阅读说明：本技术 一种柔性电路板用复合材料的制备方法 (Preparation method of composite material for flexible circuit board ) 是由 杜勇 梁晓新 田卡 何霜霜 于 2018-06-29 设计创作，主要内容包括：本发明提供了一种柔性电路板用复合材料的制备方法,包括：A)晶须状Ba<Sub>2</Sub>Ti<Sub>9</Sub>O<Sub>20</Sub>粉体、硅胶与溶剂混合,烘干,得到混合物；B)将所述混合物压制成型、粉碎,得到复合颗粒；将所述复合颗粒球磨、干燥,得到粉体颗粒；C)将所述粉体颗粒压制成型、烧结,得到柔性电路板用复合材料。本发明通过将晶须状Ba<Sub>2</Sub>Ti<Sub>9</Sub>O<Sub>20</Sub>粉体和硅胶复合制备柔性基板材料,将聚合物的易加工性能与陶瓷的优良介电性能、热性能结合起来,更能实现电路元器件的设计及加工要求。同时,采用晶须代替其他陶瓷粉体,更能有提供柔性基板材料等介电性能及抗弯曲强度和弹性模量,更有利于柔性元器件的加工及应用。(The invention provides a preparation method of a composite material for a flexible circuit board, which comprises the following steps: A) whisker-like Ba 2 Ti 9 O 20 Mixing the powder, silica gel and a solvent, and drying to obtain a mixture; B) pressing and molding the mixture, and crushing to obtain composite particles; ball-milling and drying the composite particles to obtain powder particles; C) and pressing, molding and sintering the powder particles to obtain the composite material for the flexible circuit board. The invention is realized by the use of whisker-shaped Ba 2 Ti 9 O 20 The flexible substrate material is prepared by compounding the powder and the silica gel, the easy processing performance of the polymer is combined with the excellent dielectric performance and thermal performance of the ceramic, and the design and processing requirements of circuit components can be further met. Meanwhile, the whisker is adopted to replace other ceramic powder, so that the dielectric properties such as flexible substrate materials and the like, bending strength resistance and elastic modulus can be provided, and the processing and application of flexible components are facilitated.)

1. A method for preparing a composite material for a flexible circuit board comprises the following steps:

A) whisker-like Ba₂Ti₉O₂₀Mixing the powder, silica gel and a solvent, and drying to obtain a mixture;

B) pressing and molding the mixture, and crushing to obtain composite particles; ball-milling and drying the composite particles to obtain powder particles;

C) and pressing, molding and sintering the powder particles to obtain the composite material for the flexible circuit board.

2. The method according to claim 1, wherein step a) comprises whisker-like Ba₂Ti₉O₂₀The preparation method of the powder comprises the following steps:

nanowhisker-like Ti0₂And Ba (OH)₂Carrying out hydrothermal reaction to obtain a reaction product;

washing, drying and calcining the reaction product to obtain the whisker-shaped Ba₂Ti₉O₂₀And (3) powder.

3. The method according to claim 1, wherein step a) comprises whisker-like Ba₂Ti₉O₂₀The volume ratio of the powder to the silica gel is 1: (0.1-0.5).

4. The production method according to claim 1, wherein the molding pressure in step B) is 40MPa, and the dwell time is 2 min.

5. The method of claim 1, wherein the composite particles in the ball mill of step B): distilled water: the mass ratio of the zirconium balls is 1:1: 2; the rotating speed of the ball mill is 120-; the drying specifically comprises the following steps: vacuum drying at 100 deg.C for 48 h.

6. The method according to claim 1, wherein the molding pressure in the step C) is 40 to 90 MPa.

7. The preparation method as claimed in claim 1, wherein the sintering in step C) is carried out under the protection of inert gas, the temperature rise rate of the sintering is 1-3 ℃/min, the sintering temperature is 120-200 ℃, and the heat preservation time is 2-4 h.

8. The method for preparing in accordance with claim 1, wherein step a) said nanowhisker-like Ti0₂The preparation method specifically comprises the following steps:

taking TiCl₄Mixing and stirring KOH, and adjusting the pH value to 12-14 to obtain a mixed solution;

subjecting the mixed solution to ultrasonic oscillation and high-pressure reaction, and separating to obtain the nano-whisker-shaped Ti0₂。

9. A composite material for a flexible circuit board, characterized by being prepared by the preparation method of any one of claims 1 to 8.

10. A flexible circuit board, characterized in that it is made of the composite material prepared by the preparation method of any one of claims 1 to 8.

Technical Field

The invention relates to the technical field of materials, in particular to a preparation method of a composite material for a flexible circuit board.

Background

Ba₂Ti₉O₂₀Is an important ferroelectric and piezoelectric ceramic material, is a basic raw material for producing multilayer ceramic capacitors (MLLC), thermistors (PTCR) and the like,it has excellent dielectric properties (e.g., 46, 83700GHz, 56 × 10-6/° c), and is widely used in many fields such as mobile communications, satellite television broadcasting communications, radar, and satellite positioning and navigation systems, which are of 300MHz to 40GHz series. Ba₂Ti₉O₂₀Microwave circuit substrate materials are an important product in electronic technology, and are mainly applied to mobile phones, power amplifiers, frequency converters, various combined antennas, digital circuits and the like. Most of the conventional microwave circuit substrate materials are ceramic materials, the synthesis temperature of the conventional microwave circuit substrate materials is high, the materials are hard and brittle, the processing performance is poor, the design and processing requirements of piezoelectric components with complex shapes and structures cannot be completely met, and the conventional microwave circuit substrate materials are not suitable for large-area use, arrangement and the like and limit the development of the conventional microwave circuit substrate materials. The flexible substrate material is widely applied as a high-elasticity electronic material, can ensure that the flexible circuit can be subjected to random reversible deformation, and has broad development prospect.

To meet the flexibility requirement of the substrate material, organic materials with high elasticity are selected, but the materials are generally poor in thermal property and limited in dielectric property, so that the application of the materials is limited. The composite material can have the excellent performance of each component, and has great application prospect in the aspect of functional materials.

Disclosure of Invention

In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing a composite material for a flexible circuit board, and the composite material for a flexible circuit board prepared by the present invention has good dielectric properties, high bending strength and high elastic modulus.

The invention provides a preparation method of a composite material for a flexible circuit board, which comprises the following steps:

A) whisker-like Ba₂Ti₉O₂₀Mixing the powder, silica gel and a solvent, and drying to obtain a mixture;

B) pressing and molding the mixture, and crushing to obtain composite particles; ball-milling and drying the composite particles to obtain powder particles;

C) and pressing, molding and sintering the powder particles to obtain the composite material for the flexible circuit board.

Preferably, step (ii)A) The whisker-shaped Ba₂Ti₉O₂₀The preparation method of the powder comprises the following steps:

nanowhisker-like Ti0₂And Ba (OH)₂Carrying out hydrothermal reaction to obtain a reaction product;

washing, drying and calcining the reaction product to obtain the whisker-shaped Ba₂Ti₉O₂₀And (3) powder.

Preferably, the whisker-like Ba of step A)₂Ti₉O₂₀The volume ratio of the powder to the silica gel is 1: (0.1-0.5).

Preferably, the molding pressure in the step B) is 40MPa, and the dwell time is 2 min.

Preferably, the composite particles in the ball mill of step B): distilled water: the mass ratio of the zirconium balls is 1:1: 2; the rotating speed of the ball mill is 120-; the drying specifically comprises the following steps: vacuum drying at 100 deg.C for 48 h.

Preferably, the molding pressure in the step C) is 40-90 MPa.

Preferably, the sintering in the step C) is carried out under the protection of inert gas, the temperature rise rate of the sintering is 1-3 ℃/min, the sintering temperature is 120-200 ℃ and the heat preservation time is 2-4 h.

Preferably, said nanowhisker-like Ti0 of step A)₂The preparation method specifically comprises the following steps:

taking TiCl₄Mixing and stirring KOH, and adjusting the pH value to 12-14 to obtain a mixed solution;

subjecting the mixed solution to ultrasonic oscillation and high-pressure reaction, and separating to obtain the nano-whisker-shaped Ti0₂。

The invention provides a composite material for a flexible circuit board, which is prepared by the preparation method in any one of the technical schemes.

The invention provides a flexible circuit substrate which is made of a composite material prepared by the preparation method in any one of the technical schemes.

Compared with the prior art, the invention provides a preparation method of a composite material for a flexible circuit board, which comprises the following steps: A) whisker-like Ba₂Ti₉O₂₀Mixing the powder, silica gel and a solvent, and drying to obtain a mixture; B) pressing and molding the mixture, and crushing to obtain composite particles; ball-milling and drying the composite particles to obtain powder particles; C) and pressing, molding and sintering the powder particles to obtain the composite material for the flexible circuit board. The invention is realized by the use of whisker-shaped Ba₂Ti₉O₂₀The flexible substrate material is prepared by compounding the powder and the silica gel, the easy processing performance of the polymer is combined with the excellent dielectric performance and thermal performance of the ceramic, and the design and processing requirements of circuit components can be further met. Meanwhile, the whisker is adopted to replace other ceramic powder, so that the dielectric properties such as flexible substrate materials and the like, bending strength resistance and elastic modulus can be provided, and the processing and application of flexible components are facilitated.

Drawings

FIG. 1 shows Ba in different whisker shapes₂Ti₉O₂₀The relation curve of the dielectric constant epsilon r of the filling composite material of the filling amount;

FIG. 2 is a graph showing the effect of elastic modulus of composite materials with different PTEF incorporation amounts in examples 2 to 6 of the present invention;

FIG. 3 is a graph showing the effect of bending strength of composite materials with different amounts of incorporation in examples 2 to 6 of the present invention;

FIG. 4 is a whisker-like Ba for composite material prepared in example 1 of the present invention₂Ti₉O₂₀SEM picture of (1);

FIG. 5 shows PTEF and Ba prepared in example 1 of the present invention₂Ti₉O₂₀SEM images of composite materials prepared by mixing.

Detailed Description

The invention provides a preparation method of a composite material for a flexible circuit board, and a person skilled in the art can appropriately improve process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the scope of the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.

The invention provides a preparation method of a composite material for a flexible circuit board, which comprises the following steps:

A) whisker-like Ba₂Ti₉O₂₀Mixing the powder, silica gel and a solvent, and drying to obtain a mixture;

B) pressing and molding the mixture, and crushing to obtain composite particles; ball-milling and drying the composite particles to obtain powder particles;

C) and pressing, molding and sintering the powder particles to obtain the composite material for the flexible circuit board.

Whisker: refers to a fiber that is formed naturally or grown in a single crystal form under artificially controlled conditions (main form), has a very small diameter (on the order of micrometers), does not contain defects (grain boundaries, dislocations, voids, etc.) that are normally present in materials, and has a highly ordered atomic arrangement, so that its strength is close to the theoretical value of a complete crystal.

Preparation of the flexible substrate material, ceramic powder and PTFE are mixed in equal proportion to prepare the PTFE/ceramic composite material. The composite material prepared by the method has the advantages that both epsilon r and zeta f are increased along with the increase of the volume fraction of the ceramic, the toughness and the elongation of the material are reduced by adding PTFE, but the composite material can keep good stretchability; however, with the increase of ceramic particles, the epsilon r of the material has good temperature stability and easy processing, and the heat conductivity and the thermal expansion diffusion coefficient are improved. The invention creatively adopts the mixture of the crystal whisker and the PTFE, and aims at the defects that the traditional microwave dielectric ceramic material has high brittleness and can not completely meet the design and processing requirements of piezoelectric components with more complex shapes and structures, and the like. Meanwhile, the whisker is adopted to replace other ceramic powder, so that the dielectric properties such as flexible substrate materials and the like, bending strength resistance and elastic modulus can be provided, and the processing and application of flexible components are facilitated.

Firstly, the invention makes the whisker-shaped Ba₂Ti₉O₂₀Mixing the powder, silica gel and solvent.

According to the invention, said whisker-like Ba₂Ti₉O₂₀The preparation method of the powder is preferably as follows:

nanowhisker-like Ti0₂And Ba (OH)₂Carrying out hydrothermal reaction to obtain a reaction product;

washing, drying and calcining the reaction product to obtain the whisker-shaped Ba₂Ti₉O₂₀And (3) powder.

Wherein, the nano whisker Ti0₂The preparation method of (2) is preferably specifically:

taking TiCl₄Mixing and stirring KOH, and adjusting the pH value to 12-14 to obtain a mixed solution;

subjecting the mixed solution to ultrasonic oscillation and high-pressure reaction, and separating to obtain the nano-whisker-shaped Ti0₂。

More preferably specifically:

weighing TiCl₄KOH is used as a mineralizer, the mixture is placed in a glass beaker which is called with distilled water, the concentration of the Ti ion solution is adjusted to be 0.1-1mol/L, the mixture is stirred for 30min under a magnetic stirrer, and the pH value of the solution is controlled to be 12-14 in the process; placing the obtained mixed solution in ultrasonic waves for ultrasonic oscillation for 1h to ensure that the powder is uniformly dispersed in the solution; placing the solution after ultrasonic oscillation in a 150ml high-pressure reaction kettle, wherein the solution filling rate is 50-90%, the reaction temperature is 140-180 ℃, and the reaction time is 4-8 h; finally separating the obtained mixed solution in an ion separator to obtain the nano whisker-shaped Ti0₂。

Preparing to obtain the nano-whisker-shaped Ti0₂Then, the nano whisker-shaped Ti0 is added₂And Ba (OH)₂Carrying out hydrothermal reaction, mixing the Ti and Ba according to a molar ratio of 5:1, placing the obtained mixed solution into a high-pressure reaction kettle, wherein the solution filling ratio is 80%, the hydrothermal reaction temperature is 140-200 ℃, and the hydrothermal reaction time is 12-48 h.

Washing and centrifugally separating the reacted product, drying and calcining at 700-1200 ℃ for 2-6h to obtain whisker-shaped Ba₂Ti₉O₂₀And (3) powder.

Preparing to obtain whisker-shaped Ba₂Ti₉O₂₀After powdering, the whisker-like Ba is added₂Ti₉O₂₀Mixing the powder, silica gel and absolute ethyl alcohol as a solvent; the whisker-shaped Ba₂Ti₉O₂₀The volume ratio of the powder to the silica gel is preferably 1: (0.1 to 0.5); the mixing is specifically as follows: stirring for 1h under a magnetic stirrer; dispersing the mixture in a beaker by ultrasonic waves for 1-4h to uniformly mix the components, and drying the mixture in a boiling water bath after the dispersion is finished to obtain PTEF and Ba₂Ti₉O₂₀And (3) mixing.

And (3) pressing, molding and crushing the mixture to obtain the composite particles.

The preferable concrete is as follows: the obtained PTEF and Ba₂Ti₉O₂₀Loading the mixture into a steel grinding tool, and hydraulically forming under 40MPa for 2min to obtain PTEF and Ba₂Ti₉O₂₀The biscuit of (1). Crushing the obtained biscuit to obtain PTEF/Ba₂Ti₉O₂₀Composite particles.

The present invention is not limited to the specific operations of forming and shredding, as will be appreciated by those skilled in the art.

And performing ball milling and drying on the composite particles to obtain powder particles.

The method specifically comprises the following steps: taking the above PTEF/Ba₂Ti₉O₂₀Composite particles, according to the raw materials: distilled water: weighing zirconium balls according to the mass ratio of 1:1:2, and placing the zirconium balls in a planetary ball mill, wherein the rotation speed of the ball mill is preferably 120-400 r/min, and the ball milling time is 2-12 h. After ball milling, the obtained slurry is poured into an evaporating dish and dried in vacuum for 48 hours at 100 ℃. And (4) placing the dried material in a mortar for fully grinding to obtain powder particles with uniform size.

And then pressing and molding the powder particles. The method specifically comprises the following steps: and (3) sieving the obtained powder particles by a 80-120-mesh sample sieve, and pressing the granulated powder into a biscuit under the molding pressure of 40-90 MPa.

Putting the obtained biscuit into vacuum sinteringSintering in a furnace under the protection of inert gas, preferably with simultaneous introduction of N₂Performing atmosphere protection, wherein the temperature rise rate of sintering is 1-3 ℃/min, the sintering temperature is 120-200 ℃, the heat preservation time is 2-4 h, and the Ba can be obtained by cooling to room temperature along with the furnace₂Ti₉O₂₀the/PTEF composite ceramic. Namely the composite material for the flexible circuit board

The flexible microwave substrate material prepared by mixing the ceramic material and the organic silica gel in proportion can overcome the defects that the conventional microwave dielectric ceramic material has high brittleness and is not easy to bend, and the design and processing requirements of piezoelectric components can not be met. The crystal structure of the crystal whisker is relatively complete, does not contain defects such as holes, dislocation, particle interface and the like, and has the advantages of high breaking strength, high elastic modulus, high temperature resistance, no fatigue effect and the like compared with the conventional micron powder, nanometer powder and long fiber. The invention adds the crystal whisker into the ceramic material to improve the toughness, aging resistance, dielectric property and the like of the ceramic material.

The invention provides a composite material for a flexible circuit board, which is prepared by the preparation method in any one of the technical schemes.

The invention provides a flexible circuit substrate which is made of a composite material prepared by the preparation method in any one of the technical schemes.

The specific method for manufacturing the flexible circuit substrate is not limited in the invention, and the flexible circuit substrate can be made of the composite material.

The invention provides a preparation method of a composite material for a flexible circuit board, which comprises the following steps: A) whisker-like Ba₂Ti₉O₂₀Mixing the powder, silica gel and a solvent, stirring and drying to obtain a mixture; B) pressing and molding the mixture, and crushing to obtain composite particles; ball-milling and drying the composite particles to obtain powder particles; C) and pressing, molding and sintering the powder particles to obtain the composite material for the flexible circuit board. The invention is realized by the use of whisker-shaped Ba₂Ti₉O₂₀The flexible substrate material is prepared by compounding the powder and the silica gel, the easy processing performance of the polymer is combined with the excellent dielectric performance and thermal performance of the ceramic, and the design and processing requirements of circuit components can be further met. Meanwhile, the whisker is adopted to replace other ceramic powder, so that the dielectric properties such as flexible substrate materials and the like, bending strength resistance and elastic modulus can be provided, and the processing and application of flexible components are facilitated.

In order to further illustrate the present invention, the following describes a method for preparing a composite material for a flexible circuit board in detail with reference to the following embodiments.