CN110028324A - A kind of preparation method of nitride ceramics - Google Patents

A kind of preparation method of nitride ceramics Download PDF

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CN110028324A
CN110028324A CN201910457324.0A CN201910457324A CN110028324A CN 110028324 A CN110028324 A CN 110028324A CN 201910457324 A CN201910457324 A CN 201910457324A CN 110028324 A CN110028324 A CN 110028324A
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nitride ceramics
solvent
solute
preparation
infiltration
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CN110028324B (en
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伍尚华
聂光临
黎业华
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Guangdong University of Technology
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Guangdong University of Technology
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    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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Abstract

The invention belongs to ceramic materials preparation technology field more particularly to a kind of preparation methods of nitride ceramics.The present invention includes: successively to form nitride ceramics mixture and preheating；Pre-burning green body is immersed in non-water base impregnant solution and carries out infiltration processing, is then immersed in precipitant solution and carries out in-situ precipitate；Non- water base impregnant solution includes solute A and solvent A, and solute A is rare earth nitrades and alkaline earth nitrate, and solvent A is organic solvent；Precipitant solution includes solute B and solvent B, and solute B is amine organic matter, and solvent B is organic solvent；Infiltration green body is successively dried, calcined and is sintered, nitride ceramics is obtained.The application solves the technical problem for reducing its thermal conductivity due to hydrolysis and the additionally introducing for oxygen impurities of nitride ceramics powder in tradition infiltration sedimentation, and the in-situ precipitate after infiltrating makes sintering aid dispersing uniformity good, is conducive to the thermal conductivity and reliability that promote nitride ceramics.

Description

A kind of preparation method of nitride ceramics
Technical field
The invention belongs to the preparation technical field of ceramic material more particularly to a kind of preparation methods of nitride ceramics.
Background technique
Nitride ceramics is a kind of important structure and functional material, have good mechanics, chemistry, electricity, calorifics and High-temperature physical property has a wide range of applications in industries such as metallurgy, aviation, chemical industry, ceramics, electronics, machinery and semiconductors.Nitridation Silicon, aluminium nitride are the hot spots of research with application.Wherein, aluminium nitride ceramics has high heat conductance (theoretical thermal conductivity 320Wm-1· K-1), excellent electrical insulation capability, with the similar thermal expansion coefficient of chip materials such as silicon and GaAs, lower dielectric constant and Dielectric loss, nontoxic equal excellent properties, makes the ideal candidates material of ceramic heat-dissipating device in high energy/high-frequency integrated circuit Material, the extensive concern by academia and industrial circle.As the development of science and technology is reformed, for the special-shaped ceramics portion of high thermal conductivity The demand of part is growing, such as: 3-D abnormal ceramic package and radiating element (microchannel base in microelectronics technology Plate), the permanent magnet moment-meter skeleton of strapdown inertial navigation system dynamically tuned gyro, DTG, great power LED allotype insulation radiator Part etc. is required to the ceramic form parts using high thermal conductivity.The theoretical thermal conductivity of silicon nitride ceramics is up to 200-320Wm-1·K-1, and good mechanical performance, bending strength is up to 600-900MPa, and fracture toughness is up to 4-7MPam1/2, it is that high-power half is led The ideal heat-radiating substrate material of body device, in space flight and aviation, electric car, rail traffic, photovoltaic inversion, wind-power electricity generation, intelligence The fields such as power grid, large scale industry automation variable frequency have broad application prospects.
Nitride ceramics is typical covalent key compound, and sintering temperature is usually higher.To have obtained fully dense nitrogen Compound ceramics, are usually added into rare-earth oxide or alkaline earth oxide as sintering aid.Rare-earth oxide or Alkaline earth oxide primarily serves both sides effect as sintering aid: 1. forming liquid phase, promotes the burning of nitride ceramics Knot densification, reduces the sintering temperature of nitride ceramics；2. reacting to form with nitride ceramics powder surface oxide Two-phase is conducive to the thermal conductivity for promoting nitride ceramics to reduce nitride ceramics lattice oxygen content.Currently, rare earth metal Oxide or alkaline earth oxide sintering aid mainly introduce in such a way that mechanical ball mill mixes, and this method is simple, easily In operation, but ball milling mixing easily leads to sintering aid dispersion unevenly, this is to consistency, the thermal conductivity for promoting nitride ceramics It is unfavorable with reliability.And it infiltrates sedimentation nanoscale of the sintering aid in ceramics may be implemented and be uniformly distributed, and aoxidizing It is applied in aluminium, zirconia ceramics preparation, and its rarely seen preparation for being applied to nitride ceramics.This is because current infiltration Sintering aid constituent element is usually prepared into water base impregnant by sedimentation, then by way of ammonia precipitation process, by sintering aid Constituent element is introduced into ceramics.It since nitride ceramics is under aqueous environment, easily hydrolyzes, can then additionally introduce oxygen element, The thermal conductivity of nitride ceramics can be drastically reduced in later period sintering process.If existing infiltration sedimentation is applied to nitride The preparation of ceramics, can to introduce more oxygen element in nitride ceramics, be unfavorable for the promotion of nitride ceramics thermal conductivity.Cause This, it would be highly desirable to a kind of novel infiltration sedimentation is developed, makes the preparation it is suitable for nitride ceramics, is both able to achieve sintering aid It is evenly dispersed, and can to avoid nitride ceramics infiltration precipitation process in hydrolyze.
Summary of the invention
In view of this, the purpose of the application is to provide a kind of non-water base infiltration sedimentation, it is intended to improve sintering aid Dispersing uniformity, and overcome nitride ceramics powder in the water base infiltration sedimentation of tradition that hydrolysis and oxygen impurities easily occur simultaneously The defect additionally introduced, the thermal conductivity and consistency of nitride ceramics can be improved.
The present invention provides a kind of preparation methods of nitride ceramics, comprising the following steps:
Nitride ceramics mixture is successively carried out molding and preheating by step 1, obtains pre-burning green body；
Step 2 will carry out infiltration processing in the non-water base impregnant solution of pre-burning green body immersion, then remove described pre- It after burning the non-water base impregnant solution of remnants of billet surface, then is dipped in precipitant solution and carries out in-situ precipitate, soaked Seep green body；
Wherein, the non-water base impregnant solution includes solute A and solvent A, and the solute A is solvable under non-water environment In the rare earth nitrades or/and alkaline earth nitrate of the solvent A, the solvent A is that can dissolve the solute A under non-water environment Organic solvent；The precipitant solution includes solute B and solvent B, the solute B described molten to dissolve under non-water environment The amine organic matter of agent B, the solvent B are the organic solvent that can dissolve the solute B under non-water environment；
The infiltration green body is successively dried, calcines and sintering processes by step 3, obtains nitride ceramics.
It should be noted that step 1 further includes ungrease treatment according to different forming methods；Degreasing, drying, is forged at pre-burning Burn and sintering processes be this field routine method, according to the raw material of actual product or product need use different moldings, Degreasing, pre-burning, drying, calcining and sintering processing.
It should be noted that the nitride ceramics mixture of step 1 can make pottery according to different forming methods for nitride Porcelain slurry, or nitride ceramics powder mixture.
Specifically, forming method can be forming method for 3D printing, or wet process forming method, it can also be with For dry shaping method, dry shaping method can be the methods of dry-pressing formed, cold isostatic compaction, and the application is not to molding side Method is specifically limited.
Preferably, the nitride of the nitride ceramics mixture is selected from aluminium nitride, silicon nitride, nitridation in step 1 One of boron, gallium nitride, titanium nitride or transition metal nitride.
More preferably, the nitride of the nitride ceramics mixture is selected from aluminium nitride or silicon nitride in step 1.
It should be noted that using this Shen when the nitride of the nitride ceramics mixture is aluminium nitride or silicon nitride The thermal conductivity of aluminium nitride ceramics or silicon nitride ceramics can be improved in preparation method please.
Preferably, the porosity of the pre-burning green body is 20-50% in step 1.
It should be noted that the foundation that the nitridation species of nitride ceramics mixture are selected from are as follows: rare earth nitrades introduce Rare earth oxide and alkaline earth nitrate introduce alkaline earth oxide can be used as its sintering aid；Rare earth oxide helps The uniform introducing of agent is able to ascend its thermal conductivity.
It is furthermore preferred that the nitride of the nitride ceramics mixture is selected from aluminium nitride, the nitride ceramics of the application is mixed Conjunction object be resin matrix aluminium nitride ceramic slurry, resin matrix aluminium nitride ceramic mixture include aluminum nitride ceramic powder, photosensitive resin, Dispersing agent and photoinitiator.Wherein, photosensitive resin is selected from epoxy acrylate, n-butyl acrylate, Isooctyl acrylate monomer, methyl Hydroxy-ethyl acrylate, hydroxy propyl methacrylate, vinylacetate, vinyl pyrrolidone, hexanediyl ester, season penta One in tetra-acrylate, urethane acrylate, neopentylglycol diacrylate or dipentaerythritol hexaacrylate Kind is several；Dispersing agent be selected from BYK AT204,9076 BYK, BYK 9077, BYK P104S, 110 BYK, BYK W9010, SOLSPERSE 8000, SOLSPERSE 17000, SOLSPERSE 24000 are any one or more of, and dispersing agent volume accounts for nitrogen Change the 1.5%~2% of aluminium ceramic powder quality；Photoinitiator be selected from Darocur 1173, TPO, Irgacure 819, Irgacure 184, Irgacure 127, Irgacure 369, Irgacure 907 are any one or more of, photoinitiator Volume accounts for the 0.1%~3% of photosensitive resin quality.
Preferably, the rare earth ion of the rare earth nitrades is selected from Y in step 23+、La3+、Sm3+Or Dy3+It is described non-aqueous Base infiltrates agent solution；The alkaline-earth metal ions of the alkaline earth nitrate are selected from Mg2+Or Ca2+。
Preferably, the concentration of the solute A of the non-water base impregnant solution is 0.1-1.5mol/L in step 2.
Preferably, the solvent A is selected from one of ethyl alcohol, isopropanol, acetone and ether or a variety of in step 2.
More preferably, the non-water base impregnant solution be selected from the ethanol solution of yttrium nitrate, yttrium nitrate aqueous isopropanol, The ethanol solution of lanthanum nitrate, the ethanol solution of samaric nitrate, the acetone soln of samaric nitrate, the ethanol solution of dysprosium nitrate, dysprosium nitrate One of diethyl ether solution, the ethanol solution of magnesium nitrate, the ethanol solution of calcium nitrate or acetone soln of calcium nitrate.
Preferably, the amine organic matter of the solute B is selected from ethylenediamine, diethylamine, triethylamine, triethylene in step 2 One of diamines and monoethanolamine are a variety of.
Preferably, the solvent B is in ethyl alcohol, isopropanol, acetone, ether, toluene and dimethylbenzene in step 2 It is one or more.
More preferably, the precipitant solution is selected from the ethanol solution of ethylenediamine, the acetone soln of ethylenediamine, diethylamine The first of aqueous isopropanol, the ethanol solution of diethylamine, the diethyl ether solution of diethylamine, the ethanol solution of triethylamine, triethylene diamine Benzole soln, the xylene solution of triethylene diamine, the ethanol solution of triethylene diamine, the acetone soln of triethylene diamine, a second One of the ethanol solution of hydramine, acetone soln of monoethanolamine.
It should be noted that the nitride ceramics mixture of the application may be other nitride ceramics mixed materials, The component of other nitride ceramics mixtures can be adjusted according to actual needs, and the application does not make pottery to other nitride and mixes Material repeats one by one.
It should be noted that such as needing using binary or ternary complex sintering aids, unit required for can preparing is non- Water base infiltration agent solution carries out secondary or infiltrates precipitating three times, sintering aid constituent element is successively introduced；Binary or three can also be prepared The non-water base impregnant solution of member carries out primary infiltration precipitating, while binary or ternary sintering aid being introduced.
Specifically, this application provides a kind of specific preparation sides of nitride ceramics based on photocuring 3D forming technique Method, comprising the following steps:
Step A, nitride ceramics slurry is successively formed, degreasing and preheating, obtains pre-burning green body；
Step B, the pre-burning green body is immersed in non-water base impregnant solution and carries out infiltration processing, then removed described pre- It after burning the non-water base impregnant solution of remnants of billet surface, then is dipped in precipitant solution and carries out in-situ precipitate, soaked Seep green body；
Wherein, the non-water base impregnant solution includes solute A and solvent A, and the solute A is solvable under non-water environment In the rare earth nitrades or/and alkaline earth nitrate of the solvent A, the solvent A is that can dissolve the solute A under non-water environment Organic solvent；The precipitant solution includes solute B and solvent B, the solute B described molten to dissolve under non-water environment The amine organic matter of agent B, the solvent B are the organic solvent that can dissolve the solute B under non-water environment；
Step C, the infiltration green body is successively dried, calcined and sintering processes, obtain nitride ceramics.
Wherein, the solid content of the nitride ceramics slurry is more than or equal to 40vol%.
Specifically, the forming technique is photocuring 3D forming technique in step A.(also referred to as 3D is beaten increases material manufacturing technology Print technology) as a kind of emerging molding fabrication techniques, it is solid with single layer based on the 3D printing technique of digital light processing (DLP) Change that speed is fast, formed precision is high, system structure low to ceramic slurry viscosity requirement is simple and the advantages that being easily achieved, in ceramics There is extraordinary application prospect in form parts preparation field.Photocuring 3D forming technique is using digital light processing 3D printing Machine can prepare nitride ceramics form parts using photocuring 3D forming technique, can also prepare nitride ceramics regular portion Part.The optical maser wavelength of the Stereolithography of photocuring 3D forming technique is 250~460nm, and light exposure is 4~100mJ/cm2, beat Printing thickness is 10~50 μm, and the monolayer immobilization time is 1~15s.
It should be noted that the forming technique of the application may be other conventional molding techniques, other forming techniques Operating parameter can be adjusted according to actual needs, and the application does not repeat other forming techniques one by one.
More specifically, this application provides a kind of specific preparations of aluminium nitride ceramics based on photocuring 3D forming technique Method, comprising the following steps:
Step 1: Behavior of Slurry for Aluminum Nitride Ceramics is successively formed, degreasing and preheating, pre-burning green body is obtained；
Infiltration processing is carried out Step 2: the pre-burning green body is immersed in non-water base impregnant solution, then described in removal It after the non-water base impregnant solution of remnants of pre-burning billet surface, then is dipped in precipitant solution and carries out in-situ precipitate, obtain Infiltrate green body；
Wherein, the non-water base impregnant solution includes solute A and solvent A, and the solute A is solvable under non-water environment In the rare earth nitrades and alkaline earth nitrate of the solvent A, the solvent A is that can dissolve the solute A's under non-water environment Organic solvent；The precipitant solution includes solute B and solvent B, the solute B are that the solvent is dissolved under non-water environment The amine organic matter of B, the solvent B are the organic solvent that can dissolve the solute B under non-water environment；
Step 3: the infiltration green body is successively dried, is calcined and sintering processes, aluminium nitride ceramics is obtained.
More preferably, the pH value of the precipitant solution is 10~12.
Preferably, the time of the infiltration processing is 1-24h in step 2, the temperature of the infiltration processing is 25-50 DEG C, the time of the in-situ precipitate is 0.2-4h.
More preferably, in step 1, the step of degreasing successively includes: vacuum degreasing and air degreasing；Vacuum degreasing It is that the green compact of nitride ceramics sizing material forming are placed in vacuum drying oven, 400 are warming up to the rate of heat addition of 0.5~3 DEG C/min~ 600 DEG C, wherein at interval of 100 DEG C of 0.5~2h of heat preservation；After the completion of vacuum degreasing, green body is placed in Muffle furnace, in air atmosphere It is lower to carry out further degreasing except carbon, 400~450 DEG C, and 2~4h of heat preservation are warming up to the rate of heat addition of 0.5~3 DEG C/min, so After cool to room temperature with the furnace, obtain nitride ceramics green body.
More preferably, the preheating is that the nitride ceramics green body after degreasing is placed in atmosphere furnace in step 1, Under flowing nitrogen atmosphere, be warming up to 1400~1600 DEG C with the rate of heat addition of 5~10 DEG C/min, and keep the temperature 1~2h, then with Furnace is cooled to room temperature, and obtains pre-burning green body.
More preferably, the drying temperature is 50~80 DEG C in step 3, drying time is 2~12h.
More preferably, in step 3, the calcination processing technique are as follows: be warming up to 300 with the rate of heat addition of 2~10 DEG C/min ~450 DEG C, and keep the temperature 2~6h, then furnace cooling.
More preferably, in step 3, the sintering process are as follows: 1700 are warming up to the rate of heat addition of 5~10 DEG C/min~ 2000 DEG C, 2~8h is kept the temperature, then furnace cooling obtains aluminium nitride ceramics.
Traditional infiltration agent solution is it is easier that nitride ceramics powder hydrolyzes, to additionally introduce more in the prior art Oxygen impurities, be unfavorable for the preparation of high thermal conductivity nitride ceramics；And oxide sintering aid is introduced by traditional ball-milling technology, it is difficult To realize the evenly dispersed of sintering aid, uneven, thermal conductivity and densification so as to cause nitride ceramics microstructure obtained Degree reduces.Therefore, the present invention provides a kind of preparation methods of high thermal conductivity Nitride features.Traditional infiltration agent solution and precipitating Agent solution is group water solution, is dissolved as solvent to impregnant and precipitating reagent using water, and the invention proposes a kind of non- Water base infiltration precipitation system (including non-water base impregnant solution and non-water base precipitant solution) can avoid nitride ceramics powder Contact and hydrolysis with water avoid additionally introducing for oxygen impurities, and the in-situ precipitate after infiltration realizes the equal of sintering aid Even dispersion, is conducive to the thermal conductivity for promoting aluminium nitride ceramics product, and the nitride ceramics that the preparation method of the application obtains has The advantage that consistency is high, microstructure is uniform, thermal conductivity is high and shape and structure designability is strong.
The application can solve the hydrolysis and oxygen impurities in traditional water base infiltration sedimentation due to nitride ceramics powder Additionally introduce and make its thermal conductivity reduce technical problem, and infiltrate after in-situ precipitate make sintering aid dispersing uniformity Well, the technology that sintering aid uneven dispersion in traditional ball mill mixing technique causes its thermal conductivity and consistency to reduce is overcome Defect.
Present applicant proposes non-water base infiltration sedimentation, it is applicable not only to promote the thermal conductivity of aluminium nitride, silicon nitride ceramics Rate；Other easy preparations for occurring to hydrolyze ceramic (nitride or carbide ceramics) are also applied for, realize uniformly dividing for sintering aid Dissipate the performance (calorifics, electricity, magnetics, mechanical property etc.) for then improving nitride, carbide ceramics.It is all to design according to the present invention Any change made by thought is all within protection scope of the present invention.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described.
Fig. 1 is the process flow chart of the preparation method of nitride ceramics provided by the present application；
Fig. 2 is the work of the preparation method of the nitride ceramics provided by the embodiments of the present application based on photocuring 3D printing technique Skill flow chart；
Specifically:
(1) special-shaped green compact molding: AIN powder, photosensitive resin, dispersing agent and photoinitiator ball milling mixing, preparation are obtained Resin base ceramic slurry carries out Stereolithography using based on photocuring 3D printing technique, aluminium nitride ceramics abnormity green compact is made；
(2) degreasing, pre-burning: carrying out degreasing to obtained aluminium nitride ceramics abnormity green compact, and aluminium nitride ceramics abnormity is made Green body；It is subsequently placed in atmosphere furnace and carries out preheating, aluminium nitride ceramics abnormity pre-burning green body is made；
(3) aluminium nitride ceramics abnormity pre-burning green body obtained infiltration, in-situ precipitate: is placed in the non-water base impregnant of preparation In solution, after infiltration processing 1~for 24 hours, takes out and clean the infiltration agent solution of pre-burning billet surface, be subsequently placed in configured precipitating 0.2~2h of in-situ precipitate is carried out in agent solution, and aluminium nitride ceramics abnormity is made and infiltrates green body；
(4) dry, calcining: aluminium nitride ceramics abnormity obtained infiltration green body is placed in baking oven and is dried, so The aluminium nitride ceramics abnormity infiltration green body after drying is placed in Muffle furnace afterwards and carries out calcination processing, aluminium nitride ceramics abnormity is made Calcine green body；
(5) it is sintered: aluminium nitride ceramics abnormity obtained calcining green body being placed in atmosphere furnace and is sintered densification, is made Aluminium nitride ceramics form parts.
Specific embodiment
The present invention provides a kind of preparation method of nitride ceramics, for solving traditional infiltration sedimentation it is easier that Nitride ceramics powder occurs hydrolysis and additionally introduces the technological deficiency of oxygen impurities, realizes sintering using the in-situ precipitate after infiltration Auxiliary agent it is evenly dispersed, it is intended to improve the thermal conductivity and consistency of nitride ceramics.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.
Wherein, it is commercially available or self-control that embodiments herein is raw materials used.
Embodiment 1
The embodiment of the present application provides the preparation method of the first nitride ceramics, the specific steps are as follows:
1,68 parts by weight aluminum nitride ceramic powders, 32 parts by weight hexanediyl esters, 1 parts by weight BYK 9076 are weighed 0.068 part of 1173 photoinitiator of Darocur is added after ball milling 10h for dispersing agent, continues ball milling 5min, and obtained solid content is The Behavior of Slurry for Aluminum Nitride Ceramics of 40vol%.
2, photocuring 3D printing molding is carried out using photocuring 3D printer, control optical maser wavelength is 250nm, and light exposure is 100mJ/cm2, the monolayer immobilization time is 1s, and printing thickness is 50 μm；According to preset 3 d structure model carry out 3D printing at The aluminium nitride ceramics green compact of abnormity are made in type.
3, aluminium nitride ceramics green compact are placed in vacuum drying oven and carry out ungrease treatment, risen to the rate of heat addition of 0.5 DEG C/min 400 DEG C, wherein at interval of 100 DEG C of heat preservation 2h；After cooling to room temperature with the furnace, vacuum degreasing treated green compact taking-up is placed in In Muffle furnace, 450 DEG C are risen to the rate of heat addition of 3 DEG C/min, and keep the temperature 2h, cool to room temperature with the furnace, aluminium nitride green body is made.
4, aluminium nitride green body is placed in atmosphere furnace and carries out preheating, under flowing nitrogen atmosphere, with 10 DEG C/min's The rate of heat addition rises to 1600 DEG C, and keeps the temperature 1h, then, cools to room temperature with the furnace, obtains pre-burning green body.
5, the Y (NO of 42 parts by weight is utilized3)·6H2O and the dehydrated alcohol of 58 parts by weight prepare Y3+Concentration is 1.5mol/L Non- water base impregnant solution, pre-burning green body is placed in non-water base impregnant solution, 1h is handled under 50 DEG C of infiltration temperatures, takes Out and clean the non-water base impregnant solution of pre-burning billet surface.
6, the ethylenediamine ethanol solution for being 12 by the method secure ph that dehydrated alcohol is added dropwise into ethylenediamine, obtains Precipitant solution, then will infiltration treated that green body is placed in the precipitant solution, take out after in-situ precipitate 2h to get infiltration Green body.
7, infiltration green body obtained is placed in baking oven and is dried, with 80 DEG C of heat treatment 2h, to remove infiltration base Internal remaining alcohol solvent.
8, the aluminium nitride ceramics infiltration green body after drying is placed in Muffle furnace and carries out calcination processing, in air atmosphere, 450 DEG C are risen to the rate of heat addition of 2 DEG C/min, after keeping the temperature 2h, furnace cooling is made aluminium nitride ceramics and calcines green body.
9, aluminium nitride ceramics calcining green body is placed in atmosphere furnace and is sintered, under flowing nitrogen atmosphere, with 10 DEG C/rate of heat addition of min rises to 2000 DEG C, 2h is kept the temperature, then furnace cooling is up to aluminium nitride ceramics component.
The aluminium nitride ceramics component of the present embodiment can be the ceramic component of abnormity, or regular ceramic component. It is 99.8% using the consistency that Archimedes's drainage measures aluminium nitride ceramics component made from the present embodiment, utilizes flicker method The room temperature thermal conductivity measured is 205Wm-1·K-1, that is, it is excellent to illustrate that the aluminium nitride ceramics component obtained of the present embodiment has Heating conduction and compactness.
Embodiment 2
The embodiment of the present application provides the preparation method of second of nitride ceramics, the specific steps are as follows:
1,72 parts by weight aluminum nitride ceramic powders, 12 parts by weight of polyurethane acrylate, 14.6 parts by weight of acrylic acid are weighed 0.8 part of 184 photoinitiator of Irgacure is added in N-butyl, 1.4 parts by weight SOLSPERSE, 8000 dispersing agent, ball milling afterwards for 24 hours, Continue ball milling 10min, the Behavior of Slurry for Aluminum Nitride Ceramics that solid content is 44vol% is made.
2, photocuring 3D printing molding is carried out using photocuring 3D printer, control optical maser wavelength is 460nm, and light exposure is 4mJ/cm2, the monolayer immobilization time is 15s, and printing thickness is 10 μm；According to preset 3 d structure model carry out 3D printing at The aluminium nitride ceramics green compact of abnormity are made in type.
3, aluminium nitride ceramics green compact are placed in vacuum drying oven and carry out ungrease treatment, rise to 600 with the rate of heat addition of 3 DEG C/min DEG C, wherein at interval of 100 DEG C of heat preservation 0.5h；After cooling to room temperature with the furnace, vacuum degreasing treated green compact taking-up is placed in In Muffle furnace, 400 DEG C are risen to the rate of heat addition of 0.5 DEG C/min, and keep the temperature 4h, cool to room temperature with the furnace, aluminium nitride base is made Body.
4, aluminium nitride green body is placed in atmosphere furnace and carries out preheating, under flowing nitrogen atmosphere, with adding for 5 DEG C/min Hot rate rises to 1400 DEG C, and keeps the temperature 2h, then, cools to room temperature with the furnace, obtains pre-burning green body.
5, the Dy (NO of 5.5 parts by weight is utilized3)·6H2O and the dehydrated alcohol of 94.5 parts by weight prepare Dy3+Concentration is The non-water base impregnant solution of 0.1mol/L, pre-burning green body is placed in non-water base impregnant solution, under 25 DEG C of infiltration temperatures The non-water base impregnant solution of pre-burning billet surface is taken out and cleaned to processing for 24 hours,.
6, the ethylenediamine ethanol solution for being 10 by the method secure ph that dehydrated alcohol is added dropwise into diethylamine, obtains Precipitant solution, then will infiltration treated that green body is placed in the precipitant solution, take out after in-situ precipitate 0.2h to get leaching Seep green body.
7, infiltration green body obtained is placed in baking oven and is dried, with 50 DEG C of heat treatment 12h, to remove infiltration base Internal remaining alcohol solvent.
8, the aluminium nitride ceramics infiltration green body after drying is placed in Muffle furnace and carries out calcination processing, in air atmosphere, 300 DEG C are risen to the rate of heat addition of 10 DEG C/min, after keeping the temperature 6h, furnace cooling is made aluminium nitride ceramics and calcines green body.
9, aluminium nitride ceramics calcining green body is placed in atmosphere furnace and is sintered, under flowing nitrogen atmosphere, with 5 DEG C/rate of heat addition of min rises to 600 DEG C, after keeping the temperature 0.5h, 1700 DEG C are risen to the rate of heat addition of 5 DEG C/min, keeps the temperature 8h, so Furnace cooling is afterwards up to aluminium nitride ceramics component.
The aluminium nitride ceramics component of the present embodiment can be the ceramic component of abnormity, or regular ceramic component. It is 98.6% using the consistency that Archimedes's drainage measures aluminium nitride ceramics component made from the present embodiment, utilizes flicker method The room temperature thermal conductivity measured is 168Wm-1·K-1, that is, it is excellent to illustrate that aluminium nitride ceramics component made from the present embodiment has Heating conduction and compactness.
Embodiment 3
The embodiment of the present application provides the preparation method of second of nitride ceramics, the specific steps are as follows:
1,70 parts by weight aluminum nitride ceramic powders, 14 parts by weight pentaerythritol tetraacrylates, 14.9 parts by weight first are weighed 0.3 part of TPO photoinitiator is added after ball milling 12h for base hydroxy-ethyl acrylate, 1.1 parts by weight BYK W9010 dispersing agents, continues ball 8min is ground, the Behavior of Slurry for Aluminum Nitride Ceramics that solid content is 42vol% is made.
2, photocuring 3D printing molding is carried out using photocuring 3D printer, control optical maser wavelength is 460nm, and light exposure is 15mJ/cm2, the monolayer immobilization time is 5s, and printing thickness is 20 μm；According to preset 3 d structure model carry out 3D printing at The aluminium nitride ceramics green compact of abnormity are made in type.
3, aluminium nitride ceramics green compact are placed in vacuum drying oven and carry out ungrease treatment, rise to 500 with the rate of heat addition of 2 DEG C/min DEG C, wherein at interval of 100 DEG C of heat preservation 1h；After cooling to room temperature with the furnace, vacuum degreasing treated green compact taking-up is placed in horse Not in furnace, 420 DEG C are risen to the rate of heat addition of 1 DEG C/min, and keep the temperature 3h, cool to room temperature with the furnace, aluminium nitride green body is made.
4, aluminium nitride green body is placed in atmosphere furnace and carries out preheating, under flowing nitrogen atmosphere, with adding for 8 DEG C/min Hot rate rises to 1500 DEG C, and keeps the temperature 1.5h, then, cools to room temperature with the furnace, obtains pre-burning green body.
5, the Sm (NO of 36 parts by weight is utilized3)·6H2O and the dehydrated alcohol of 64 parts by weight prepare Sm3+Concentration is 1mol/L Non- water base impregnant solution, pre-burning green body is placed in non-water base impregnant solution, handles 12h under 40 DEG C of infiltration temperatures, Take out and clean the non-water base impregnant solution of pre-burning billet surface.
6, the ethylenediamine aqueous isopropanol for being 11 by the method secure ph that isopropanol is added dropwise into diethylamine, obtains Precipitant solution, then will infiltration treated that green body is placed in the precipitant solution, take out after in-situ precipitate 1h to get infiltration Green body.
7, infiltration green body obtained is placed in baking oven and is dried, with 60 DEG C of heat treatment 10h, to remove infiltration base Internal remaining ethyl alcohol and isopropanol solvent.
8, the aluminium nitride ceramics infiltration green body after drying is placed in Muffle furnace and carries out calcination processing, in air atmosphere, 400 DEG C are risen to the rate of heat addition of 5 DEG C/min, after keeping the temperature 4h, furnace cooling is made aluminium nitride ceramics and calcines green body.
9, aluminium nitride ceramics calcining green body is placed in atmosphere furnace and is sintered, under flowing nitrogen atmosphere, with 2 DEG C/rate of heat addition of min rises to 500 DEG C, after keeping the temperature 1h, 1800 DEG C are risen to the rate of heat addition of 8 DEG C/min, keeps the temperature 4h, then Furnace cooling is up to aluminium nitride ceramics component.
The aluminium nitride ceramics component of the present embodiment can be the ceramic component of abnormity, or regular ceramic component. The consistency 99.2% that aluminium nitride ceramics component made from the present embodiment is measured using Archimedes's drainage, is surveyed using flicker method The room temperature thermal conductivity obtained is 182Wm-1·K-1, that is, illustrate that aluminium nitride ceramics component made from the present embodiment has excellent lead Hot property and compactness.
Comparative example 1
This application provides a kind of methods that traditional water base infiltration sedimentation prepares nitride ceramics, and specific steps are such as Under:
1,70 parts by weight aluminum nitride ceramic powders, 14 parts by weight pentaerythritol tetraacrylates, 14.9 parts by weight first are weighed 0.3 part of TPO photoinitiator is added after ball milling 12h for base hydroxy-ethyl acrylate, 1.1 parts by weight BYK W9010 dispersing agents, continues ball It grinds 8min and the Behavior of Slurry for Aluminum Nitride Ceramics that solid content is 42vol% is made.
2, curing molding is carried out using photocuring 3D printer, control optical maser wavelength is 460nm, light exposure 15mJ/ cm2, the monolayer immobilization time is 5s, and printing thickness is 20 μm；3D printing molding is carried out according to preset 3 d structure model, is made The aluminium nitride ceramics green compact of abnormity.
3, aluminium nitride ceramics green compact are placed in vacuum drying oven and carry out ungrease treatment, rise to 500 with the rate of heat addition of 2 DEG C/min DEG C, wherein at interval of 100 DEG C of heat preservation 1h；After cooling to room temperature with the furnace, vacuum degreasing treated green compact taking-up is placed in horse Not in furnace, 420 DEG C are risen to the rate of heat addition of 1 DEG C/min, and keep the temperature 3h, cools to room temperature with the furnace and obtain aluminium nitride green body.
4, aluminium nitride green body is placed in atmosphere furnace and carries out preheating, under flowing nitrogen atmosphere, with adding for 8 DEG C/min Hot rate rises to 1500 DEG C, and keeps the temperature 1.5h, and aluminium nitride ceramics pre-burning green body can be obtained by then cooling to room temperature with the furnace.
5, the Sm (NO of 36 parts by weight is utilized3)·6H2The deionized water of O and 80 parts by weight prepares Sm3+Concentration is 1mol/L Infiltration agent solution, aluminium nitride pre-burning green body is placed in infiltration agent solution, handles 12h under 40 DEG C of infiltration temperatures, is taken out simultaneously Clean the infiltration agent solution of pre-burning billet surface.
6, the ammonia spirit that secure ph is 11, then will infiltration treated that green body is placed in ammonia spirit, it is in situ heavy It is taken out after the 1h of shallow lake and infiltrates green body to get aluminium nitride.
7, aluminium nitride obtained infiltration green body is placed in baking oven, with 60 DEG C of heat treatment 10h, with residual in removal infiltration green body The moisture stayed.
8, the aluminium nitride ceramics infiltration green body after drying is placed in Muffle furnace, in air atmosphere, with adding for 5 DEG C/min Hot rate rises to 400 DEG C, and after keeping the temperature 4h, furnace cooling is made aluminium nitride ceramics and calcines green body.
9, aluminium nitride ceramics calcining green body is placed in atmosphere furnace, under flowing nitrogen atmosphere, with the heating speed of 2 DEG C/min Rate rises to 500 DEG C, after keeping the temperature 1h, rises to 1800 DEG C with the rate of heat addition of 8 DEG C/min, keeps the temperature 4h, then furnace cooling is up to nitrogen Change aluminium ceramic component.
This comparative example the difference from embodiment 1 is that, this comparative example use Sm (NO3)·6H2The aqueous solution of O is impregnant Solution, ammonia spirit are precipitant solution.The cause of aluminium nitride ceramics made from this comparative example is measured using Archimedes's drainage Density is 98.8%, and the room temperature thermal conductivity measured using flicker method is only 68Wm-1·K-1, illustrate conventional method using aqueous Infiltration agent solution and precipitant solution, rare earth nitrades are deposited in the hole of pre-burning green body, due to infiltration agent solution and Precipitant solution contains moisture, so that pre-burning green body easily hydrolyzes in infiltration precipitating and the drying process in later period, thus Additional oxygen is introduced in aluminium nitride ceramics, causes the thermal conductivity of aluminium nitride ceramics obtained lower.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. a kind of preparation method of nitride ceramics, which comprises the following steps:
Nitride ceramics mixture is successively carried out molding and preheating by step 1, obtains pre-burning green body；
Step 2 will carry out infiltration processing in the non-water base impregnant solution of pre-burning green body immersion, then remove the presintered compact It after the non-water base impregnant solution of remnants in body surface face, then is dipped in precipitant solution and carries out in-situ precipitate, obtain infiltration base Body；
Wherein, the non-water base impregnant solution includes solute A and solvent A, and the solute A is dissolves in institute under non-water environment The rare earth nitrades or/and alkaline earth nitrate of solvent A are stated, the solvent A is that can dissolve having for the solute A under non-water environment Solvent；The precipitant solution includes solute B and solvent B, the solute B are that the solvent B is dissolved under non-water environment Amine organic matter, the solvent B is the organic solvent that can dissolve the solute B under non-water environment；
The infiltration green body is successively dried, calcines and sintering processes by step 3, obtains nitride ceramics.
2. preparation method according to claim 1, which is characterized in that in step 1, the nitrogen of the nitride ceramics mixture Compound is selected from one of aluminium nitride, silicon nitride, boron nitride, titanium carbonitride or transition metal nitride.
3. preparation method according to claim 1, which is characterized in that in step 1, the porosity of the pre-burning green body is 20-50%.
4. preparation method according to claim 1, which is characterized in that in step 1, the forming technique be photocuring 3D at Type technology.
5. the preparation method according to claim 4, which is characterized in that in step 2, the non-water base impregnant solution it is molten The concentration of matter A is 0.1-1.5mol/L.
6. preparation method according to claim 1, which is characterized in that in step 2, the rare earth ion of the rare earth nitrades Selected from Y3+、La3+、Sm3+Or Dy3+, the alkaline-earth metal ions of the alkaline earth nitrate are selected from Mg2+Or Ca2+。
7. preparation method according to claim 1, which is characterized in that in step 2, the solvent A is selected from ethyl alcohol, isopropyl One of alcohol, acetone and ether are a variety of.
8. preparation method according to claim 1, which is characterized in that in step 2, the amine organic matter of the solute B is selected From one of ethylenediamine, diethylamine, triethylamine, triethylene diamine and monoethanolamine or a variety of.
9. preparation method according to claim 1, which is characterized in that in step 2, the solvent B is selected from ethyl alcohol, isopropyl One of alcohol, acetone, ether, toluene and dimethylbenzene are a variety of.
10. preparation method according to claim 1, which is characterized in that in step 2, the time of the infiltration processing is 1- For 24 hours, the temperature of the infiltration processing is 25-50 DEG C, and the time of the in-situ precipitate is 0.2-4h.
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