TWI378908B - Ceramic composite material with both dielectric and magnetic properties - Google Patents

Description

IX. INSTRUCTIONS: TECHNICAL FIELD OF THE INVENTION The present invention relates to a composite material, and more particularly to a magnetic dielectric ceramic composite material. [Prior Art] Due to the rapid development of wireless communication, RF components are constantly moving toward frequency, integration and modularization, and the requirements for anti-electromagnetic interference performance are getting higher and higher. Therefore, how to develop a high-performance, small-volume high-frequency (80〇·2〇〇〇ΜΗζ) composite L/C EMI waver has become an important research topic. However, high-frequency composite L/C ΕΜΙ filtering is currently being produced. The method of the device is to use a plurality of dielectric and magnetic layers of different functions to be stacked and co-fired into a composite component by a lamination technique. Since this technology involves the co-firing behavior of dielectric, magnetic, and conductive materials, co-firing mismatch will cause interface reaction and interface diffusion, and at the same time cause great internal stress inside the component, resulting in delamination, The phenomenon of camber. This limits the speed of development of such components. Since L/C EMI composite components are fabricated by stacking multiple layers of dielectric and magnetic layers, it is necessary to consider the compatibility of the inductor and capacitor materials. If a composite material with both magnetic and dielectric properties of excellent south frequency characteristics can be produced, the process of the high frequency ΕΜΙ filter can be simplified and the freedom of composite component design and product yield can be improved. At present, in the production of composite components, the methods used are mostly multi-layer dielectric and magnetic layers with different functions to laminate low-level 1 1378908 co-fired ceramics (LTCC) technology. Because of the difference between different materials, the J. The incompatibility and the densification rate mismatch make the laminated low temperature co-fired ceramics susceptible to co-firing defects, de-sensitization, crack formation and initiation. In order to avoid the formation of sintering defects, the inconsistency of the sintering shrinkage rate can be minimized and reduced during the heat treatment by adding a sintering aid, a low softening point glass or a liquid phase sintering in a dielectric and magnetic ceramic system. The tensile stress. In recent years, another method for solving the shrinkage rate during sintering has been developed. The dielectric is mixed with a magnetic Tauman powder which is sintered to become a composite ceramic body having magnetic and dielectric properties. This method can avoid the inconsistency of the shrinkage rate of different ceramic material system layers during sintering, but still needs to consider the coordination of the dielectric powder and the magnetic powder during sintering.

Mitsubishi and Samsung are introducing EMI filters using a distributed constant type (distHbuted e〇n_ 咖) line method using a composite powder with both dielectric and properties. In addition, it is also possible to use ceramic composite powders of different mixing ratios as a buffer layer of a low-temperature co-fired ceramic dielectric layer and a magnetic layer to make it a third matrix between the dielectric layer and the magnetic layer of the build-up element. The layer is used to slow down the defects which may occur due to the inconsistent sintering rate and the chemical reaction between the dielectric layer and the magnetic layer, thereby obtaining a material which can be co-fired at a low temperature, and has both dielectric and magnetic properties. Dielectric ferromagnetic composite [丨, 2] has Ti〇2-NiCuZn ferrites, 6 1378908

Pb(MgW3Nb2/3)03-Pb(Zn1/3Nb2/3)03-PbTi03, (PMZNT)+Ni〇 2Cu〇 2Zn0 6Fe204,

BaTi03+NiG 2Cu0 2Zn0 6Fe丨9604 ' Garnet ferrite + Pb(Zr〇52Ti.48)〇3 and Ba3C〇2Fe24041 + ZnTi〇3, and can be adjusted by adjusting dielectric materials and ferromagnetic materials The ratio changes the nature.

The dielectric material systems reported in the literature are mostly ferroelectric and cannot be used in the high frequency section (800-2000 MHz). In addition, PMZNT and PZT are both excellent dielectric materials, but they have been gradually reduced in use due to the introduction of lead-free materials in recent years. The dielectric materials commonly used are BaTi〇3 and Ba0 · Nd2〇3. Ti〇2, but the sintering temperature is often above 950. Therefore, a dielectric/ferromagnetic composite material which can be sintered at a low temperature and has an adjustable property is developed. There is currently quite a potential research direction. [Summary of the Invention.]

In view of the fact that existing magnetic dielectric ceramic composites are at high sintering temperatures: often causing defects in material properties, the object of the present invention is to provide a magnetic dielectric ceramic composite material by mixing dielectric and magnetic porcelain and a suitable amount of glass. The sintering aid is fired at a low temperature to produce a composite material having both dielectric and magnetic properties. In order to achieve the above object, the magnetic dielectric ceramic composite material of the present invention comprises: 丨$Taowman material, the composition of which includes bismuth (Ba), 鈥d), ruthenium (Bi) and chin (Ti) The ear ratio is known: out: we 7!378908 =1 : 1.6 : 0.4 : 4 ; burn,,. The auxiliary component contains bismuth (Bi), boron (b), bismuth (Si)* and zinc (Zn), and the molar ratio thereof is Bi:B:Si:Zn = 25:30:35 . . 10, (10) The auxiliaries account for 25 wt% of the sum of the cerium ceramic material and the sintering aid; and a ferrite magnet material whose composition is composed of nickel (Ni), steel (Cu), bis (Zn) and iron (Fe) ), the Mohr ratio is Ni: Cu: & • Fe = 〇_58 : 0.12 : 〇·3 : K98. Preferably, the sum of the electric ceramic material and the sintering aid accounts for the content range of the overall magnetic dielectric ceramic composite material & 2% correction to 8〇wt%, the ferrite magnet material accounts for the overall magnetic dielectric The content of the ceramic composite material ranges from 20_/〇 to 8〇wt%, and the sum of the dielectric ceramic material, the sintering aid and the ferrite magnet material constitutes 100 wt% of the magnetic dielectric ceramic composite material. Specific efficacies that can be achieved by the present invention include: #1 · The present invention develops a high-temperature L/C ΕΜΙ composite that can be sintered at a low temperature (S 95 〇. (and at the same time has excellent high-frequency dielectric, magnetic composite material' The process of the component simplifies and simultaneously increases the freedom of design of the composite component and the yield of the product. 2. Since the component of the present invention does not contain lead, it is an environmentally-friendly and error-free composite material. ''Embodiment> The present invention The magnetic dielectric ceramic composite material comprises a dielectric ceramic material, a sintering aid and a ferrite magnet material, and the composition of the dielectric ceramic 1378908 material comprises barium (Ba), strontium (Nd), and bismuth (Bi). And titanium (Ti), the molar ratio of Ba: Nd : Bi : Ti = 1 : 1.6 : 0.4 : 4, the composition of the sintering aid contains bismuth (Bi), boron (B), bismuth (Si) And zinc (Zn) 'the molar ratio is Bi : B : Si : Zn = 25 : 30 : 35 : 10 , the sintering aid accounts for 25wt ° of the sum of the dielectric ceramic material and the sintering aid (hereinafter referred to as B) The composition of the ferrite magnet material is nickel (Nl), copper (Cu), rhenium (zn) and iron (Fe). Ear ratio of Ni: Cu:

Zn. Fe = 〇·58 : 〇12 : 〇3 : i 98 (hereinafter referred to as n), the above-mentioned magnetic dielectric ceramic composite material is abbreviated as BxNy, wherein X is the sum of the content of the dielectric ceramic material and the sintering aid, and the range From 2 to 8 (80 wt%), y is the content of the ferrite magnet material, ranging from 2 (20 wt%) to 8 (8 wt%), x + y = i 〇. The method and materials used to describe the invention are intended to be within the scope of the appended claims. Example 1: Preparation of Dielectric Ceramic Materials

The following examples are given to make the features and advantages of the present invention more in no way to limit the scope of the invention, but rather

Ti〇2 is the starting material, and the proportion of 〇3 · 4Ti〇2 is determined.

The raw material powder is mixed 1* to 12〇〇. 〇: and a powder is obtained, and 9 (3) powder is determined by XRD to be pure phase BaNd (44-0061) ‘see the figure-picture (Fig. BaNd2Ti4〇12). Example 1. Preparation of sintering aids Starting from H3B〇3, Bi203, Si〇2 and Zn〇 The above raw materials are based on Bi: B: Si: Zn = 25: 30: 35: ίο# # a υ The ratio is prepared as a glass sintering aid powder, the preparation process is as follows.

(1) Wet mixing the raw material powder by adding alcohol to the horse brain mortar, and drying to obtain a sample; (2) placing the sample in a white gold crucible at a temperature of 1〇〇c/± + Raised to 1000 〇C, taken out after 30 minutes of holding temperature and quenched in water to obtain a vitreous powder; (3) The obtained glass powder is refined by ball milling for 48 hours;

1 6Bl〇4Ti4〇i2 is marked as (4) The density of the glass powder measured by the pycnometer is about 6.58 g/cm3; (5) The melting point of the glass powder by DTA is about 641 0C. Example 3: Preparation of ferrite magnet material NiO, CuO, ZnO and Fe203 were used as starting materials, and the above raw materials were made of Ni:Cu : Zn : Fe = 0.58 : 0.12 : 〇.3 : 1 A · y Proportionally prepared ferrite magnet material powder, the preparation process is as follows. (1) The raw material powder according to the dosage is arranged in a ball-wet wet mixing method, and the mixture is dried for 24 hours, and dried to obtain a sample; 10 1378908 (2) The sample is 4Y/min. The heating rate was raised to 74 〇 (>c and held for 2 hours) and then cooled by natural furnace cooling. Example 4: Preparation of Magnetic Dielectric Ceramics

The prepared dielectric ceramic powder is added to the glass sintering aid (hereinafter, the dielectric ceramic fiber and the glass sintering aid are collectively referred to as B), wherein the sintering aid accounts for 25 wt% of B, and then B and ferrite The magnet powder (hereinafter referred to as N) is mixed with each other in different proportions, and the mixed sample is expressed as BxNy 'where the sum of the dielectric ceramic (four) material and the sintering aid accounts for the content ratio of the whole sample, ranging from 2 (20 scratches) to 8 ( 8〇wt%), y is the proportion of ferrite magnets in the whole sample, ranging from 2 (20 Wt%) to 8 (80 wt%), of which 100 wt%) 'Preparation process and material quality x+y =io (that is, the test results are as follows:

(1) Add the mixed ###################################################################################################### The raw material is produced, and the (10) MPa is added by cold equalization to increase the density of the green embryo. In addition, according to the above method, the t 20 mm of the measured electrical property is required to be used. The special specification of the ring (raw i Μ) embryo body mold is uniaxially added to 3GGMPa to make the ring () sintering test. It is also carried out at 900 °C. If the body is not sensitive enough, then the situation will be repeated. Take 950. (: Sintering, the sample obtained by the company is relatively dan, now,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Kemi 梓 11 1378908, and relative density = (body density / theoretical density) x 丄〇〇%, where the density of the composite is calculated using the mixing ruie:

_ WB+WN • ~^Db+Wn/Dn • WB. Total weight of dielectric ceramic material and sintering aid; wN: weight of ferrite magnet material; DB: sum of dielectric ceramic material and sintering aid Density; Lu DN: Density of ferrite magnet material. (3) For the sample sintered at 900 °C, only the relative density of B6N4 and B8N2 is more than 9〇%; the sample is sintered at 95〇%. "And s ' except for B2N8', the relative density of the samples is greater than 90 〇 / 〇 ° For B2N8 'the relative density of samples sintered at 9 〇〇〇 c and 950 〇 c can be increased from 75% to 89% , showing an increase in sintering temperature 'The relative density of the sintered body can be effectively improved, see the second figure; • (4) Observed by the microstructure, as the X content increases, the grain size also increases. Referring to the third figure, the observation of the above microstructure is carried out by scanning electron microscopy (Hitachi, 4100) to observe the microstructure of the sintered body. 'The sintered body is polished first, and then the sample is placed in deionized water to supersonicize. After shaking for 10 minutes, heat-etching was carried out for 3 〇 minutes at a temperature lower than the sintering temperature of 50 ° C. The sample was attached to the stage with a tape and coated with a conductive silver paste; (5) by diffraction results It is known that the samples of different proportions are mainly 12 1378908 NCZ ferrite magnet phase and phase 'B2N8 sample, even if a large amount of glass sintering aid is added, no new secondary phase is formed, and the above crystal phase is identified. XRD (Siemems D5000, Cu-Ka) Identification of the phase states. The scanning speed is 0.04 Vsec. and the broom angle 0) is 20. To 50. (6) For samples sintered at 950 °C, the dielectric constant is lower and less stable between 10 MHz and 60 MHz at lower frequencies, between 60 MHz and 1000 MHz. Maintaining a fixed relative dielectric constant' When the x content in the sample increases, the relative dielectric constant also increases, and the relative dielectric constant (10~1000MHz) can be adjusted from 1〇 to 46, see section (4) For samples sintered at 900 〇C, the initial permeability can be maintained at a stable value in the range of 1 〇 to 100 MHz, and the value (10 to 1 〇〇) (MHz) can be adjusted between 2 and 14; after 100MHz, the initial magnetic coefficient changes continuously with frequency, first reaches a maximum value and then continues to decrease, see the fifth figure, the above electrical and magnetic The measurement system uses the lCr meter (YHP 4291A, YHP Co. Ltd.) to measure the initial magnetic permeability of the ring sample and the dielectric constant of the cylindrical body between the frequencies i MHz and 1 GHz. The present invention has been passed through 9 〇〇. (: The sample with sintering increases with the content of dielectric ceramic material, and the relative dielectric constant (1〇 to l〇〇〇MHz) can be adjusted between 10 and 46. The initial magnetic permeability (丨〇到!(9)μ Between 13 I is adjusted between 2 1 14 and the resonance frequency of magnetic f can be gated to around 100 MHz. Therefore, it is a magnetic dielectric ceramic composite that can be sintered at low temperature and has adjustable properties. Brief description of the formula] The first figure is the XRD pattern of the powder sample of the dielectric ceramic material obtained by sintering at 12 GG ° C. The first figure is the relative density of the sample of the magnetic dielectric ceramic composite of each composition. The figure is the SEM microstructure of the magnetic dielectric ceramic composite sample of each composition ((4) MN8, (8) b4N0, (4) B0m, (4) B8N2). The fourth figure is 950. (: Magnetic composition of each composition obtained by sintering) The relative dielectric constant of the composite material varies with frequency. The fifth figure is 950. (The initial magnetic permeability of the magnetic dielectric ceramic composite of each composition obtained by sintering under the frequency changes. Description] [References] !· TM Peng, RT Hsu, and JH Jean, tlLow-fire processing and properties of ferrite + dielectric ceramic composite,” j. Am. Ceram. Soc., 89, 2822, (2006) 2. RT Hsu, TM Peng, and JH Jean "Electrical properties of low-fire ferroelectric + ferromagnetic ceramic composite," Jpn. J. Appl_ Phy·, 45, 5841, (2006)

Claims (1)

1378908 X. Patent application scope: 1 · A magnetic dielectric H composite (4), which contains a dielectric ceramic material, Α ”" component contains barium (Ba), titanium _, money (, titanium (9), its molar The ratio is mi - = 1 : 1.6 : 0.4 : 4 ; - sintering aid, the composition of which contains barium (8) bismuth (8) and zinc (Zn), and the molar ratio is Bi:B:si:Znm5: • 1〇 'The sintering_25 wt% of the sum of the dielectric materials and the sintering aids; and the ferrite magnet material's composition is the inclusion of (4), copper, zinc (tetra) and iron (four), the molar ratio of which is Mm: Fe = 0.58 : 0.12 : 0.3 : 1.98. 2. The magnetic dielectric ceramic material according to claim 1, wherein the sum of the dielectric ceramic material and the wrapping aid occupies the overall magnetic dielectric The content of the ceramic composite material ranges from 2〇•8〇Wt%, and the ferrite magnet material accounts for the content of the whole magnetic dielectric material from W to 80wt%. The dielectric ceramic material is: Ke sintering additive and The sum of the ferrite magnet materials constitutes 100% of the magnetic and composite materials. I XI, Schema: as shown in the next page 15