CN116003137B - Hydration-resistant aluminum nitride powder and preparation method and application thereof - Google Patents
Hydration-resistant aluminum nitride powder and preparation method and application thereof Download PDFInfo
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- CN116003137B CN116003137B CN202310003219.6A CN202310003219A CN116003137B CN 116003137 B CN116003137 B CN 116003137B CN 202310003219 A CN202310003219 A CN 202310003219A CN 116003137 B CN116003137 B CN 116003137B
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Abstract
The invention relates to a hydration-resistant aluminum nitride powder, and a preparation method and application thereof. The preparation method of the hydration-resistant aluminum nitride powder comprises the following steps: grinding and mixing aluminum nitride powder, water-soluble poly-polycarboxylic acid and absolute ethyl alcohol to obtain mixed slurry; drying and sieving to obtain the hydration-resistant aluminum nitride powder; wherein the molecular weight of the polycarboxylic acid is 300-1500.
Description
Technical Field
The invention belongs to the field of preparation of aluminum nitride materials, and particularly relates to a hydration-resistant aluminum nitride powder, and a preparation method and application thereof.
Background
The aluminum nitride ceramic has the advantages of high heat conductivity, low dielectric constant, high resistivity, good chemical stability and corrosion resistance, and the like, is matched with the silicon thermal expansion coefficient, and has wide application prospect in the fields of electronic information, energy chemical industry, transportation and the like. Wherein the theoretical thermal conductivity of the monocrystalline AlN can reach 320W/m.K, and the monocrystalline AlN is the traditional Al 2 O 3 The characteristic of the electronic packaging substrate material is several times that of the electronic packaging substrate material, so that the electronic packaging substrate material is an ideal heat dissipation and packaging material for a new generation of large-scale integrated circuits, semiconductor module circuits and high-power devices.
Although aluminum nitride has many advantages, aluminum nitride has higher reactivity with water, and can react with water to form Al in a humid environmentOH) 3 And release the irritant ammonia gas, and the reaction products finally generate Al in the sintering process of AlN ceramics 2 O 3 While Al is 2 O 3 The O atoms of (2) are liable to enter the AlN lattice and generate Al vacancies (V Al ) Defects and O replace N atom defects, thereby reducing the thermal conductivity of the material. On the other hand, the hydrolytic behavior of aluminum nitride powder also makes it difficult to prepare high-solid-content slurry, thereby severely impeding the development of the water-based forming process of aluminum nitride ceramics, which is costly and has adverse effects on the environment and human body. Therefore, it is important to improve the hydration resistance of the aluminum nitride powder.
Currently, the main methods for waterproof modification of aluminum nitride powder surface include inorganic acid modification, surfactant modification, heat treatment modification, and the like. Although the method can improve the hydration resistance of the aluminum nitride powder to a certain extent, certain defects exist: (1) Treatment of aluminum nitride powder with inorganic acid (phosphoric acid, silicic acid, etc.) can cause difficulty in removal of P, si, etc. during sintering, form impurities in ceramic sintered body, and seriously affect the performance of aluminum nitride ceramic; (2) The aluminum nitride powder modified by the surfactant has good hydration resistance, but can influence the dispersibility of the water-based aluminum nitride slurry, and is not beneficial to the preparation of aluminum nitride ceramic materials; (3) The oxygen content in the powder can be obviously increased by adopting heat treatment modification, and finally the thermal conductivity of the aluminum nitride ceramic can be reduced.
Disclosure of Invention
Aiming at the problems that aluminum nitride powder is easy to hydrolyze and is difficult to store and difficult to mold by adopting a water-based casting process, the invention provides aluminum nitride powder with simple preparation method and excellent hydration resistance, and a preparation method and application thereof.
In a first aspect, the present invention provides a method for preparing hydration-resistant aluminum nitride powder, comprising: grinding and mixing aluminum nitride powder, water-soluble poly-polycarboxylic acid and absolute ethyl alcohol to obtain mixed slurry; drying and sieving to obtain the hydration-resistant aluminum nitride powder; wherein the molecular weight of the polycarboxylic acid is 300-1500.
Preferably, the water-soluble polycarboxylic acid is selected from at least one of hydrolyzed polymaleic anhydride, a equine propylene copolymer, or polyepoxysuccinic acid.
Preferably, the addition amount of the water-soluble polycarboxylic acid is controlled to be 3-7 wt.% of the mass of the aluminum nitride powder.
Preferably, the grinding mode adopts planetary ball milling or stirring grinding; the grinding speed is 100-400 r/min, the grinding time is 3-48 h, the grinding temperature is 25-40 ℃, the grinding balls are zirconia balls, and the ball material mass ratio is 2-4:1.
Preferably, the solid content of the mixed slurry is controlled to be 50 to 80wt.%.
Preferably, the drying mode is as follows: firstly, rotary evaporation drying is carried out, and then secondary high-temperature drying is carried out; the temperature of the secondary high-temperature drying is 70-120 ℃ and the time is 4-12 h.
In a second aspect, the invention provides the hydration-resistant aluminum nitride powder obtained by the preparation method, and the surface of the hydration-resistant aluminum nitride powder particle has a hydration-resistant wrapping structure with the thickness of 5-8 nm.
Preferably, under the magnetic stirring at room temperature of 200-600 r/min, the hydration-resistant aluminum nitride powder is dispersed in deionized water and can be kept for more than 90 hours without hydrolysis; under the planetary ball milling condition of 200-250 r/min, the hydration-resistant aluminum nitride powder can be dispersed in deionized water for more than 24 hours without hydrolysis.
In a third aspect, the invention provides an application of the hydration-resistant aluminum nitride powder in preparing an aluminum nitride ceramic substrate by water-based tape casting.
Advantageous effects
The invention adopts polybasic carboxylic acid as modifier, and uses carboxylic acid groups in polymers with different molecular weights and Al (OH) on the surface of aluminum nitride powder 3 Or chelate formed by AlOOH film reaction and matched with long chain winding action of polymer to form compact hydration-resisting film, so as to prevent aluminium nitride from further contacting with water and attain the hydration-resisting effect; in addition, the polycarboxylic acid is a commercial water treatment agent, has no phosphorus and toxicity, is environment-friendly and can be degraded by microorganisms;
the preparation process is simple by adopting a one-time mixing mode such as a planetary ball milling or stirring mill milling process, key parameters influencing the milling efficiency such as ball material ratio, solid content, milling temperature and the like are changed, the effective collision times of powder and zirconia balls are improved, active sites on the surface of aluminum nitride powder are increased, the surface of powder particles is fully coated, and the hydration resistance of the aluminum nitride powder is further improved;
according to the invention, a two-stage drying process is adopted, wherein the rotary evaporation drying can effectively recover the organic solvents such as absolute ethyl alcohol and the like, so that the environmental pollution is reduced, meanwhile, the generation of hard agglomeration of powder is avoided, and the powder sieving efficiency is improved; the secondary high-temperature drying can ensure that no organic solvent remains in the modified powder;
the aluminum nitride powder prepared by the invention has excellent hydration resistance, the pH change of the suspension is very small after the aluminum nitride powder is dispersed in deionized water for 90 hours under the room temperature magnetic stirring condition of 200-600 r/min, the aluminum nitride powder still has good hydration resistance after the aluminum nitride powder is dispersed in deionized water for 24 hours under the planetary ball milling condition of 200-250 r/min, and the aluminum nitride powder has remarkable application value in the aluminum nitride powder storage and water-based forming process.
Drawings
FIG. 1 is a graph showing the pH of a suspension over time after the hydration-resistant aluminum nitride powder prepared in example 1 and the original aluminum nitride powder are magnetically stirred and dispersed in deionized water for 90 hours;
FIG. 2 is a graph showing the comparison of XRD test results of powder baking after the hydration-resistant aluminum nitride powder prepared in example 1 of the present invention and the original aluminum nitride powder are magnetically stirred and dispersed in deionized water for 90 hours;
FIG. 3 is a graph showing the pH of slurry over time after the hydration-resistant aluminum nitride powder prepared in example 1 and the original aluminum nitride powder were planetary ball-milled and dispersed in deionized water for 24 hours;
FIG. 4 is a graph showing the comparison of XRD test results of the hydration-resistant aluminum nitride powder prepared in example 1 after being subjected to planetary ball milling and dispersed in deionized water for 24 hours, and then the powder is dried;
FIG. 5 is a drawing of an AlN cast biscuit obtained by casting a slurry prepared from the hydration-resistant aluminum nitride powder prepared in example 1;
FIG. 6 is an XRD pattern of an AlN cast biscuit obtained by casting a slurry prepared from the hydration-resistant aluminum nitride powder prepared in example 1;
FIG. 7 is a graph showing the pH of a suspension over time after the hydration-resistant aluminum nitride powder prepared in example 2 and the original aluminum nitride powder are magnetically stirred and dispersed in deionized water for 90 hours;
FIG. 8 is a graph showing the comparison of XRD test results of powder baking after the hydration-resistant aluminum nitride powder prepared in example 2 and the original aluminum nitride powder are magnetically stirred and dispersed in deionized water for 90 hours;
FIG. 9 is a graph showing the pH of slurry over time after the hydration-resistant aluminum nitride powder prepared in example 2 and the original aluminum nitride powder were planetary ball-milled and dispersed in deionized water for 24 hours;
FIG. 10 is a graph showing the comparison of XRD test results of the hydration-resistant aluminum nitride powder prepared in example 2 after being subjected to planetary ball milling and dispersed in deionized water for 24 hours, and then dried;
FIG. 11 is a graph showing the comparative state of the slurry before and after grinding after planetary ball milling of the modified aluminum nitride powder prepared in comparative example 1 was dispersed in deionized water for 2 hours;
FIG. 12 is a graph showing the pH change with time after planetary ball milling of the modified aluminum nitride powder prepared in comparative example 2 is dispersed in deionized water for 10 hours, and the state of the modified aluminum nitride powder before and after slurry grinding;
FIG. 13 is a graph showing the results of XRD test of the hydration-resistant aluminum nitride powder prepared in comparative example 3 after being dispersed in deionized water by magnetic stirring for 90 hours, and dried;
fig. 14 is a graph showing the results of XRD test of the powder obtained in comparative example 4 after planetary ball milling and dispersing in deionized water for 5 hours.
Detailed Description
The invention is further illustrated by the following embodiments, it being understood that the following embodiments are merely illustrative of the invention and not limiting thereof.
According to the invention, the aluminum nitride powder is treated by using a surface modification technology, so that the aluminum nitride powder is prevented from being hydrolyzed in a wet environment and an aqueous solution, and the hydration resistance of the aluminum nitride powder is improved.
The following exemplarily illustrates a preparation method of the hydration-resistant aluminum nitride powder provided by the invention, which comprises the following steps: mixing aluminum nitride powder with water-soluble polycarboxylic acid and absolute ethyl alcohol; grinding to obtain uniformly dispersed mixed slurry; and drying and sieving to obtain the hydration-resistant aluminum nitride powder. In an alternative embodiment, the sintering aid yttrium oxide powder may also be added at the same time as the aluminum nitride powder is modified.
In an alternative embodiment, the median particle size of the aluminum nitride powder may be 0.5 to 1.5 μm.
In some embodiments, the water-soluble polycarboxylic acid may be selected from at least one of hydrolyzed polymaleic anhydride, a equine propylene copolymer, or polyepoxysuccinic acid. Compared with small molecular acids such as citric acid and oxalic acid, the polycarboxylic acid contains more carboxylate radicals and has a certain long-chain structure, and can ionize several times of carboxylate radicals and hydroxyl radicals of the citric acid and the oxalic acid in water, and the polycarboxylic acid and Al (OH) on the surface of aluminum nitride powder 3 Or the chelate formed by AlOOH film reaction and the physical package of long chain of poly-polycarboxylic acid together form the protective film with hydration-resistant effect.
The molecular weight of the polycarboxylic acid may be controlled to 300 to 1500. Polymers of different molecular weights are more prone to produce dense protective films than polymers of a single molecular weight; meanwhile, the excessive molecular weight and the overlong molecular chain of the polycarboxylic acid can lead to the mutual entanglement among polymer molecular chains and the like, thereby weakening the hydration-resistant effect.
The invention adopts water-soluble polybasic carboxylic acid with dispersion effect to carry out surface modification treatment on aluminum nitride powder, wherein the water-soluble polybasic carboxylic acid passes through carboxylic acid groups on the surfaces of aluminum nitride powder particles and Al (OH) on the surfaces of the powder 3 Or the chelate formed by AlOOH film reaction and the long chain winding action of the polymer form a compact hydration-resistant film, and finally the hydration-resistant aluminum nitride powder with a stable package structure can be obtained.
Preferably, the addition amount of the water-soluble polycarboxylic acid can be controlled to 3 to 7wt.% of the aluminum nitride powder mass.
The grinding mode can adopt planetary ball milling or stirring grinding. The grinding speed can be 100-400 r/min, the grinding time can be 3-48 h, the grinding temperature can be controlled to be 25-40 ℃, the grinding balls can be zirconia balls, and the ball mass ratio can be controlled to be 2-4:1.
In some embodiments, the solids content of the mixed slurry may be controlled to be 50 to 80wt.%.
The invention adopts a one-step mixed grinding mode which can be amplified industrially, such as planetary ball milling or stirring mill grinding technology, has simple preparation process, and simultaneously improves the effective collision times of the powder and the zirconia balls, increases the active sites on the surface of the aluminum nitride powder, promotes the full reaction of the powder and the modifier, ensures the full coating of the surface of the powder particles, and further improves the hydration resistance of the aluminum nitride powder by controlling the key parameters such as ball material ratio, solid content, grinding temperature and the like which affect the grinding efficiency. Meanwhile, in the grinding process of slurry, the high-speed collision of powder and grinding balls can cause the temperature of a system to rise, the modification reaction of the poly-polycarboxylic acid can be accelerated when the temperature rises, but the volatilization of absolute ethyl alcohol can be caused when the temperature is too high, so that potential safety hazards are generated.
The drying mode can be as follows: firstly, rotary evaporation drying is carried out, and then secondary high-temperature drying is carried out; the temperature of the secondary high-temperature drying can be 70-120 ℃ and the time can be 4-12 h. According to the invention, a two-stage drying process is adopted, wherein the rotary evaporation drying can effectively recover the organic solvents such as absolute ethyl alcohol and the like, so that the environmental pollution is reduced, meanwhile, the generation of hard agglomeration of powder is avoided, and the powder sieving efficiency is improved; the secondary high-temperature drying can ensure that no organic solvent remains in the modified powder.
The surface of the hydration-resistant aluminum nitride powder particle obtained by the preparation method provided by the invention has a stable water-resistant wrapping structure, and the water-resistant wrapping structure is formed by chelating a-COO-Al-bond generated by reacting polycarboxylic acid with a certain chain length with an aluminum nitride hydrolytic membrane, and is adsorbed on the surface of the powder to form stable connection. In some embodiments, the thickness of the outer wrap structure may be controlled to be between 5 and 8nm. The thickness of the wrapping structure is too large, the collision between the grinding ball and the powder is easy to cause the wrapping structure to drop from the surface of the powder particles in the process of preparing the hydration-resistant aluminum nitride powder slurry, and water molecules are contacted with the powder in the drop gaps to cause the hydrolysis of the aluminum nitride; the thickness of the wrapping structure is too small, powder and water molecules cannot be effectively prevented from contacting in the slurry grinding process, and the hydration-resistant effect cannot be achieved.
The modified aluminum nitride powder provided by the invention has excellent hydration resistance: under the magnetic stirring at room temperature of 200-600 r/min, the hydration-resistant aluminum nitride powder can be dispersed in deionized water to keep the hydration-resistant aluminum nitride powder from being hydrolyzed for more than 90 hours; under the planetary ball milling condition of 200-250 r/min, the hydration-resistant aluminum nitride powder can be dispersed in deionized water for more than 24 hours without hydrolysis.
The water-soluble polycarboxylic acid used in the invention belongs to polymer electrolyte and contains-COO - The isosspersion group and a certain long chain structure have steric hindrance effect in the powder dispersing process, and can be dispersed in aqueous solution to form stable aqueous slurry without adding dispersing agent in water-based molding application. Meanwhile, the chemical property is stable, the adhesive can be used under the condition of below 350 ℃, and the requirement on the drying temperature in the water-based tape casting forming process is met.
Therefore, the modified aluminum nitride powder obtained by modifying the aluminum nitride powder by adopting the water-soluble polycarboxylic acid has good hydration resistance effect and certain dispersibility, and can be directly subjected to water-based tape casting to prepare the aluminum nitride ceramic substrate. The polycarboxylic acid adopted by the invention can be used as a hydration-resistant modifier for aluminum nitride powder and can be used as a dispersing agent for aluminum nitride water-based molding slurry.
In some embodiments, the slurry for preparing the aluminum nitride ceramic substrate by the water-based tape casting process can be prepared by mixing the hydration-resistant aluminum nitride powder, deionized water, a binder, a plasticizer and a defoaming agent. The binder of the water-based casting forming slurry can be cationic water-soluble polyurethane emulsion with the glass transition temperature of-5 to-15 ℃, and the solid content of the water-based casting forming slurry can be controlled to be 50-80 wt.%.
The aluminum nitride ceramic substrate comprises a plurality of layers of films prepared from hydration-resistant aluminum nitride powder water-based casting slurry. In an alternative embodiment, the film thickness of each thin film of the ceramic substrate after the casting and drying may be controlled to be 0.08-0.15 mm.
The present invention will be described in more detail by way of examples. It should also be understood that the following examples are given by way of illustration only and are not to be construed as limiting the scope of the invention, since various insubstantial modifications and adaptations of the invention to those skilled in the art based on the foregoing disclosure are intended to be within the scope of the invention and the specific process parameters and the like set forth below are merely one example of a suitable range within which one skilled in the art would choose from the description herein without being limited to the specific values set forth below.
Example 1
100g of aluminum nitride powder with the median particle size of 1.5 mu m, 4g of yttrium oxide powder, 5g of hydrolyzed polymaleic anhydride and 50g of absolute ethyl alcohol are added into a ball milling tank, zirconia balls are used as milling balls, the ball material ratio is 2:1, the ball milling rotating speed is 250r/min, the ball milling time is 24h, and the milling temperature is 32 ℃; and (3) carrying out rotary evaporation drying on the obtained slurry at the water bath of 80 ℃, then putting the slurry into a drying oven of 100 ℃ for drying for 4 hours, crushing the slurry, and sieving the crushed slurry with a 80-mesh sieve to obtain the hydration-resistant aluminum nitride powder.
The hydration-resistant aluminum nitride powder and the original aluminum nitride powder prepared in example 1 were dispersed in deionized water by magnetic stirring according to a mass fraction of 2wt.% respectively, the stirring rotation speed was 300r/min, and the change of the pH value of the suspension with time was measured.
FIG. 1 is a graph showing the pH of a suspension over time after the hydration-resistant aluminum nitride powder prepared in example 1 and the original aluminum nitride powder were magnetically stirred and dispersed in deionized water for 90 hours. Fig. 2 is a graph comparing the results of XRD test performed by drying the powder after the hydration-resistant aluminum nitride powder prepared in example 1 of the present invention and the original aluminum nitride powder are magnetically stirred and dispersed in deionized water for 90 hours. From the graph, the original aluminum nitride powder has obvious hydration behavior after the powder is dispersed in deionized water for 1h, and the modified hydration-resistant aluminum nitride powder basically has no hydration behavior after being magnetically stirred for 90h, which indicates that the hydration-resistant aluminum nitride powder prepared in the embodiment 1 has good hydration resistance.
The hydration-resistant aluminum nitride powder and the original aluminum nitride powder prepared in example 1 were respectively ball-milled and dispersed in deionized water according to a mass fraction of 60wt.%, and the ball-milling rotation speed was 200r/min, and the change of the pH value of the slurry with time was measured.
Fig. 3 is a graph showing the change of the slurry pH with time after the hydration-resistant aluminum nitride powder prepared in example 1 and the original aluminum nitride powder were planetary ball-milled and dispersed in deionized water for 24 hours. FIG. 4 is a graph showing the results of XRD test of the hydration-resistant aluminum nitride powder obtained in example 1 after planetary ball milling and dispersing in deionized water for 24 hours (Y 2 O 3 The diffraction peak is a sintering aid added in powder modification treatment, and does not influence hydration-resistant modification of aluminum nitride). As can be seen from fig. 3, after the powder is dispersed in deionized water for 1h, the original aluminum nitride powder starts to be hydrated, and after the modified hydration-resistant aluminum nitride powder is subjected to planetary ball milling for 24h, hydration behavior does not substantially occur, which indicates that the hydration-resistant aluminum nitride powder prepared in example 1 has good hydration resistance.
The hydration-resistant aluminum nitride powder prepared in example 1 was mixed with a binder, a plasticizer, a defoaming agent and deionized water to prepare an AlN slurry having a solid content of 73wt.%, and the AlN slurry was deaerated and cast to obtain an aluminum nitride ceramic casting film having a smooth surface and a film thickness of about 0.12 mm.
Fig. 5 is a view of an AlN cast biscuit obtained by casting a slurry prepared from the hydration-resistant aluminum nitride powder prepared in example 1. From the figure, the AlN water-based casting biscuit which is free of air holes, free of cracks, smooth in surface and uniform in film thickness is successfully prepared by adopting the hydration-resistant aluminum nitride powder and the casting scheme.
FIG. 6 is a block diagram of a powder of hydration-resistant aluminum nitride prepared by the method of example 1And (5) carrying out casting molding on the slurry to obtain the XRD pattern of the AlN casting biscuit. As can be seen from the figure, the biscuit XRD detection result has no Al (OH) 3 Diffraction peaks appear, which shows that the hydration-resistant aluminum nitride powder prepared by adopting the embodiment 1 has better hydration-resistant effect and meets the requirement of preparing AlN biscuit by water-based casting molding.
Example 2
100g of aluminum nitride powder with the median particle size of 1.33 mu m, 4g of yttrium oxide powder, 5g of Martensitic copolymer and 50g of absolute ethyl alcohol are added into a ball milling tank, zirconia balls are used as milling balls, the ball material ratio is 2:1, the ball milling rotating speed is 250r/min, the ball milling time is 24h, and the milling temperature is 32 ℃; and (3) rotary evaporation drying the obtained slurry in a water bath at 80 ℃, then putting the slurry into a drying oven at 70 ℃ for drying for 8 hours, crushing the slurry, and sieving the crushed slurry with a 80-mesh sieve to obtain the hydration-resistant aluminum nitride powder.
The hydration-resistant aluminum nitride powder and the original aluminum nitride powder prepared in example 2 were magnetically stirred and dispersed in deionized water according to a mass fraction of 2wt.% respectively, the stirring rotation speed was 300r/min, and the change of the pH value of the suspension with time was measured.
Fig. 7 is a graph showing the pH of a suspension with time after the hydration-resistant aluminum nitride powder prepared in example 2 and the original aluminum nitride powder were magnetically stirred and dispersed in deionized water for 90 hours. Fig. 8 is a graph comparing the results of XRD test performed by drying the powder after the hydration-resistant aluminum nitride powder prepared in example 2 and the original aluminum nitride powder were magnetically stirred and dispersed in deionized water for 90 hours. From the graph, after the powder is dispersed in deionized water for 1h, the original aluminum nitride powder has obvious hydration behavior, and the modified hydration-resistant aluminum nitride powder basically has no hydration behavior after being magnetically stirred for 90h, which indicates that the hydration-resistant aluminum nitride powder prepared in the embodiment 2 has good hydration resistance.
The hydration-resistant aluminum nitride powder and the original aluminum nitride powder obtained in this example 2 were ball-milled and dispersed in deionized water according to a mass fraction of 60wt.%, respectively, the ball-milling rotation speed was 200r/min, and the change of the pH value of the slurry with time was measured.
FIG. 9 is a diagram showing the hydration-resistant aluminum nitride powder obtained in example 2And a comparison chart of the pH value of slurry after original aluminum nitride powder is subjected to planetary ball milling and dispersed in deionized water for 24 hours. FIG. 10 is a graph showing the results of XRD test of the hydration-resistant aluminum nitride powder obtained in example 2 after planetary ball milling and dispersing in deionized water for 24 hours, after drying the powder (Y appearing in the figure 2 O 3 The diffraction peak is a sintering aid added in powder modification treatment, and does not influence hydration-resistant modification of aluminum nitride). From the graph, after the powder is dispersed in deionized water for 1h, the original aluminum nitride powder starts to be hydrated, and after the modified hydration-resistant aluminum nitride powder is subjected to planetary ball milling for 24h, hydration behavior does not basically occur, which indicates that the hydration-resistant aluminum nitride powder prepared in the embodiment 2 has good hydration resistance.
Comparative example 1
100g of aluminum nitride powder with the median particle size of 1.33 mu m, 5g of oxalic acid and 60g of absolute ethyl alcohol are added into a ball milling tank, zirconia balls are used as grinding balls, the ball-material ratio is 3:1, the ball milling rotating speed is 250r/min, and the ball milling time is 24 hours; and drying the obtained slurry in a drying oven at 60 ℃ for 12 hours, crushing, and sieving with a 80-mesh sieve to obtain the modified aluminum nitride powder.
The modified aluminum nitride powder prepared in comparative example 1 was ball-milled and dispersed in deionized water according to a mass fraction of 76wt.%, and the pH value of the slurry was measured at intervals of 2 hours at a speed of 250r/min by adding 4.5g of a polyacrylic acid dispersant due to poor dispersibility of the modified powder.
FIG. 11 is a graph showing the comparative state of the slurry before and after grinding after planetary ball milling of the modified aluminum nitride powder prepared in comparative example 1 was dispersed in deionized water for 2 hours. From the graph, the pH initial value of the prepared slurry is 5.58, the slurry is solidified after ball milling for 2 hours, and the powder subjected to diacid oxalic acid modification treatment is smelled with pungent ammonia gas, so that the powder has poor hydration resistance and cannot meet the actual requirements of water-based molding application.
Comparative example 2
100g of aluminum nitride powder with the median particle size of 1.33 mu m, 5g of citric acid and 76g of absolute ethyl alcohol are added into a ball milling tank, zirconia balls are used as grinding balls, the ball-material ratio is 3:1, the ball milling rotating speed is 250r/min, and the ball milling time is 24 hours; and drying the obtained slurry in a drying oven at 60 ℃ for 12 hours, crushing, and sieving with a 80-mesh sieve to obtain the modified aluminum nitride powder.
The modified aluminum nitride powder prepared in comparative example 2 was ball-milled and dispersed in deionized water according to a mass fraction of 76wt.%, and 8g of polyacrylic acid dispersant was added due to poor dispersibility of the modified powder, the ball-milling speed was 250r/min, and the change of the pH value of the slurry with time was measured every 2 hours.
FIG. 12 is a graph showing the pH change with time after planetary ball milling of the modified aluminum nitride powder prepared in comparative example 2 was dispersed in deionized water for 10 hours, and the state of the modified aluminum nitride powder before and after slurry grinding. From the graph, the pH initial value of the prepared slurry is 4.25, the pH of the prepared slurry is 6.65 after 8 hours, and the slurry is cured after 10 hours and smells the pungent ammonia gas, which indicates that the powder modified by the citric acid of the tribasic acid has unsatisfactory hydration resistance and cannot meet the actual requirements of water-based molding application.
Comparative example 3
An anti-hydration aluminum nitride was prepared as in example 1, except that: the addition amount of the modifier hydrolyzed polymaleic anhydride is 1g.
The hydration-resistant aluminum nitride powder prepared in comparative example 3 was magnetically stirred and dispersed in deionized water according to a mass fraction of 2wt.%, the stirring rotation speed was 300r/min, and after magnetically stirred and dispersed for 90 hours, the powder was dried for XRD test.
Fig. 13 is a comparative graph showing the XRD test result of the powder of hydration-resistant aluminum nitride prepared in comparative example 3 after being dispersed in deionized water by magnetic stirring for 90 hours. As can be seen from the figure, after the powder is stirred and dispersed in deionized water for 90 hours, the modified hydration-resistant aluminum nitride powder has been hydrated, and Al (OH) appears in the XRD pattern 3 Diffraction peaks, compared with example 1, the powder modified by adding 1% hydrolyzed polymaleic anhydride in comparative example 3 has poorer hydration resistance.
Comparative example 4
An anti-hydration aluminum nitride was prepared as in example 1, except that: the stirring mode of the treated powder is stirring and dispersing treatment by a stirring paddle, the stirring rotating speed is 250r/min, and the stirring time is 12h.
The hydration-resistant aluminum nitride powder prepared in comparative example 4 is ball-milled and dispersed in deionized water according to the mass fraction of 60wt.%, the ball milling rotation speed is 200r/min, and the powder is dried for XRD test after planetary ball milling and dispersion for 24 hours.
Fig. 14 is a graph showing the results of XRD test of the powder obtained in comparative example 4 after planetary ball milling and dispersing in deionized water for 5 hours. As can be seen from the figure, the modified hydration-resistant aluminum nitride powder treated by stirring and dispersing has Al (OH) in XRD pattern after 5h of planetary ball milling 3 Diffraction peaks, the modified powder of comparative example 4, which was subjected to stirring, also had a poor hydration-resistant effect as compared with example 1.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Many modifications and substitutions of the present invention will become apparent to those of ordinary skill in the art upon reading the foregoing. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (7)
1. The preparation method of the hydration-resistant aluminum nitride powder is characterized by comprising the following steps of: grinding and mixing aluminum nitride powder, water-soluble poly-polycarboxylic acid and absolute ethyl alcohol to obtain mixed slurry; drying and sieving to obtain the hydration-resistant aluminum nitride powder;
wherein the water-soluble polybasic carboxylic acid is at least one selected from hydrolytic polymaleic anhydride, a horse propylene copolymer or polyepoxysuccinic acid, and the molecular weight is 300-1500;
the addition amount of the water-soluble polycarboxylic acid is controlled to be 3-7 wt% of the mass of the aluminum nitride powder;
the surface of the hydration-resistant aluminum nitride powder particle has a hydration-resistant wrapping structure with the thickness of 5-8 nm.
2. The preparation method according to claim 1, wherein the grinding mode adopts planetary ball milling or stirring grinding; the grinding speed is 100-400 r/min, the grinding time is 3-48 h, the grinding temperature is 25-40 ℃, the grinding balls are zirconia balls, and the ball material mass ratio is 2-4:1.
3. The method of claim 1, wherein the mixed slurry has a solids content of 50 to 80 wt%.
4. The method according to claim 1, wherein the drying is performed by: firstly, rotary evaporation drying is carried out, and then secondary high-temperature drying is carried out; the temperature of the secondary high-temperature drying is 70-120 ℃ and the time is 4-12 h.
5. A hydration-resistant aluminum nitride powder obtained by the production method according to any one of claims 1 to 4.
6. The hydration-resistant aluminum nitride powder according to claim 5, wherein the hydration-resistant aluminum nitride powder is dispersed in deionized water under the magnetic stirring at room temperature of 200-600 r/min, and can be kept from being hydrolyzed by 90-h; under the planetary ball milling condition of 200-250 r/min, the hydration-resistant aluminum nitride powder can be dispersed in deionized water to keep more than 24h from hydrolysis.
7. Use of the hydration-resistant aluminum nitride powder according to claim 5 in the preparation of aluminum nitride ceramic substrates by water-based tape casting.
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| CN111875386A (en) * | 2020-08-07 | 2020-11-03 | 福建臻璟新材料科技有限公司 | Aluminum nitride ceramic substrate and preparation method thereof |
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