CN111847888A

CN111847888A - Multifunctional ceramic and its production method and application

Info

Publication number: CN111847888A
Application number: CN202010751117.9A
Authority: CN
Inventors: 法布里齐亚·盖佐
Original assignee: Shenzhen Green Blue Technology Co ltd
Current assignee: Shenzhen Green Blue Technology Co ltd
Priority date: 2020-07-30
Filing date: 2020-07-30
Publication date: 2020-10-30

Abstract

The invention discloses a multifunctional ceramic and a manufacturing method and application thereof. Is composed of a traditional ceramic material and a core material; the core material can be any material with a cell structure, the cell structure with any shape and size and the cell structure with different cell wall thicknesses, and the prepared multifunctional ceramic is a ceramic body with a periodic cell structure, and the cell elements are arranged periodically; the core material may also be a material without periodic cells; the properties of the multifunctional ceramic are used to create a combination of properties of its starting materials, which are selected with consideration for the specific properties desired in the final material. The invention also discloses a preparation method of the multifunctional ceramic, which comprises an additional step determined by the selection of the core material and the ceramic body material compared with the traditional preparation process. Can be made into performance-enhancing materials, and can also be made into new materials with additional functions. The invention also discloses application of the multifunctional ceramic.

Description

Multifunctional ceramic and its production method and application

Technical Field

The invention relates to a ceramic and a manufacturing method and application thereof, belongs to the field of ceramic materials and the field of multifunctional materials, and particularly relates to a multifunctional ceramic and a manufacturing method and application thereof.

Background

Technique 1 high impact strength material technique and debris confinement

Ceramic materials are widely used in ballistic/impact and high-speed impact protection materials and systems in general, especially in the field of protection technology, including helmets, products of ballistic jackets, armor and materials for space vehicles/satellite applications/aviation applications/marine applications, etc., due to their excellent compression and impact strength, up to extreme impact conditions or compression and high temperatures. In this case, reinforced ceramics and ceramic layered systems are generally used (Ep0287918a1, US 2009/0114083).

In ballistic protection systems, the ideal goal is to obtain materials with as low a weight per unit volume as possible, which prevent penetration of bullets and their fragments. There are several solutions in this field, which are usually implemented not by a single material but by a layered material system. The disadvantage is that the current solutions are layered systems of ceramic materials, which usually result in high weight, and alternatives are high strength fibre reinforced composite materials, but their ballistic properties are limited by the impact velocity of the projectile, so these materials still need to be used in combination with heavy ceramics. There is a need for materials that have high impact strength and are lighter.

Technique 2 Metamaterial Technology (MTM)

Metamaterials are artificial engineering materials with periodic microstructures and have the ability to manipulate incident electromagnetic waves. An artificial periodic structure is actually an arrangement of conductive microstructures (resonant at certain frequencies) printed on the circuit board material. They are designed to achieve dielectric and permeability constants not possible with standard materials. Filters, absorbers, antennas, lenses, radomes are a large number of applications that can benefit from MTMS integration into existing materials and components. Since it was initially demonstrated that the electromagnetic properties of devices from lenses to antennas may be enhanced, the progress from microwave frequencies to GHz and THz frequencies has also been developed towards new concepts for devices with true structural properties (WO2012/1520022a 1). The same principles used in MTM of electromagnetic devices have been proposed for acoustic applications. The disadvantage is that the applications envisaged by these patents and most MTMs are still very limited because of the lack of practical methods and manufacturing methods to implement in real structural materials. At present, the metamaterial is still in a shape cut on a material sheet or a conductive particle or a material deposited on the surface of a plane material. These conductive structures are made by depositing nanoparticles on a substrate like the latest terahertz devices (US9030286B2), or traditional lithographic methods. The same authors of the present invention have for the first time attempted to manufacture practical MTM devices or materials with structural strength in WO2012/152022a1, however in all these previous patents no solution has been proposed to manufacture real, while also ceramic metamaterials.

Technique 3 Low temperature Co-fired ceramic technique (LTCC)

Inventions like CN108218406A and other LTCC materials clearly demonstrate the importance of this technology for the construction of antennas, radars, radomes, LEDs, etc. These patents focus primarily on the mixing of ceramic powders and efforts to change the percentage of their composition to reduce dielectric constant and loss (or vice versa). These patents show limitations in this field because, in terms of mechanical properties, ceramic mixtures with possibly better other properties cannot be used, and most ceramics have very high dielectric constants because they represent an extremely dense medium through which waves can pass. For this reason, scientists spend a great deal of effort to change the composition of ceramics.

Low temperature co-fired ceramic (LTCC) technology is the dominant technology for manufacturing the most common ceramic materials for communication devices, portable electronic devices, and the like. This technique and the materials it produces can offer the following advantages:

(1) miniaturization of electronic components.

In mobile communication such as wireless communication and satellite communication, recent development of communication systems using microwaves having frequencies between MHz and 300GHz has made electronic components smaller. As performance, durability, and structural strength have improved, the demand for lightweight and small-sized devices has also increased. LTCC technology is suitable for the fabrication of very high frequency small devices, and only high Q (quality factor) materials are available, so ceramics are currently the only choice. The size of these elements depends on the frequency of the electromagnetic waves used. The current application and the progress made in the field show that for devices with the frequency being more than or equal to 1-2 GHz, the materials with the dielectric constant being within the range of 20-40 are widely applied to various devices such as antennas, and the materials such as filters and the like which are usually used for the applications are made of high-frequency low-temperature sintered dielectric ceramics.

(2) Allowing lamination.

For this reason, higher circuit integration can be obtained compared to a PCB-based package, and a multifunctional module can be realized by mounting active elements in the module using, for example, a cavity method. The ceramic film can be obtained by casting.

(3) The sintering temperature is low.

The most fundamental feature of LTCC is to allow the manufacture of a low dielectric ceramic composition and then form a substrate with a relatively low dielectric constant, low loss and high Q value (compared to all other available ceramics). Generally, such compositions comprise 50-90 wt% of a borosilicate-based glass composition and 10-50 wt% of a filler, such as silica. Here, the glass softens below 700 ℃, forms a liquid around 850 ℃, and provides densification at 850 to 950 ℃, where LTCC is preferably sintered. The filler improves the mechanical strength of the sintered ceramic.

(4) Is environment-friendly.

The lower temperatures at which ceramics are manufactured require less energy consumption, thus reducing the production of greenhouse gases.

LTCC technology for high frequency applications has many advantages, but its development requires some major breakthroughs. The main problems relate to the strict requirements on the materials and the limited options. Research in this area has been limited by the borosilicate-based glass composition (and possibly a few other borosilicate-based glass compositions).

Technique 4 insulating materials and material systems

Heat insulation material: in order to limit heat transfer between the two environments, it is necessary to use an insulator material. Ceramics and their foams are one of the solutions in applications where the temperature does not allow the application of polymer-based materials. Generally, in this field, the possibilities are limited by the small range of choices of materials that can be used and the associated costs, and the need to reach certain high impact and compression strengths.

Electrical insulating material: if the operating temperature is high, low losses are required and only ceramic materials can be used. Here, LTCC can still serve many applications.

Irradiating the insulating material: in nuclear power plants, these materials are the most basic requirements. Extremely high density ceramics are required in these applications. The progress in this field has been stable for decades, since the choice of materials that can meet the requirements is extremely limited.

Technology 5 air and Water purification Filter technology, including catalytic ceramic materials

In view of the growing concern about environmental pollution, air and water purification systems are now being intensively studied. Water purification filters are usually made of activated carbon filters or, depending on the application-ceramic composite/ceramic porous material and filler, it is also very common to use silver nanoparticles or titanium dioxide, for example. In recent years, activated carbon has also been used to remove organic molecules from indoor air. Great efforts have been made to improve the absorption properties of these materials. Research is being directed toward ultra lightweight, multifunctional components and high temperature resistant materials for this area.

Technique 6 ceramic technique for medical treatment, also known as bioceramic

This field has been developing over the last decades and advances have been made, in particular, in the field of biocompatible materials, such as materials with high histocompatibility, which are resistant to the immune system, and materials that exhibit high resistance, compressive strength and durability, such as ceramics and other materials such as titanium. Bioceramics are an important class of biomaterials, primarily used for surgical implants. In this area, there is a constant effort and solutions are being developed towards materials with a combination of functions, such as drug delivery, mineral growth potential, cell growth potential, ability to let blood flow through and capillary growth, etc. More material choices are required.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a multifunctional ceramic and a preparation method and application thereof. The principles and manufacturing methods proposed by the present invention allow the production of materials with enhanced performance from existing solutions (materials and material systems) and also new materials with additional functionality.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a multifunctional ceramic I, which comprises a traditional ceramic material and a core material;

the conventional ceramic materials are well-known ceramic materials including, but not limited to, low temperature co-fired ceramics, high temperature co-fired ceramics, and ultra high temperature co-fired ceramics;

the core material is a material with a periodic cell structure, the cell structure has shape, size and cell wall thickness, the prepared multifunctional ceramic is a ceramic body with a periodic cell structure, and cell elements are arranged periodically; the shapes include, but are not limited to, honeycomb cells, circular cells, or specially designed, the periodic cell structures being constant or variable along the thickness and/or along the plane; the size is the cellular size of the periodic unit and is 0.2-50 mm; the thickness of the cell wall is 0.5-10 mm, and can be as small as 25-200 mu m if a film is manufactured.

Furthermore, the minimum size of the unit cell can reach 0.2 mm-0.3 mm, for example, the metal can reach 0.5-0.6 mm.

Further, the core material thickness typically has various standard thicknesses of 3, 3.5, 4, 5, 6, 10, 15, 20 and 25 mm; the maximum commercial thickness can reach 100 mm; the thickness of the core material in the finally formed ceramic material can be overlapped through the lamination of the unit core material; the minimum thicknesses that can be used are also: 0.50mm, 0.70mm, 1.00 mm. Other thicknesses between these ranges may be customized.

In addition, we can 3D print the core material, so we are not limited to use of these commercial products, and therefore not limited to the thickness and size of the core material on the market, because the 3D printing technology can let users customize their own core material and its size.

The properties of the multifunctional ceramic are used to create a combination of properties of its starting materials, which are selected with consideration for the specific properties desired in the final material.

Further, the core materials include, but are not limited to, polymer cores, polymer-based reinforced composites, paper cores, paper-reinforced cores, metal-based composites, fiber-reinforced composites, including two groups of multifunctional ceramics: the periodic porous multifunctional ceramic (A1) has a ceramic with integrated periodic porosity, in which the cell structures are ordered in a precise periodic manner, the walls of the core cells being empty; and a periodic non-porous multifunctional ceramic (B1), a ceramic with a periodic dense cell structure, the core cell walls not being empty.

The polymeric core includes, but is not limited to, thermoset or thermoplastic polymers and derivative composites: polypropylene cores, polymethylmethacrylate, polymer-based composites with any filler or reinforcement, graphene cores, amorphous carbon cores; such thermoset polymers include, but are not limited to, polyurethanes, polyimides, cyanates, and epoxies; the thermoplastic polymers include, but are not limited to, acrylic (PMMA), nylon, PC, PE, PP, ABS; the metal core includes, but is not limited to, silver, copper, gold.

Further, the core material is a material that is fired at a temperature below the sintering temperature of the ceramic body, the resulting ceramic is a porous multifunctional ceramic material, obtained or arranged in a precise periodic manner, the core exhibits internal pores that are empty; the core material is a material which does not burn, melt or change during sintering of the ceramic body, the obtained ceramic is a non-porous multifunctional ceramic material, a periodic compact core structure is obtained, and the core is not hollow.

The invention provides a multifunctional ceramic II which comprises a traditional ceramic material and a core material;

the core material is a non-periodic cell structure material; the shape uses a core with randomly distributed fibers or openings; the core materials include, but are not limited to, metal cores, metal foams, metal matrix composites, alloy core materials, polymeric foams, random fiber foams, ceramic reinforced polymers, including two groups of multifunctional ceramics: aperiodic porous multifunctional ceramic (a2), the core being empty; non-periodic non-porous multifunctional ceramics (B2), the core not being empty;

The metal core includes, but is not limited to, silver, copper, gold; the core material may also be titanium carbide, titanium, zirconium nitrate.

Further, the core material is a material that is burned at a temperature lower than the sintering temperature of the ceramic body, the obtained ceramic is a porous multifunctional ceramic material, a core structure is obtained or arranged in a non-periodic manner, and the core is hollow with internal pores; the core material is a material which does not burn, melt or change at all when the ceramic body is sintered, the obtained ceramic is a non-porous multifunctional ceramic material, a non-periodic compact core structure is obtained, and the core is not empty.

The core material may be any material, may have any shape and size of unit, and may also be 3D printed, selected with the particular properties desired for the final material in mind, including but not limited to polymer cores, polymer-based reinforced composites, paper cores, paper-reinforced cores, metal foams, metal-based composites, alloy core materials, polymeric foams, random fiber foams, fiber-reinforced composites, ceramic materials, ceramic-reinforced polymers, titanium carbide, titanium, zirconium nitrate, graphite composites, and carbon fiber composites; including but not limited to honeycomb cells, round cells or specially designed, cores with randomly distributed fibers or openings may also be used;

the polymeric core includes, but is not limited to, thermoset or thermoplastic polymers and derivative composites: polypropylene cores, polymethylmethacrylate, polymer-based composites with any filler or reinforcement, graphene cores, amorphous carbon cores;

such thermoset polymers include, but are not limited to, polyurethanes, polyimides, cyanates, and epoxies; the thermoplastic polymers include, but are not limited to, acrylic (PMMA), nylon, PC, PE, PP, ABS;

the metal core includes, but is not limited to, aluminum, copper, silver, gold;

the periodic cell structure is constant or variable along the thickness and/or along the plane.

Such properties include, but are not limited to, mechanical, impact, ultra-lightweight, electromagnetic, insulative, compressive strength stiffness, dielectric, thermal conductivity, electrical conductivity, biocompatibility, biodegradability, zero toxicity, eco-friendliness, and allow integration of other functions; such other functions include, but are not limited to, data collection, intelligence, sensing, drug delivery capabilities.

The specific properties required for the final material may be tailored to have specific highly improved properties and/or additional functions, including but not limited to electromagnetic/electrical/improved ballistic/improved dielectric/ultra lightweight, etc., as well as combinations of these properties.

The size of a representative single cell of material is smaller than the size of the particular perturbation/stimulus applied to the material; the perturbation/stimulus includes, but is not limited to, pressure, electromagnetic stimulus, acoustics, shock, impact, insulation properties.

In other words, the novel multifunctional ceramic material described above is any ceramic material having a specific engineered internal structure. It comprises two main types of multifunctional ceramics: group 1, porous multifunctional ceramics a, core material is a material that burns at a temperature below the sintering temperature of the ceramic body, resulting in a ceramic with integrated engineered (periodic or aperiodic) porosity; the core structure is arranged either in a precisely periodic manner (a1) or in an aperiodic manner (a2), for both cases the core appears to be hollow with internal voids; and group 2, non-porous multifunctional ceramics B, the core material being a material that does not burn, melt or undergo any change upon sintering the ceramic body, resulting in a ceramic with a dense core structure that is periodic (B1) or aperiodic (B2), the core not being empty.

The core material is a material that burns at a temperature below the sintering temperature of the ceramic body: if the selected original ceramic component is low temperature co-fired ceramic (LTCC) and the sintering temperature is lower than 1000 ℃, the core material is selected from polymer-based materials; if the sintering temperature of the LTCC ceramic body is about 1000 ℃, a metal core, graphite and carbon fiber composite material with the sintering temperature lower than 1000 ℃ can also be used; if the selected original ceramic component is high temperature co-fired ceramic (HTCC) and the sintering temperature is higher than 1000 ℃ and about 1600 ℃, the core material is selected from polymer-based materials, some metals with the melting point lower than the sintering temperature of the ceramic component and ceramic reinforcing material polymers, and can also be LTCC ceramic; if the raw ceramic component selected is ultra high temperature co-fired temperature ceramic (UHTCC) with a sintering temperature above 1600 deg.C and around 2000 deg.C, the core material is selected from polymer-based materials, metals, and ceramic-reinforced polymers.

The core material is a material that does not burn, melt or undergo any change upon sintering of the ceramic body: if the selected original ceramic component is low temperature co-fired ceramic (LTCC) and the sintering temperature is lower than 1000 ℃, the core material is selected from metal, alloy, metal matrix composite and high temperature ceramic; graphite and carbon fiber composites, metal fiber reinforced polymer composites can also be used if the sintering temperature of the LTCC ceramic body is between 550 ℃ and 800 ℃; if the selected original ceramic component is high temperature co-fired ceramic (HTCC) and the sintering temperature is higher than 1000 ℃ and about 1600 ℃, the core material is selected from metal and high temperature ceramic; if the selected original ceramic component is ultra-high temperature co-fired temperature ceramic (UHTCC), the core material is selected from ultra-high temperature ceramic such as titanium carbide, titanium, zirconium nitrate and the like.

The core material may be any material that the designer chooses from among already existing materials and products, or is specifically made for the desired material. The core material used for preparing the group 1 ceramics includes any core material having a periodic structure, such as a honeycomb core, a circular core, a rectangular core, etc., and a core material having a non-periodic structure; core materials for making group 2 ceramics include, but are not limited to, metal foams, polymeric foams, random fiber foams, and the like.

Following the guidelines of the present invention, the integration of these core materials into the initial ceramic body results in two sets of multifunctional ceramics: porous multifunctional ceramics, the ceramic material at the end of the manufacturing process presents a porous core; non-porous multifunctional ceramics, exhibiting a dense core.

The invention provides a multifunctional ceramic, which is a multilayer ceramic material system, wherein the ceramic material can be any one of the materials, and the ceramic materials are combined and laminated, and the number of layers is two or more; the core material of each layer is the same; minimum thickness of layer minimum thickness of core material can be produced by currently available technology or future technological advances. The technique for forming the ceramic layer is by casting, with the minimum thickness currently achievable being less than 200 microns. Depending on the initial slurry, the equipment and process used, the final tape can be as small as 20-50 microns.

In particular, each layer may be a periodic porous multifunctional ceramic material or a periodic non-porous multifunctional ceramic material or an aperiodic non-porous multifunctional ceramic material.

The invention provides a multifunctional ceramic, which is a multilayer ceramic material system, wherein the ceramic material can be any one of the materials and/or traditional ceramic materials, and the ceramic materials are combined and laminated, and the number of layers is two or more; the core material of each layer is different; the minimum thickness of the layer is the minimum thickness of the core material that can be produced by currently available technology or future technological advances. The technique for forming the ceramic layer is by casting, with the minimum thickness currently achievable being less than 200 microns. Depending on the initial slurry, the equipment and process used, the final tape can be as small as 20-50 microns.

Specifically, the first layer of the multi-layer ceramic material system may be a conventional ceramic material or a periodic porous multifunctional ceramic material or a periodic non-porous multifunctional ceramic material or an aperiodic non-porous multifunctional ceramic material, the second layer may be a conventional ceramic material or a periodic porous multifunctional ceramic material or a periodic non-porous multifunctional ceramic material or an aperiodic non-porous multifunctional ceramic material, and the third layer may be a conventional ceramic material or a periodic porous multifunctional ceramic material or a periodic non-porous multifunctional ceramic material or an aperiodic non-porous multifunctional ceramic material.

The invention provides a preparation method of multifunctional ceramic, which comprises the following additional steps in addition to the mixing and sintering of ceramic slurry in the traditional preparation process: integrating core material into the prepared initial ceramic slurry; compressing the ceramic slurry before sintering; removing gas, foaming agent, dispersing agent and additive in the ceramic slurry in the sintering process; an additional step of adjusting or changing the temperature ramp of the sintering process as determined by the core material and ceramic body material selection.

The dispersing agent is: low molecular weight dispersant: sodium pyrophosphate, ammonium citrate, sodium tartrate, sodium succinate, triolein, phosphate, and/or a high molecular weight dispersant: polyacrylic acid (PAA), polymethacrylic acid (PMAA), polymaleic acid (HPMA), ammonium polyacrylate, sodium polysulfone, Polyethyleneimine (PEI), menglan fish oil, random copolymer comb polymers;

the adhesive is polyvinyl alcohol (PVA), polyvinyl alcohol, polyvinyl butyral (PVB), polyvinyl formal (PVF), polyethylene oxide, ethylene-vinyl acetate copolymer, modified starch, carboxymethyl cellulose products, dextrin wax emulsion, polyethylene glycol, lignosulfonate, methyl cellulose, paraffin, polyacrylate and/or Binder for Binder ceramic processing;

the additive is a surfactant/foaming agent/foam stabilizer; the surfactant/foaming agent can be natural soap or synthetic emulsifier, the natural soap is fatty acid or abietic acid soap, and the fatty acid soap comprises alkali metal salts of oleic acid, palmitic acid and stearic acid; the foaming agent may be selected from urea, starch, carbon powder, sodium silicate, sodium carbonate Na₂CO₃Potassium carbonate K₂CO₃Silicon carbide SiC, calcium carbonate CaCO₃Magnesium carbonate, manganese oxide MNO₂、(NH₄)₂CO₃Sulfate and carbonate derived materials; the foaming agent can also be waste materials such as fly ash, carbon black hollow particles, lead-zinc ore tailings and the like; the foam stabilizer is selected from manganese dioxide and zinc oxide, or may be composed of boric acid, chromium green and titanium oxide, or a composition using boric acid and titanium oxide.

Further, the sintering temperature is typically set to be higher than the combustion temperature of all additives, blowing agents, and other additional chemicals added to the ceramic mixture, in order to remove all gases, blowing agents, dispersants, and additives formed in the ceramic slurry.

Further, the additional step of adjusting or changing the temperature ramp of the sintering process, which is determined by the selection of the core material and the ceramic body material, is specifically as follows:

A) if the material chosen is to obtain the porous multifunctional ceramic a of the invention (core material burning, melting during sintering), an additional step is to plan a temperature ramp for burning the core material;

B) if the material is chosen in order to obtain the non-porous multifunctional ceramic B of the invention (the core material does not burn during sintering), the sintering of the ceramic material will follow the conventional sintering of the ceramic body. In this case, in practice, the core is not affected by the maximum temperature required to sinter the ceramic body.

As described in particular embodiments of the present invention.

The invention provides a preparation method of multifunctional ceramic, which comprises the following steps:

1) the construction (design, calculation and evaluation) of the performance of the needed multifunctional ceramic material;

2) selecting ceramic powder components and their core materials, including but not limited to core material type, thickness, cell size, cell shape, cell wall thickness;

3) preparing ceramic slurry in a traditional mode, wherein the preparation method comprises the steps of mixing a plurality of kinds of nano powder, adding a particle dispersing agent, a foaming agent, an additive and the like to form uniform ceramic slurry;

4) integrating a core material into the ceramic slurry;

5) standing and solidifying the ceramic slurry;

6) compressing the dried ceramic slurry;

7) sintering the multifunctional ceramic material:

removing gas in the ceramic material; removing additives having additional micropores due to the addition of foaming agents and/or dispersants and/or additives to their composition that aid in the uniform distribution of the different ceramic particles, or due to the addition of additional micropores that were already forming in the ceramic body; removing gas generated by the additive; the sintering temperature is typically set to be higher than the combustion temperature of all additives, blowing agents and other additional chemicals added to the ceramic mixture;

the second step of sintering may depend on the core material (unit cell, size, wall thickness, material, etc.) and the final performance requirements of the new multifunctional ceramic material.

The method comprises the following specific steps: periodic porous multifunctional ceramics a1, ceramics with integrated periodic porosity, in which the cell structures are ordered in a precise periodic manner, the core cell walls being empty; and periodic non-porous multifunctional ceramics B1, ceramics with periodic dense cell structure, the core cell wall is not empty; aperiodic porous multifunctional ceramic A2, the core cell wall is empty; aperiodic non-porous multifunctional ceramic B2, core cell walls were not empty. The melting temperature and combustion temperature characteristics of the core material may be such that a suitable rate of temperature rise is used to combust the core material and slowly eliminate the gases produced. If the goal is not to burn the core, the sintering process of the ceramic material should be carefully considered in order to maintain the core.

Further, in step 1), the performance of the multifunctional ceramic material can be established by using commercially available numerical simulation software, including but not limited to one or more of Ansys, Comsol, and HFSS.

Further, in step 2), a core material that can be completely melted into the ceramic slurry, i.e., a core material having a relatively short thickness, must be selected.

Further, in step 6), the pressure of the compression may be 1 to 5 mpa, or more.

Further, in step 6), the compression of the ceramic slurry is selected to deform the core material, a mold capable of maintaining the deformed state of the core material and the shape of the slurry is required, and the periodicity of the final material in the thickness and/or plane is not uniform.

Further, in step 7), a second step of sintering,

if the core material is fired at a temperature higher than that used in the first sintering step, a second ramp is used to fire the core, resulting in a porous multifunctional ceramic A, periodic (A1) or non-periodic (A2), with integrated periodic or non-periodic porosity; the core material of the periodic porous multifunctional ceramic A1 has a periodic cell structure, the cell structures are orderly arranged in a precise periodic mode, and the cell walls of the core are empty; the core material of the aperiodic porous multifunctional ceramic A2 has no periodic cell structure, and the core material is empty after being sintered;

if the core material is not melted at the final sintering temperature of the ceramic, it retains its structure when the whole material is subjected to standard sintering, which results in a solid non-porous multifunctional ceramic material B which is periodic (B1) or non-periodic (B2); the periodic non-porous multifunctional ceramic B1 has a core with a periodic compact cell structure, and the cell wall of the core is not empty; the aperiodic non-porous multifunctional ceramic B2 has a core of dense material that is not empty. The core material is not burned when the ceramic is sintered.

Further, in step 7), the obtained periodic or aperiodic porous multifunctional ceramic, the hollow holes left by the core material can be filled with other materials, including but not limited to metal, polymer, piezoelectric material, or materials with additional functions, including but not limited to materials with sensing function.

Further, in step 7), the other material may solidify to form a solid structure, or may simply cover the cell walls without completely filling the cavity.

Furthermore, in step 7), the other material may be a metal or a conductive core with conductive particles as fillers, and is integrated into a ceramic material with a sintering temperature higher than the melting temperature of the conductive core; when the ceramic solidifies, the core walls melt and the material forming the cell walls will collect at the cell bottom; in this case, a conductive plate having the same shape as the original empty core cell or only the shape of the cell wall will be formed at the bottom of the cell.

Further, in step 7), the other material may be a second ceramic slurry; the first manufacturing process produces a ceramic with open periodic porosity that will serve as the mold, and a second ceramic slurry is injected into the pores of the main ceramic body, and the entire material is sintered a second time to crystallize the core.

Further, step 7) comprises another possibility of integrating one type of cyclomonic core and then another type of cyclomonic core; the result will be a ceramic body with a bi-periodic structure consisting of rigid walls and periodic open pores; the manufacturing process includes the integration of any core material with the shape of the core cell, and the core material can also be printed in 3D.

Further, step 7) comprises another possibility of integrating the metal foam into the ceramic slurry; in this case, the sintering retains the core and forms a heterogeneous high temperature ceramic metal material with potentially superior impact properties; the core is not periodic and the new ceramic material obtained is a randomly distributed mixture of the two materials metal foam and ceramic material.

Further, step 7) involves another possibility that the core material integrated into the ceramic slurry may also be other ceramic materials in the prior art.

The invention provides the application of the multifunctional ceramic material in the preparation of ceramic foam.

Method for the preparation of ceramic foams with a high structural periodicity core according to which the ceramic body can be designed to integrate additional porosity in the form of bubbles or hollow spheres of different materials (glass beads, fly ash, hollow silica particles, hollow TiO2 nanoparticles, hollow silver nanoparticles, etc.) to create a distributed microporosity in the body; the ceramic foam may be integrated with a core material and will produce a ceramic foam with microporosity organized in a periodic manner or form a ceramic foam with a specific solid core structure; the ceramic foam may be porous or non-porous.

The invention provides application of the multifunctional ceramic material in preparing a ceramic film.

A method of making a multifunctional ceramic film, using the method described above, the manufacture of the film will undergo processes including, but not limited to, casting; the periodic cell structure of the multifunctional ceramic thin film is not printed/deposited on the film, etc., but is a part thereof; the core material may consist of a layer of deposition that produces a defined pattern that may be obtained by photolithography, printing, chemical deposition or other techniques for producing thin layers of material; the ceramic slurry is spread on a substrate of a core material on which a pattern has been formed, a core material of a periodic unit structure deposited/printed thereon, or the like, and sintered to integrate the periodic structure into a thin film.

The invention provides application of the multifunctional ceramic material in preparation of a three-dimensional ceramic metamaterial with high impact strength and high temperature resistance.

The novel multifunctional ceramic metamaterial is a three-dimensional metamaterial with high impact strength and high temperature resistance, and is a multifunctional ceramic material which is sintered and integrated with a traditional ceramic material and comprises but not limited to an absorber, a filter, an acoustic and electromagnetic stealth device with multifunctional characteristics and the like.

The invention provides application of the multifunctional ceramic material in preparing a plasma ceramic material.

The novel plasma material is a porous material with periodicity, definite definition and ordered arrangement, and comprises but is not limited to a multifunctional ceramic material with high temperature, high impact, high corrosion resistance, ultra-light characteristic and electric conduction.

The invention provides application of the multifunctional ceramic material in preparing a high-impact-strength ceramic material.

The core material of the novel high-impact strength material can be titanium, ferromagnetic material or other materials, and the highly structured ceramic is finally obtained; the shape of the core element may be any shape that meets the requirements for better performance and debris protection in ballistic applications or high impact velocity applications; or integrating intelligent features in porous bodies or ultra-light magnetic cores.

The invention provides application of the multifunctional ceramic material in preparation of a biological ceramic material.

The novel multifunctional ceramic biomaterial is prepared by integrating the bioceramic slurry with a periodic or aperiodic core material according to the preparation method, so as to prepare the periodic or aperiodic multifunctional bioceramic, wherein the cell wall of the core is empty, and the gap can be used as a carrier for drug delivery and cell growth.

The original ceramic slurry is a material of biological ceramics, then a core is integrated into the ceramic material, and after sintering, the biological ceramic slurry becomes a new material and has a periodic/aperiodic porous core (if the core is not combusted during ceramic sintering, the core can also be nonporous).

The invention provides application of the multifunctional ceramic material in preparing intelligent ceramics.

The novel intelligent ceramic is prepared by integrating ceramic slurry with a periodic core material according to the preparation method, so that the periodic porous multifunctional ceramic is prepared, the cell wall of the core is hollow, and the gap can be used as a carrier for integrating wires and sensors.

The invention provides application of the multifunctional ceramic material in preparation of a high-temperature heat-conducting ceramic material.

The novel high-temperature heat conduction material fills the pores in the ceramic body left by the cell walls of the original core of the porous multifunctional ceramic with a high-heat conduction material according to the preparation method.

The present invention provides the use of a multifunctional ceramic material as described above for the preparation of air and water filtration system materials.

The novel high-performance air and water filtering system, periodic or aperiodic porous multifunctional ceramics can better absorb or intercept the filtered pollution elements into the core gap and then remove the pollution elements.

The invention provides application of the multifunctional ceramic material in preparing an environment-friendly high-strength ceramic material.

The novel environment-friendly high-strength material can realize the functions which can only be realized by high-sintering temperature ceramics and can also be realized by low-temperature co-firing, including but not limited to the preparation of ultra-light ceramic materials by low-temperature co-firing.

The invention provides application of the multifunctional ceramic material in preparing a low-temperature co-fired ceramic material.

The novel low-temperature co-fired ceramic integrates a core material into a low-temperature co-fired ceramic slurry, wherein the core material has a periodic structure or an aperiodic structure;

the core material periodic structure shape includes but is not limited to round, square, honeycomb;

the core material includes, but is not limited to, a polymer core, a polymer-based reinforced composite, a paper core, a paper-reinforced core, a metal foam, a metal-based composite, an alloy core material, a polymeric foam, a random fiber foam, a fiber-reinforced composite, a ceramic material, a ceramic-reinforced polymer, titanium carbide, titanium, zirconium nitrate, a graphite composite, and a carbon fiber composite;

the novel low-temperature co-fired ceramic material can be periodic porous multifunctional ceramic and ceramic with integrated periodic porosity, wherein cellular structures are orderly arranged in a precise periodic mode, and the wall of a core cell is hollow; or periodic non-porous multifunctional ceramics, ceramics with periodic compact cellular structure, and core single cell wall not empty; or aperiodic porous multifunctional ceramics, the core cell wall is empty; or aperiodic non-porous multifunctional ceramics, the core cell wall is not empty.

Further, the novel ceramic is prepared by a different preparation method according to different requirements of ceramic materials, and any conventional ceramic slurry preparation method or novel method can be adopted so as to best prepare the ceramic, including but not limited to the following preparation methods:

preparing a solution with the mass ratio of ethanol to methyl ethyl ketone being 70: 30-75: 25, and mixing;

adding the ceramic mixed powder in two steps, mixing and preparing powder;

adding polybutyral into MEK/ethanol solution, wherein the polybutyral accounts for 1% -25% of the MEK/ethanol solution;

coating lubricating grease on the inner wall of the plastic circular mold, and pouring ceramic slurry into the plastic circular mold;

adding a core with unit cells, wherein the thickness of the core material is less than the total thickness of the ceramic slurry;

drying the ceramic slurry, and compressing the ceramic slurry after drying;

and (3) sintering:

sintering of the A-type porous multifunctional material: heating to 250-450 ℃ at the speed of 2-5 ℃/min; stabilizing for 1-4 hours; heating to 500-; stabilizing for 1-2 hours; heating to 550 ℃ and 900 ℃ at the speed of 2-5 ℃/min, and solidifying the ceramic body; the ceramic structure is cured for 1-3 hours.

Sintering of B-type non-porous multifunctional material: heating to 250-450 ℃ at the speed of 2-5 ℃/min; stabilizing for 1-4 hours; heating to 500-800 ℃ at the speed of 2-5 ℃/min; stabilizing for 1-2 hours; heating to 550-1600 ℃ at the speed of 2-5 ℃/min, and solidifying the ceramic body; the ceramic structure is cured for 1-3 hours.

Still further, the temperature is typically raised by 2-5 ℃ per minute, but other rates may be considered if the same results are obtained in terms of the final material quality, such as the structural integrity of the ceramic inner core, the periodic structural integrity of the empty spaces left by the core, etc., remaining unchanged.

Furthermore, the preparation method of the novel ceramic also comprises the step of adding fly ash microspheres or hollow glass particles into the mixture.

Compared with the prior art, the invention has the following beneficial effects:

the present invention provides a new class of ceramic materials, including the principles and methods required to combine different materials to achieve desired properties and additional functionality; these materials may be comprised of ceramic bodies having a periodic structure, with the various aspects of having random arrangements within a representative unit cell also being discussed herein, and may include materials having no periodic cells. Briefly, the properties of new materials are the combination of properties of the original materials used to create them. The present invention also includes providing a method of manufacturing such new materials, set forth in general form, but including any alternative manufacturing process for the new materials. The present disclosure is not limited to the starting materials and methods of manufacture, but includes all methods of making the same new class of materials. These materials are superior to traditional ceramic materials in mechanical, impact, ultra-lightweight, electromagnetic, insulating properties, etc., and allow for integration of other functions (data collection, intelligence, sensing, drug delivery capabilities, etc.).

The principle and the manufacturing method provided by the invention improve the performance of the existing ceramic material, including any type of ceramic material composition and composite material thereof. In the field of thermal insulation materials, where high temperature materials with high electrical resistance and optimal thermal insulation properties are required, the application of the design principles of the present invention can modify existing materials (or select new materials) used in such applications, not only to greatly improve these properties, but also to add additional functionality, so that this process will result in a new enhanced multifunctional material. In the field of high impact strength, ballistic performance, where materials with extreme impact strength are required, the principles and manufacturing methods proposed in the present invention allow the production of performance enhancing materials for existing solutions (materials and material systems) as well as new materials with additional functionality.

Application of the principles and manufacturing methods described herein creates a new class/group of materials (not only one material, but a new family of multifunctional ceramics) that can be used in different scientific, engineering, and medical fields characterized by enhanced properties and increased versatility.

Drawings

FIG. 1 is a periodic porous multifunctional ceramic material of the present invention;

FIG. 2 is a non-periodic porous multifunctional ceramic material of the present invention;

FIG. 3 is a periodic non-porous multifunctional ceramic material of the present invention;

FIG. 4 is a non-periodic, non-porous multifunctional ceramic material of the present invention;

FIG. 5 is an example of a periodic multifunctional ceramic material of the present invention;

wherein A1-B1 is a periodic multifunctional ceramic material, A2-B2 is a traditional ceramic material, and C is a core material;

FIG. 6 is an example of different shapes of periodic core material single cells;

wherein A is a honeycomb material, B is a square single cell, C is a round single cell, and D is a 3D printing core of any shape;

FIG. 7 is an example of an aperiodic core material;

wherein A is a metal foam core material, and B is a random plastic fiber core material;

FIG. 8 is a flow chart of the manufacturing process of the multifunctional ceramic material of the present invention;

FIG. 9 is an example of the temperature change in the sintering step of the multifunctional ceramic of the present invention;

FIG. 10 is a graph showing an example of temperature change in the sintering step of the porous multifunctional ceramic according to the present invention;

FIG. 11 is an example of the temperature change in the sintering step of the non-porous multifunctional ceramic according to the present invention;

FIG. 12 is a schematic diagram of a first porosity and a second porosity of the multifunctional ceramic according to the present invention;

FIG. 13 is a schematic representation of another possibility for inclusion of the periodic porous multifunctional ceramic of the present invention;

wherein A is a side view and B is a top view;

FIG. 14 is a view showing a multifunctional ceramic having a bi-periodic structure according to the present invention; wherein A) is a side view and B) is a top view;

FIG. 15 shows the core material of the present invention after melting and collecting at the bottom of the cell structure; wherein A) to B) are two examples respectively;

FIG. 16 is a schematic view of a multifunctional ceramic multilayer material system according to the present invention; a) -c) is various multilayer material system examples;

FIG. 17 is a simplified schematic illustration of a multi-layer material system; a) -b) is various multilayer material system examples;

FIG. 18 shows the implementation of the new material;

a is an LTCC coreless material sample, B is a circular honeycomb plastic core integrated in an LTCC slurry new material sample, C is a second sample with a honeycomb core, D is a second sample with a honeycomb core, the sintering temperature and/or the quantity of hollow spheres are/is too high, and E is the circular honeycomb plastic core after the sample of B is sintered, so that a porous periodic structure is kept.

Detailed Description

The invention belongs to the field of ceramic materials, and relates to the most common properties of ceramic materials: high temperature, high compression, high impact and high corrosion resistance; also relates to the field of multifunctional materials, namely materials with comprehensive functions of intelligence, data acquisition, sensing and the like. In fact, these materials not only improve physical properties, but also have additional integrated functions and "capabilities", which are partially listed in the present invention as some of the products that may be obtained using these materials.

The present market, the solutions for the ceramic materials of the present invention are not available: there is no existing material consisting of ceramics with well defined periodic or highly organized structures, nor is there a material with multiple reinforcing properties or additional functions, so that these new materials can have different functions. These new materials are all designed to achieve specific additional properties or to enhance existing properties. Some examples will be given in the following embodiments. The principles and manufacturing techniques of the present invention overcome all of the limitations set forth in the background section.

The invention comprises the following steps: a new class of ceramic materials, referred to herein as "multifunctional ceramics", includes the principles and methods required to combine different materials to achieve desired properties and additional functionality; these materials may be composed of ceramic bodies having a periodic structure, and the present invention will also discuss various cases having random arrangements within representative unit cells. The dimensions of a representative single cell of material are smaller than the size of the specific perturbation/stimulus (pressure, electromagnetic stimulus, acoustics, shock, impact, insulating properties, etc.) applied to the material, and therefore the mechanical, electromagnetic, acoustic, etc. properties of such new materials are determined by the principle of the general theory of homogenizing material properties. These materials may also include materials that are made without periodic cells. Briefly, the properties of new materials are combined from the properties of the original materials used to create them.

The invention also includes 2: a method of manufacturing such new materials, set out in general form, but including any alternative manufacturing process to the new materials.

The present disclosure is not limited to the starting materials and methods of manufacture, but includes all methods of making the same new class of materials. These materials are superior to traditional ceramic materials in mechanical, impact, ultra-lightweight, electromagnetic, insulating properties, etc., and allow for integration of other functions (data collection, intelligence, sensing, drug delivery capabilities, etc.). These properties include, for example, high compressive or impact strength, impact resistance, stiffness, dielectric properties, thermal conductivity, electrical conductivity, other specific magnetic and electromagnetic properties, light weight, biocompatibility, biodegradability, zero toxicity, eco-friendliness, smart functions, and other properties required by the target application.

The present invention is one kind of new ceramic material and its making process and application.

In particular, the multifunctional ceramic of claims 1, 4 is a ceramic material, which is manufactured in such a way that it produces an internal structure with a specific design, which is constant or variable along the thickness and/or along the plane. These materials have higher performance than the original ceramic materials. The internal structure of this particular design, i.e. the core material (core), can be any material with a periodic cell structure of any shape and size, different cell wall thickness, etc.; or a material with no periodic structure (e.g., foam). The ceramic material thus produced is a new material with a specific internal structure, the characteristics of the final new material being different from those of the original ceramic. The original ceramic was sintered (in the conventional manner of making ceramic materials) without core integration. The final ceramic material obtained by applying the principle and the manufacturing method of the invention has the following characteristics: improved properties or added key functions depending on the initial design and material selection. As a result, each combination of ceramic powder components and cores provides a new material, thus creating a new class by applying the method of the present invention.

Claims 1, 4 comprise two groups of multifunctional ceramics: a first group of ceramics with integrated specific porosity, which is divided into two types, one with cell structures ordered in a precise periodic manner, with cell walls empty, being a periodic porous multifunctional ceramic material, as shown in fig. 1, and the other with integrated specific non-periodic pores, being a non-periodic porous multifunctional ceramic material, as shown in fig. 2; and a second group of non-porous core ceramic materials, the core after sintering is not empty and is divided into two types, one type is a periodic non-porous multifunctional ceramic material with an integrated specific periodic structure, as shown in fig. 3, and the other type is a non-periodic non-porous multifunctional ceramic material without an integrated specific periodic structure, as shown in fig. 4.

The periodic multifunctional ceramic material of the present invention is shown in FIG. 5(A1-B1) (wherein a represents a side view and B represents a top view). I.e., a periodic multifunctional ceramic material, is formed from the material of fig. 5(a2-B2) (where a represents a side view and B represents a top view) in combination with the material of fig. 5C, which is shown in fig. 5(a 1-B1). When the core material is aperiodic, the resulting multifunctional ceramic material is an aperiodic multifunctional ceramic material.

In order to prepare the multifunctional ceramics of the present invention, there are some options in the design stage, which will lead to different results:

1. the ceramic material, such as the host material shown in FIG. 5(A2-B2) (where a represents a side view and B represents a top view), can be any material, including high temperature ceramics and low temperature co-fired ceramics (LTCC). Due to the high concern of environmental issues, the manufacture of low energy ceramic (LTCC) is a particular concern of the present invention.

2. The core material, as shown in FIG. 5C, is a separate material, and may be any material, and may have units of any shape and size. The periodic structure core material is shown in FIG. 6(A-D), and the non-periodic structure core material is shown in FIG. 7(A-B), but not limited to the kind shown in the figure. FIG. 6D is from Wu et al, "Materials and Design" Journal,180(2019) 107950. The choice must be considered according to the specific properties required for the final material. The cores of different materials currently marketed for different applications are: polymeric cores, paper reinforced cores (particularly for use in composite manufacturing and aerospace industries), metallic cores, and the like.

In fig. 6, a honeycomb core structure is very popular, and as shown in fig. 6A, the basic unit shape of the material is hexagonal. The choice of core is not limited to commercially available ones, as the possibilities become unlimited if a 3D printer is used. Cores with specific cell shapes, cell sizes, cell wall thicknesses, etc. can be created. The material of these cores may be a polymer, a metal (e.g., aluminum steel, copper, silver, gold, titanium, etc.), or a ceramic. For example, in some applications, an aluminum sheet of a particular thickness may be laser-punched, and the aluminum sheet becomes a core material to have the desired thickness and cell shape. The unit cells can also be different in the same core material, as a three-dimensional and laser cutting instrument and three-dimensional printing can achieve such effects.

3. The process for preparing these multifunctional ceramics, unlike the conventional process, will include additional steps including the integration of the core material into the prepared initial ceramic slurry (also called ceramic green body), as well as additional steps during sintering. The invention provides the basic steps to be followed for the preparation of multifunctional ceramics starting from the traditional way of bonding refractory powders and then sintering, without excluding other potential routes and preparation ways that can be simply modified in order to achieve the same result.

The design of the multifunctional material can be done using one of many commercially available numerical simulation software (e.g., Ansys, Comsol, HFSS, etc.), and in the case of simpler configurations can even be derived intuitively (from field experience) or theoretically. Once the ceramic refractory powder and core material are selected, the preparation of the multifunctional ceramic follows one of the traditional ceramic preparation methods (high or low sintering temperature). This step requires attention.

The preparation of the ceramic material according to claims 1, 4 in claim 9 follows the traditional method of preparing a slurry starting from refractory ceramic powders; the choice of these materials depends on the properties and application of the target material. Ceramics are of a wide variety and therefore, we have different compositions and sintering temperatures. Since the novelty of the present invention is the addition of a core material to the original ceramic slurry, the manufacturing process is essentially different from any ceramic manufacturing process in other literature, the entire process being summarized in fig. 8. This figure represents the case of the novel ceramic preparation and sintering; such new steps would also be required if there were alternative processes (e.g., casting processes, etc.) and other routes that might be explored in the future. In its basic principle, the manufacturing process comprises the following steps:

1) the construction (design, calculation and evaluation) of the performance of the needed multifunctional ceramic material; since the final material is a combination of two (or more) different materials, their combination will result in material properties that are completely different from those of the original conventional ceramic material.

2) The ceramic powder composition and its core (core material, thickness, cell size, cell shape, cell wall thickness, etc.) are selected to achieve the desired properties. If the material scientist/designer/engineer is experienced, he can intuitively guess the resulting properties, and therefore can choose the ceramic material and core directly and verify the properties after manufacturing by testing the final new material. Otherwise some computation is required.

3) Ceramic slurry is prepared in a conventional manner, which includes mixing several kinds of nano-powder, adding a particle dispersant, a foaming agent, an additive, etc., to form uniform ceramic slurry.

4) The core material is integrated into the ceramic slurry. This step is a new basic step for the preparation of these new materials.

5) In order to consolidate the ceramic slurry, a standing is performed.

6) The dried ceramic slurry is compressed. The pressure may be 1 to 5 mpa, or higher. It has to be noted that to obtain a very dense slurry and a good crystal structure of the final new material, pressure is usually applied to the ceramic slurry before sintering. The green body is typically in a mold and the material is then compressed. In order to enable the material to be compacted, a core must be selected that is completely melted into the ceramic slurry, that is, a core having a relatively short thickness.

7) Sintering of multifunctional ceramic materials is generally carried out in steps:

first, sintering should be noted to remove gases from the ceramic slurry; and removing additives that have been added to their composition to aid in the uniform distribution of the different ceramic particles, such as foaming agents and/or dispersants, or that have been contributing to the formation of additional pores within the ceramic body, resulting in additives having additional pores. Gases formed due to additives and the like added to the ceramic slurry to aid the mixture, as the temperature increases, these chemicals evaporate and slowly leave the ceramic body.

An example of the sintering temperature is shown in fig. 9, and the first step sintering: here, it is usual to remove all the gases formed in the ceramic slurry. This temperature is generally set to a temperature higher than that of all additives, blowing agents and other additional chemicals added to the ceramic mixture in order to foam, homogenize or contribute to the quality of the final product in all desired ways. At this step, if the core material is made of a material having a melting temperature equal to or lower than the first sintering temperature step, the core material may also start to burn or melt. In this step, the temperature is typically raised to 250 ℃ or 300 ℃, which is a slow temperature gradient, which may typically be 2 ℃ to 5 ℃ per minute.

In a

second sintering step

9A or 9B: in order to achieve good crystallization of the ceramic material, it is normal to divide the sintering ramp into several steps, these different temperature ramps allowing to slowly achieve complete crystallization of the material and to obtain excellent quality in terms of material homogeneity and material properties. The temperature and rate of the ramp (temperature increase over time) should be studied and determined on a case-by-case basis. If the core material is sintered at a higher temperature than the first sintering ramp, it may be necessary to consider that the speed of the second sintering ramp is slower than usual for conventional ceramic materials without a core material; or additional steps may be added. The reason for this is that the rate and temperature should be such that the core will not damage the interior of the ceramic material during combustion. In fact, the combustion of a large amount of material generates internal pressure, which may lead to the formation of major internal defects because the ceramic material has not yet crystallized, in other cases the core may be a structure made of another ceramic material, the sintering temperature of which is different from that of the ceramic body, and therefore additional sintering ramps should be added to allow sintering of the different material. The second sintering step is the result of the core material being important to obtain the final new material for all the materials described in the present invention, especially for the source ceramic slurry. These examples do not limit the inventive possibilities.

The presence of the core material may affect the rate of temperature ramping and the considerations described in the additional steps. For example, in order to slowly melt and burn the core material and slowly discharge all of the gases in the slurry being sintered, the temperature ramp during sintering needs to be performed at a much slower rate than is typically used for the same material (coreless), if necessary. In this sense, the conventional sintering process should be carefully redesigned or studied according to the result (final material) we want to obtain. The general process is shown in figure 8. Here, the first step "design" means that once we have selected the ceramic powder composition and prepared the slurry, the sintering temperature (final temperature) is already determined by the slurry we prepared, but the sintering process (different temperature gradients and steps) may differ by the core material, and we may need more "steps" or slower ramps before reaching the maximum temperature of the sintering process.

The end result is different depending on what core the designer chooses: a core that burns before the ceramic slurry is fully sintered, or a core that resists the sintering process of the ceramic slurry. These two main classes will lead to new ceramic materials, either porous or non-porous.

If the goal is to obtain a porous multifunctional material (class A), the sintering process should proceed as shown in FIG. 8, step 9A, with the core material burning. The second step of sintering depends on the core material (unit cell, size, wall thickness, etc.) and the desired result. If the core material is a polymeric material that burns at a temperature higher than the temperature used in the first sintering step (to scavenge gases trapped in the ceramic slurry), it is contemplated that a second ramp may be used to burn the core. It is recommended that the gas and the combustion core are not removed from the ceramic slurry at the same temperature, and the movement of the gas through the ceramic slurry and the melting and vaporization of the core may destroy the stability of the cell structure of the internal material. The final result of 9A is shown in FIG. 1(A-B) (in the figure, a represents a side view, and B represents a top view) and FIG. 2 (in the figure, a represents a top view, and B represents a side view).

Core materials include, but are not limited to, thermoset or thermoplastic polymers and derivative composites: polypropylene cores, polymethylmethacrylate, polymer-based composites with any filler or reinforcement, graphene cores, amorphous carbon cores. In general, any material that melts and burns at a temperature below that used to sinter the main ceramic body. Thermoset polymers include, but are not limited to, polyurethanes, polyimides, cyanates, and epoxies; thermoplastic polymers include, but are not limited to, acrylic (PMMA), nylon, PC, PE, PP, ABS; metal cores include, but are not limited to, aluminum, silver, copper, gold.

The 9A sintering route was chosen with the goal of combustion core. If the core is a polymeric material or any material having a melting temperature and a firing temperature below the maximum temperature required to sinter the ceramic body, the core will burn during sintering. Therefore, it is necessary to properly design and integrate a temperature ramp throughout the sintering process to adequately burn the core. As shown in fig. 10.

In more detail, if the raw ceramic component of choice is a low temperature co-fired ceramic (LTCC), the sintering temperature of the material (as shown for commercial LTCC ceramics) is typically below 1000 ℃. Some desirable LTCC is also at from 550 ℃ to 800 ℃. To obtain a porous multifunctional ceramic using LTCC ceramics, the core material is selected from polymer-based materials, since these materials mostly melt below 550 ℃. If the sintering temperature of the LTCC ceramic body is about 1000 ℃, metal cores such as copper and the like can be used, and in the temperature range, graphite and carbon fiber composite materials can be used as cores and paper cores. The slope is recommended to be 2-5 ℃/min, and can reach 400 ℃ at most; for reinforced paper based materials, the temperature ramp is recommended to be up to 500 ℃; copper softens at about 1000 c and leaves a cavity in the ceramic body. Most polymer-based reinforced composites will also burn at temperatures below 1000 c. Thus, raising the temperature to these values will ensure complete combustion of the core material within the ceramic body.

If the raw ceramic component of choice is a high temperature co-fired ceramic (HTCC), the final sintering temperature (as known in the literature and commercial products) is above 1000 deg.C, most likely around 1600 deg.C. In this case, the core may be any polymer based material, some metal and ceramic reinforcement polymer, or may be an LTCC ceramic.

If the raw ceramic composition chosen is an ultra high temperature co-fired temperature ceramic (UHTCC), the final sintering temperature (as known in the literature and commercial products) is above 1600 deg.C, most likely around 2000 deg.C. In this case, the core may be any polymer-based material, most metals, and ceramic reinforced polymers, most of which cannot withstand such high temperatures.

In the present invention, the class (class a) of "porous multifunctional ceramic materials" is divided into two sub-classes, i.e. periodic (fig. 1) or non-periodic (fig. 2) porous multifunctional ceramics. This difference is not derived from any additional step in the manufacturing method, but from the different core material selected in step 2b in fig. 8. Specifically, the method comprises the following steps:

if the core selected in step 2b is a material exhibiting a periodically arranged structure, cells of any size and shape and any cell wall thickness, such as the well-known honeycomb material or the example given in fig. 6, the final ceramic will be a multifunctional ceramic with periodic internal porosity. In the present invention, this subclass is identified as periodic porous multifunctional ceramic material (a 1).

If the core selected in step 2b is a material without periodicity, such as any material foam with arbitrary porosity, e.g. fig. 7, the final multifunctional ceramic will have aperiodic/arbitrary porosity. In the present invention, this subclass is identified as non-periodic porous multifunctional ceramic materials (a 2).

If the goal is to obtain a non-porous multifunctional material (class B), the sintering process should proceed as shown in step 9B in FIG. 8, without burning the core material. In this case, the core does not melt at the final sintering temperature of the ceramic, and retains its structure when the entire material is subjected to standard sintering, which results in a solid material with a hard core completely incorporated therein, as shown in fig. 3(a-B) (in which a represents a side view and B represents a top view), and fig. 4 (in which a represents a side view and B represents a top view).

The 9B sintering route was chosen with the goal of sintering the ceramic body while retaining the core integrated therein. If the core material is a material having a melting temperature and a firing temperature higher than the temperature required to sinter the ceramic body, the core will remain unchanged within the body during sintering. As shown in fig. 11.

In more detail, if the raw ceramic component of choice is a low temperature co-fired ceramic (LTCC), the sintering temperature of the material is typically 1000 ℃ and some of the desired LTCC's are also made at temperatures of 550 ℃ to 800 ℃. To obtain a multifunctional ceramic with a solid integrated core using LTCC ceramics, the core material can be selected from, for example, metals, alloys, metal matrix composites, high temperature ceramics, etc. We can also use some metal cores, such as copper, if the LTCC ceramic body is sintered at temperatures between 550 ℃ and 800 ℃. In this temperature range we can also use graphite and carbon fibre composites as cores, the softening temperature of the metal fibre reinforced polymer composite being mostly above 600 ℃, so that sintering of the material will follow the conventional sintering process, since in this case there is no need to remove the core. All temperature gradients are recommended to be 2-5 deg.c/min.

If the raw ceramic component of choice is a high temperature co-fired ceramic (HTCC), the final sintering temperature (as known in the literature and commercial products) is above 1000 deg.C, most likely around 1600 deg.C. In this case, the core material may be metallic or ceramic which can withstand such high temperatures.

If the raw ceramic composition chosen is ultra high temperature co-fired temperature ceramic (UHTCC), only a few other HTCC materials, such as ultra high temperature ceramics like titanium carbide, titanium, zirconium nitrate, etc., can become potential core materials.

In the present invention, the class of "non-porous multifunctional ceramic materials" (class B) is divided into two sub-classes, namely periodic (fig. 3) or non-periodic (fig. 4) non-porous multifunctional ceramics. This difference is not derived from any additional step in the manufacturing method, but from the different core material selected in step 2b in fig. 8. Specifically, the method comprises the following steps:

if the core selected in step 2B is a material exhibiting a periodic arrangement of structures, in the present invention, this subclass is identified as periodic non-porous multifunctional ceramic material (B1).

If the core selected in step 2B is a material without periodicity, in the present invention this subclass is identified as non-periodic non-porous multifunctional ceramic material (B2).

And (3) final sintering step: aiming to fully crystallize the ceramic material.

The above mentioned is that a core must be chosen which is completely integrated in the ceramic slurry, that is to say a core having a relatively short thickness. The same thickness as the slurry can cause the core to buckle or deform slightly. As described below, buckling of the core may be a particular desired result, a result that is to be deliberately achieved. This will create a material with a periodic cell structure, the periodicity of which is not constant throughout the thickness.

Claim 9 includes the principle of selecting the core material to deform when the ceramic slurry is pressurized. If this is part of the manufacturing plan, the periodicity in the thickness and/or plane of the final material will be non-uniform. This step requires a mold. The mold can maintain the deformed state of the core material and the shape of the slurry. In this particular case, if the core material is a polymer, a hollow structure is left in the ceramic body, which is irregular in thickness.

Also, for high temperature core materials, when the cell walls are thin and easily deformable, the material remains compressed after sintering, and as a result of this process has a periodic structure, the periodicity of which is irregular in thickness. This particular result may be advantageous, for example, for high impact speeds and shrapnel confinement, as it increases more heterogeneity and chance within the ceramic body to stop a shot, or may incorporate a core material designed to behave like a spring under deformation. After sintering, the deformation energy is stored in the material and is released only in the event of a collision or crack of the ceramic body (useful for impact applications). This particular final material has a higher impact strength.

Claim 9 includes a method of preparing ceramic foams with additional high structural periodicity cores (porous or non-porous). In this case, the ceramic body can be designed to incorporate additional porosity in the form of bubbles or hollow spheres of different materials (glass beads, fly ash, hollow silica particles, hollow TiO2 nanoparticles, hollow silver nanoparticles, etc.) to create distributed microporosity in the body. The ceramic foam may then be integrated with a core material and will produce a ceramic foam having a second order porosity or form a foam having a particular solid core structure.

As shown in fig. 12, details in the material results include making a porous or non-porous structure with additional specific microporosity to the ceramic foam. Due to the addition of the foaming agent to the slurry (removed in the first sintering ramp), a material with microporosity can be formed after sintering. In the present invention, this porosity is referred to as "secondary porosity" to distinguish it from the primary porosity due to the fact that the core burns and the voids left (walls of core material no longer exist). As shown particularly in fig. 12, the first porosity is due to the periodic/aperiodic porosity resulting from the burning of the core, and the second porosity is due to the microporosity resulting from the addition of a blowing agent to the ceramic slurry (ceramic foam is an additional lightweight material used in many different fields). The size of the "micropores" is exaggerated in the figure, and these are generally micropores in the ceramic body.

Claim 9 includes variations of

steps

9A and 9B as shown in figure 13(a-B) below. Alternative methods of preparation may produce multifunctional ceramics in which the voids left by the core material may be filled with other materials, metals or polymers after the sintering process and cooling to room temperature. This additional step allows for the injection of another material into the void left by the core. The second material will solidify to form a solid structure or simply cover the cell wall without completely filling the cavity, forming a waveguide (in the case of electromagnetic applications) or vascular system in general. This process may also lead to the following possibilities: in the case of a multifunctional ceramic having a periodic porous core, a conductive material such as copper may be injected into the voids of the original core structure. Since copper melts at 1000 ℃ or higher, it is necessary to use a high-temperature sintered ceramic at 1000 ℃ or higher. The metal solidifies in the voids left by the walls of the core cell, forming a conductive periodic structure. This is an equivalent result of integrating a 3D printed copper core into a low temperature co-fired ceramic, except that we can use a high temperature ceramic (this property may be required for some applications), by melting the metal we can coat on the walls of the original core material unit and obtain a "waveguide" result, as in fig. 13 (a-B).

Another alternative method according to claim 9 is to inject a second ceramic slurry into the multifunctional ceramic obtained by a manufacturing method according to claim 9. For example, the first manufacturing process produces a high temperature ceramic with open periodic porosity. The material will be used as a mold and a second aqueous ceramic slurry is injected into the pores of the main ceramic body. The entire material will be sintered a second time to crystallize the core. In this case, the preparation will result in the ceramic material having a ceramic core of a different material. Various applications for these materials include ultra-high impact ceramics.

Another possibility comprised in claim 9 is, for example, the integration of a metal-periodic cell core followed by the integration of a polymer-periodic cell core. The result will be a ceramic body with a bi-periodic structure consisting of rigid walls and periodic porosity, as shown in fig. 14. In this case, the component (1) is for example a copper plate with wires/needles. (1) Any other composition of different materials is possible. The component (1) is then inserted into the ceramic slurry (2), where we have inserted a periodic core (3). The component (1) is designed in such a way that each wire/line of the board will be located within a single unit of the periodic core. Depending on the material of the component (1), we can obtain two different results: the component (1) is melted or burned (a), or the component (1) remains in the solid state (B) after sintering. This is a situation where a bi-periodicity is created within the ceramic material. The fabrication process includes any integration of the core material with the shape of the core cells, and the core material can be actually 3D printed. This provides a variety of choices for the choice of materials and end result. The final ceramic may be sandwiched between two layers. These additional layers may be any material as claimed in claims 1, 4 or conventional materials. They may also be manufactured according to claim 9 or in a conventional manner. Such layered structures are commonly used for impact resistant panels.

Another option included in claim 9 is the manufacture of multifunctional ceramic membranes. The same procedure as in claim 9 will be employed, but the film fabrication will be subjected to a process such as a casting method which is then used in the present invention for the fabrication of the multifunctional ceramic film, and these materials will also be included in claims 1, 4. The main difference from the existing membrane having a periodic cell structure is that the periodic cell structure is not printed/deposited on the membrane, etc., but is a part thereof. The core material may consist of a layer deposition that produces a defined pattern that may be obtained by photolithography, printing, chemical deposition or other techniques for producing thin layers of material. Ceramic film casting is a well-known technique, simply, to disperse a slurry on a flat surface to form a film. The film is then sintered at the necessary temperature to form a thin ceramic. In this case, the ceramic slurry may be laid on a substrate of a core on which a pattern has been formed, a core of a definite periodic unit structure deposited/printed thereon, or the like. Sintering integrates the periodic structure into the film. The core material and ceramic body will have a single uniform thickness to form a film and the casting technique can very accurately control the final film thickness.

An additional alternative of claim 9 comprises integrating a metallic conductive core (e.g. a copper core or a polymer based material with conductive particles as fillers) into a ceramic material with a sintering temperature above the melting temperature of the conductive core. When the ceramic solidifies, the core walls melt and the material forming the cell walls will collect at the cell bottom. In this case, a conductive plate of the same shape as the original empty core cell or only the shape of the cell wall will be formed at the bottom of the cell (a mold may be required to allow the molten material to have the core cell shape). As in fig. 15. It is possible to purposefully plan for the core material to melt rather than vaporize.

One example of the present invention is the integration of metal foam into ceramic slurry. In this case, the sintering retains the core and forms a heterogeneous high temperature ceramic metal material with potentially superior impact properties. In this case, the core is not periodic as before, but is a random mix of the two materials, as in fig. 7. The representative cells can still be modeled using some homogenization technique to predict the bulk material properties. If the core is such a metal foam, the core is not periodic, so the new ceramic is one in which the new ceramic is "metal". According to the theory of homogeneous properties, finally, the new multifunctional ceramic material is characterized by the fact that this is a combination of the properties of the two materials, a ceramic having improved properties due to the presence of the metal part.

Another example of the present invention is the integration of polymeric foam into a ceramic slurry, as shown in fig. 2. The core inside the sintered ceramic is empty, which results in a high porosity for either the high or low sintered ceramic. The same porosity may be filled with another material, copper, polymer, etc. This situation can be exploited in filtering technology.

By adopting the novel method provided by the invention, periodic (unit cell is non-porous or porous) or non-periodic (non-porous or porous) multifunctional ceramics, LTCC or high-temperature sintered ceramics can be realized. In other aspects:

they can be manufactured not only as thick substrates but also in a layered structure, as shown in fig. 16, 17. The core at each layer may be different. The thickness of the layers may be the same as the minimum thickness of the core material that can be produced by currently available technology or future technological advances. The number of layers of the multilayer ceramic material system can be set according to actual needs, and each layer can be a traditional ceramic material or a periodic porous multifunctional ceramic material or a periodic non-porous multifunctional ceramic material or a non-periodic non-porous multifunctional ceramic material. As shown in fig. 16, the multilayer ceramic material system may be two layers, a first layer may be a periodic porous/non-porous ceramic material, such as a core material that is a ceramic material of honeycomb pores; the second layer may be of the same or different ceramic material, such as the same honeycomb pore ceramic material, or porous/dense square/hexagonal cells of ceramic material. As shown in fig. 17, the multilayer ceramic material system can also be three layers, and the multifunctional ceramic material can be surrounded by a conventional ceramic material, and can be a periodic porous multifunctional ceramic material or a periodic non-porous multifunctional ceramic material or a non-periodic non-porous multifunctional ceramic material. The number of layers in the invention is not limited to 2 or 3, and may be 2 to 10, and any material combination in the invention may be combined in a multilayer material system, where 2 or 3 layers are only examples, so as to let the reader understand the material process.

Ceramic tapes and films are currently on the market, and sintering of the film material according to the invention, using the same basic principle as casting, is mainly distinguished and novel by the

additional step

9A or 9B of claim 9 and thus by the new method for manufacturing these materials. In the case of periodic porosity, the final material may be filled with soft polymer materials, piezoelectric materials, etc., depending on the application, or additional functions may be added, such as sensing.

By utilizing the method provided by the invention, the bioceramic which cannot be subjected to 3D printing due to the high strength performance and the requirement of high-temperature materials can be better prepared. The porous 3D core inside the final ceramic may reproduce a network of capillaries, helping bone regeneration or other cell growth. First, a polymer core having a desired shape is manufactured using a 3D printing technique, and then the core is integrated into a ceramic slurry, thereby manufacturing a final multifunctional ceramic. During sintering, the polymer core material will be burned. The final multifunctional bioceramic will exhibit internal porosity left by the core material. Generally, bioceramics are ceramics having excellent mechanical properties, and are generally achieved by sintering ceramics at high temperatures. To date, no bioceramic has been shown to be as novel as the bioceramic of the present invention. They are all bulk materials. With the present invention we can create these same materials with additional functionality, e.g. 3D printed polymer core material previously similar to vascular system can be integrated into ceramic slurry. The ceramic slurry will flow through the structure and be fully embedded. After the sintering process (usually at high temperatures), bioceramics are a new type of ceramics (with properties different from the original ceramics due to their porosity) with well-designed porosity, in which case capillaries that contribute to cell growth can be accommodated, and these solutions are very desirable in the medical field.

Ultra-light ceramics are necessary for space assembly, and the inventive material can now provide the possibility of integrating communication lines, better heating systems, etc. The devices, systems and components may be better able to heat and cool, and ideally the network may be designed to carry water or other liquids, or there may be a conductive network to heat the entire material.

The present invention also provides a method of fabricating a device using Metamaterial Technology (MTM), particularly for applications requiring high temperature and high structural strength.

Of interest are low dielectric and low loss materials. These materials of the present invention are clearly ideal substrates for electronic components. In the particular case of low dielectric constant and low loss LTCC materials, the present invention provides a method of making materials with a porosity periodicity that positively ensures, in terms of homogenization properties, that the new materials have a much lower dielectric constant than materials made using the same ceramic powder mixture, without porosity or random porosity (if foam is used). In addition, losses are reduced because there is generally no relaxation of the ceramic, and dissipation effects may occur only when the wavelength of the material is comparable to the unit cell size representing the periodicity of the ceramic body. In the present invention, there is a particular design of the porosity of the material due to the space left by the core cell walls.

A wave propagating perpendicular to the surface of the material has a wavelength greater than the size of the unit cells representing the periodicity of the ceramic body, so that the wave does not perceive nor is affected by the inhomogeneity of the unit cell material. The present invention provides the possibility to reconsider many materials that were previously excluded due to their high dielectric constant as a design choice. In this regard, the characteristic constants of the ceramic material can be designed as is done in metamaterial design, depending on the application. In fact, unit cell porosity (in the case of low dielectric and low loss applications) or unit cells with denser walls (for high dielectric and high loss materials) is the fundamental unit of material property uniformity. All the advantages of this technique will be retained.

The present invention proposes the principle and the manufacturing method for improving the performance of the existing ceramic material, including any type of ceramic material composition and its composite material. For example, in the field of thermal insulation materials, if a high temperature material with high electrical resistance and optimal thermal insulation properties is desired, the application of the design principles of the present invention can modify existing materials (or select new materials) used in such applications, not only to greatly improve these properties, but also to add additional functionality, so that this process will result in a new enhanced multifunctional material. In another example, if materials with extreme impact strength are required in the high impact strength, ballistic performance areas, the principles and manufacturing methods proposed by the present invention can produce performance enhancing materials for existing solutions (materials and material systems) as well as new materials with additional functionality.

Thus, the application of the principles and manufacturing methods described herein creates a new class/group of materials (not only one material, but a new family of multifunctional ceramics) that can be used in different scientific, engineering, and medical fields characterized by enhanced properties and increased versatility.

In view of the above, the main novelty of the present invention is the integration of the core into the green body while preparing the ceramic material to obtain a new class of materials. The core will be completely immersed in the ceramic slurry. Once the final step of ceramic preparation is reached, firing of the particular ceramic prepared will produce two main different results depending on the desired final material properties. If the core is a polymeric/composite material that burns at a lower temperature than the ceramic part, sintering burns the core material and crystallizes the ceramic, leaving the space occupied by the core walls free. This can be done to obtain a specific ceramic structure with periodic porous bodies. If the core is a material that can withstand high temperature sintering, the final ceramic will have a periodic cell dense core. Both of these results apply equally to non-periodic cores, such as non-periodic cellular foams and specially designed non-periodic non-cellular cores.

Since the core may serve different functions, the material according to claims 1, 4 and the material manufactured according to the basic principle of claim 9 may be designed as an overall final material with specific highly improved properties and/or additional functions, such as electromagnetic function/electrical function/improved impact function/improved dielectric constant (lower or higher), ultra lightweight, etc., as well as combinations of these properties.

The novel multifunctional ceramic material has wide application prospect in the fields of communication equipment, aerospace devices, building engineering, environmental protection, medical treatment and the like. In all these applications, they have the following advantages over the existing materials:

1) higher electromagnetic performance can be realized;

2) higher sound insulation/heat insulation/electric insulation performance can be achieved;

3) can be manufactured in a layered system, as shown in fig. 16 and 17;

4) allows the design and manufacture of entirely new telecommunication/audio equipment;

5) allows the design and manufacture of new metamaterial products and devices;

6) allows the design and manufacture of new air and water purification systems;

7) allowing for the design and manufacture of high temperature/high strength/high impact/biomaterial and additional intelligence/magnetism/drug delivery, etc. multiple functions.

The invention can create the following new materials, and has great benefits for the development of society and new material technology:

1. novel multifunctional ceramic metamaterial.

By this method, three-dimensional metamaterials (absorbers, filters, acoustic and electromagnetic cloaking devices with multifunctional properties, etc.) with high impact strength and high temperature resistance can be obtained. In the specific case of metamaterials, electromagnetic and acoustic, the present invention opens a new world of possibilities for engineering metamaterials with properties that do not exist today. The electromagnetic properties (permittivity, loss, permeability, etc.) of the ceramic material can in fact be designed with an additional degree of freedom. The core may be copper or other conductive material. The properties of the metamaterial can be tailored based on the overall response of the copper-ceramic material to a particular electromagnetic frequency. For example, a high-quality three-dimensional electromagnetic absorber can be manufactured. Alternatively, low dielectric ceramics may be made from ceramic-refractory powder mixtures, which have previously been excluded due to their high dielectric constant, and are now the choice.

In fact, for a multifunctional ceramic with periodic open porosity, porosity will be the primary variable that helps reduce the dielectric constant, not just the material composition. The nuclei of the porous periodic structure will significantly reduce the overall dielectric constant, which is also a result of the calculations for homogenizing the material properties. The same principle applies to acoustic metamaterials, where the properties of bulk materials can now be designed with a higher degree of freedom, since the present invention now gives a rich choice of "real" materials with high temperature, high impact resistance, etc. to design and manufacture these metamaterials. Potential acoustic and electromagnetic cloaking can be achieved. The combination of these two functions is only dependent on the design, but the present invention provides additional material to fully fulfill these functions.

2. Novel plasma materials and devices.

Surface plasmons that have been theoretically demonstrated in the past are believed to be generated from porous materials that are periodic, well-defined, and well-ordered. In general, the materials theoretically contemplated in the literature are conductive materials. These theoretical results, in most cases, have never been achieved in practice due to the lack of prior art techniques to achieve these materials. The present invention allows for the design of plasma materials because ceramics can now be designed with regular periodic porosity and can be high temperature, high impact, highly corrosion resistant and have ultra light weight characteristics.

3. Novel high impact strength materials.

The core may be titanium or other material, eventually highly structured ceramic (in the section referring to the alternative materials (results) obtainable using the principles and manufacturing methods of the present invention), and the shape of the core element may be any shape that meets the requirements for better performance and debris protection in ballistic applications or high impact velocity applications. The integration of intelligent features in the porous body or ultra-light magnetic core contributes to the repulsion of the projectile. One limiting factor in current protective technology material design is the excessive weight of high strength ceramics. For this reason, there are lighter cores of material, such as titanium or ferromagnetic materials, which can exert a repulsive electromagnetic force on the impact projectile, which can eventually lead to advances in designing better products and achieve bodywork and vehicle/aircraft/spacecraft protection not previously possible. The integration of intelligent features in the porous body or ultra-light magnetic core contributes to the repulsion of the projectile. One limiting factor in current protective technology material design is the excessive weight of high strength ceramics.

4. A novel multifunctional ceramic biomaterial.

The core integrated in the bioceramic slurry can be burned and the interstices can act as vessels for drug delivery, cell growth, etc.

5. Novel intelligent pottery.

The core may burn, leaving room for the integration of wires and sensors.

6. Novel high temperature heat conducting or insulating materials.

For example, in the case of a high thermal conductivity material, the pores within the ceramic body left by the walls of the original core may be filled with a high thermal conductivity material. This will result in a core that can heat the entire material. The new properties of these materials may include new specifically designed electromagnetic properties (e.g., metamaterial cores integrated into ceramic bodies) and higher thermal properties. The copper heats up faster than the rest of the ceramic body, which helps to cause the temperature of the entire material to rise naturally and rapidly. The application fields of prospect are the application fields of green building, aerospace, energy conservation and the like.

7. Novel high performance air and water filtration systems.

The proposed material allows to integrate a system, eventually clearing the absorbed or trapped waste, like a vascular system, absorbing the elements trapped in the pores and washing them away, reaching or opening an electromagnetic field or the like to trap the contaminating atoms and ions after their end of their useful life.

Such as in the case of next generation water or air filters, the contaminating particles are trapped in filter material, which is now almost unrecoverable. The presence of a network of blood vessels (e.g., a copper network of current through the material, a porous microchannel system, etc.) integrated into the material may help to increase the function of the filter, such as opening a magnetic field, or passing liquid through the filter material and many other solutions, which help these contaminant particles to pass through the filter and be collected for ultimate disposal. The detailed design of the potential filter cleaning system will depend on the target filter type and contaminant type.

8. Novel environment-friendly high-strength material.

Currently, there are some applications where only high sintering temperature ceramics have promising functionality. However, the low-temperature co-fired ceramic can be used at present, and has great energy-saving potential. All ultra-light versions of these materials also achieve the goals of improved fuel and energy savings.

9. Novel catalysts, sensors and new energy materials.

The new materials can also be applied as new sensors, batteries, solar cells and the like. Films and layers with integrated conductive networks have a wide range of applications in batteries and solar cells.

Since these new materials can be used in very different applications, the background art includes material and processing aspects belonging to different scientific fields. Here, without excluding other possibilities that may arise in other applications and that may be easily identified by experts in these particular fields, the following lists examples of the greatest benefit that will be obtained by implementing the new material design and manufacturing method of the present invention.

The preferred embodiments of the present invention also provide a few examples of materials that can be produced by applying the proposed design of the present invention and its proposed manufacturing process.

In the present invention, low temperature co-fired ceramic (LTCC) or high temperature sintered mixed ceramic powder (refractory powder) (raw ceramic material-material (1)) fig. 5(a2-B2) is prepared according to a conventional procedure for preparing ceramic slurry including a binder, a particle dispersant, an additive, etc. The refractory powder is selected according to the application and the material properties depend on the composition of the mixture.

The present invention also selects the core material (2) as shown in fig. 5C or fig. 7. The core may be any material having periodic cells and/or structures of any shape, as well as metal and/or other materials. These materials may be purchased, or three-dimensionally printed, as illustrated periodically in FIG. 6. A wide variety of core materials are commercially available; they may be of plastic or metal, ceramic, etc. materials with honeycomb cells, circular cells or specially designed and engineered. The core may also be a core/foam material with randomly distributed fibers or open cells, as shown in fig. 7.

Using the manufacturing method according to claim 9 of the present invention, the combination of the raw ceramic material (1) and the core material (2) will produce new materials such as multifunctional ceramic materials with periodic unit cell structures (group 3-1) as shown in fig. 1 and 3, or multifunctional ceramic materials with non-periodic material cores (group 3-2) as shown in fig. 2 and 4. The final material in the multifunctional ceramic material (3) of the present invention can be divided into two groups according to periodic division.

The multifunctional ceramic material of the present invention can be divided into two groups (e.g., A, B groups) according to whether or not the core is burned.

Group a (achieved by step 9A in fig. 8): a material in which the core is burned at a temperature below the sintering temperature of the ceramic body. Group a can be represented simply in fig. 1 and 2, where the core material is burned at high temperature and the final material exhibits porosity within the ceramic body.

If the ceramic component chosen in the raw ceramic material (1) is a low temperature co-fired ceramic (LTCC), the final sintering temperature is below 1000 ℃ and some very promising LTCC ceramics are also prepared at very low temperatures from 550 ℃ to 800 ℃. The core material (2) is then mainly a core of a polymer material, since most of these materials melt, soften and burn below 550 ℃, typically below 800 ℃ in case of polymer based materials (fibre reinforced composites, polymers with ceramic fillers, etc.). The core material can also be a metallic material, such as copper, if the sintering temperature of the LTCC ceramic body is between 900 ℃ and 1000 ℃. In this temperature range (probably below 1000 ℃), we can also use graphite and carbon fibre composites as cores, paper cores, metal fibre reinforced polymer composites.

If the ceramic component chosen in the raw ceramic material (1) is a high temperature co-fired ceramic (HTCC), the final sintering temperature (as known from literature and commercial products) is above 1000 ℃, most likely around 1600 ℃. In this case, the core may be any polymer based material, some metals, and ceramic reinforcement polymer or LTCC ceramic.

If the ceramic component chosen in the raw ceramic material (1) is an ultra high temperature co-fired temperature ceramic (UHTCC), the final sintering temperature (as known from literature and commercial products) is higher than 1600 ℃, most likely around 2000 ℃. In this case, the core may be any polymer-based material, most metals, and ceramic reinforced polymers, most of which cannot withstand such high temperatures.

Group B (achieved by step 9B in fig. 8): materials having a core material that can withstand extreme temperatures, thereby subjecting the core material to a sintering process. Group B as shown in fig. 3 and 4, in which the core is not affected by high temperature and will be preserved during sintering, thereby forming a ceramic material with a solid cell structure, the core being a different material than the ceramic body.

If the ceramic component of the raw ceramic material (1) is selected to be a low temperature co-fired ceramic (LTCC), the final sintering temperature (e.g. a commercial LTCC ceramic) is below 1000 ℃, and some very promising LTCC ceramics are also prepared at very low temperatures from 550 ℃ to 800 ℃. The core material (2) is selected to be one that does not change during the sintering of the ceramic, softening, melting and combustion induced changes, such as most metals, metal matrix composites, some ceramic reinforced polymers, metal matrix composites and high temperature ceramics. Most metals and metal alloys do not soften at higher temperatures. It is also possible to use some metal cores, such as copper, if the sintering temperature of the LTCC ceramic body is between 550 ℃ and 800 ℃, which is characteristic of typical LTCC ceramic applications in the telecommunications field.

If the ceramic component chosen in the raw ceramic material (1) is a high temperature co-fired ceramic (HTCC), the final sintering temperature (as known from literature and commercial products) is above 1000 ℃, most likely around 1600 ℃. In this case the core material may be any material, metallic, or ceramic, and thus other HTCC ceramics and some metals, which can withstand such high temperatures.

If the ceramic component selected from the raw ceramic material (1) is ultra-high temperature ceramic, only other HTCC materials such as titanium carbide, titanium, zirconium nitrate and other ultra-high temperature ceramics can become potential core materials.

Fillers such as nanoparticles, hollow nanoparticles, fibers, nanofibers, etc. may also be used in the present invention, and the integration goals of these additional fillers are fundamentally different, e.g., the hollow particles will form a porous ceramic body; metal fibers can increase the electrical resistance of the ceramic body, and so on. On this ceramic body we can add a core material. Additional foaming agents may also be added to the ceramic slurry to obtain ceramic foam; the material (1) may thus also be a foam.

In the present invention, the first porosity (primary porosity) is due to the novel manufacturing method and materials of the present invention (adding a core material that burns and leaves voids in the ceramic body upon sintering); the second porosity is a general porosity that conventional ceramic foams can have. In the present invention, all ceramic slurries can be made into foams, but the main objective of the present invention is to add a specific engineered porosity, unlike the traditional "voids/bubbles" randomly dispersed in the material.

The metal foam with large open cells allows for complete integration of the ceramic slurry and can also be used as material (2) for the manufacture of these new materials, as shown in fig. 4.

Another possibility is: after the porous multifunctional ceramic is sintered, the network formed by the wires, the sensor, the conductive material, the magnetic material, the soft filling material and the like can fill the gap left in the core part. Any material may be used to fill the porosity depending on the intended application.

In this case, the hollow walls of the cells can also simply be coated with, for example, an electrically conductive material. In this way periodic waveguides can be produced in the ceramic. The new material may be part of a layered system or may be a core material, as shown in fig. 13.

The scope of the following examples is to demonstrate that the materials of claims 1, 4 are possible and can be obtained using the method of claim 9. The specific material properties of different samples vary depending on the ceramic refractory powder and core material, core shape and size, core wall thickness, etc. The core or ceramic composition was different in each sample, and experiments were also performed on the different sintering temperatures to determine which sintering temperature produced the best material. In general, the sintering ramp and sintering temperature should be carefully selected to achieve the desired results. One key factor is that the combustion of the core should be done slowly so as not to compromise the stability of the internal material structure.

All of the examples described successfully produced these materials, as shown in fig. 18. In fig. 18A, the LTCC sample had 5% fly ash without a core material, the sintering temperature was 800 ℃, and the sintering process was performed on the same sample without a core. In fig. 18B, the sample has a circular honeycomb plastic core integrated into the LTCC slurry, which is the sample obtained after the drying step. In fig. 18C, the second sample has a honeycomb core, which after sintering, maintains a porous periodic structure. In fig. 18D, a second sample has the same honeycomb core, however, when the sintering temperature and/or the number of hollow spheres is too high, the porous core portion is filled with the ceramic material. In fig. 18E, the porous periodic structure is maintained after sintering of the sample of fig. 18B. Specific morphological details and physical properties can be tested using standard methods.

The invention will now be further illustrated with reference to specific examples.

Example 1

A preparation method of an ultra-light glass foam with periodic porous pores comprises the following steps:

ceramic powder composition: low temperature sintering ceramic mixed powder (LTCC, mainly Al, Si, B \ mainly contains alumina, boron, silicon dioxide, and may also contain magnesium, cobalt, nickel or selenium);

core material: a PP (polypropylene) core of round unit cells;

preparing ethanol (C)₂H₆O) and Methyl Ethyl Ketone (MEK) at a mass ratio of 70:30, and mixing the two. Adding low-temperature sintering ceramic mixed powder (LTCC, mainly Al, Si and B \ mainly contains alumina, boron and silicon dioxide, and can also contain magnesium, cobalt, nickel or selenium) with the sintering temperature of 800-900 ℃ in two steps: 31.35g of the powder was added and mixed, and 187.44g was added and mixed. 218.79g of powder were prepared in 108.48g of ethanol/MEK solution.

To the first compound, 10.76g PVB (polybutyral C) was added to the solution₈H₁₄O₂). The solution contains 25 parts of PVB, 125 parts (MEK/ethanol solution). Typically, in these experiments, the weight change of PVB in the entire fire-resistant powder system was between 1% and 5%. Then 2.5g of fly ash microspheres (also known as ceno microspheres) were added to the mixture. Then, grease was applied to the inner wall of a plastic circular mold having a diameter of 5cm, and the ceramic slurry was poured therein. The final weight of the ceramic slurry sample in the mold was 57.79 g. Then a PP (polypropylene) core with round unit cells was added. The core material has a thickness less than the total thickness of the ceramic slurry and is therefore completely incorporated therein. And drying the ceramic slurry. After drying, the ceramic slurry is compressed to a high powder packing. The thickness of the core material does not affect the compression process. After this step, the sintering comprises:

1. heating to 300 ℃ at a rate of 5 ℃/min (1 hour) to remove gases from the binder and additives in the ceramic slurry that aid in mixing/homogenizing the ceramic slurry;

the ceramic is stable for 1 hour at the temperature of 2.300 ℃, so that the gas in the ceramic body can be conveniently removed, and the core material is slowly combusted;

heating to 500 deg.C at a rate of 3.5 deg.C/min to burn the core material;

4.500 ℃ for 1 hour, helping to purge gas from the core;

when the temperature is raised to 800 deg.C (1 hr) at 5.5 deg.C/min, the ceramic body becomes a hard solid material

6.800 ℃, the ceramic structure was cured for 2 hours.

Due to the presence of the fly ash particles, the resulting material has a secondary porosity, the first due to the periodic voids left by the core cell walls, the second due to the internal nature of the integrated hollow microsphere material, and the final product is an ultra-light glass foam with periodic porous pores.

Example 2

A preparation method of honeycomb porous dense glass (LTCC ceramic) comprises the following steps:

ceramic powder composition: low temperature sintering ceramic mixed powder (LTCC);

core material: an epoxy core of the honeycomb unit cell;

20g of LTCC glass frit, 2% PAA, 70:30 ethanol and MEK solution (2% PVB) were mixed.

Ceramic powder, dispersant and other fillers are added to the honeycomb core while achieving a certain uniform aqueous consistency. The ceramic slurry is air dried and then compressed. The sintering process comprises the following steps:

1.5 ℃/min, reaching 50 percent of sintering temperature (400 ℃) in 4 hours, burning the core and removing gas;

2. maintaining a stable temperature of 500 ℃ for 1 hour to remove all gases from the sample;

3. raising the temperature to 800 ℃ and reaching the final temperature within 3 hours;

4. stabilized at 800 ℃ for 2 hours and then cooled.

A dense glass with honeycomb porosity was obtained.

Example 3

A preparation method of porous dense glass (LTCC ceramic) with honeycomb comprises the following steps:

core material: a polycarbonate core of honeycomb cells;

20g of LTCC glass frit, 2% PAA, 5g of fly ash were added to a 70:30 solution of ethanol and MEK (2% PVB) and mixed. The polycarbonate honeycomb core was added while achieving a certain uniform aqueous consistency. The ceramic slurry is air dried and then compressed. The core material has no effect on the compression process. The sintering process comprises the following steps:

4. stabilized at 800 ℃ for 2 hours and then cooled.

The result was a dense sample with a honeycomb porous structure.

Example 4

A preparation method of an ultralight ceramic foam with periodic porosity comprises the following steps:

core material: a polypropylene (PP) core of round-bore unit cells;

20g of LTCC sintered at 700 ℃ 2% PAA;

PVB in 75:25 ethanol/MEK solution accounts for 2%;

2.5g of 3M K1 glass beads were added to the mixture. Integration of a polypropylene (PP) round hole core; and drying and compressing the ceramic slurry.

And (3) sintering:

1.3 hours, 5.5 ℃/min to 400 ℃;

2. stabilizing at 400 ℃ for 1 hour;

3. reach 650 ℃ within 2 hours, 2 ℃/min;

4. stabilized at 650 ℃ for 2 hours and then cooled.

The result is an ultra-light ceramic foam with periodic porosity.

Example 5

A preparation method of a periodic honeycomb pore glass sample comprises the following steps:

core material: a polycarbonate core of honeycomb cells;

20g of LTCC glass frit, 2% PAA, 70:30 ethanol and MEK solution (2% PVB) were mixed. Integration of polycarbonate honeycomb core. And drying and compressing the ceramic slurry. And (3) sintering:

burning the core material at 1.2.5 deg.C/min to 300 deg.C;

2. stabilization at 300 ℃ for 3 hours;

3. reaching 700 ℃ within 2 hours and 3.3 ℃/min;

4. stabilized at 700 ℃ for 1 hour and then cooled.

The samples had periodic cellular pores.

Example 6

A preparation method of compact ultralight ceramic with a hard periodic structure comprises the following steps:

core material: a honeycomb cell aluminum core;

20 grams of LTCC glass powder; PAA 2%; 75 parts by weight of PVB accounting for 2% in 25 parts of ethanol/MEK solution; 3g of fly ash; mixing; and integrating an aluminum core. And drying and compressing the ceramic slurry.

And (3) sintering:

1.2 hours to 300 ℃;

2. stabilization at 300 ℃ for 3 hours;

3. rise to 550 ℃ in 2 hours;

4. stabilized at 550 ℃ for 1 hour and then cooled.

The sample was a dense ultra-light ceramic with a hard periodic structure.

Example 7

core material: a honeycomb cell aluminum core;

20 grams of LTCC glass powder; PAA 2%; 75 parts by weight of PVB accounting for 2% in 25 parts of ethanol/MEK solution; 3g of fly ash; mixing;

and integrating an aluminum core. And drying and compressing the ceramic slurry.

And (3) sintering:

heating to 300 ℃ for 1.3 hours;

2.300 ℃ for 3 hours;

3. raising to 600 ℃ in 2 hours;

4. stabilized at 600 ℃ for 2 hours and then cooled.

The results were the same as in example 6. The different properties of all these materials require testing and measurement.

Example 8

core material: 3D printing a honeycomb hole copper core;

and (4) integrating a copper core. And drying and compressing the ceramic slurry.

And (3) sintering:

heating to 300 ℃ for 1.3 hours;

2.300 ℃ for 3 hours;

3. rise to 800 ℃ in 2 hours;

4. stabilized at 800 ℃ for 2 hours and then cooled.

The different properties of all these materials require testing and measurement. The result is a hard, periodic structure of ultra-light ceramics

Example 9

A preparation method of aperiodic ultralight ceramic foam comprises the following steps:

core material: aluminum metal foam with the aperture of 2-5 mm;

20g of LTCC sintered at 650 ℃ 2% PAA;

PVB in 75:25 ethanol/MEK solution accounts for 2%;

2.5g of 3M K1 glass beads were added to the mixture. Integration of an aluminum metal foam core; and drying and compressing the ceramic slurry.

And (3) sintering:

1.3 hours, 5 ℃/min to 300 ℃;

2. stabilizing at 300 ℃ for 1 hour;

3. reaching 600 ℃ within 2 hours, 2 ℃/min;

4. stabilized at 600 ℃ for 2 hours and then cooled.

The result is an ultra-light ceramic foam with aperiodic filling.

Example 10

core material: aluminum metal foam with the aperture of 2-5 mm;

20g of LTCC sintered at 660 ℃ 2% PAA;

PVB in 75:25 ethanol/MEK solution accounts for 2%;

And (3) sintering:

1.3 hours, 5.5 ℃/min to 400 ℃;

2. stabilizing at 400 ℃ for 1 hour;

3. reaching 600 ℃ within 2 hours, 2 ℃/min;

4. stabilized at 600 ℃ for 2 hours and then cooled.

The result is an ultra-light ceramic foam with aperiodic porosity.

These experiments are intended to demonstrate that the new materials described in claims 1, 4 can be achieved by applying the principles and manufacturing methods described in claim 9.

The invention does not limit the preparation process for obtaining the material according to claims 1, 4, nor the different functional ceramics that can be obtained and that have characteristics similar to the periodic cellular structure or the random macrostructural nucleus according to claims 1, 4.

The present invention is not limited to the above-described embodiments, and various changes and modifications of the present invention are intended to be included within the scope of the claims and the equivalent technology of the present invention if they do not depart from the spirit and scope of the present invention.

Claims

1. A multifunctional ceramic, characterized in that: is composed of a traditional ceramic material and a core material;

the core material is a material with a periodic cell structure, the cell structure has shape, size and cell wall thickness, the prepared multifunctional ceramic is a ceramic body with a periodic cell structure, and cell elements are arranged periodically; including but not limited to honeycomb cells, circular cells, or specially designed, the periodic cell structure being constant or variable along the thickness and/or along the plane.

2. The multifunctional ceramic of claim 1, wherein:

the core material includes, but is not limited to, a polymer core, a polymer-based reinforced composite, a paper core, a paper-reinforced core, a metal-based composite, a fiber-reinforced composite, including two groups of multifunctional ceramics: the periodic porous multifunctional ceramic has ceramic integrated with periodic porosity, wherein cellular structures are orderly arranged in a precise periodic manner, and the walls of core cells are empty; and periodic non-porous multifunctional ceramics, ceramics with periodic dense cell structures, the core cell walls not being empty.

3. The multifunctional ceramic of claim 1, wherein:

the core material is a material which is burnt at a temperature lower than the sintering temperature of the ceramic body, the obtained ceramic is a porous multifunctional ceramic material, and is obtained or arranged in an accurate periodic manner, and the core is hollow with internal pores;

the core material is a material which does not burn, melt or change during sintering of the ceramic body, the obtained ceramic is a non-porous multifunctional ceramic material, a periodic compact core structure is obtained, and the core is not hollow.

4. A multifunctional ceramic, characterized in that: is composed of a traditional ceramic material and a core material;

the core material is a non-periodic cell structure material; the shape uses a core with randomly distributed fibers or openings; the core materials include, but are not limited to, metal cores, metal foams, metal matrix composites, alloy core materials, polymeric foams, random fiber foams, ceramic reinforced polymers, including two groups of multifunctional ceramics: aperiodic porous multifunctional ceramics, the core is empty; non-periodic non-porous multifunctional ceramics, the core is not empty.

5. The multifunctional ceramic of claim 4, wherein:

the core material is a material which is burnt at a temperature lower than the sintering temperature of the ceramic body, the obtained ceramic is a porous multifunctional ceramic material, a core structure is obtained or arranged in a non-periodic mode, and the core is hollow and has internal pores;

the core material is a material which does not burn, melt or change at all when the ceramic body is sintered, the obtained ceramic is a non-porous multifunctional ceramic material, a non-periodic compact core structure is obtained, and the core is not empty.

6. A multifunctional ceramic, characterized in that: is a multilayer ceramic material system, the ceramic material can be the material as defined in any one of claims 1 to 5, the ceramic material is combined and laminated, and the number of layers is two or more; the core material of each layer is the same; minimum thickness of layer minimum thickness of core material, 200 microns or 20-50 microns, can be produced with current technology or future technological advances.

7. A multifunctional ceramic, characterized in that: is a multilayer ceramic material system, the ceramic material can be the material as defined in any one of claims 1 to 5 and/or a traditional ceramic material, the ceramic material is combined and laminated, and the number of layers is two or more; the core material of each layer is different; the minimum thickness of the layer is the minimum thickness of the core material that can be produced by currently available technology or future technological advances, 200 microns or 20-50 microns.

8. A method for manufacturing multifunctional ceramics is characterized by comprising the following additional steps besides the mixing and sintering of ceramic slurry in the traditional preparation process:

integrating core material into the prepared initial ceramic slurry; compressing the ceramic slurry before sintering; removing gas, foaming agent, dispersing agent and additive in the ceramic slurry in the sintering process; an additional step of adjusting or changing the temperature ramp of the sintering process as determined by the core material and ceramic body material selection.

9. The manufacturing method of the multifunctional ceramic is characterized by comprising the following steps:

4) integrating a core material into the ceramic slurry;

5) standing and solidifying the ceramic slurry;

6) compressing the dried ceramic slurry;

7) sintering the multifunctional ceramic material:

removing gas in the ceramic material, removing foaming agent and/or dispersing agent and/or additive, and removing gas generated by the additive;

the second step of sintering depends on the final performance requirements of the core material (unit cell, size, wall thickness, material, etc.) and the multifunctional ceramic material.

10. The manufacturing method according to claim 9, characterized in that: in step 1), the multifunctional ceramic material performance can be established by using commercial numerical simulation software, including but not limited to one or more of Ansys, Comsol and HFSS.

11. The manufacturing method according to claim 9, characterized in that: in step 2), a core material that can be completely melted into the ceramic slurry, i.e., the core material has a relatively short thickness, must be selected.

12. The manufacturing method according to claim 9, characterized in that: in step 6), the principle that the ceramic slurry is compressed to deform the core material is selected, a mold capable of keeping the deformation state of the core material and the shape of the slurry is needed, and the periodicity of the final material on the thickness and/or the plane is not uniform.

13. The manufacturing method according to claim 9, characterized in that: in step 7), a second step of sintering,

if the core material is fired at a temperature higher than the temperature used in the first sintering step, a second ramp is used to fire the core, resulting in a porous multifunctional ceramic, periodic or aperiodic, with integrated periodic or aperiodic porosity; the core material of the periodic porous multifunctional ceramic has a periodic cell structure, the cell structures are orderly arranged in a precise periodic mode, and the cell wall of the core is empty; the core material of the aperiodic porous multifunctional ceramic has no periodic cellular structure, and the core material is empty after being sintered;

if the core material is not melted at the final sintering temperature of the ceramic, it retains its structure when the entire material is subjected to standard sintering, which results in a periodic or aperiodic solid non-porous multifunctional ceramic; the periodic non-porous multifunctional ceramic has a core with a periodic compact cell structure, and the cell wall of the core is not empty; the aperiodic, non-porous, multifunctional ceramic has a core of dense material that is not empty.

14. The manufacturing method according to claim 13, characterized in that: in step 7), the obtained porous multifunctional ceramic with periodicity or aperiodicity, the hollow holes left by the core material can be filled with other materials, including but not limited to metal, polymer, piezoelectric material, or materials with additional functions, including but not limited to materials with sensing function;

or, integrating one periodical unit cell core and then integrating the other periodical unit cell core; the result will be a ceramic body with a bi-periodic structure consisting of rigid walls and periodic open pores; the manufacturing process comprises the integration of any core material and the shape of the core cell, and the core material can also be subjected to 3D printing;

alternatively, the metal foam is integrated into the ceramic slurry; in this case, the sintering retains the core and forms a heterogeneous high temperature ceramic metal material with potentially superior impact properties; the core is not periodic and the new ceramic material obtained is a randomly distributed mixture of the two materials metal foam and ceramic material.

15. The manufacturing method according to claim 14, characterized in that: in step 7), the other material may solidify to form a solid structure, or may simply cover the cell walls without completely filling the cavity;

or the other material is a metal or a conductive core taking conductive particles as fillers, and is integrated into a ceramic material with the sintering temperature higher than the melting temperature of the conductive core; when the ceramic solidifies, the core walls melt and the material forming the cell walls will collect at the cell bottom; in this case, a conductive plate having the same shape as the original empty core cell or only the shape of the cell wall will be formed at the bottom of the cell;

alternatively, the other material is a second ceramic slurry; the first manufacturing process produces a ceramic with open periodic porosity that will serve as a mold, and a second ceramic slurry is injected into the pores of the main ceramic body, and the entire material is sintered a second time to crystallize the core.

16. Use of the multifunctional ceramic material of claim 1 for the preparation of:

A) a ceramic foam;

B) a ceramic film;

C) a three-dimensional ceramic metamaterial with high impact strength and high temperature resistance;

D) high impact strength ceramics;

E) a bioceramic;

F) intelligent ceramics;

G) high temperature heat conducting ceramic;

H) air and water filtration system materials;

I) low temperature co-fired ceramic.