CN107365155B - Low-temperature sintering aid system of aluminum nitride ceramic - Google Patents
Low-temperature sintering aid system of aluminum nitride ceramic Download PDFInfo
- Publication number
- CN107365155B CN107365155B CN201710503152.7A CN201710503152A CN107365155B CN 107365155 B CN107365155 B CN 107365155B CN 201710503152 A CN201710503152 A CN 201710503152A CN 107365155 B CN107365155 B CN 107365155B
- Authority
- CN
- China
- Prior art keywords
- aluminum nitride
- sintering aid
- low
- aid system
- temperature sintering
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/581—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on aluminium nitride
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3239—Vanadium oxides, vanadates or oxide forming salts thereof, e.g. magnesium vanadate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Products (AREA)
Abstract
The invention relates to a low-temperature sintering aid system of aluminum nitride ceramics, which comprises a component A and a component B; the component A is TiO2、ZrO2、HfO2At least one of; the component B is V2O5、Nb2O5、Ta2O5At least one of (1). Compared with the scheme reported in the literature at present, the scheme of the sintering aid provided by the invention can realize the densification process of the material in a shorter time, has simple and reliable process and can obtain higher thermal conductivity.
Description
Technical Field
The invention provides a sintering aid system which is low in sintering temperature, short in heat preservation time and capable of effectively realizing densification, and aims at solving the problems of high sintering temperature, long sintering time and high cost of aluminum nitride ceramics, and belongs to the field of preparation processes and application of ceramics.
Background
With the development of modern technologies, especially the development of electronic packaging technology, the increase of integration level of power electronic devices, and the application of LED lighting, heat dissipation becomes a key problem to be solved urgently. If the generated heat cannot be dissipated in time, the temperature of the semiconductor chip can be raised, so that the performance of an electronic device is unstable, or the junction temperature of the LED is raised, so that the luminous efficiency is reduced, and the service life is shortened. The heat dissipation problem has become a key to restrict the application of power electronic components and high-power LEDs. A commonly used substrate material is Al2O3BeO, SiC and AlN. A12O3The ceramic is the most mature ceramic substrate material at present, has low price, good thermal shock resistance and electrical insulation performance and mature manufacturing and processing technology, thereby being widely used and accounting for 90 percent of the ceramic substrate material. However, Al2O3The thermal conductivity of the LED is only about 22-28W/m.K, and the LED can not meet the heat dissipation requirement of a high-power LED. Silicon carbide (SiC) ceramics have high thermal conductivity and a thermal expansion coefficient most similar to that of Si, but have poor insulation properties and are difficult to sinterTo produce a dense product. Although a high thermal conductivity SiC substrate (270W/m.K) can be obtained by adding a small amount of beryllium oxide sintering aid and adopting a hot-pressing sintering method, the loss is large, the hot-pressing cost is high, and the development and the large-scale application of the high thermal conductivity SiC substrate are limited. BeO ceramic is a ceramic substrate material with the best heat conducting property at present, the comprehensive dielectric property of the ceramic substrate material is good, but the heat conductivity of the ceramic substrate material is greatly reduced along with the temperature rise, in addition, the BeO has high toxicity, the use of the ceramic substrate material is limited, the BeO production is not allowed in Japan at present, and the BeO-containing electronic products are also limited in Europe.
AlN ceramic is a novel packaging material which is well seen by experts at home and abroad, and has excellent electric heating performance. Compared with aluminum oxide, the aluminum nitride has high thermal conductivity which is 5-10 times that of the aluminum oxide, and is suitable for high-power, high-lead and large-size chips; the thermal expansion coefficient of the material is matched with that of silicon, and the dielectric constant is lower; the material has high mechanical strength. The AlN ceramic has great development potential as a high thermal conductivity and high sealing material, and is an important development direction for the research of ceramic packaging materials. It is expected that AlN ceramics will eventually replace the present Al in both the substrate and package areas2O3And BeO ceramics.
However, the aluminum nitride powder has high cost and is difficult to sinter, so that the cost of the aluminum nitride substrate is high, and the low-cost and mass application requirements of the LED industry cannot be met. The price of the aluminum nitride powder produced in China at present is low, although the oxygen content is high, the application requirement of the LED can be met, and the key problem is to reduce the sintering cost.
The aluminum nitride ceramic is non-oxide ceramic, and pure aluminum nitride is difficult to sinter and compact at high temperature, and a sintering aid is usually required to be added. The sintering aid mainly has the functions of reacting with aluminum oxide on the surface of aluminum nitride in the sintering process to generate a low-melting-point composite oxide, generating a liquid phase to surround aluminum nitride powder, achieving the purposes of wetting, pasting, tensioning and surface activation, and promoting the densification of a blank; secondly, the liquid phase is uniformly distributed near the aluminum nitride crystal boundary and the triple point to form an oxygen trap which can capture the oxygen in the aluminum nitride and segregate at the triple point after cooling, so that the aluminum nitride crystal grains can be in close contact, thereby achieving the improvementThe purpose of the thermal conductivity of the aluminum nitride ceramic. The conventional AlN ceramic sintering aid mainly comprises Y2O3、CaO、Er2O3、Yb2O3、Sm2O3、Dy2O3、Li2O、B2O3、CaF2、YF3、CaC2And the like or mixed use, not only can effectively promote the sintering of the AlN powder, but also is beneficial to improving the heat conductivity of the sintered product. However, the sintering temperature is 1700-1850 ℃, the heat preservation time is long, and the sintering cost is high. The development of LEDs, especially in the field of civil lighting, requires a continuous cost reduction, at a cost level comparable to that of the current fluorescent or incandescent lamps, just to be marketed. Cost issues are currently a key factor limiting the application of aluminum nitride substrates in the LED field.
The low-temperature sintering can effectively reduce the sintering cost and is one of the focuses of domestic and foreign concerns. There have been a number of literature reports. A commonly used sintering aid system has Y2O3And CaO or Y2O3，CaO，Li2O, it is also possible to use other rare earth oxides such as Dy2O3Substituted Y2O3With CaF2Substituted for CaO by Li2CO3Substituted Li2O, and the like. These sintering aid systems often require long heat preservation time, and after the introduction of Ca, the Ca can generate a liquid phase with alumina, so that the Ca has good wettability on AlN particles, which often causes serious reduction of thermal conductivity, and even more, the cost cannot be effectively reduced.
Disclosure of Invention
Aiming at the problems, the invention provides a low-temperature sintering aid system for aluminum nitride ceramics, which comprises a component A and a component B;
the component A is TiO2、ZrO2、HfO2Preferably TiO2、ZrO2、HfO2One of (1);
the component B is V2O5、Nb2O5、Ta2O5At least one of (a) and (b),preferably V2O5、Nb2O5、Ta2O5One kind of (1).
The invention provides a novel sintering aid system based on long-term sintering research of aluminum nitride ceramics. Adopts a binary component, the component A contains TiO2，ZrO2，HfO2At least one of; the component B contains V2O5，Nb2O5，Ta2O5At least one of (1). The combination of the two is used as a sintering aid, wherein the sintering aid system can form a liquid phase at a lower temperature, the liquid phase is used for promoting sintering, meanwhile, the sintering aid system reacts with oxygen impurities to form aluminate, a second phase is precipitated during cooling, and oxygen is consolidated on a grain boundary by using the second phase, so that the oxygen content of a sintered body is reduced, and the thermal conductivity of the aluminum nitride ceramic is improved.
Preferably, the mass ratio of the component A to the component B is 1: (1-5). When the value is within the range, the viscosity of a grain boundary phase is favorably reduced, low-temperature sintering is promoted, and the thermal conductivity of the aluminum nitride ceramic is ensured.
Preferably, the particle size distribution of the low-temperature sintering aid system is 50 nm-50 microns.
On the other hand, the invention also provides a preparation method of the aluminum nitride ceramic, which comprises the following steps:
dissolving aluminum nitride powder and the warm sintering aid system in an organic solvent, adding a dispersing agent, a binder and a plasticizer, and uniformly mixing to prepare a blank, wherein the mass ratio of the aluminum nitride powder to the low sintering aid system is (90-95): (5-10);
and calcining the obtained blank at 1600-1700 ℃ for 1-12 hours to obtain the aluminum nitride ceramic.
Specifically, the low-temperature sintering aid provided by the invention has the following characteristics. Firstly, the sintering aid cannot enter aluminum nitride crystal lattices in a solid solution manner, so that the serious reduction of the thermal conductivity of the aluminum nitride caused by the solid solution is avoided; secondly, the sintering aid system can generate a low-temperature liquid phase in the sintering process, effectively moisten the surfaces of the aluminum nitride ceramic particles, promote particle rearrangement and the sintering process, and reduce the sintering temperature (1600-1700 ℃); the densification process can also be achieved in a shorter time (1-2 hours). In addition, after sintering, the sintering aid and the aluminum nitride particles have poor wettability and are easy to retract to a three-way crystal boundary position, so that aluminum nitride crystal grains can be ensured to be contacted with each other, and conditions are created for controlling the thermal conductivity of the aluminum nitride ceramic. Therefore, the sintering aid system provided by the invention can realize the densification process of the aluminum nitride ceramic in a shorter time, and lays a foundation for the preparation of the high-thermal-conductivity aluminum nitride ceramic system.
Preferably, the organic solvent is at least one of ethanol, butanone, toluene, n-hexane, methanol, xylene, n-propanol and n-butanol, preferably ethanol/butanone, ethanol/toluene, ethanol/n-hexane, butanone/methanol, xylene/n-propanol or xylene/n-butanol, and the addition amount is 15-30 wt% of the total mass of the aluminum nitride powder and the low-temperature sintering aid system.
Preferably, the dispersant is at least one of triolein, phosphate ester, castor oil herring oil, ascorbic acid and terpineol, and the addition amount of the dispersant is 0.5-4 wt% of the total mass of the aluminum nitride powder and the low-temperature sintering aid system.
Preferably, the binder is polyvinyl butyral or/and polymethyl methacrylate, and the addition amount of the binder is 6-9 wt% of the total mass of the aluminum nitride powder and the low-temperature sintering aid system.
Preferably, the plasticizer is dibutyl phthalate DBP or/and dibutyl benzyl phthalate BBP, and the adding amount is 7-12 wt% of the total mass of the aluminum nitride powder and the low-temperature sintering aid system.
Preferably, the temperature rise rate of the calcination is 1-15 ℃/min. Preferably, the particle size of the aluminum nitride powder is 100 nm-10 μm.
In still another aspect, the present invention also provides an aluminum nitride ceramic prepared according to the above method.
Compared with the scheme reported in the literature at present, the scheme of the sintering aid provided by the invention can realize the densification process of the material in a shorter time, has simple and reliable process and can obtain higher thermal conductivity. Thereby greatly reducing the sintering cost. The invention is suitable for low-temperature sintering of aluminum nitride ceramics, and can meet the requirements of industry, aviation, aerospace, national defense and the like. The system can realize the sintering of the aluminum nitride ceramic at relatively low temperature in a short time, and the compactness reaches more than 99 percent.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
Aiming at the problem of high sintering cost of the aluminum nitride ceramic substrate, the invention provides a novel low-temperature sintering aid system for aluminum nitride ceramic in order to further shorten the sintering time and reduce the sintering cost. The sintering aid comprises two components: component A and component B. The sintering aid component A is transition element oxide comprising TiO2、ZrO2、HfO2And the like. The sintering aid component B is a high-valence transition element oxide comprising V2O5、Nb2O5、Ta2O5And the like. Wherein the weight ratio of the component A to the component B can be 1:1 to 1: 5. The particle size of the two sintering aids (component a and component B) is from 50nm to 50 microns. In general, the sintering aid system for low-temperature sintering of aluminum nitride ceramics adopts low-cost bi-component transition metal oxide as a composite sintering aid system, and the liquid phase is generated at low temperature to promote the mass transfer process and achieve densification. And the liquid phase can generate a crystalline phase after sintering, so that the influence on the thermal conductivity of the ceramic is small. The low-temperature sintering aid system provided by the invention is low in cost, can effectively realize low-temperature sintering of the aluminum nitride ceramic, and has small influence on the thermal performance of the final aluminum nitride ceramic. The method is suitable for the preparation of low-cost aluminum nitride ceramic substrates and the application in the field of LEDs.
The low-temperature sintering scheme provided by the invention has the advantages of simple and reliable process, low cost and easiness in operation. Is suitable for low-temperature sintering of aluminum nitride ceramics. The following is an exemplary description of the method for preparing the aluminum nitride ceramic provided by the present invention.
Pottery (porcelain)Mixing the porcelain powder with a sintering aid, and dispersing in an organic solvent. Specifically, aluminum nitride powder and the low-temperature sintering aid system are dissolved in an organic solvent, then a dispersing agent, a binder and a plasticizer are added and uniformly mixed to prepare a blank, and the mass ratio of the aluminum nitride powder to the low-temperature sintering aid system can be (90-95): (5-10). The low-temperature sintering aid system provided by the invention comprises a component A (TiO)2、ZrO2、HfO2Etc.) and component B (V)2O5、Nb2O5、Ta2O5Etc.). The weight ratio of component a to component B may be from 1:1 to 1: 5. The particle size of the aluminum nitride powder can be 100 nm-10 mu m. In addition, the method for forming the blank includes, but is not limited to, casting, dry pressing, cold isostatic pressing, gel casting, and the like.
In the present invention, the organic solvent may be at least one of ethanol, butanone, toluene, n-hexane, methanol, xylene, n-propanol, and n-butanol, and preferably ethanol/butanone, ethanol/toluene, ethanol/n-hexane, butanone/methanol, xylene/n-propanol, or xylene/n-butanol. The addition amount of the aluminum nitride powder can be 15-30 wt% of the total mass of the aluminum nitride powder and the low-temperature sintering aid system.
In the invention, the commonly used dispersing agent is triolein, phosphate ester, castor oil herring oil, ascorbic acid, terpineol and the like, and the addition amount of the dispersing agent can be 0.5-4 wt% of the total mass of the aluminum nitride powder and the low-temperature sintering aid system.
In the invention, the common binder comprises polyvinyl butyral, polymethyl methacrylate and the like, and the addition amount of the binder can be 6-9 wt% of the total mass of the aluminum nitride powder and the low-temperature sintering aid system.
In the invention, common plasticizers include dibutyl phthalate (DBP) and dibutyl phthalate (BBP), and the addition amount of the plasticizers can be 7-12 wt% of the total mass of the aluminum nitride powder and the low-temperature sintering aid system.
And calcining the obtained blank at 1600-1700 ℃ for 1-12 hours to obtain the aluminum nitride ceramic. The temperature rise rate of the calcination is 1-15 ℃/min.
Hair brushThe density of the aluminum nitride ceramic is measured to be 99-99.5% by adopting an Archimedes drainage method. The thermal conductivity of the alumina ceramic measured by a laser thermal conductivity meter is 130-160 W.m-1·K-1。
The invention provides a method for adopting a low-temperature sintering aid to reduce the sintering cost, and the compact aluminum nitride ceramic can be obtained by sintering in the temperature range of 1600-1700 ℃. Compared with the common low-temperature sintering aid reported at home and abroad, the sintering aid can realize the densification of the material in a relatively short time by adopting a rapid sintering method, thereby greatly reducing the sintering cost and creating conditions for the application of the AlN ceramic substrate.
The present invention will be described in further detail with reference to examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. Unless otherwise specified, the particle size of the aluminum nitride powder in the following examples is generally 100nm to 10 μm. The particle size distribution of the low-temperature sintering aid system is 50 nm-50 microns.
Example 1
95g of aluminum nitride powder, 5g of sintering aid titanium oxide and vanadium oxide are added into a 21g ethanol/butanone solvent system (the mass ratio of ethanol to acetone is 40: 60), and the ratio of titanium oxide to vanadium oxide is 1: 1. 2g of triolein is adopted as a dispersing agent, 8g of PVB is added as a binder after ball milling, 8g of DBP is used as a plasticizer, defoaming and casting are carried out after ball milling again, and a casting film with the thickness of 0.15-0.2mm is prepared. Sintering the casting film in a carbon tube furnace after debonding, wherein the temperature rise rate reaches 1650 ℃ at 5 ℃/min, and the sintering is realized by heat preservation for 2 h. A dense, integral aluminum nitride substrate can be obtained.
Example 2
94g of aluminum nitride powder, 6g of sintering aid titanium oxide and niobium oxide were added in 21g of an ethanol/toluene solvent system (ethanol to toluene mass ratio 40: 60) with a ratio of titanium oxide to niobium oxide of 1: 2. 2.5g of phosphate ester is adopted as a dispersing agent, 8.5g of PVB is added as a binder after ball milling, 9g of DBP is used as a plasticizer, defoaming and casting are carried out after ball milling again, and a casting film with the thickness of 0.15-0.2mm is prepared. Sintering the casting film in a carbon tube furnace after debonding, wherein the temperature rise rate reaches 1650 ℃ at 5 ℃/min, and the sintering is realized by heat preservation for 2 h. A dense, integral aluminum nitride substrate can be obtained.
Example 3
93g of aluminum nitride powder, 7g of sintering aid titanium oxide and tantalum oxide were added in a 21g ethanol/n-hexane solvent system (the mass ratio of ethanol to n-hexane was 50: 50), and the ratio of titanium oxide to tantalum oxide was 1: 3. Adopting 2.0g of castor oil as a dispersing agent, adding 9g of PVB as a binder and 10g of DBP as a plasticizer after ball milling, defoaming and casting after ball milling again, and preparing a casting film with the thickness of 0.15-0.2 mm. Sintering the casting film in a carbon tube furnace after debonding, reaching 1650 ℃ at the heating rate of 5 ℃/min, and preserving heat for 2h to realize sintering. A dense, integral aluminum nitride substrate can be obtained.
Example 4
92g of aluminum nitride powder, 8g of sintering aid, namely zirconium oxide and niobium oxide are added into a 21g butanone/methanol solvent system (the mass ratio of butanone to methanol is 50: 50), and the ratio of the zirconium oxide to the niobium oxide is 1: 4. Adopting 2g of ascorbic acid as a dispersing agent, adding 7.5g of PVB as a binder and 8.5g of BBP as a plasticizer after ball milling, defoaming and casting after ball milling again, and preparing a casting film with the thickness of 0.15-0.2 mm. Sintering the casting film in a carbon tube furnace after debonding, and preserving heat for 2h at a temperature rise rate of 5 ℃/min to 1650 ℃ to realize sintering. A dense, integral aluminum nitride substrate can be obtained.
Example 5
90g of aluminum nitride powder, 10g of sintering aid hafnium oxide and niobium oxide are added into a 21g xylene/n-propanol solvent system (the mass ratio of xylene to n-propanol is 50: 50), and the ratio of hafnium oxide to niobium oxide is 1: 5. 1.8g of triolein is adopted as a dispersing agent, 8.5g of PVB is added as a bonding agent after ball milling, 10g of BBP is used as a plasticizer, defoaming and casting are carried out after ball milling again, and a casting film with the thickness of 0.15-0.2mm is prepared. Sintering the casting film in a carbon tube furnace after debonding, wherein the temperature rise rate reaches 1650 ℃ at 5 ℃/min, and the sintering is realized by heat preservation for 2 h. A dense, integral aluminum nitride substrate can be obtained.
Table 1 shows the preparation and performance parameters of the aluminum nitride substrates obtained in examples 1 to 5 of the present invention:
Claims (8)
1. a method for preparing aluminum nitride ceramics is characterized by comprising the following steps:
dissolving aluminum nitride powder and a low-temperature sintering aid system in an organic solvent, adding a dispersing agent, a binder and a plasticizer, and uniformly mixing to prepare a blank, wherein the mass ratio of the aluminum nitride powder to the low-temperature sintering aid system is (90-95): (5-10), wherein the low-temperature sintering aid system comprises a component A and a component B; the component A is TiO2、ZrO2、HfO2At least one of (A) and (B), the component B is V2O5、Nb2O5、Ta2O5At least one of; the mass ratio of the component A to the component B is 1: (1-5);
calcining the obtained blank at 1600-1650 ℃ for 1-12 hours to obtain aluminum nitride ceramic; the aluminum nitride ceramic has a density of 99-99.5% and a thermal conductivity of 130-160 W.m-1·K-1。
2. The method of claim 1, wherein the low temperature sintering aid system has a particle size distribution of 50nm to 50 μm.
3. The method according to claim 1, wherein the aluminum nitride powder has a particle size of 100nm to 10 μm;
the organic solvent is at least one of ethanol, butanone, toluene, n-hexane, methanol, xylene, n-propanol and n-butanol, and the addition amount of the organic solvent is 15-30 wt% of the total mass of the aluminum nitride powder and the low-temperature sintering aid system.
4. The preparation method according to claim 1, wherein the dispersant is at least one of triolein, phosphate, castor oil herring oil, ascorbic acid and terpineol, and the addition amount is 0.5 to 4wt% of the total mass of the aluminum nitride powder and the low-temperature sintering aid system.
5. The preparation method according to claim 1, wherein the binder is polyvinyl butyral or/and polymethyl methacrylate, and the addition amount is 6-9 wt% of the total mass of the aluminum nitride powder and the low-temperature sintering aid system.
6. The preparation method according to claim 1, wherein the plasticizer is dibutyl phthalate (DBP) or/and dibutyl phthalate (BBP), and the addition amount is 7-12 wt% of the total mass of the aluminum nitride powder and the low-temperature sintering aid system.
7. The production method according to any one of claims 1 to 6, wherein the temperature increase rate of the calcination is 1 to 15 ℃/min.
8. An aluminum nitride ceramic prepared according to the method of any one of claims 1 to 7, wherein the aluminum nitride ceramic has a density of 99 to 99.5% and a thermal conductivity of 130 to 160W-m-1·K-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710503152.7A CN107365155B (en) | 2017-06-27 | 2017-06-27 | Low-temperature sintering aid system of aluminum nitride ceramic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710503152.7A CN107365155B (en) | 2017-06-27 | 2017-06-27 | Low-temperature sintering aid system of aluminum nitride ceramic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107365155A CN107365155A (en) | 2017-11-21 |
| CN107365155B true CN107365155B (en) | 2020-09-18 |
Family
ID=60305159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710503152.7A Active CN107365155B (en) | 2017-06-27 | 2017-06-27 | Low-temperature sintering aid system of aluminum nitride ceramic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107365155B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109896865B (en) * | 2017-12-08 | 2021-05-25 | 中国科学院上海硅酸盐研究所 | Method for improving toughness of aluminum oxide ceramic |
| CN108947539B (en) * | 2018-09-11 | 2021-05-25 | 中国科学院上海硅酸盐研究所 | Silicon nitride ceramic material for mobile phone back plate and preparation method thereof |
| CN112939617B (en) * | 2021-03-11 | 2022-10-21 | 北京理工大学 | Method for screening functional ceramic sintering aid |
| CN113773091B (en) * | 2021-08-11 | 2023-10-24 | 臻金新材(深圳)有限公司 | Aluminum nitride ceramic casting slurry, aluminum nitride ceramic substrate and preparation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4786448A (en) * | 1985-08-29 | 1988-11-22 | Toshiba Tunglogy Co., Ltd. | Plastic processing method of pressure or pressureless sintered ceramic body |
| CN1269384C (en) * | 2000-01-13 | 2006-08-09 | 住友电气工业株式会社 | Ceramic heater |
| CN101113096A (en) * | 2006-07-28 | 2008-01-30 | 通用电气公司 | Presintering process for reducing inequality in density of sintered material |
| CN102239227A (en) * | 2008-12-03 | 2011-11-09 | 奥斯兰姆施尔凡尼亚公司 | Sealing composition for sealing aluminum nitride and aluminum oxynitride ceramics |
| CN106380207A (en) * | 2015-12-07 | 2017-02-08 | 蒋宏凯 | Preparation method for aluminum nitride substrate |
-
2017
- 2017-06-27 CN CN201710503152.7A patent/CN107365155B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4786448A (en) * | 1985-08-29 | 1988-11-22 | Toshiba Tunglogy Co., Ltd. | Plastic processing method of pressure or pressureless sintered ceramic body |
| CN1269384C (en) * | 2000-01-13 | 2006-08-09 | 住友电气工业株式会社 | Ceramic heater |
| CN101113096A (en) * | 2006-07-28 | 2008-01-30 | 通用电气公司 | Presintering process for reducing inequality in density of sintered material |
| CN102239227A (en) * | 2008-12-03 | 2011-11-09 | 奥斯兰姆施尔凡尼亚公司 | Sealing composition for sealing aluminum nitride and aluminum oxynitride ceramics |
| CN106380207A (en) * | 2015-12-07 | 2017-02-08 | 蒋宏凯 | Preparation method for aluminum nitride substrate |
Non-Patent Citations (2)
| Title |
|---|
| Nb2O5对氧化铝陶瓷烧结性能和显微结构的影响;刘于昌 等;《福州大学学报（自然科学版）》;20061031;第34卷(第5期);第708-711页 * |
| 低温烧结氮化铝陶瓷烧结助剂的研究进展;王超 等;《粉末冶金技术》;20090228;第27卷(第1期);第62-66页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107365155A (en) | 2017-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109400175B (en) | Preparation method of high-thermal-conductivity silicon nitride ceramic substrate material | |
| CN107365155B (en) | Low-temperature sintering aid system of aluminum nitride ceramic | |
| JP6591455B2 (en) | High thermal conductivity silicon nitride sintered body, silicon nitride substrate, silicon nitride circuit substrate and semiconductor device using the same | |
| JP2013032265A (en) | Alumina zirconia sintered board for semiconductor device and manufacturing method therefor | |
| KR102270157B1 (en) | Aluminum oxynitride ceramic heater and method for preparing the same | |
| CN101734923A (en) | Aluminum nitride porous ceramic and preparation method thereof | |
| CN111285692A (en) | High-thermal-conductivity Si3N4Ceramic and preparation method thereof | |
| CN115028461A (en) | Method for preparing high-thermal-conductivity silicon nitride ceramic substrate through silicon powder tape casting | |
| CN108863395B (en) | High-thermal-conductivity and high-strength silicon nitride ceramic material and preparation method thereof | |
| CN113213894A (en) | High-purity alumina ceramic substrate and preparation process thereof | |
| CN115028460A (en) | Preparation method of high-thermal-conductivity silicon nitride ceramic substrate | |
| JP4571728B2 (en) | Silicon nitride sintered body and manufacturing method thereof | |
| CN112028636A (en) | Preparation method of high-thermal-conductivity aluminum nitride/graphene composite ceramic device | |
| WO2020059035A1 (en) | Aluminum nitride sintered compact and method for producing same | |
| CN109592983B (en) | High-thermal-conductivity liquid-phase sintered silicon carbide ceramic and preparation method thereof | |
| JP6284609B2 (en) | Aluminum nitride sintered body | |
| KR20190032966A (en) | Tape casting slurry composition for manufacturing silicon nitride sintered body | |
| JP2018184316A (en) | Aluminum nitride sintered body and manufacturing method thereof | |
| JP6062912B2 (en) | Aluminum nitride sintered body and manufacturing method thereof | |
| JP2742600B2 (en) | Aluminum nitride sintered body and method for producing the same | |
| JP3683067B2 (en) | Aluminum nitride sintered body | |
| CN109336609A (en) | One kind is highly thermally conductive, be electrically insulated liquid phase sintering silicon carbide ceramic and its SPS preparation process | |
| JP2002029851A (en) | Silicon nitride composition, method for manufacturing sintered silicon nitride compact using the same and sintered silicon nitride compact | |
| JPH10251069A (en) | Silicon nitride circuit board and semiconductor device | |
| JP4868641B2 (en) | Method for manufacturing aluminum nitride substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |