CN100363301C - Ceramic capacity medium with low consumption and high pressure resisting and preparation process thereof - Google Patents

Abstract

The present invention discloses a low-loss high pressurization ceramic capacitor dielectric. According to 100 wt% of BaTiO3, the present invention adds the constituents by following weight percentage: 0.5 to 1.2% of niobium nickel compound, 0.1 to 0.3% of niobium manganese compound, 0.25 to 1% of MnCO3 and 4 to 5% glass powder. The present invention simultaneously discloses a preparation method of the ceramic capacitor dielectric. The present invention previously synthesizes precursors of the niobium nickel compound and the niobium manganese compound, and then, carries out proportioning; after the processes of ball milling, drying, graining, round sheet-shaped green compact forming by pressing, and sintering under the temperature of 1125 to 1135 DEG C, the ceramic capacitor dielectric is made after heat preservation for 2 to 4 hours. Because the method adopts a titanium position precursor doping modification technique, the method avoids mesophase which is generated in a sintering process, and thereby, the doping effect is good. The ceramic capacitor dielectric has the characteristics of low loss and high pressurization.

Description

A kind of ceramic capacity medium with low consumption and high pressure resisting and preparation method thereof

Technical field

The present invention relates to a kind of ceramic composition, particularly a kind of is the ceramic capacitor dielectric and preparation method thereof of base with the barium titanate.

Background technology

In recent years, (low temperature limit-55 ℃ of operation temperature area is shown in the X representative X7R ceramic capacitor dielectric material have been carried out extensive studies both at home and abroad, 7 represent high temperature limit+125 ℃ of operation temperature area, the velocity of variation of the electrical capacity of R representative all temperature spots in operation temperature area during with respect to 25 ℃ of room temperatures be less than or equal to ± and 15%), wherein with BaTiO ₃For the stupalith of base can be to environment generation pollution in producing and using, the ceramic dielectric excellent property that makes and stable, thereby be subjected to showing great attention to of people always, develop also rapid unusually.Yet in some field, as military affairs and spationautics Application Areas, X7R series can not adapt to the application under the hot environment, the X8R series of getting up of development (wherein the high temperature limit of 8 expression operation temperature areas is for+150 ℃) barium phthalate base ceramic capacity medium material can make the work high-temperature zone of anti-electromagnetic interference (EMI) wave filter extend to 150 ℃ at present.But in this operation temperature area scope, though this series ceramic condenser dielectric volume change rate can reach the requirement of X8R, its dielectric loss is still more than 1%, and compressive strength is not very high (about 7kv/mm), therefore can not adapt to some special occasions fully, as the use of military engineering aspect.

Summary of the invention

Technical problem to be solved by this invention is at the BaTiO that is base with the barium titanate ₃-NiO-Nb ₂O ₅Further make improvements on the basis of ternary system ceramics capacitor dielectric material, a kind of low consumption and high pressure resisting is provided, and the low ceramic capacitor dielectric of sintering temperature and preparation method thereof.

For achieving the above object, the present invention takes following technical scheme to be achieved:

A kind of ceramic capacity medium with low consumption and high pressure resisting, it presses BaTiO ₃Weight be 1, add the composition of following weight percentage ratio: 0.5～1.2% niobium nickel compound, 0.1～0.3% niobium manganic compound, 0.25～1%MnCO ₃Form with 4～5% glass powder.Described niobium nickel compound is the Nb by weight percent 99.6～99.8% ₂O ₅Form with 0.2～0.4% NiO; Described niobium manganic compound is the Nb by weight percent 99.2～99.6% ₂O ₅With 0.4～0.8% MnCO ₃Form; Described glass powder is the composition by following weight per-cent: 25～35% Bi ₂O ₃, 15～25% Pb ₃O ₄, 30～40% ZnO, 10～20% H ₃BO ₃Form.

The preparation method of above-mentioned ceramic capacity medium with low consumption and high pressure resisting, it comprises the steps:

(1) at first with Nb ₂O ₅With NiO by weight percentage 99.6～99.8% and 0.2～0.4%, Nb ₂O ₅And MnCO ₃By weight percentage 99.2～99.6% and 0.4～0.8% respectively weighing mix, sieve, in 800～1000 ℃ of calcinings, make precursor niobium nickel compound and niobium manganic compound through ball milling, oven dry;

(2) by weight percentage, will form Bi ₂O ₃25～35%, Pb ₃O ₄15～25%, ZnO 30～40%, H ₃BO ₃10～20% thorough mixing, melt quenching, levigate, sieve, make glass powder;

(3) the initial feed barium titanate is carried out pre-burning and handle, press BaTiO ₃Weight be 1, add the component of following weight percentage ratio: 0.5～1.5% niobium nickel compound, 0.1～0.3% niobium manganic compound, 0.25～1%MnCO ₃With 4～5% glass powder batching, institute joins raw material and mixes the back ball milling with deionized water at least 4 hours, and the adding weight percent is the granulation of sieving of 5%～7% binding agent after the oven dry;

(4) the granulation powder is pressed into the disc green compact under the pressure of 4～6Mpa, at last in electric furnace through 3～4 hours to 500～600 ℃ binder removals at least 0.5 hour, be heated to 1125-1135 ℃ through 2～3 hours again and burn till, be incubated 2～4 hours and promptly make ceramic capacitor dielectric.

NiO, Nb in the described step (1) ₂O ₅And MnCO ₃Preferably select analytical pure level chemical reagent for use.

The invention has the beneficial effects as follows, at BaTiO ₃-NiO-Nb ₂O ₅Add an amount of MnCO in the three-part system ₃Can significantly increase the density of porcelain body, loss is obviously descended, and improve compressive strength.Cooperate an amount of glass powder of interpolation to make fusing assistant, the sintering temperature of porcelain can be reduced to 1125 ℃～1135 ℃, thus but lower Ag (70%)/Pd (30%) electrode of use cost.

In addition, the preparation method of ceramic capacitor dielectric of the present invention adopts titanium position precursor doping modification method, promptly synthetic in advance precursor niobium nickel compound and niobium manganic compound, can avoid in sintering process, producing intermediate phase like this, as the Jiao Lvshi phase,, therefore can cause the deterioration of dielectric material performance because Jiao Lvshi is not a perovskite structure mutually, doping vario-property is fallen short of success for lack of final effort, and the inventive method has overcome this shortcoming well.Prepared ceramic capacitor dielectric not only can satisfy the performance requriements of X8R material, also have dielectric loss low (tg δ≤0.007), the disruptive strength height (advantage of Eb 〉=13kv/mm) simultaneously concurrently, be particularly suitable for making high temperature resistant, high-tension low-loss EMI filtering laminated ceramic capacitor, have bright development prospect.

Embodiment

The present invention is described in further detail below with reference to specific embodiment:

Embodiment 1

(1) at first chooses chemical reagent NiO, the MnCO of analytical pure level (99.9%) ₃And Nb ₂O ₅, by weight Nb ₂O ₅9.96g and NiO 0.04g, Nb ₂O ₅9.92g and MnCO ₃0.08g, mix with electronic balance weighing respectively, cross 250 holes/cm ²Sub-sieve, and, make precursor niobium nickel compound and niobium manganic compound through ball milling, oven dry respectively at 800 ℃ and 900 ℃ of calcinings;

(2) press the composition of table 1, through thorough mixing, melt quenching, levigate, cross 6000 holes/cm ²Sub-sieve makes glass powder a, b, c.

The composition weight g of table 1 glass powder

Form code name	Bi 2O 3	Pb 3O 4	ZnO	H 3BO 3	Add up to
						a	25	25	30	20	100
b	35	15	40	10	100
						c	30	20	35	15	100

(3) get the BaTiO that pre-burning is handled ₃100g adds niobium nickel compound 0.5g, niobium manganic compound 0.3g, MnCO ₃0.75g, glass powder a 5g batching, it forms code name is A, institute joins raw material and mixes the back ball milling with deionized water 4 hours, in 120 ℃ of oven dry, the paraffin of adding 5g, 1000 holes/cm ²The sub-sieve granulation;

(4) the granulation powder is pressed into three groups totally 9 on the disk green compact of Φ 20mm * 1～1.5mm respectively under 4Mpa, 5Mpa and 6Mpa pressure, at last in electric furnace through 3.5 hours to 550 ℃ de-waxings 0.5 hour, be heated to 1125～1135 ℃ through 2 hours again and burn till, be incubated 2～4 hours and promptly make ceramic capacitor dielectric; To burn till the upper and lower surface-coated silver of sample slurry, after 800 ℃ ± 20 ℃ burning infiltrations prepare electrode, carry out every dielectric properties test.

Embodiment 2

By weight: Nb ₂O ₅9.98g and NiO 0.02g, Nb ₂O ₅9.96g and MnCO ₃0.04g composition with reference to the step (1) of embodiment 1 preparation precursor niobium nickel compound and niobium manganic compound, wherein the calcining temperature of niobium nickel compound and niobium manganic compound is respectively 900 ℃ and 1000 ℃.

Get the BaTiO that pre-burning is handled ₃100g adds above-mentioned niobium nickel compound 1.5g, niobium manganic compound 0.2g, MnCO ₃1g, glass powder b 4g batching, it forms code name is B, the raw material ball milling was joined 5 hours by institute, add the granulation of 6g paraffin, the disk green compact that are pressed in electric furnace through 3 hours to 600 ℃ de-waxings 0.5 hour, be heated to 1125～1135 ℃ through 3 hours again and burn till, other processing step and specimen electrode preparation are with embodiment 1.

Embodiment 3

By weight: Nb ₂O ₅9.97g and NiO 0.03g, Nb ₂O ₅9.97g and MnCO ₃0.03g composition with reference to the step (1) of embodiment 1 preparation precursor niobium nickel compound and niobium manganic compound, wherein the calcining temperature of niobium nickel compound and niobium manganic compound is respectively 1000 ℃ and 900 ℃.

Get the BaTiO that pre-burning is handled ₃100g adds above-mentioned niobium nickel compound 1g, niobium manganic compound 0.1g, MnCO ₃0.25g, glass powder c 5g batching, it forms code name is C, the raw material ball milling was joined 5 hours by institute, added the granulation of 7g paraffin, through 4 hours to 500 ℃ de-waxings 1 hour, other processing step and specimen electrode preparation were with embodiment 1 in electric furnace for the disk green compact that are pressed into.

The prescription of the foregoing description is formed A, B, C in burning till step, can respectively get three on the dry-pressing green compact of different ingredients, by 9 is one group, respectively at 1125 ℃, 1130 ℃, 1135 ℃ three temperature spots burn till and be incubated respectively 4 hours simultaneously, 3 hours, 2 hours, make 27 samples of three groups of different ingredients and firing temperature at last, therefrom 9 good samples of sintering of sort out are surveyed its dielectric properties, and it the results are shown in table 2.

Max| Δ C/C in the table 2 _{25 ℃}| the warm area scope of value (%) is-55 ℃～+ 150 ℃.

The test result of table 2 ceramic capacitor dielectric sample of the present invention

Form code name	Firing temperature ℃	Soaking time (hour)	The sample dielectric properties
							ε	tanδ	Max|ΔC/C 25℃|(％)	Eb(kv/mm)
			A	1125	4	2936					0.006	14	13.6
1130	3	2938					0.006	14	13.8
				1135	2	2945				0.006	14	14
B	1125	4					2924	0.006	13				13.4
			1130	3	2935	0.006				13	13.5
	1135	2					2954	0.006	13			13.6
			C	1125	4	2915				0.006	14		13.5
1130	3	2936					0.006	14	13.7
				1135	2	2953				0.006	14	14

Claims (3)

1. a ceramic capacity medium with low consumption and high pressure resisting is characterized in that it presses BaTiO ₃Weight be 1, add the composition of following weight percentage ratio: 0.5～1.5% niobium nickel compound, 0.1～0.3% niobium manganic compound, 0.25～1%MnCO ₃With 4～5% glass powder;

Described niobium nickel compound is by the Nb of weight percent 99.6～99.8% ₂O ₅Form with 0.2～0.4% NiO;

Described niobium manganic compound is by the Nb of weight percent 99.2～99.6% ₂O ₅With 0.4～0.8% MnCO ₃Form;

Described glass powder is by the composition of following weight per-cent: 25～35% Bi ₂O ₃, 15～25% Pb ₃O ₄, 30～40% ZnO, 10～20% H ₃BO ₃Form.

2. the preparation method of a ceramic capacity medium with low consumption and high pressure resisting is characterized in that, it comprises the steps:

(1) at first with Nb ₂O ₅With NiO by weight percentage 99.6～99.8% and 0.2～0.4%, Nb ₂O ₅And MnCO ₃By weight percentage 99.2～99.6% and 0.4～0.8% respectively weighing mix, sieve, in 800～1000 ℃ of calcinings, make precursor niobium nickel compound and niobium manganic compound through ball milling, oven dry;

(2) by weight percentage, will form Bi ₂O ₃25～35%, Pb ₃O ₄15～25%, ZnO 30～40%, H ₃BO ₃10～20% thorough mixing, melt quenching, levigate, sieve, make glass powder;

(3) the initial feed barium titanate is carried out pre-burning and handle, press BaTiO ₃Weight be 1, add the component of following weight percentage ratio: 0.5～1.5% niobium nickel compound, 0.1～0.3% niobium manganic compound, 0.25～1%MnCO ₃With 4～5% glass powder batching, institute joins raw material and mixes the back ball milling with deionized water at least 4 hours, and the adding weight percent is the granulation of sieving of 5%～7% binding agent after the oven dry;

(4) the granulation powder is pressed into the disc green compact under the pressure of 4～6Mpa, at last in electric furnace through 3～4 hours to 500～600 ℃ binder removals at least 0.5 hour, be heated to 1125-1135 ℃ through 2～3 hours again and burn till, be incubated 2～4 hours and promptly make ceramic capacitor dielectric.

3. the preparation method of ceramic capacity medium with low consumption and high pressure resisting according to claim 2 is characterized in that, described NiO, Nb ₂O ₅And MnCO ₃Select analytical pure level chemical reagent for use.