CN111171249A - Photocuring dielectric functional gradient composite material, and preparation method and application thereof - Google Patents
Photocuring dielectric functional gradient composite material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a photocuring dielectric functional gradient composite material and a preparation method thereof. The raw materials of the photocuring dielectric functional gradient composite material comprise photosensitive resin and inorganic powder, wherein the photosensitive resin comprises 20-80 parts by mass of acrylic acid oligomer, 30-70 parts by mass of acrylate monomer, 1-6 parts by mass of photoinitiator and 0-2 parts by mass of auxiliary agent. The invention combines the preparation of the light-cured resin and the dielectric composite material and also combines the 3D printing technology. The invention prepares the single-layer composite material with adjustable and controllable dielectric constant according to the distribution of the high-voltage electric field, uses the high-dielectric material at the part with stronger electric field, uses the low-dielectric material at the part with weaker electric field, and effectively keeps the uniformity of the high-voltage electric field. The composite material can be widely applied to high-voltage insulation.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a photocuring dielectric functional gradient composite material, and a preparation method and application thereof.
Background
In the electrical field, the uneven distribution of the electric field is a main cause of dielectric breakdown and poor electric resistance. The traditional shape control method is limited in effect, and the method of adjusting the dielectric property of the insulating material, namely adopting the shape control method, can be a fundamental way for solving the stress concentration of a local electric field. The dielectric gradient material is used as a method for controlling material characteristics, and has great potential in regulating electric field distribution and improving the electric resistance of the insulator. Dielectric gradient materials have long been the target of many researchers in the field of high voltage insulation. The dielectric gradient realization process is always the key point of the dielectric gradient material research and is also the difficulty of the dielectric gradient material research.
In recent years, additive manufacturing (often referred to as 3D printing) techniques featuring material build-up molding have provided entirely new implementations of dielectric gradient materials. The 3D printing is an advanced manufacturing technology developed along with the integration of multiple disciplines such as information, materials and manufacturing, and has the core technical characteristics of accumulating point by point to form a surface and accumulating the surface by surface to form an integer. If the 3D printing technology is combined with the preparation of the dielectric gradient material, the dielectric constant epsilon is adjusted by controlling the mixing proportion of accumulating the material face by face or even point by point, the combination of shape control and controllability is realized, and the manufacture of the dielectric gradient material is hopefully realized. Among the various 3D printing technologies, Stereolithography (SLA) is currently the most deeply studied, technically mature, and widely used technology. The technology takes photosensitive resin as a raw material, controls ultraviolet laser beams to be cured and molded by a computer, and has the characteristics of high processing precision, good surface quality and the like.
The single inorganic ceramic material has high dielectric constant, but needs high-temperature sintering in the preparation process, has complex process, low breakdown strength and single dielectric property, and cannot fundamentally solve the problems of breakdown damage and poor electric resistance of the high-voltage insulator. The polymer material has the advantages of excellent processing performance, low dielectric loss, high breakdown field strength and the like, but the dielectric constant of the polymer material is generally lower (less than 10), and obviously, the single polymer material cannot meet the requirement of the high dielectric field. In recent years, researches show that polymer-based composite materials with high dielectric constant, low dielectric loss and high breakdown field strength can be prepared by compounding a polymer and an inorganic material according to a certain proportion.
At present, most of polymer matrix composite materials are prepared by a thermal curing method, the thermal curing method needs a large amount of organic solvents, the energy consumption is high, the surface of the prepared material is easy to be rough, and the current research is limited to the gradient of 3-5 layers, interlayer bonding and multilayering. Compared with thermal curing, the UV light curing technology has the advantages of fast curing, energy conservation, environmental protection and the like, and has great application potential in the high-tech field. The material is the basis for realizing 3D printing of the dielectric gradient material. However, the main material for photo-curing is photosensitive resin, but the dielectric constant of the photosensitive resin material is single and uncontrollable, which limits the application of photo-curing technology in the preparation of polymer-based dielectric materials.
Disclosure of Invention
In order to solve the problems of complex preparation process of the dielectric gradient material, single dielectric property of the material, difficult adhesion between layers and the like, the invention adopts photosensitive resin as a polymer matrix, adopts inorganic material as filler, combines a Digital Light Processing (DLP) technology in 3D printing, controls the mixing proportion of accumulated materials of each layer through a computer, adjusts the dielectric constant epsilon, combines shape control and property control, and realizes the manufacture of the dielectric function gradient insulator.
Specifically, the invention provides a method for preparing a photocuring dielectric functional gradient composite material by 3D printing, which comprises the following steps:
(1) mixing 20-80 parts by weight of acrylate oligomer, 30-70 parts by weight of acrylate monomer, 1-6 parts by weight of photoinitiator and 0-2 parts by weight of auxiliary agent to obtain a resin matrix; mixing inorganic powder and the resin matrix according to different proportions to obtain composite material mixture slurry with different inorganic powder contents; carrying out photocuring on the composite material mixture slurry with different inorganic powder contents to obtain composite materials with different inorganic powder contents; measuring dielectric properties of each composite material with different inorganic powder contents; determining an effective dielectric property theoretical model suitable for the composite material;
(2) setting a computer program according to the dielectric property requirement of the material and the theoretical model of the effective dielectric property suitable for the composite material determined in the step (1), controlling the dosage of the resin matrix and the inorganic powder in the step (1) when each layer of the dielectric gradient composite material is printed, uniformly mixing the resin matrix and the inorganic powder, and performing photocuring to obtain each layer of the dielectric gradient composite material.
In one or more embodiments, the acrylate oligomer is selected from one or more of epoxy acrylates, urethane acrylates, polyester acrylates, and polyether acrylates.
In one or more embodiments, the acrylic monomer is selected from one or more of 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, and ethoxylated trimethylolpropane triacrylate.
in one or more embodiments, the photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, α -hydroxyisobutyrophenone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.
In one or more embodiments, the resin matrix contains 0.5 to 2 parts by weight of an auxiliary agent, and the auxiliary agent comprises 0.2 to 1.5 parts by mass of a dispersing agent and 0.3 to 1.5 parts by mass of an anti-settling agent.
In one or more embodiments, the inorganic powder is selected from one or more of metal oxides, perovskite-type oxides, and high dielectric materials having a core-shell structure.
In one or more embodiments, the inorganic powder has a particle size of 0.05 to 15 μm and a refractive index of 1.6 to 2.6.
In one or more embodiments, the resin matrix contains 50 ± 3 parts by weight of epoxy acrylate, 50 ± 3 parts by weight of 1, 6-hexanediol diacrylate, 3 ± 1 part by weight of 1-hydroxy-cycloethylphenyl ketone, 1 ± 0.5 part by weight of photoinitiator 819, 1 ± 0.5 part by weight of dispersant, and 1 ± 0.5 part by weight of anti-settling agent, and the inorganic powder is alumina, preferably with a particle size of 14 ± 1 μm and a refractive index of 1.74 ± 0.1.
In one or more embodiments, the resin matrix contains 40 ± 3 parts by weight of urethane acrylate, 60 ± 3 parts by weight of tricyclodecane dimethanol diacrylate, 2 ± 1 parts by weight of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 2 ± 1 parts by weight of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 1.2 ± 0.5 parts by weight of dispersant and 0.6 ± 0.5 parts by weight of anti-settling agent, and the inorganic powder is barium titanate, preferably having a particle size of 0.5 ± 0.05 μm and a refractive index of 2.4 ± 0.1.
In one or more embodiments, in the step (1) and/or the step (2), the light source has a wavelength of 355 to 405nm and an intensity of 1 to 10mW/cm during photocuring2The exposure time of the single layer is 1-10 s, and the thickness of the single layer is 0.01-0.1 mm.
The invention also provides a photocured dielectric functionally graded composite material prepared by the method according to any embodiment of the invention.
The invention also provides an insulator comprising the photocured dielectric functionally graded composite material according to any embodiment of the invention.
Drawings
FIG. 1 is a graph showing the change of the relative dielectric constant with the volume fraction of alumina of the composite material obtained in example 1.
FIG. 2 is a graph showing the change of the relative dielectric constant with the volume fraction of barium titanate of the composite material obtained in example 2.
In FIG. 3, FIG. a, FIG. b and FIG. c are schematic structural views of composite materials of comparative example 1, comparative example 2 and example 1, respectively, wherein r is1Denotes the position of the layer of material 1, r2Denotes the position of the 500 th layer of material, r3Indicating the material of the 1000 th layerPosition epsilonr1、εr2And εrRepresents the dielectric constant.
In fig. 4, curve a is the dielectric constant value of each of the composite layers of comparative example 1, curve b is the dielectric constant value of each of the front 500 and rear 500 layers of the composite of comparative example 2, and curve c is the dielectric constant value of the composite layers 1, 200, 300, 400, 600, 700, 800, 1000 of example 1, wherein r is1Denotes the position of the layer of material 1, r2Denotes the position of the 500 th layer of material, r3Indicating the location of the 1000 th layer of material.
FIG. 5 is a graph of electric field as a function of number of layers simulated as a function of electric field and dielectric permittivity, where curve a corresponds to the composite of comparative example 1, curve b corresponds to the composite of comparative example 2, curve c corresponds to the composite of example 1, and r1Denotes the position of the layer of material 1, r2Denotes the position of the 500 th layer of material, r3Indicating the location of the 1000 th layer of material.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as amounts, amounts and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
Herein, unless otherwise specified, the ratio refers to a mass ratio, and the percentage refers to a mass percentage.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
In order to solve the problems of complex preparation process of the dielectric gradient material, single dielectric property of the material, difficult interlayer adhesion and the like, the invention optimizes the components of photosensitive resin, acrylate monomer, initiator and the like, introduces functional inorganic filler into the photosensitive resin, develops a system suitable for photocuring, combines a Digital Light Processing (DLP) technology in 3D printing, and controls the mixing ratio of accumulated materials of each layer through a computer to realize the 3D printing of the dielectric gradient material.
The method for preparing the dielectric functional gradient composite material comprises the following steps:
(1) mixing 20-80 parts by weight of acrylate oligomer, 30-70 parts by weight of acrylate monomer, 1-6 parts by weight of photoinitiator and 0-2 parts by weight of auxiliary agent to obtain a resin matrix; mixing inorganic powder and the resin matrix according to different proportions to obtain composite material mixture slurry with different inorganic powder contents; carrying out photocuring on the composite material mixture slurry with different inorganic powder contents to obtain composite materials with different inorganic powder contents; measuring dielectric properties of each composite material with different inorganic powder contents; determining an effective dielectric property theoretical model suitable for the composite material;
(2) setting a computer program according to the dielectric property requirement of the material and the theoretical model of the effective dielectric property suitable for the composite material determined in the step (1), controlling the dosage of the resin matrix and the inorganic powder in the step (1) when each layer of the dielectric gradient composite material is printed, uniformly mixing the resin matrix and the inorganic powder, and performing photocuring to obtain each layer of the dielectric gradient composite material.
The resin matrix of the invention comprises or consists of acrylate oligomer, acrylate monomer, photoinitiator and optional auxiliary agent.
The acrylate oligomer suitable for use in the present invention is preferably selected from one or more of epoxy acrylates, urethane acrylates, polyester acrylates, polyether acrylates. In certain embodiments, the acrylate oligomer used in the present invention is an epoxy acrylate and/or a urethane acrylate. In certain embodiments, the resin matrix contains 30 to 70 parts by weight, such as 40 to 60 parts by weight, 40 to 50 parts by weight of the acrylate oligomer.
The acrylate monomer suitable for use in the present invention is preferably selected from one or more of 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol diacrylate and ethoxylated trimethylolpropane triacrylate. In certain embodiments, the acrylate monomer used in the present invention is 1, 6-hexanediol diacrylate and/or tricyclodecane dimethanol diacrylate. In certain embodiments, the resin matrix contains 30 to 70 parts by weight, such as 40 to 60 parts by weight, 50 to 60 parts by weight of acrylate monomers.
Herein, the parts by weight are generally based on 100 parts by weight of the total weight of the acrylate oligomer and the acrylate monomer, unless otherwise specified.
In certain embodiments, the resin matrix comprises 40 to 60 parts by weight, such as 50 + -5 parts by weight, 50 + -3 parts by weight of the epoxy acrylate, and 40 to 60 parts by weight, such as 50 + -5 parts by weight, 50 + -3 parts by weight of the 1, 6-hexanediol diacrylate.
In certain embodiments, the resin matrix comprises 30 to 50 parts by weight, such as 40 + -5 parts by weight, 40 + -3 parts by weight of the urethane acrylate and the resin matrix comprises 50 to 70 parts by weight, such as 60 + -5 parts by weight, 60 + -3 parts by weight of the tricyclodecane dimethanol diacrylate.
the photoinitiators suitable for use in the present invention are preferably selected from one or more of 1-hydroxycyclohexylphenylketone, α -hydroxyisobutyrylbenzene, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, in certain embodiments the photoinitiators used in the present invention are two or three selected from 1-hydroxycyclohexylphenylketone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, in certain embodiments the resin matrix contains 2 to 5 parts by weight, e.g., 3 to 5 parts by weight, 3.5 to 4.5 parts by weight, 4 parts by weight or so of photoinitiator, in certain embodiments the photoinitiators used in the present invention consist of 1-hydroxycyclohexylphenylketone and phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide in a mass ratio of about 3:1, and the photoinitiator is composed of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide in a mass ratio of about 2:2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide and phenylbis 2: 4, 6-trimethylbenzoyl-diphenylphosphine oxide in a mass ratio of about 2: 2.
The resin matrix of the present invention preferably comprises an auxiliary agent. The adjuvants suitable for use in the present invention may be one or more of those commonly used in the art, including but not limited to dispersants, precipitants, and the like. It will be understood by those skilled in the art that the adjuvants described herein do not include the inorganic powders described herein. In certain embodiments, the adjuvant comprises or consists of a dispersant and a precipitating agent. In certain embodiments, the resin matrix contains 0.5 to 2 parts by weight, such as 1 to 2 parts by mass, of an auxiliary; preferably, the auxiliary agent comprises 0.2-1.5 parts by mass, such as 0.5-1.5 parts by mass of the dispersant and 0.3-1.5 parts by mass, such as 0.5-1.5 parts by mass of the anti-settling agent. In certain embodiments, the adjuvant comprises or consists of a dispersant and a precipitant in a mass ratio of 2:1 to 1:2, such as 2:1 to 1: 1.
In some embodiments, the resin matrix comprises 30 to 70 parts by weight (e.g., 40 to 60 parts by weight, 40 to 50 parts by weight) of the acrylate oligomer, 30 to 70 parts by weight (e.g., 40 to 60 parts by weight, 50 to 60 parts by weight) of the acrylate monomer, 1 to 6 parts by weight (e.g., 2 to 5 parts by weight, 3 to 5 parts by weight, 3.5 to 4.5 parts by weight, 4 parts by weight, or so) of the photoinitiator, and 0 to 2 parts by weight (e.g., 0.5 to 2 parts by weight, 1 to 2 parts by weight) of the auxiliary, or a mixture of 30 to 70 parts by weight (e.g., 40 to 60 parts by weight, 40 to 50 parts by weight) of the acrylate oligomer, 30 to 70 parts by weight (e.g., 40 to 60 parts by weight, 50 to 60 parts by weight) of the acrylate monomer, 1 to 6 parts by weight (e.g., 2 to 5 parts by weight, 3 to 5 parts by weight, and 4 parts by weight), About 3.5 to 4.5 parts by weight, about 4 parts by weight) of a photoinitiator and 0 to 2 parts by weight (e.g., 0.5 to 2 parts by weight, 1 to 2 parts by weight) of an auxiliary.
The inorganic powder suitable for use in the present invention is preferably selected from one or more of metal oxides, perovskite-type oxides, and high dielectric materials having a core-shell structure. Herein, a high dielectric material refers to a material having a relative dielectric constant greater than 10. The metal oxide may be, for example, alumina. The perovskite oxide may be, for example, barium titanate. In certain embodiments, the inorganic powders used in the present invention are metal oxides and/or perovskite-type oxides, such as alumina and/or barium titanate. The inorganic powder suitable for the present invention has a particle size of preferably 0.05 to 15 μm and a refractive index of preferably 1.6 to 2.6.
It will be understood by those skilled in the art that, in the present invention, the resin matrix and the inorganic powder used in step (2) are the same as those used in step (1).
In the present invention, the method for preparing the composite material in step (1) is not particularly limited, and may be a conventional method for preparing a photocurable composite material; step (2) preferably prepares the composite material by 3D printing, i.e. preferably prepares the composite material by using a 3D printer.
When the 3D printer is used for preparing the photocuring composite material, the resin matrix can be placed into one medicine cylinder of the printer, and the inorganic powder can be placed into the other medicine cylinder of the printer; when printing each layer of material, the medicine jar filled with the resin matrix and the medicine jar filled with the inorganic powder respectively feed the medicine jar for containing the resin matrix and the inorganic powder, and the raw materials (the resin matrix and the inorganic powder) in the medicine jar filled with the resin matrix and the inorganic powder are stirred, mixed uniformly, then flow out and are exposed and molded to obtain each layer of material of the dielectric function gradient composite material.
In the present invention, mixing the respective components of the resin matrix and mixing the resin matrix and the inorganic powder are preferably performed under vacuum conditions, for example, by mixing with vacuum mechanical stirring.
In the step (1) or the step (2), when the composite material mixture slurry (i.e. the mixture of the resin matrix and the inorganic powder) is subjected to photocuring, the wavelength of a light source is preferably 355-405 nm; the intensity of the light source is preferably 1-10 mW/cm2E.g., 3-8 mW/cm2(ii) a The exposure time for a single layer is preferably 1 to 10s, for example 1 to 5s, and the thickness of the single layer is preferably 0.01 to 0.1mm, for example 0.05. + -. 0.02 mm. The dielectric function gradient composite material prepared by the method does not need to be subjected to degreasing, sintering and other processes.
In the present invention, the method for determining the dielectric properties of the composite material is a method conventional in the art. In certain embodiments, determining the dielectric properties of the composite is determining the relative dielectric constant of the composite; the relative permittivity of the composite material may be measured, for example, by measuring the capacitance of the composite material and calculating the relative permittivity from the relationship between the capacitance and the relative permittivity.
In the present invention, the theoretical model of effective dielectric properties may be any of various models known in the art that can estimate the dielectric properties of a composite material based on the content of filler (e.g., inorganic powder in the present invention) and the dielectric properties of the filler and resin matrix. In certain embodiments, the present invention determines theoretical models of effective dielectric properties suitable for composite materials by simulation. As will be understood by those skilled in the art, the theoretical model of effective dielectric properties herein is for a composite material, and means that the measured values of the dielectric properties of the composite material at different inorganic powder contents are closer to the estimated values of the dielectric properties calculated from the model. In certain embodiments, a theoretical model of effective dielectric properties refers to a model that is capable of estimating the dielectric constant of a composite material based on the filler content and the dielectric constants of the filler and resin matrix.
In certain embodiments, the theoretical model of effective dielectric properties is the loyenga model:
wherein epsiloneffIs the effective dielectric constant, epsilon, of the composite material1And ε2Dielectric constants, phi, of the inorganic powder and resin matrix, respectively1Is the volume fraction of the inorganic powder; preferably, the inorganic powder is alumina, preferably with a particle size of 14 ± 1 μm and a refractive index of 1.74 ± 0.1; preferably, the resin matrix contains 40 to 60 parts by weight, such as 50 plus or minus 5 parts by weight and 50 plus or minus 3 parts by weight of the epoxy acrylate, and the resin matrix contains 40 to 60 parts by weight, such as 50 plus or minus 5 parts by weight and 50 plus or minus 3 parts by weight of the 1, 6-hexanediol diacrylate.
In certain embodiments, the theoretical model of effective dielectric properties is a J-S model:
in the formula, epsiloneffIs the effective dielectric constant, epsilon, of the composite material1、ε2Dielectric constants of the inorganic powder and the resin matrix, respectively, v1V and v2The volume fractions of the inorganic powder and the resin matrix respectively; preferably, the inorganic powder is barium titanate, preferably having a particle size of 0.5 ± 0.05 μm and a refractive index of 2.4 ± 0.1; preferably, the resin matrix contains 30 to 50 parts by weight, for example, 40 ± 5 parts by weight, and 40 ± 3 parts by weight of the urethane acrylate, and the resin matrix contains 50 to 70 parts by weight, for example, 60 ± 5 parts by weight, and 60 ± 3 parts by weight of the tricyclodecane dimethanol diacrylate.
In the invention, the effective dielectric property theoretical model suitable for the composite material can be determined by comparing the actually measured dielectric property of the composite material to be prepared under different inorganic powder contents with the dielectric property estimated value calculated according to the effective dielectric property theoretical model. In certain embodiments, the present invention determines theoretical models of effective dielectric properties suitable for a composite material by simulation.
In the invention, the computer program is set according to the dielectric property requirement of the material and the theoretical model of the effective dielectric property suitable for the composite material determined in the step (1), and the computer program can be set according to the dielectric property requirement of each layer of the composite material, and then the theoretical model of the effective dielectric property suitable for the composite material determined in the step (1). Calculating the respective use amounts of the resin matrix and the inorganic powder when each layer of the dielectric functionally gradient composite material is printed by the set computer program according to the preset dielectric properties of each layer of the composite material and the theoretical model of the effective dielectric properties suitable for the composite material determined in the step (1), thereby realizing the control of the use amounts of the resin matrix and the inorganic powder when each layer of the dielectric functionally gradient composite material is printed; in certain embodiments, the computer program configured is also capable of controlling the feeding of the resin matrix and the inorganic powder. In certain embodiments, the present invention presets the dielectric constants of the layers of the composite material based on the dielectric properties requirements of the material, and sets the computer program based on the preset dielectric constants of the layers of the composite material and the theoretical model of effective dielectric properties for the composite material determined in step (1).
In certain embodiments, the method of the present invention for preparing a dielectric functionally graded composite material comprises the steps of:
(1) mixing 20-80 parts by weight of acrylate oligomer, 30-70 parts by weight of acrylate monomer, 1-6 parts by weight of photoinitiator and 0-5 parts by weight of auxiliary agent to obtain a resin matrix; mixing the resin matrix and the inorganic powder according to different proportions to obtain composite material mixture slurry with different inorganic powder contents; carrying out photocuring on the composite material mixture slurry to obtain composite materials with different inorganic powder contents, wherein the wavelength of a light source is preferably 355-405 nm, and the intensity of the light source is preferably 1-10 mW/cm2The single-layer exposure time is preferably 1-10 s, and the single-layer film thickness is excellentSelecting the thickness of the material to be 0.01-0.1 mm; measuring the dielectric properties of the composite material; determining an effective dielectric property theoretical model suitable for the composite material;
(2) mixing the acrylate oligomer, the acrylate monomer, the photoinitiator and the auxiliary agent according to the proportion in the step (1) to obtain a resin matrix, and placing the resin matrix in a medicine cylinder of a printer; putting inorganic powder into another cylinder of the printer; setting a computer program according to the dielectric property requirement of the material and the theoretical model of the effective dielectric property determined in the step (1) and suitable for the composite material, controlling the feeding amount of the material in a medicine cylinder filled with the resin matrix and a medicine cylinder filled with the inorganic powder respectively to the medicine cylinders used for containing the resin matrix and the inorganic powder when printing each layer of material, uniformly stirring and mixing the raw materials in the medicine cylinders filled with the resin matrix and the inorganic powder, then flowing out and carrying out exposure forming to obtain each layer of material of the dielectric functional gradient composite material, wherein the wavelength of a light source is preferably 355-405 nm, and the intensity of the light source is preferably 1-10 mW/cm2E.g., 3-8 mW/cm2The single-layer exposure time is preferably 1 to 10s, for example, 1 to 5s, and the single-layer film thickness is preferably 0.01 to 0.1mm, for example, 0.05. + -. 0.02 mm.
In the present invention, the number of layers of the dielectric functionally graded composite material obtained by printing is not particularly limited, and may be, for example, 100 to 5000 layers, 200 to 2000 layers, 500 to 1500 layers, 800 to 1200 layers, or the like.
In some embodiments, the resin matrix of the present invention comprises 50 ± 3 parts by weight of epoxy acrylate, 50 ± 3 parts by weight of 1, 6-hexanediol diacrylate, 3 ± 1 parts by weight of 1-hydroxy-cycloethylphenyl ketone, 1 ± 0.5 parts by weight of photoinitiator 819, 1 ± 0.5 parts by weight of dispersant and 1 ± 0.5 parts by weight of anti-settling agent, the inorganic powder is alumina, preferably with a particle size of 14 ± 1 μm and a refractive index of 1.74 ± 0.1; preferably, the number of layers of the dielectric functionally graded material is 200-2000 layers, such as 800-1200 layers; preferably, the monolayer thickness is 0.05 ± 0.02 mm.
In some embodiments, the resin matrix of the present invention comprises 40 ± 3 parts by weight of urethane acrylate, 60 ± 3 parts by weight of tricyclodecane dimethanol diacrylate, 2 ± 1 parts by weight of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 2 ± 1 parts by weight of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 1.2 ± 0.5 parts by weight of dispersant and 0.6 ± 0.5 parts by weight of anti-settling agent, and the inorganic powder is barium titanate, preferably having a particle size of 0.5 ± 0.05 μm and a refractive index of 2.4 ± 0.1; preferably, the number of layers of the dielectric functionally graded material is 200-2000 layers, such as 800-1200 layers; preferably, the monolayer thickness is 0.05 ± 0.02 mm.
The invention includes a photocurable functionally graded composite material prepared by a process according to any of the embodiments herein. Preferably, the number of layers of the dielectric functionally graded material of the present invention is 200 to 2000 layers. Preferably, the monolayer thickness is 0.05 ± 0.02 mm.
The invention can prepare composite materials with adjustable and controllable dielectric constants of all layers according to the distribution of the high-voltage electric field, uses high-dielectric materials at the parts with stronger electric field, uses low-dielectric materials at the parts with weaker electric field, and effectively keeps the uniformity of the high-voltage electric field. Therefore, the method is particularly suitable for preparing the photocuring dielectric function gradient composite material with adjustable and controllable dielectric property.
The photocuring dielectric functional gradient composite material can effectively keep the uniformity of a high-voltage electric field, and can be widely applied to high-voltage insulation. Accordingly, the present invention also includes an insulator comprising the photocurable functionally graded composite material of the present invention; preferably, the insulator is a high voltage insulator.
Compared with the prior art, the invention has the following advantages:
1. the method for preparing the dielectric functional gradient composite material adopts a Digital Light Processing (DLP) technology in 3D printing, and has the advantages of fast curing, energy conservation, environmental protection and the like compared with a thermal curing forming technology;
2. the dielectric properties of each layer of material of the dielectric function gradient composite material can be designed and regulated according to the actual electric field distribution, the limitation of the traditional single-property material is broken, and the high-voltage electric field can be well homogenized;
3. the dielectric function gradient composite material is prepared by the method, and degreasing and sintering are not needed;
4. the dielectric function gradient composite material has the advantages of high dielectric constant, low dielectric loss, high breakdown strength, uniform electric field distribution in a high-voltage electric field and the like;
5. the invention utilizes computer program to control the dosage of resin matrix and inorganic powder when printing each layer of material, can realize the preparation of the dielectric function gradient composite material with complicated and variable dielectric property (such as dielectric constant) of each layer, for example, the dielectric function gradient composite material with gradually changed dielectric constant of each layer can be prepared.
The invention will now be described by way of specific examples, which are intended to provide a better understanding of the contents of the invention. It is to be understood that these examples are illustrative only and not limiting. The starting materials and reagents used in the examples were, unless otherwise specified, those conventionally available on the market. The experimental methods, preparation methods and detection methods used in the examples are all conventional methods unless otherwise specified. The instruments and devices used in the examples are conventional in the art unless otherwise specified.
In the following examples and comparative examples, the dispersant was BYK-9010 and the anti-settling agent was BYK-410.
In the following examples and comparative examples, the capacitance of the composite material was measured using an Agilent E4980A impedance analyzer, and the dielectric constant was calculated from the relationship between the capacitance and the dielectric constant. Namely, it is
ε＝CMedium/CVacuum
In the formula, epsilon, CMediumAnd CVacuumThe relative permittivity of the dielectric, the capacitance of the dielectric material, and the vacuum parallel plate capacitor capacitance, respectively. The dielectric constant is determined by the dielectric itself, independent of the magnitude of the applied electric field and the electrode material. Where capacitance C is proportional to the dielectric permittivity and electrode plate area and inversely proportional to the inter-plate distance (i.e., dielectric thickness), i.e.:
wherein A, t, ε0And epsilon is the area of the polar plate and the distance between polar plates respectivelyVacuum dielectric constant and relative dielectric constant of the dielectric, wherein0Is 8.85X 10-12F/m。
Example 1
This example prepares a functionally graded dielectric composite.
Determination of the dielectric constant distribution of the composite material as a function of the alumina content: 50 parts by weight of epoxy acrylate, 50 parts by weight of 1, 6-hexanediol diacrylate, 3 parts by weight of 1-hydroxy-cycloethylphenyl ketone (photoinitiator 184), 1 part by weight of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (photoinitiator 819), 1 part by weight of a dispersant and 1 part by weight of an anti-settling agent are mixed and stirred uniformly to form a resin matrix. Taking 5 parts of resin matrix, respectively adding a certain amount of alumina (the granularity is 15 mu m, the refractive index is 1.74) into each resin matrix, uniformly stirring to obtain composite material mixture slurry with the alumina volume number of 10%, 20%, 30%, 40% and 50%, respectively, and carrying out photocuring to obtain composite material samples with the film thickness of 0.05mm and different alumina contents, wherein the wavelength of a light source is 405nm, and the intensity of the light source is 4mW/cm2The exposure time of the monolayer was 2s, and the relative dielectric constant at 50Hz of each sample after curing was measured, and the results are shown in FIG. 1. The dielectric constant distribution of the composite material of the present example was found by simulation to conform to the loyenga model:
wherein epsiloneffIs the effective dielectric constant, epsilon, of the composite material1And ε2Dielectric constants, phi, of the alumina and resin matrices, respectively1Is the volume fraction of alumina. From this, it is known that the dielectric properties of the composite material are distributed according to the loyenga model when alumina is used as the filler.
Preparing a dielectric functional gradient composite material: mixing and stirring uniformly 50 parts by weight of epoxy acrylate, 50 parts by weight of 1, 6-hexanediol diacrylate, 3 parts by weight of 1-hydroxy-cyclohexyl phenyl ketone, 1 part by weight of photoinitiator 819, 1 part by weight of dispersant and 1 part by weight of anti-settling agent, and placing the mixture in a No. 1 medicine jar; aluminum oxide (particle size of15 μm, refractive index 1.74) powder was placed in # 2 jar. According to the dielectric property requirement of the material and a Looyenga model, a computer program is set, the feeding amount of the No. 1 medicine cylinder and the feeding amount of the No. 2 medicine cylinder for feeding the No. 3 medicine cylinder are controlled, and the materials are leveled on a printing platform after being stirred at a high speed and are exposed and cured for 1000 layers. Wherein the wavelength of the light source is 405nm, and the intensity of the light source is 4mW/cm2The exposure time of the single layer is 2s, the thickness of the single layer is 0.05mm, and the relative dielectric constant of each preset layer material at 50Hz is shown in FIG. 4.
Example 2
This example prepares a functionally graded dielectric material.
And (3) determining the dielectric constant distribution of the composite material along with the change of the content of barium titanate: 40 parts by weight of urethane acrylate, 60 parts by weight of tricyclodecane dimethanol diacrylate, 2 parts by weight of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (photoinitiator TPO), 2 parts by weight of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 1.2 parts by weight of a dispersant and 0.6 part by weight of an anti-settling agent were mixed and stirred uniformly to form a resin substrate. Taking 10 parts of resin matrix, respectively adding a certain amount of barium titanate (the granularity is 0.5 mu m, the refractive index is 2.4) into each resin matrix, uniformly stirring to obtain composite material mixture slurry with the volume fractions of 5%, 10%, 15%, 20% and 25% of barium titanate respectively, and curing a composite material film with the film thickness of 0.03mm, wherein the wavelength of a light source is 405nm, and the intensity of the light source is 6.5mW/cm2The monolayer exposure time was 3.5 s. The relative dielectric constant of the sample at 50Hz was measured and the results are shown in FIG. 2. The dielectric constant distribution of the composite material of the present example was found by simulation to conform to the J-S model:
in the formula, epsiloneffIs the effective dielectric constant, epsilon, of the composite material1、ε2Dielectric constants of barium titanate and resin matrix, respectively, v1V and v2The volume fractions of barium titanate and the resin matrix, respectively. From this, it is understood that when barium titanate is used as a filler, the dielectric properties of the material are expressed by J-an S-model distribution.
Preparing a dielectric functional gradient composite material: mixing and stirring uniformly 40 parts by weight of urethane acrylate, 60 parts by weight of tricyclodecane dimethanol diacrylate, 2 parts by weight of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, 2 parts by weight of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 1.2 parts by weight of dispersant and 0.6 part by weight of anti-settling agent, and placing the mixture in a No. 1 medicine cylinder; barium titanate (particle size 0.5 μm, refractive index 2.4) powder was placed in # 2 jar. And setting a computer program according to the dielectric property requirement of the material and the J-S model, controlling the feeding amount of the No. 1 medicine cylinder and the No. 2 medicine cylinder to the No. 3 medicine cylinder respectively, leveling on a printing platform after high-speed stirring, and carrying out exposure curing to obtain 1000 layers. Wherein the wavelength of the light source is 405nm, and the intensity of the light source is 6.5mW/cm2The single-layer exposure time was 3.5s, and the single-layer film thickness was 0.03 mm.
Comparative example 1
This comparative example prepared a single dielectric material.
Preparation of a single dielectric material: uniformly mixing 50 parts by weight of epoxy acrylate, 50 parts by weight of 1, 6-hexanediol diacrylate, 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 1 part by weight of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 1 part by weight of a dispersant and 1 part by weight of an anti-settling agent to form a resin matrix; taking 30 parts by volume of resin matrix, adding 70 parts by volume of alumina (the granularity is 15 mu m, the refractive index is 1.74), and mechanically stirring for 1h to obtain composite material mixture slurry; the prepared slurry was placed in a printer cartridge for printing for a total of 1000 layers. Wherein the wavelength of the light source is 405nm, and the intensity of the light source is 4mW/cm2The single-layer exposure time was 2s, and the single-layer film thickness was 0.05 mm. The relative dielectric constant of each layer of the sample was measured at 50Hz, and as a result, as shown in fig. 4, the dielectric material of comparative example 1 was measured to have a relative dielectric constant of 6.07.
Comparative example 2
This comparative example prepared a dual dielectric material.
Preparing a dual-medium material: 50 parts by weight of epoxy acrylate, 50 parts by weight of 1, 6-hexanediol diacrylate, 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone and 1 part by weight of phenylMixing bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 70 parts by weight of alumina (particle size of 15 mu m and refractive index of 1.74), 1 part by weight of dispersant and 1 part by weight of anti-settling agent, mechanically stirring for 1h to obtain composite material mixture slurry, and placing the composite material mixture slurry in a No. 1 medicine jar; mixing 50 parts by weight of bisphenol A epoxy acrylate, 50 parts by weight of 1, 6-hexanediol diacrylate, 3 parts by weight of photoinitiator 184, 1 part by weight of photoinitiator 819, 30 parts by weight of alumina (the particle size is 15 mu m, the refractive index is 1.74), 1 part by weight of dispersant and 1 part by weight of anti-settling agent, mechanically stirring for 1h to obtain composite material mixture slurry, and placing the composite material mixture slurry into a No. 2 medicine cylinder; printing the slurry in the No. 1 cartridge to 500 layers according to the computer program setting, and then printing the slurry in the No. 2 cartridge to 500 layers on the original sample to obtain the final sample. Wherein the wavelength of the light source is 405nm, and the intensity of the light source is 4mW/cm2The single-layer exposure time was 2s, and the single-layer film thickness was 0.05 mm. The relative dielectric constant of each layer of the sample at 50Hz was tested, and as a result, as shown in fig. 4, the relative dielectric constant of the first 500 layers of the dual dielectric material of comparative example 2 was measured to be 8.21, and the relative dielectric constant of the second 500 layers was measured to be 6.07.
The dielectric constants of the respective layers of the materials obtained in example 1, comparative example 1 and comparative example 2 were measured, and the results are shown in fig. 4.
Fig. a, b and c in fig. 3 are schematic structural views of materials of comparative example 1, comparative example 2 and example 1, respectively, fig. 4 is a dielectric constant distribution of the materials of example 1, comparative example 1 and comparative example 2, and fig. 5 is an electric field distribution of the materials of example 1, comparative example 1 and comparative example 2 applied in a high voltage electric field. The electric field distribution of a single dielectric material in a high-voltage electric field is not uniform, such as curve a in fig. 5, which is very likely to cause high-voltage breakdown and dielectric breakdown. The electric field distribution of the dual-dielectric material in the high-voltage electric field is shown as a curve b in fig. 5, and although the dual-dielectric material can alleviate the phenomenon of nonuniform electric field distribution to a certain extent, the interface electric field of the dual-dielectric material is unstable, and the dielectric breakdown can be caused after long-term use. Curve c in fig. 5 shows the electric field distribution of the dielectric gradient material in the high-voltage electric field, and it can be seen that the dielectric gradient material can effectively and uniformly distribute the electric field to a great extent, and the material has a very wide application prospect in high-voltage insulation, and is expected to be produced in a large scale by combining with the photocuring 3D printing technology.
Claims (10)
1. A method for preparing a photocuring dielectric functional gradient composite material through 3D printing is characterized by comprising the following steps:
(1) mixing 20-80 parts by weight of acrylate oligomer, 30-70 parts by weight of acrylate monomer, 1-6 parts by weight of photoinitiator and 0-2 parts by weight of auxiliary agent to obtain a resin matrix; mixing inorganic powder and the resin matrix according to different proportions to obtain composite material mixture slurry with different inorganic powder contents; carrying out photocuring on the composite material mixture slurry with different inorganic powder contents to obtain composite materials with different inorganic powder contents; measuring dielectric properties of each composite material with different inorganic powder contents; determining an effective dielectric property theoretical model suitable for the composite material;
(2) setting a computer program according to the dielectric property requirement of the material and the theoretical model of the effective dielectric property suitable for the composite material determined in the step (1), controlling the dosage of the resin matrix and the inorganic powder in the step (1) when each layer of the dielectric gradient composite material is printed, uniformly mixing the resin matrix and the inorganic powder, and performing photocuring to obtain each layer of the dielectric gradient composite material.
2. The method of claim 1, wherein the acrylate oligomer is selected from one or more of epoxy acrylates, urethane acrylates, polyester acrylates, and polyether acrylates.
3. The method of claim 1, wherein the acrylic monomer is selected from one or more of 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, and ethoxylated trimethylolpropane triacrylate.
4. the method of claim 1, wherein the photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, α -hydroxyisobutyrophenone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.
5. The method of claim 1, wherein the resin matrix comprises 0.5 to 2 parts by weight of an auxiliary agent, the auxiliary agent comprising 0.2 to 1.5 parts by mass of a dispersant and 0.3 to 1.5 parts by mass of an anti-settling agent.
6. The method according to claim 1, wherein the inorganic powder is selected from one or more of metal oxides, perovskite-type oxides, and high dielectric materials having a core-shell structure.
7. The method of claim 1, wherein the inorganic powder has a particle size of 0.05 to 15 μm and a refractive index of 1.6 to 2.6.
8. The method according to claim 1, wherein in the step (1) and/or the step (2), the light source has a wavelength of 355 to 405nm and an intensity of 1 to 10mW/cm during photocuring2The exposure time of the single layer is 1-10 s, and the thickness of the single layer is 0.01-0.1 mm.
9. A photocured dielectric functionally gradient composite prepared by the method of any one of claims 1-8;
preferably, the resin matrix contains 50 plus or minus 3 parts by weight of epoxy acrylate, 50 plus or minus 3 parts by weight of 1, 6-hexanediol diacrylate, 3 plus or minus 1 part by weight of 1-hydroxy-cycloethyl phenyl ketone, 1 plus or minus 0.5 part by weight of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 1 plus or minus 0.5 part by weight of dispersant and 1 plus or minus 0.5 part by weight of anti-settling agent, the inorganic powder is alumina, preferably the particle size is 14 plus or minus 1 μm, and the refractive index is 1.74 plus or minus 0.1;
preferably, the resin matrix contains 40 + -3 parts by weight of urethane acrylate, 60 + -3 parts by weight of tricyclodecane dimethanol diacrylate, 2 + -1 parts by weight of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 2 + -1 parts by weight of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 1.2 + -0.5 parts by weight of dispersant and 0.6 + -0.5 parts by weight of anti-settling agent, and the inorganic powder is barium titanate, preferably having a particle size of 0.5 + -0.05 μm and a refractive index of 2.4 + -0.1.
10. An insulator comprising the photocurable functionally graded composite material of claim 9.
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