CN102211928A - Magnetoelectric composite material with huge dielectric constant and high residual magnetization strength, and preparation method thereof - Google Patents

Abstract

The invention provides a magnetoelectric composite material with a huge dielectric constant and high residual magnetization strength, and a preparation method thereof. The method comprises the following steps: according to a chemical general formula BaFe12O19, carrying out ball-milling on BaCO3 and Fe2O3, then drying, sieving, briquetting, pre-roasting and smashing so as to obtain BaFe12O19 powder; according to the chemical formula Ba0.6SrO0.4TiPO3, carrying out ball-milling on BaCO3, SrCO3 and TiO3 powders, then drying, sieving, briquetting, pre-roasting and smashing so as to obtain Ba0.6SrO0.4TiO3 powder; evenly mixing the BaFe12O19 powder with the Ba0.6SrO0.4TiPO3 powder so as to obtain a mixture; adding a polyvinyl alcohol (PVA) binder in the mixture, granulating and sieving so as to obtain mixed composite material powder; and heating the mixed composite material powder for removing the binder, and then sintering so as to obtain the magnetoelectric composite material. The magnetoelectric composite material has a huge dielectric constant and a high magnetic conductivity, wherein the dielectric constant of the composite material is up to 51200-198000 (100Hz), and the residual magnetization strength of the composite material is 5-27emu/g.

Description

A kind of magnetic electric compound material and preparation method thereof with huge dielectric constant and high residual magnetization

Technical field

The invention belongs to material science, relate to a kind of magnetic electric compound material and preparation method thereof with huge dielectric constant and high residual magnetization.

Background technology

Along with electronics and information industry are more and more higher for the requirement of integrated level, often on very little chip integrated components and parts number in necessarily.Therefore comprise that the microminiaturization and the miniaturization of the components and parts of electrical condenser are inexorable trends.And the big more material of effective dielectric constant takies identical resource and can obtain bigger electric capacity, thereby satisfies the function on the various circuit.Therefore, the huge dielectric constant material just can use less resources, takies volume still less.Therefore, research and develop out huge dielectric constant material efficiently and crucial meaning is arranged for the development of large-scale integrated circuit technology.In addition, along with the develop rapidly of information and radio communication technology, the size of electron device is more and more littler, and integrated level is more and more higher.This just requires electronic material to have multi-functional characteristic, for example, and magnetic dielectric properties, magneto-optical property etc.In order to satisfy the requirement of multi-functional components and parts, people just prepare the magnetic electric compound material aspect and have carried out many research work.These matrix materials have electric capacity and inductance characteristic simultaneously, can be used to prepare compact filter, antenna, EMI suppressor etc.Have at present that though the magnetic electric compound material of huge dielectric constant has high-k but magnetic is very weak, because the content lower (being lower than 50%) of magneticsubstance wherein.Still there is not at present a kind of magnetic electric compound material that had both had huge dielectric constant and high residual magnetization.

Summary of the invention

The object of the present invention is to provide a kind of magnetic electric compound material and preparation method thereof with huge dielectric constant and high residual magnetization.

For achieving the above object, the composition expression formula of matrix material of the present invention is xBaFe ₁₂O ₁₉/ (1-x) Ba _0.6Sr _0.4TiO ₃, wherein x is BaFe ₁₂O ₁₉Mass percent, and 0.2≤x≤0.8.

Preparation method of the present invention may further comprise the steps:

1) presses chemical general formula BaFe ₁₂O ₁₉Take by weighing analytically pure BaCO ₃And Fe ₂O ₃Preparation back ball milling 4 hours, oven dry is sieved then, and briquetting through 1100 ℃ of pre-burnings 3 hours, is crossed 120 mesh sieves after then the gained bulk sample being pulverized and is obtained BaFe ₁₂O ₁₉Powder;

2) press chemical general formula Ba _0.6Sr _0.4TiO ₃Take by weighing analytically pure BaCO ₃, SrCO ₃And TiO ₂Preparation back ball milling 4 hours, oven dry is sieved then, and briquetting through 1150 ℃ of pre-burnings 3 hours, is crossed 120 mesh sieves after then the gained bulk sample being pulverized and is obtained Ba _0.6Sr _0.4TiO ₃Powder;

3) press xBaFe ₁₂O ₁₉/ (1-x) Ba _0.6Sr _0.4TiO ₃Mass ratio with BaFe ₁₂O ₁₉And Ba _0.6Sr _0.4TiO ₃Powder mix mixture, wherein x is BaFe ₁₂O ₁₉Mass percent, and 0.2≤x≤0.8;

4) the PVA tackiness agent granulation of adding mixture quality umber 8%～15% is sieved through 60 orders and 120 eye mesh screens, obtains the mixed powder of required matrix material;

5) with the mixed powder compression moulding on demand of matrix material,, be incubated 4 hours and get rid of tackiness agent PVA, became porcelain in 0.5～2 hour, promptly obtain this magnetic electric compound material at 1300～1350 ℃ of following sintering at 550 ℃.

Described PVA tackiness agent employing mass concentration is 5% polyvinyl alcohol water solution.

The prepared magnetic electric compound material of the present invention has huge dielectric constant and high magnetic permeability, and the specific inductivity of this matrix material is up to 51200～198000 (100Hz), and residual magnetization is 5～27emu/g.

Description of drawings

Fig. 1 works as BaFe ₁₂O ₁₉Mass ratio be 80%, Ba _0.6Sr _0.4TiO ₃Mass ratio be 20%, the dielectric properties of matrix material when sintering temperature is 1300 ℃, the specific inductivity during 100Hz is 198000;

Fig. 2 works as BaFe ₁₂O ₁₉Mass ratio be 60%, Ba _0.6Sr _0.4TiO ₃Mass ratio be 40%, the dielectric properties of matrix material when sintering temperature is 1320 ℃, the specific inductivity during 100Hz is 185000;

Fig. 3 works as BaFe ₁₂O ₁₉Mass ratio be 40%, Ba _0.6Sr _0.4TiO ₃Mass ratio be 60%, the dielectric properties of matrix material when sintering temperature is 1330 ℃, the specific inductivity during 100Hz is 187000;

Fig. 4 works as BaFe ₁₂O ₁₉Mass ratio be 20%, Ba _0.6Sr _0.4TiO ₃Mass ratio be 80%, the dielectric properties of matrix material when sintering temperature is 1350 ℃, the specific inductivity during 100Hz is 51200;

Fig. 5 works as BaFe ₁₂O ₁₉Mass ratio be 80%, Ba _0.6Sr _0.4TiO ₃Mass ratio be 20%, the magnetic hysteresis loop of matrix material when sintering temperature is 1300 ℃, residual magnetization is 27emu/g;

Fig. 6 works as BaFe ₁₂O ₁₉Mass ratio be 60%, Ba _0.6Sr _0.4TiO ₃Mass ratio be 40%, the magnetic hysteresis loop of matrix material when sintering temperature is 1320 ℃, residual magnetization is 19emu/g;

Fig. 7 works as BaFe ₁₂O ₁₉Mass ratio be 40%, Ba _0.6Sr _0.4TiO ₃Mass ratio be 60%, the magnetic hysteresis loop of matrix material when sintering temperature is 1330 ℃, residual magnetization is 13emu/g;

Fig. 8 works as BaFe ₁₂O ₁₉Mass ratio be 20%, Ba _0.6Sr _0.4TiO ₃Mass ratio be 80%, the magnetic hysteresis loop of matrix material when sintering temperature is 1350 ℃, residual magnetization is 5emu/g.

Embodiment

Below in conjunction with accompanying drawing the present invention is described in further detail.

Embodiment 1:1) presses chemical general formula BaFe ₁₂O ₁₉Take by weighing analytically pure BaCO ₃And Fe ₂O ₃Preparation back ball milling 4 hours, oven dry is sieved then, and briquetting through 1100 ℃ of pre-burnings 3 hours, is crossed 120 mesh sieves after then the gained bulk sample being pulverized and is obtained BaFe ₁₂O ₁₉Powder;

2) press chemical general formula Ba _0.6Sr _0.4TiO ₃Take by weighing analytically pure BaCO ₃, SrCO ₃And TiO ₂Preparation back ball milling 4 hours, oven dry is sieved then, and briquetting through 1150 ℃ of pre-burnings 3 hours, is crossed 120 mesh sieves after then the gained bulk sample being pulverized and is obtained Ba _0.6Sr _0.4TiO ₃Powder;

3) press 0.8BaFe ₁₂O ₁₉// 0.2Ba _0.6Sr _0.4TiO ₃Mass ratio with BaFe ₁₂O ₁₉And Ba _0.6Sr _0.4TiO ₃Powder mix mixture;

4) mass concentration of adding mixture quality umber 8% is 5% polyvinyl alcohol water solution granulation, sieves through 60 orders and 120 eye mesh screens, obtains the mixed powder of required matrix material;

5) with the mixed powder compression moulding on demand of matrix material,, be incubated 4 hours and get rid of tackiness agent PVA, became porcelain in 2 hours, promptly obtain 0.8BaFe at 1300 ℃ of following sintering at 550 ℃ ₁₂O ₁₉// 0.2Ba _0.6Sr _0.4TiO ₃Magnetic electric compound material.Referring to Fig. 1, the specific inductivity during 100Hz is 198000.Referring to Fig. 5, residual magnetization is 27emu/g.

Embodiment 2:1) presses chemical general formula BaFe ₁₂O ₁₉Take by weighing analytically pure BaCO ₃And Fe ₂O ₃Preparation back ball milling 4 hours, oven dry is sieved then, and briquetting through 1100 ℃ of pre-burnings 3 hours, is crossed 120 mesh sieves after then the gained bulk sample being pulverized and is obtained BaFe ₁₂O ₁₉Powder;

2) press chemical general formula Ba _0.6Sr _0.4TiO ₃Take by weighing analytically pure BaCO ₃, SrCO ₃And TiO ₂Preparation back ball milling 4 hours, oven dry is sieved then, and briquetting through 1150 ℃ of pre-burnings 3 hours, is crossed 120 mesh sieves after then the gained bulk sample being pulverized and is obtained Ba _0.6Sr _0.4TiO ₃Powder;

3) press 0.6BaFe ₁₂O ₁₉/ 0.4Ba _0.6Sr _0.4TiO ₃Mass ratio with BaFe ₁₂O ₁₉And Ba _0.6Sr _0.4TiO ₃Powder mix mixture;

4) mass concentration of adding mixture quality umber 15% is 5% polyvinyl alcohol water solution granulation, sieves through 60 orders and 120 eye mesh screens, obtains the mixed powder of required matrix material;

5) with the mixed powder compression moulding on demand of matrix material,, be incubated 4 hours and get rid of tackiness agent PVA, became porcelain in 1.5 hours, promptly obtain 0.6BaFe at 1320 ℃ of following sintering at 550 ℃ ₁₂O ₁₉/ 0.4Ba _0.6Sr _0.4TiO ₃Magnetic electric compound material.

Referring to Fig. 2, the specific inductivity during 100Hz is 185000.Referring to Fig. 6, residual magnetization is 19emu/g.

Embodiment 3:1) presses chemical general formula BaFe ₁₂O ₁₉Take by weighing analytically pure BaCO ₃And Fe ₂O ₃Preparation back ball milling 4 hours, oven dry is sieved then, and briquetting through 1100 ℃ of pre-burnings 3 hours, is crossed 120 mesh sieves after then the gained bulk sample being pulverized and is obtained BaFe ₁₂O ₁₉Powder;

2) press chemical general formula Ba _0.6Sr _0.4TiO ₃Take by weighing analytically pure BaCO ₃, SrCO ₃And TiO ₂Preparation back ball milling 4 hours, oven dry is sieved then, and briquetting through 1150 ℃ of pre-burnings 3 hours, is crossed 120 mesh sieves after then the gained bulk sample being pulverized and is obtained Ba _0.6Sr _0.4TiO ₃Powder;

3) press 0.4BaFe ₁₂O ₁₉/ 0.6Ba _0.6Sr _0.4TiO ₃Mass ratio with BaFe ₁₂O ₁₉And Ba _0.6Sr _0.4TiO ₃Powder mix mixture;

4) mass concentration of adding mixture quality umber 10% is 5% polyvinyl alcohol water solution granulation, sieves through 60 orders and 120 eye mesh screens, obtains the mixed powder of required matrix material;

5) with the mixed powder compression moulding on demand of matrix material,, be incubated 4 hours and get rid of tackiness agent PVA, became porcelain in 1 hour, promptly obtain 0.4BaFe at 1330 ℃ of following sintering at 550 ℃ ₁₂O ₁₉/ 0.6Ba _0.6Sr _0.4TiO ₃Magnetic electric compound material.

Referring to Fig. 3, the specific inductivity during 100Hz is 187000.Referring to Fig. 7, residual magnetization is 13emu/g.

Embodiment 4:1) presses chemical general formula BaFe ₁₂O ₁₉Take by weighing analytically pure BaCO ₃And Fe ₂O ₃Preparation back ball milling 4 hours, oven dry is sieved then, and briquetting through 1100 ℃ of pre-burnings 3 hours, is crossed 120 mesh sieves after then the gained bulk sample being pulverized and is obtained BaFe ₁₂O ₁₉Powder;

2) press chemical general formula Ba _0.6Sr _0.4TiO ₃Take by weighing analytically pure BaCO ₃, SrCO ₃And TiO ₂Preparation back ball milling 4 hours, oven dry is sieved then, and briquetting through 1150 ℃ of pre-burnings 3 hours, is crossed 120 mesh sieves after then the gained bulk sample being pulverized and is obtained Ba _0.6Sr _0.4TiO ₃Powder;

3) press 0.2BaFe ₁₂O ₁₉/ 0.8Ba _0.6Sr _0.4TiO ₃Mass ratio with BaFe ₁₂O ₁₉And Ba _0.6Sr _0.4TiO ₃Powder mix mixture;

4) mass concentration of adding mixture quality umber 12% is 5% polyvinyl alcohol water solution granulation, sieves through 60 orders and 120 eye mesh screens, obtains the mixed powder of required matrix material;

5) with the mixed powder compression moulding on demand of matrix material,, be incubated 4 hours and get rid of tackiness agent PVA, became porcelain in 0.5 hour, promptly obtain 0.2BaFe at 1350 ℃ of following sintering at 550 ℃ ₁₂O ₁₉/ 0.8Ba _0.6Sr _0.4TiO ₃Magnetic electric compound material.

Referring to Fig. 4, the specific inductivity during 100Hz is 51200.Referring to Fig. 8, residual magnetization is 5emu/g.

Claims (3)

1. magnetic electric compound material with huge dielectric constant and high residual magnetization, it is characterized in that: the composition expression formula of this matrix material is xBaFe ₁₂O ₁₉/ (1-x) Ba _0.6Sr _0.4TiO ₃, wherein x is BaFe ₁₂O ₁₉Mass percent, and 0.2≤x≤0.8.

2. preparation method with magnetic electric compound material of huge dielectric constant and high residual magnetization is characterized in that may further comprise the steps:

1) presses chemical general formula BaFe ₁₂O ₁₉Take by weighing analytically pure BaCO ₃And Fe ₂O ₃Preparation back ball milling 4 hours, oven dry is sieved then, and briquetting through 1100 ℃ of pre-burnings 3 hours, is crossed 120 mesh sieves after then the gained bulk sample being pulverized and is obtained BaFe ₁₂O ₁₉Powder;

2) press chemical general formula Ba _0.6Sr _0.4TiO ₃Take by weighing analytically pure BaCO ₃, SrCO ₃And TiO ₂Preparation back ball milling 4 hours, oven dry is sieved then, and briquetting through 1150 ℃ of pre-burnings 3 hours, is crossed 120 mesh sieves after then the gained bulk sample being pulverized and is obtained Ba _0.6Sr _0.4TiO ₃Powder;

3) press xBaFe ₁₂O ₁₉/ (1-x) Ba _0.6Sr _0.4TiO ₃Mass ratio with BaFe ₁₂O ₁₉And Ba _0.6Sr _0.4TiO ₃Powder mix mixture, wherein x is BaFe ₁₂O ₁₉Mass percent, and 0.2≤x≤0.8;

4) the PVA tackiness agent granulation of adding mixture quality umber 8%～15% is sieved through 60 orders and 120 eye mesh screens, obtains the mixed powder of required matrix material;

5) with the mixed powder compression moulding on demand of matrix material,, be incubated 4 hours and get rid of tackiness agent PVA, became porcelain in 0.5～2 hour, promptly obtain this magnetic electric compound material at 1300～1350 ℃ of following sintering at 550 ℃.

3. the preparation method with magnetic electric compound material of huge dielectric constant and high residual magnetization according to claim 2 is characterized in that: described PVA tackiness agent employing mass concentration is 5% polyvinyl alcohol water solution.

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