 0.02 <SEP> 5.0 <SEP> 1300 <SEP> 4.12 <SEP> 5 <SEP> 113 <tb> No.18 <SEP> 55 <SEP> 0.02 <SEP> 7.0 <SEP> 1300 <SEP> 4.16 <SEP> 5 <SEP> 111 <tb> <SEP> --------------------------------------------------------------------------------- TABLE 3 ---------------------------------------------------------------------------------- EMI6.3 Sample <SEP> mol <SEP> % <SEP> Substituting <SEP> Accing <SEP> amount <SEP> Firing <SEP> Density <SEP> Pore <SEP> Thermal <tb> of <SEP> amount <SEP> y <SEP> of <SEP> (parts <SEP> by <SEP> temper- <SEP> (g/cm3) <SEP> rank <SEP> expansion <tb> TiO2 <SEP> Bi2O3 <SEP> weight) <SEP> ature <SEP> coeffi <tb> of <SEP> ZnO <SEP> C <SEP> cient <SEP> &alpha; ; <tb> <SEP> (x <SEP> 10-7 <SEP> 1/ C) <tb> --------------------------------------------------------------------------------- <tb> No.19 <SEP> 55 <SEP> 0.05 <SEP> 1.0 <SEP> 1350 <SEP> 4.21 <SEP> 5 <SEP> 111 <tb> I <SEP> No.20 <SEP> 70 <SEP> 0.05 <SEP> 1.0 <SEP> 1300 <SEP> 4.27 <SEP> 5 <SEP> 100 <tb> I <SEP> No.21 <SEP> 75 <SEP> 0.05 <SEP> 1.0 <SEP> 1300 <SEP> 4.26 <SEP> 5 <SEP> 98 <tb> No.22 <SEP> 80 <SEP> 0.05 <SEP> 1.0 <SEP> 1300 <SEP> 4.27 <SEP> 5 <SEP> 96 <tb> No.23 <SEP> 85 <SEP> 0.05 <SEP> 1.0 <SEP> 1300 <SEP> 4.27 <SEP> 5 <SEP> 94 <tb> --------------------------------------------------------------------------------- TABLE 4 EMI7.1 Sample <SEP> mol <SEP> % <SEP> Substituting <SEP> Adding <SEP> amount <SEP> Firing <SEP> Density <SEP> Pore <SEP> Thermal <tb> of <SEP> amount <SEP> y <SEP> of <SEP> (parts <SEP> by <SEP> temper- <SEP> (g/cm3) <SEP> rank <SEP> expansion <tb> TiO2 <SEP> Bi2O3 <SEP> weight) <SEP> ature <SEP> coeffi <tb> of <SEP> ZnO <SEP> C <SEP> cient <SEP> &alpha; <tb> (x <SEP> 10-7 <SEP> 1/ C) <tb> -------------------------------------------------------------------------------- <tb> No.24 <SEP> 40 <SEP> 0.02 <SEP> 3.0 <SEP> 1350 <SEP> 3.89 <SEP> 3 <SEP> 111 <tb> No.25 <SEP> 50 <SEP> 0.02 <SEP> 3.0 <SEP> 1350 <SEP> 4.08 <SEP> 3 <SEP> 112 <tb> No.26 <SEP> 60 <SEP> 0.02 <SEP> 3.0 <SEP> 1350 <SEP> 4.13 <SEP> 5 <SEP> 109 <tb> No.27 <SEP> 70 <SEP> 0.02 <SEP> 3.0 <SEP> 1350 <SEP> 4.16 <SEP> 5 <SEP> 103 <tb> -------------------------------------------------------------------------------- TABLE 5 EMI7.2 <tb> Sample <SEP> mol <SEP> % <SEP> Substituting <SEP> Adding <SEP> amount <SEP> Firing <SEP> Density <SEP> Pore <SEP> Thermal <tb> of <SEP> amount <SEP> y <SEP> of <SEP> (parts <SEP> by <SEP> temper- <SEP> (g/cm3) <SEP> rank <SEP> expansion <tb> TiO2 <SEP> Bi2O3 <SEP> weight) <SEP> ature <SEP> coeffi <SEP> of <SEP> ZnO <SEP> C <SEP> cient <SEP> &alpha; ; <tb> (x10-7 <SEP> 1/ C <tb> -------------------------------------------------------------------------------- <tb> No.28 <SEP> 50 <SEP> 0.2 <SEP> 1.0 <SEP> 1300 <SEP> 4.83 <SEP> 3 <SEP> 111 <tb> No.29 <SEP> 55 <SEP> 0.2 <SEP> 1.0 <SEP> 1250 <SEP> 4.76 <SEP> 5 <SEP> 107 <tb> No.30 <SEP> 70 <SEP> 0.2 <SEP> 1.0 <SEP> 1250 <SEP> 4.62 <SEP> 5 <SEP> 100 <tb> No.31 <SEP> 75 <SEP> 0.2 <SEP> 1.0 <SEP> 1250 <SEP> 4.55 <SEP> 5 <SEP> 97 <tb> -------------------------------------------------------------------------------- TABLE 6 EMI7.3 Sample <SEP> mol <SEP> % <SEP> Substituting <SEP> Adding <SEP> amount <SEP> Firing <SEP> Density <SEP> Pore <SEP> Thermal <tb> of <SEP> amount <SEP> y <SEP> of <SEP> (parts <SEP> by <SEP> temper- <SEP> (g/m3) <SEP> rank <SEP> expansion <tb> TiO2 <SEP> Bi2O3 <SEP> weight) <SEP> ature <SEP> coeffiof <SEP> ZnO <SEP> C <SEP> cient <SEP> <RTI ID=7.3> &alpha; <tb> (x10-7 <SEP> 1/ C <tb> -------------------------------------------------------------------------------- <tb> No.32 <SEP> 70 <SEP> 0.05 <SEP> 1.0 <SEP> 1300 <SEP> 4.27 <SEP> 5 <SEP> 100 <tb> No.33 <SEP> 70 <SEP> 0.1 <SEP> 1.0 <SEP> 1250 <SEP> 4.39 <SEP> 5 <SEP> 102 <tb> I <SEP> No.34 <SEP> 70 <SEP> 0.2 <SEP> 1.0 <SEP> 1250 <SEP> 4.62 <SEP> 5 <SEP> 100 <tb> I <SEP> No.35 <SEP> 70 <SEP> 0.3 <SEP> 1.0 <SEP> 1250 <SEP> 4.83 <SEP> 5 <SEP> 91 <tb> TABLE 7 EMI7.4 Sample <SEP> mol <SEP> % <SEP> Substituting <SEP> Adding <SEP> amount <SEP> Firing <SEP> Density <SEP> Pore <SEP> Thermal <tb> of <SEP> amount <SEP> y <SEP> of <SEP> (parts <SEP> by <SEP> temper- <SEP> (g/cm3) <SEP> rank <SEP> expansion <tb> TiO2 <SEP> Bi2O3 <SEP> weight) <SEP> ature <SEP> coeffi <tb> of <SEP> ZnO <SEP> C <SEP> cient <SEP> &alpha; <tb> (x <SEP> 10-7 <SEP> 1/ C <tb> --------------------------------------------------------------------------------- <tb> No.? <SEP> <SEP> 80 <SEP> 0 <SEP> 1.0 <SEP> 1350 <SEP> 4.19 <SEP> 4 <SEP> 96 <SEP> I <SEP> <tb> No.37 <SEP> 80 <SEP> 0.02 <SEP> 1.0 <SEP> 1350 <SEP> 4.22 <SEP> 5 <SEP> 90 <tb> No.38 <SEP> 80 <SEP> 0.05 <SEP> 1.0 <SEP> 1300 <SEP> 4.27 <SEP> 5 <SEP> 96 <tb> ----------------------------------------------------------------------------- As mentioned above, the dielectric ceramic material of Ca0-TiO2 type according to the present invention can be made high in density by the normal firing method and at the same time, the thermal expansion coefficient a thereof can be varied from 80 to 120 x 10 7 1/OC by selecting the substituting amount of Bi. The prior art ceramic material made by the normal firing method requires a high temperature ranging from 900 to 1200 0C for calcining and a high temperature ranging from 1260 to 14000C for firing. However, according to the present invention, there was obtained such a result that the calcining can be carried out at a temperature ranging from 750 to 9000C, the firing can be carried out at a temperature ranging from 1200 to 1350 C, respectively and the temporary press treatment upon the calcining is not required. According to the present invention, by the fact that at least one kind of oxides of Bi and Zn is added to the main composition of TiO2 and CaO, it is possible to obtain a dielectric ceramic material which is less in pore and high in density by the normal firing method without using the prior art special treatments, such as the HIP and so on. In respect of the thermal expansion coefficient a, although the thermal expansion coefficient a is fundamentally varied by the ratio of Ca : Ti in this invention too, since the thermal expansion coefficient a is varied by particularly the substituting amount y of Bi and the ratio of Ca : Ti, it is possible to vary the thermal expansion coefficient &alpha; in a wide range from 80 to 120 x 10-7 1/ C. In other words, it is possible to obtain some kinds of dielectric ceramic materials by selecting thermal expansion coefficient and hence it is possible to obtain desired material characteristics (Vickers hardness, firing temperature and bending strength) without adding some kinds of additives to the main composition. Further, since the dielectric ceramic material of this invention is produced by the normal firing method, it can be produced at low cost. INDUSTRIAL APPLICABILITY The dielectric material of this invention is partic'1arly suitable for being applied to the guard member and the substrate material of the magnetic transducer head of, for example, the video tape recorder, the micro-floppy disk drive and so on.

Claims: CLAIM A dielectric ceramic material formed in such a manner that in a fundamental composition expressed as E(Cal,3/2y Biy ) 0)100-x (TiO2)x where x is selected from 40 to 85 mol %, y is selected from 0.005 to 0.6 molar ratio and/or 0.5 to 7.0 parts by weight of ZnO are added to 100 parts by weight of said fundamental composition and then a mixture is fired.

Inventors: HARAYA, KAZUNORI SONY MAGNETIC PRODUCT, INC., KITAMURA, TOMOSABURO SONY MAGNETIC PRODUCT, INC., SUZUKI, HIROYUKI SONY MAGNETIC PRODUCT, INC.
Applicants: SONY CORPORATION
Application year: 1985
Main classification: C04B35
IPC codes: H01B3, C04B35, G11B5