CN104230344A - Low-temperature sintering preparation method of AlN ceramic added with multi-element sintering aid - Google Patents
Low-temperature sintering preparation method of AlN ceramic added with multi-element sintering aid Download PDFInfo
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- CN104230344A CN104230344A CN201410428584.2A CN201410428584A CN104230344A CN 104230344 A CN104230344 A CN 104230344A CN 201410428584 A CN201410428584 A CN 201410428584A CN 104230344 A CN104230344 A CN 104230344A
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Abstract
The invention discloses a low-temperature sintering preparation method of AlN ceramic added with a multi-element sintering aid. The method comprises the following steps: by taking AlN powder as a raw material, adding two or more rear earth metal compounds and one or two alkaline earth metal compounds into the raw material to form the multi-element sintering aid, wherein the average particle size of the AlN powder is 1.1-1.5 microns, and the specific surface area is 2.8-3.2m<2>/g; uniformly mixing the multi-element sintering aid with the AlN powder raw material, after drying, adding a solid paraffin plasticizer, pelletizing, pressing and forming, performing heat preservation at 580-600 DEG C for 20-30 minutes, and sintering at a temperature of 1600-1750 DEG C for 2-6 hours to obtain an AlN ceramic material and a product in a protective atmosphere of N2 after discharging glue. The method disclosed by the invention can be used for greatly lowering the sintering temperature of the AlN ceramic and greatly improving the low-temperature sintering compaction degree of the AlN ceramic. And the prepared AlN ceramic and the product have excellent performances, uniform microstructures and fine crystalline grains.
Description
technical field:
The technology of the present invention relates to ceramic materials preparation technology field, specifically a kind of low-temperature melt producing method of AlN ceramic material of excellent property, and it is mainly used in Electronic Packaging pottery.
background technology:
Along with the development of microelectronics, the raising of electronic system integrated level causes the raising of power density, and the heat thus produced during its work increases.Traditional Al
2o
3ceramic substrate material has been difficult to meet the requirement of electronic packaging industry to the more and more higher heat dissipation performance of substrate, and AlN ceramic to have thermal conductance high, heat dissipation ability is strong, there is thermal expansivity in addition that match with Si and GaAs semiconducter device, good insulating, dielectric properties height waits feature performance benefit, and be widely used in the numerous areas such as electronics, metallurgy, machinery, military project, prospect is very wide.
AlN belongs to covalent compound, and self-diffusion coefficient is little, and sintering densification difficulty, needs to add a certain amount of sintering aid with acceleration of sintering usually.Wherein, the existence that the important reason of of the Physical and mechanical properties of AlN ceramic is O impurity is affected.All commercially available AlN powder all contain O impurity, and this O impurity mainly exists in two forms: a kind of is the Al on AlN powder surface
2o
3, another kind is the lattice O be solid-solubilized in AlN crystal grain.In sintering process, the Al on sintering aid and AlN powder surface
2o
3form liquid phase, the capillary force produced owing to generating liquid phase promotes that particle re-arrangement and dissolving-precipitation mechanism promote the densification of AlN ceramic, and sintering aid can impel lattice O to the diffusion of AlN grain surface, thus improves AlN ceramic thermal conductivity; On the other hand, the second-phase content in sintering AlN ceramic and distributing homogeneity thereof can have an impact to the Physical and mechanical properties of AlN ceramic, so it is the key preparing high-performance AlN ceramic material that the purification of AlN lattice and second-phase are uniformly distributed.From thermodynamic consideration, rare earth oxide and Al
2o
3avidity is stronger, and purification AlN lattice ability is stronger, promotes that second-phase is at AlN crystal boundary reasonable layout.In rare earth oxide, Sm
2o
3, Y
2o
3deng with Al
2o
3avidity comparatively strong, the interpolation simultaneously of two or more rare-earth oxide can play the effect of better promotion AlN ceramic sintering.
According to the bibliographical information delivered, sintering AlN ceramic usually adds rare-earth oxidation compound or alkali (soil) oxide compound does, as Li
2o, CaO, Sm
2o
3, Dy
2o
3, Y
2o
3, Er
2o
3, La
2o
3, Tb
2o
3, Yb
2o
3deng.Sintering aid is added directly in AlN powder with the form of oxide powder, there is sintering agent powder and mixes uneven in AlN powder, and the defect of segregation or disappearance locally occurs, and thus, easily causes the generation of AlN ceramic local underburnt or burn-off phenomenon when sintering.
Sm
2o
3, Y
2o
3add separately the AlN ceramic that all can obtain and there is higher-density and thermal conductivity Deng rare-earth oxide, but its sintering temperature is more than 1800 DEG C.Sintering temperature is high, consumes energy high, and production unit damage is serious, and goods are yielding, and qualification rate is low, particularly burns multilager base plate altogether to the large-sized AlN ceramic of preparation or AlN and metal and causes serious technology barrier.Choosing rational sintering aid and addition manner thereof, realize the low-temperature sintering (usually will sinter below 1800 DEG C and be called low-temperature sintering) reducing AlN ceramic, is the Main way of AlN ceramic used for electronic packaging research and development.
At present, oxide sintering aid and AlN powder are directly passed through ball mill mixing by the preparation method of conventional AlN ceramic, after compacting (curtain coating) is shaped, then obtain goods through high-sintering process.Inevitably produce pore, sintering not exclusively, the textural defect such as uneven, the second-phase skewness of grain-size, even occur that substrate is curling, cracking, the thermal conductivity of AlN ceramic prepared by low-temperature sintering and intensity are scarcely high, the performance advantage of AlN ceramic material can not be given full play to, also limited to its application in high-power electric and electronic encapsulation field.
The object of the invention is to choose new multicomponent sintering aid, adopt unique addition manner, obtain uniform microstructure by low temperature sintering technology, the AlN ceramic of thermal conductivity and good strength.
summary of the invention:
The present invention is directed to existing AlN ceramic preparation technology ubiquitous sintering aid homogeneity of ingredients and distributing homogeneity difference and sintering temperature too high and produce the problem of various Structure and Properties defect, geotechnique knows clearly a kind of AlN ceramic low-temperature melt producing method adding polynary sintering aid, each constituent element uniform composition in sintering aid, sintering agent is evenly distributed in AlN ceramic, and the liquid phase sintering of AlN ceramic can be realized below 1800 DEG C, second-phase is evenly distributed, and AlN ceramic and the product properties of preparation are excellent.
For achieving the above object, the technical solution used in the present invention is as follows:
Add an AlN ceramic low-temperature melt producing method for polynary sintering aid, the method comprises following each step:
(1) AlN compound is prepared
A, employing median size are 1.1-1.5 μm, specific surface area is 2.8-3.2 m
2the AlN powder of/g, oxygen level≤1.2wt%, carbon content≤0.06wt% is raw material;
B, get two kinds or more rare earth compounds and one or both alkaline earth metal compounds and to come from different backgrounds and possess different abilities sintering aid;
C, first polynary sintering aid is added in anhydrous ethanol solvent, Ball milling 1-1.5h, then add AlN powder, then ball milling 2-3h, make slurry, 120-140 DEG C of insulation 1-2h in loft drier is dry, for subsequent use for slurry;
(2) granulation
Add solid paraffin binder in the mixed powder of AlN and polynary sintering aid after, adopt homogeneous heating 50-60 min in 100 DEG C of water-baths, every 2-3 min stirs once, until material Homogeneous phase mixing, after 60-80 mesh sieve after cool to room temperature therebetween;
(3) press forming
Unidirectional pressing mode is adopted to prepare AlN base substrate;
(4) binder removal
AlN base substrate dry pressing prepared, at 580-600 DEG C of insulation 20-30min, is got rid of paraffin binder, is obtained AlN ceramic biscuit;
(5) sinter
AlN biscuit is placed in vacuum carbon tube furnace, at 1600-1750 DEG C, is incubated 2-6 h, furnace cooling, obtain AlN ceramic material and goods.
Described rare earth compound is the rare-earth metal nitrate of Sm, Dy, Y, Er, La, Tb, Yb etc.; Described alkaline earth metal compound is the alkine earth metal nitrate of Mg, Ca, Ba etc.
The formula of described AlN compound is: polynary sintering aid 5-10 wt%, AlN surplus.
Described solid paraffin binder quality is the 8-12% of AlN powder.
Described press forming pressure is 300-600 MPa, pressurize 4-7s.
Described sintering is at N
2carry out in protective atmosphere, N
2flow is 6-10 L/min, heating-cooling speed 8-10 DEG C/min of sintering process.
Compared with prior art, beneficial effect of the present invention is embodied in:
1, polynary sintering aid of the present invention is two kinds and above rare earth compound and alkaline earth metal compound, changes corresponding rare-earth oxide in the calcination process after powder Homogeneous phase mixing.For single rare earth sintering aid addition manner, add the AlN ceramic of this polynary sintering aid in sintering process, the liquid phase of good fluidity can be generated in 1350-1650 DEG C of temperature range, reduce the sintering temperature of AlN ceramic greatly, greatly improve the low-temperature sintering compactness extent of AlN ceramic;
2, adopt polynary sintering aid of the present invention, after AlN ceramic terminates, liquid phase is the crystalline state second-phase based on rare earth metal aluminate, and is mainly distributed in the trident grain boundaries of AlN crystal grain, contributes to improving AlN ceramic structure, improves performance;
3, adopt polynary sintering aid of the present invention, the sintering temperature of AlN ceramic comparatively single rare earth sintering aid reduces 100-200 DEG C, and microtexture evenly, crystal grain is tiny.
Accompanying drawing explanation
Fig. 1 is displaing micro tissue topography's photo of the AlN Ceramics Sintered at Low Temperature of the embodiment of the present invention 1;
Fig. 2 is the element Surface scan collection of illustrative plates on the AlN Ceramics Sintered at Low Temperature section of the embodiment of the present invention 1:
Wherein: (a) Al element Surface scan collection of illustrative plates, (b) N element Surface scan collection of illustrative plates, (c) O element Surface scan collection of illustrative plates, (d) Y element Surface scan collection of illustrative plates, (e) Sm element Surface scan collection of illustrative plates;
Fig. 3 is displaing micro tissue topography's photo of the AlN Ceramics Sintered at Low Temperature of the embodiment of the present invention 2.
Embodiment
Embodiment 1
First select that particle diameter is 1.2 μm, specific surface area is 3.0 m
2the high purity AlN powder of/g and Y (NO
3)
3, Sm (NO
3)
3, Ca (NO
3)
2polynary sintering agent raw materials of compound, the content (in 100g) of each composition is: AlN 94.0 g, Y (NO
3)
34.88 g, Sm (NO
3)
33.86 g, Ca (NO
3)
25.56 g.Sintering agent compound and 100g dehydrated alcohol are put into ball grinder, Ball milling 60 min, then the AlN powder adding 94.0 g, ball milling 180 min; By AlN and polynary sintering agent slurry after 120 DEG C of thermostatic drying chamber inner drying 2 h, then add 9.0 g solid paraffins, homogeneous heating 60 min in 100 DEG C of water-baths, stir once every 3 min therebetween, after mixed powder cool to room temperature, cross 60 mesh sieves; Powder mix adopts unidirectional pressing mode, and being pressed into diameter is 48.6 mm, and thickness is the disk of 2.9 mm, and compacting pressure is 430 MPa, pressurize 5 s; By this disk 580 DEG C of insulation 30 min binder removals in draft glue discharging furnace, be then placed in vacuum carbon tube furnace, at N
2sinter in protective atmosphere, concrete sintering process is: N
2flow is 7L/min, and sintering temperature 1700 DEG C, is incubated 4 h, heating-cooling speed 8 DEG C/min.
AlN ceramic homogeneous microstructure, the crystal grain of preparation are tiny, and its thermal conductivity is 123.8 W/ (mK), and three-point bending strength is 320.5 MPa.
Embodiment 2
First select that particle diameter is 1.2 μm, specific surface area is 3.0 m
2the high purity AlN powder of/g and Y (NO
3)
3, Sm (NO
3)
3, Ca (NO
3)
2polynary sintering agent raw materials of compound, the content of each composition (in 100 g) is: AlN 95.0 g, Y (NO
3)
35.10 g, Sm (NO
3)
36.8 g, Ca (NO
3)
22.78 g.Preparation technology is the same, and sintering temperature is 1750 DEG C.
The AlN ceramic homogeneous microstructure of preparation, grain development is complete, and its thermal conductivity is 153.7 W/ (mK), and three-point bending strength is 402.1 MPa.
Claims (6)
1. add an AlN ceramic low-temperature melt producing method for polynary sintering aid, it is characterized in that, the method comprises following each step:
(1) AlN compound is prepared
A, employing median size are 1.1-1.5 μm, specific surface area is 2.8-3.2 m2/g, the AlN powder of oxygen level≤1.2wt%, carbon content≤0.06wt% is raw material;
B, get two kinds or more rare earth compounds and one or both alkaline earth metal compounds and to come from different backgrounds and possess different abilities sintering aid;
C, first polynary sintering aid is added in anhydrous ethanol solvent, Ball milling 1-1.5h, then add AlN powder, then ball milling 2-3h, make slurry, 120-140 DEG C of insulation 1-2h in loft drier is dry, for subsequent use for slurry;
(2) granulation
Add solid paraffin binder in the mixed powder of AlN and polynary sintering aid after, adopt homogeneous heating 50-60 min in 100 DEG C of water-baths, every 2-3 min stirs once, until material Homogeneous phase mixing, after 60-80 mesh sieve after cool to room temperature therebetween;
(3) press forming
Unidirectional pressing mode is adopted to prepare AlN base substrate;
(4) binder removal
AlN base substrate dry pressing prepared, at 580-600 DEG C of insulation 20-30min, is got rid of paraffin binder, is obtained AlN ceramic biscuit;
(5) sinter
AlN biscuit is placed in vacuum carbon tube furnace, at 1600-1750 DEG C, is incubated 2-6 h, furnace cooling, obtain AlN ceramic material and goods.
2. a kind of AlN ceramic low-temperature melt producing method adding polynary sintering aid according to claim 1, it is characterized in that, described rare earth compound is the rare-earth metal nitrate of Sm, Dy, Y, Er, La, Tb, Yb etc.; Described alkaline earth metal compound is the alkine earth metal nitrate of Mg, Ca, Ba etc.
3. a kind of AlN ceramic low-temperature melt producing method adding polynary sintering aid according to claim 1, it is characterized in that, the formula of described AlN compound is: polynary sintering aid 5-10 wt%, AlN surplus.
4. a kind of AlN ceramic low-temperature melt producing method adding polynary sintering aid according to claim 1, is characterized in that, described solid paraffin binder quality is the 8-12% of AlN powder.
5. a kind of AlN ceramic low-temperature melt producing method adding polynary sintering aid according to claim 1, it is characterized in that, described press forming pressure is 300-600 MPa, pressurize 4-7s.
6. a kind of AlN ceramic low-temperature melt producing method adding polynary sintering aid according to claim 1, it is characterized in that, described sintering is at N
2carry out in protective atmosphere, N
2flow is 6-10 L/min, heating-cooling speed 8-10 DEG C/min of sintering process.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631046A (en) * | 2016-11-30 | 2017-05-10 | 莱鼎电子材料科技有限公司 | Composite sintering aid for producing aluminum nitride ceramic substrate |
| CN110395994A (en) * | 2019-08-30 | 2019-11-01 | 广东工业大学 | A kind of overlay film nitride ceramics composite granule and preparation method thereof, nitride ceramics component and preparation method thereof |
| CN112962071A (en) * | 2021-02-02 | 2021-06-15 | 长沙淮石新材料科技有限公司 | Doped aluminum scandium nitride target material and preparation method and application thereof |
| CN114956853A (en) * | 2022-05-23 | 2022-08-30 | 山东国瓷功能材料股份有限公司 | Honeycomb ceramic, preparation method and application thereof, and honeycomb filter |
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| CN101538162A (en) * | 2009-01-21 | 2009-09-23 | 北京中材人工晶体有限公司 | Preparation method for high reliability large-scale silicon nitride ceramic material |
| CN102344286A (en) * | 2010-07-27 | 2012-02-08 | 台盐实业股份有限公司 | Aluminum nitride ceramic radiating fin and manufacturing method thereof |
| CN103539457A (en) * | 2013-09-29 | 2014-01-29 | 合肥工业大学 | Preparation method of AlN ceramic base plate for microelectronic packaging |
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2014
- 2014-08-27 CN CN201410428584.2A patent/CN104230344A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101538162A (en) * | 2009-01-21 | 2009-09-23 | 北京中材人工晶体有限公司 | Preparation method for high reliability large-scale silicon nitride ceramic material |
| CN102344286A (en) * | 2010-07-27 | 2012-02-08 | 台盐实业股份有限公司 | Aluminum nitride ceramic radiating fin and manufacturing method thereof |
| CN103539457A (en) * | 2013-09-29 | 2014-01-29 | 合肥工业大学 | Preparation method of AlN ceramic base plate for microelectronic packaging |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106631046A (en) * | 2016-11-30 | 2017-05-10 | 莱鼎电子材料科技有限公司 | Composite sintering aid for producing aluminum nitride ceramic substrate |
| CN110395994A (en) * | 2019-08-30 | 2019-11-01 | 广东工业大学 | A kind of overlay film nitride ceramics composite granule and preparation method thereof, nitride ceramics component and preparation method thereof |
| CN112962071A (en) * | 2021-02-02 | 2021-06-15 | 长沙淮石新材料科技有限公司 | Doped aluminum scandium nitride target material and preparation method and application thereof |
| CN112962071B (en) * | 2021-02-02 | 2023-04-28 | 长沙淮石新材料科技有限公司 | Doped aluminum scandium nitride target material and preparation method and application thereof |
| CN114956853A (en) * | 2022-05-23 | 2022-08-30 | 山东国瓷功能材料股份有限公司 | Honeycomb ceramic, preparation method and application thereof, and honeycomb filter |
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Application publication date: 20141224 |