TW201127747A - Manufacturing method for AlN - Google Patents

Abstract

A manufacturing method for AlN comprises mixing Al powder and a modifying agent as a reactant and placing it into a container; exposing the reactant in the container to a nitrogenous gas and heating the reactant to over and above 660 DEG C to combustion wherein the modifying agent and the reactant proceeding a surface modifying reaction to form a ceramic layer on the surface of the Al powder having a combustion reaction with the nitrogenous gas to form AlN.

Description

201127747 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for preparing aluminum nitride. [Prior Art] Aluminum nitride has become an extremely important material in the industry in recent years due to its excellent thermal conductivity, good electrical insulation, low thermal expansion rate, good thermal shock resistance and good corrosion resistance. It has great application potential in many high-tech industries, such as integrated circuit packaging materials and high thermal conductivity composite materials, and can also be applied to electronic substrates, high-power LED wafer carrier boards, electronic component heat sinks or high temperature resistant containers. Production. At present, the preparation methods of conventional aluminum nitride are generally classified into a gas phase reaction method, an organic metal precursor method, an oxidized Is powder carbon reduction nitridation method, a metal ruthenium direct nitridation method, and a combustion synthesis method. In the conventional gas phase reaction method, the reaction formula is as shown in the formula (1), which is mainly operated at a temperature of 900 K to 1500 K for 5 hours or more to react to form a crystalline and amorphous aluminum nitride (A1N) powder. body.

AlCl3(g)+ 4NH3(g) -+ A]N(S) +3 ΝΗ4〇(&). (1) However, the reaction time required for the gas phase reaction method needs to be more than 5 hours, and generally The conversion of the product is only about 80%, the production cost is high and the yield is small, which is not suitable for industrial production. In the conventional organometallic precursor method, the reaction formula is as shown in the formulas (2) to (5), and the operation is carried out at a temperature of from 400 Torr to 1000 Torr, and the reaction time is required to be from 10 to 240 minutes. The base (R) will crack and break, and the product must be placed in air to heat and remove carbon. This step can lead to an increase in oxygen content at 201127747. R3A1(1)+NH3(1)-»R3A1NH3(1)................ (2) R3A1NH3(!) ^ R2A1NH2(I) +RH(g).. .......... (3) R2AINH2(1)-> RA1NH(丨)+RH(g)............. (4) RAlNH(i) 4 A1N(8) +RH (g)................... (5) In addition, this method has the problems of complicated steps, energy consumption, high cost and low yield, and is not suitable for industrial production. .

In the conventional aluminum oxide powder carbon reduction nitridation method, the reaction formula is as shown in the formula (6). The alumina powder and the carbon powder are uniformly mixed and reacted at a temperature of 1500 K to 2200 K to obtain an aluminum nitride product, and the reaction time is required to be more than 5 hours.

Al203(s)+ N2(s) + 3C(s)— 2A1N(5) +3CO(g)... (6) However, the conventional aluminum oxide carbon reduction nitridation method still needs to react at high temperature for five hours to several Ten hours' therefore has the disadvantage of time-consuming and energy-consuming; in order to make the gasification reaction complete, it is necessary to add an excess; g carbon powder to carry out the reaction, and adding excessive carbon powder will require further use of high temperature to remove the residue. Carbon' therefore needs to consume more heat; moreover, it can cause the oxygen content of aluminum nitride powder to increase in the process of carbon oxidation ☆ carbon, and 'said: the thermal conductivity of aluminum is greatly reduced, resulting in The quality of aluminum nitride powder; the long-term gas is the conventional direct method of metal aluminum nitridation, and the reaction formula is as shown in the formula (?). It is operated at a temperature of 1000 Κ to 1500 ,, and the reaction time is 5 hours or more. Mujin needs 2Al(s)+ N2(s) 2AlN(s)................ (7) However, the metal aluminum direct nitridation method also needs to be carried out at high temperature. Five to several tens of hours of operation can complete the reaction, so there are also problems with the 201127747 problem. In addition, the conventional metal aluminum direct nitriding method in the high-temperature reaction process, the powder will form a block of aluminum due to high temperature melting, causing the nitrogen bismuth not to be eaten into the block, making the reaction impossible. Therefore, it is necessary to suspend the reaction during the reaction. After cooling, the aluminum powder and the agglomerated aluminum which is melted are taken out and ground to form a granular aluminum powder, which is then placed in a high temperature furnace for reaction, and this is repeated several times. Nitrogen is in full contact with the aluminum powder to achieve high conversion. Thus, the direct nitriding method of the metal aluminum has the disadvantages of complicated processing; further, the process of the multiple grinding will introduce impurities, so that the conventional direct nitriding method of metal aluminum has time and energy consumption, The steps are complicated, the purity cannot be improved, and the impurity content is high. The above-mentioned conventional gas phase reaction method, organometallic precursor method, alumina powder carbon reduction nitridation method and metal sulphide direct nitriding method mainly have the disadvantages of excessive reaction time, and the following combustion synthesis method has relatively short reaction time. The relatively fins' can thus overcome the disadvantages of the high time cost caused by the preparation methods of the conventional aluminum nitrides described above. In the conventional combustion synthesis method, the reaction formula is also shown in the formula (7). The following is a brief description of the related art for each conventional combustion synthesis method: (a) Patent application No. 63-274605 to Japanese Patent Application Laid-Open No. Hei No. 63-274605, which is incorporated herein by reference. ), calcium nitrate (Ca(N〇3)2), yttrium oxide (y2〇3), barium carbonate (BaC03), barium nitrate (Ba(N03)2), nitric acid (Y(N〇3)3) , cerium oxide (Ce〇2) or aqueous grass 钇 (Y2 (C2〇4) 2. 8H2 〇)], mixed in an appropriate ratio, pressed into a suitable shape, and then placed in a nitrogen atmosphere of 50 atm, using electric heating The sheet is heated to ignite the reaction' to synthesize aluminum nitride (A1N) powder. However, the patent application of the Japanese Patent Application Laid-Open No. 63-274605, 201127747, is applied at a high pressure of 50 atmospheres, and the high pressure used will greatly increase the process risk. Moreover, it can also be used to generate a high pressure environment. The reaction of the equipment will result in an increase in overall equipment and operating costs. In the refractory container, the aluminum and aluminum nitride powder are mixed in an appropriate ratio, and then the whole is placed in liquid nitrogen.

(b) After the patent application of Japanese Patent Application Laid-Open No. SHO-64-76906, the liquid used in the patent application of the Japanese Patent Application No. 64-76906, the temperature of the sad nitrogen is very low, It will also increase the cost and operational complexity and risk of equipment and operation. (C) In the Japanese Patent Application Laid-Open No. 64-76905, the application of IS to nitrogen-containing m compounds [such as azide (10) (6), potassium hydride (KNS) or 4 nitriding) The powder is mixed in an appropriate proportion and placed in a fire container. 'The mixed powder is provided with a igniting agent, and the mixed powder and the igniting agent are placed in an electric heating furnace under pressure. The reaction was carried out under a nitrogen atmosphere of less than 1 〇 φ kg / C 〇r. Before the start of the reaction, the electric heating furnace is turned on to heat the reactants, and then the electric heating wire is used to heat the ignition agent, and then the combustion synthesis reaction of the synthetic nitriding is ignited to synthesize the nitrogen powder. (d) Patent No. 247897 of the Republic of China, and US 5,460,794 #. In the patent, the two cases use | Lu powder and solid nitrogen compounds as 'raw materials, the mixed powder of the two is molded and then completely coated with the ignition agent - placed in a closed container filled with nitrogen, heated and ignited The igniting agent generates a combustion synthesis reaction to form an aluminum nitride powder. (e) in the Republic of China Announcement No. 226987 and U.S. Patent No. 5,453,407, in which the use of Lu powder and solid gas-containing compounds as raw materials 201127747, and the addition of ii chemical salts, and then the three After the mixed powder is molded, it is completely covered with a igniting agent, placed in a closed container filled with nitrogen, and heated and ignited. The smoldering sword, the synthetic reaction is then ignited to synthesize the nitriding powder. The above-mentioned Japanese Patent Application Laid-Open No. 64-76905, the Republic of China No. 247897, and the Republic of China No. 226987 patent can reduce the & patents of the Japanese Patent Publication Nos. 63-274605 and 64-769-6 In addition, in order to make the reaction proceed in a self-propagating combustion mode, the solid I-containing compound must be a compound which is easily decomposed by thermal decomposition, so that the nitrogen gas generated by the thermal decomposition of the solid nitrogen-containing compound can be Reacts with aluminum powder. However, the nitrogen gas generated by the thermal decomposition of the solid nitrogen-containing compound may cause a problem that the reaction may not be caused by the pressure or the escape of nitrogen. (f) in the Patent Application No. 86103021 of the Republic of China, and in U.S. Patent No. 5,846,5〇8', the use of powdered and ammoniumized ammonium salts as raw materials, mixed powder molding, or placed in The open or porous high temperature resistant container is placed in a closed container filled with nitrogen, and the reaction is heated to generate 'aluminum nitride powder. (g) In the case of the patent application of the Republic of China on No. 86117545, the use of a compound that is decomposed or vaporized under the bribe and fUx is used as a raw material, mixed in an appropriate ratio and placed in an opening or The porous high-temperature resistant container is 'in a suitable shape and then in a sealed state filled with nitrogen gas. After heating and igniting the reaction, the nitriding powder is synthesized. A brief description of the patents of the Republic of China No. 86103021 and No. 86117545, which can be obtained by adding a toothed ammonium salt or a halogen-containing compound which can be decomposed below the melting point of the alloy, can obtain a high yield under low nitrogen pressure, although 201127747 avoids the above-mentioned Japanese Patent Publication No. 64-76905, the Republic of China No. 247897 patent and the Republic of China No. 226987 patent for the high pressure caused by the addition of α solid nitrogen compounds, but generates gas during the reaction. By-products such as hydrogen (HC1), ammonia (ΝΗ3), ammonium sulfate (NH4C1), chlorine (Cu) or carbon (C) increase the complexity and operating costs of subsequent treatments. (h) US Bulletin No. 5649278 In the patent, the powder is used as the reactant 'and 20% to 80 wt% (based on the total weight of the aluminum powder and the aluminum nitride powder) is used as a diluent, and the two are mixed. The powder mixture is placed in a high temperature resistant container such as graphite crucible or oxide ceramic, and the density of the powder mixture is between 0.5 and 1.5 g/cm3, and then placed in a reactor filled with nitrogen at 0.75. ~30 atmosphere (atm) of nitrogen Under force, heating-ignition combustion synthesis reaction to generate aluminum nitride powder. However, in the U.S. Patent No. 5,649,278, it is possible to prevent the melting of the powder, maintain the circulation of the nitrogen, and obtain a higher conversion rate, and avoid the need for further by-products such as the patent applications of the Republic of China No. 86103021 and No. 86117545. The disadvantages of removal, but the process of mixing the aluminum powder and aluminum nitride first, and the content of the diluent must be as high as 30 wt% or more to obtain a higher conversion rate, which also increases the complexity of the process. With the operating cost, and reducing the amount of feed per unit weight of the amount of nitrogen can be synthesized. In addition, the powder mixture must have a density between 〇.5g/cm3 and g/cm3, and aluminum powder and aluminum nitride having a bulk density higher than 1.25 g/cm3 or less than 〇5 g/cm3. Powder is not suitable, and this situation also limits the choice of raw materials. (1) The invention patent of the Republic of China Announcement No. 466212 and the US Patent No. 201127747 US Pat. No. 6,482,384 B1 are a method for synthesizing aluminum nitride powder. The aluminum powder is placed in an open high temperature resistant container. If the bulk density of the aluminum powder is less than 〇8g/cm3, the high temperature container is placed in a sealed chamber filled with helium, if the aluminum powder When the bulk density is greater than 〇8g/cm3, the porous aluminum tube is placed in an upright manner in the aluminum powder, or the initiator is placed on the top surface of the aluminum powder, or the porous aluminum tube is placed in the aluminum powder at the same time and in the aluminum The initiator was placed on the top of the powder, and the high temperature resistant container was placed in a sealed chamber filled with nitrogen. Thereafter, nitrogen gas is introduced into the bottom end of the high temperature resistant container, and the initiator is heated and ignited at the top end of the high temperature resistant container to cause the combustion reaction of the powder with nitrogen to form an aluminum nitride powder. However, in the invention patent of the Republic of China No. 466212 and the US Patent No. 6,482,384B1, when the aluminum powder has a high bulk density (sO.Sg/cm·5), the operation is complicated, and both are under the form of inertia. The conversion rate is only 99%, and there is still room for improvement. (1) The invention patent of the Republic of China Announcement No. 1230685 relates to a method and a device for synthesizing aluminum nitride, which utilizes a high pressure resistant reactor to mix aluminum powder with various compounds which can be synthesized, such as diluents, additives and aluminum foil. The compound such as a group is mixed to form a reactant, placed in an aluminum container having open ends, and then placed in a high pressure resistant reactor, nitrogen gas is introduced from the bottom of the vessel, and nitrogen gas is filled in the high pressure resistant reactor. To carry out a combustion synthesis reaction. In this way, a high-purity nitriding product can be obtained by reaction, and the various reagents for synthesizing aluminum nitride are burned under different pressures, different compositions, different bulk densities and various control conditions in the patent No. 1230685. The synthesis reaction is carried out to obtain a high-purity I product, which is suitable for various stacking density reactants, and can avoid the disadvantages of the complicated operation of the invention patent of the Republic of China No. 466212-10-201127747. ',,, and shirt 123 (3685 patent, because the law must be in the raw materials, medium = diluent, additives or consumables can be reacted to obtain the f product, so that the diluent, additive or (four) group added It may be a problem of V-nitriding 1 Lu product contamination, and its conversion rate is up to 99%, and there is still room for improvement in technology.

...(k) Invented the patent of the Republic of China g 1246997, the first is to put the raw materials, such as boiled or placed in the environment of high temperature and humidity, to modify the surface of the powder, so that | The surface of the powder forms a layer of oxide or hydroxide, so that the reactant does not melt during the combustion synthesis reaction, and the pores are maintained and the nitrogen is generated to generate a nitridation reaction. Nitriding! S product. In this way, it can be avoided that the Republic of China Announcement 帛i23〇685 said that the patent caused the contamination of Wei Huaming products due to the addition of _agents, additives and masses. However, this Patent No. 1,246,997 suffers from a lengthy and complicated modification of the surface of the aluminum powder prior to the combustion synthesis reaction, which causes a disadvantage of time consuming and energy consuming. (1) The invention patent of No. 1315296 of the Republic of China is a method for preparing aluminum nitride by modifying the surface of aluminum powder, which is first carried out in a holding step, and the aluminum powder is placed in a container; then a nitrogen gas is introduced. In the step of introducing, the container containing the aluminum-containing powder is placed in a nitrogen atmosphere; and then heating is performed to heat the aluminum-containing powder in the container until the aluminum-containing powder generates a combustion synthesis reaction. And after the start of the combustion synthesis reaction, an oxygen-containing gas is introduced, and the ceramic layer of the oxide or hydroxide layer is generated on the surface of the aluminum-containing powder through the oxygen-containing gas to prevent the aluminum-containing powder from being generated due to high temperature. Phenomenon; finally carry out - nitrogen backfill (four) body, and through the nitrogen, so that the gas flow through the containing powder, so that the body to work in the New Zealand (4) Lai Huaming. In this way, the patent needs to be dealt with before the combustion synthesis reaction: the defect of the process is caused by the tampering process. However, in the 1315296 tempering 4 丨丨 <+7 heart 6 ▲ patent, the oxygen-containing gas must be introduced into the combustion synthesis reaction at the beginning of the reaction to form a layer of lysate and then pass nitrogen gas to form Gasification Ming, square ^ = the effect of the same conversion rate' thus caused the process program to be more complex. In addition, because the milk containing gas which is not uniformly distributed in the stacking density of the powders is not able to uniformly flow through the surface of the powder containing the powder, and the temperature of the powder is not the same, resulting in Some of the (IV) body surfaces should be less uniform, thus causing the problem that the 131st patent is easy to have the uneven layer formed by the surface of the private surface, so that it avoids the inclusion of /p" Preferably, high conversion can be achieved only when a small amount of aluminum-containing powder is reacted, and the high conversion rate is not reproducible. For the reason of the description, it is necessary to further improve the above-mentioned nitrogen for f (IV) [Summary of the Invention] The purpose of the present invention is to improve the above disadvantages to provide a method for preparing aluminum nitride to form a high temperature resistance by uniformly reacting on the peak surface. The ceramic layer is the eye for it. The purpose of the monthly report is to provide a method for preparing nitrided I, to raise the effect of melting the aluminum powder by 12 -- 201127747 liters. The method for preparing aluminum nitride according to the present invention comprises the steps of: uniformly mixing aluminum powder and a surface modifying agent to form a reactant, and placing the reactant in a container; and heating The burning step exposes the reactants in the vessel to a nitrogen-containing gas and heats to a temperature above 660 ° C to burn the reactants during heating. The surface modifier and the aluminum powder surface-modify Reaction 'to form a ceramic on the surface of the aluminum powder

The layer 'and the powder is combusted and reacted with the nitrogen-containing gas to form aluminum nitride. The above and other objects, features and advantages of the present invention will become more <RTIgt; The method for preparing aluminum nitride comprises a reactant preparation step si to prepare a reactant, and a heating combustion step to illuminate the reactant to be exposed to the -containing material, so that the nitrogen-containing gas and the reactant are sufficiently Contacting 'Lang's the reactants for heating, the raw synthesis reaction is formed to form a nitride reduction. The reactant preparation step si and the heating and combustion less step S 2 of the present invention are respectively described in detail as follows: The reactant preparation step S1: the reactants of the preparation method of the aluminum oxide of δ ○ 、, 、, 、, 、 Aluminum powder and a ^., -if ^ surface modifiers are evenly mixed to form the anti-100 million silk to pay for the heart - Rong Ming powder can be selected for a variety of shapes ° ° more heart of ' ο 私私月 beans, For example, a sheet-like, spherical or 201127747 swarf-like powder is preferred and its content is preferably higher than 5%, and the average particle size is selected to be 〇.01~200/rm' as a reaction raw material. The surface modifying agent refers to a compound which can directly react with the Ming powder to form a pottery layer in the subsequent heating combustion step S2, or to generate an active substance at a temperature below (c) 66 (the temperature below rc is decomposed or gasified). H2Q or .2], and ''aluminum powder reacts to form a compound of the Tauman layer. The surface modifier can be (H20), sulphuric acid (A1_)3), succinic acid|g (A_4), magnesium oxychloride ( Mg(〇H)2), hydrogen-oxygen (Ca(〇H)2), and hydroquinone (Ba (called) group. The towel, the surface is changed (4) to capture the reaction in percentage of money The total weight of the material (U~·, and preferably the total weight of the reactants) If the content of the surface modifier in the reactant t is lower than 〇, the content of the surface modifier is too small to be The ceramic layer is formed on the surface of the powder; if the surface modifier is higher than 20% in the reactant, the ceramic layer may be caused by an excessively high surface modifier content. The thickness is too thick to hinder the reaction between the Ilu powder and the nitrogen-containing gas, and the reaction is completely reversed. The reaction preparation step S1 is to uniformly homogenize the aluminum powder and the surface modifier. After being combined as the reactant, the surface modifier is distributed between the particles of the powder, and the reactant is placed in the container. The device used in the present invention is mainly related to the Republic of China Announcement No. 1246997. The same, the hai can be selected from graphite 'nitriding slag (A1N), nitriding (SW) oxidized! Lu (Al2 〇 3), oxidized (Zr 〇 2) or carbonized crane (wc) In the present embodiment, a graphite crucible is selected as the container, and the plurality of perforations are preferably provided on the volume 5, and the sum of the inward-products of the perforations preferably accounts for the total surface area of the container. 50% (referred to as τ's container perforation - Η 201127747 rate) 'to enhance the contact between the listener and the reactants, thereby improving the overall reaction conversion rate. Heating and burning step S2: mouth month tea photo 1 No, the method of preparing the nitrile of the present invention, the burning step S2 is such that the reactant of the volume (4) is exposed to the nitrogen-containing gas and the reactant is heated to a temperature above 6 sails to ignite the reactant. During the heating process, the surface modifier directly or indirectly reacts with the Ming powder production. Forming an m layer on the surface of the impurity, and the f powder is nitrided by the nitrogen gas containing by combustion, and the nitrogen-containing system can be selected from nitrogen, ammonia and air. The group 'is used to provide the money to choose the source of the atomic material contained in the anti-reservoir. After the pumping straight, the _^= is placed in the vacuum withstand voltage reaction, and now the person ^ Qing 4 contains the Wei body Forced person vacuum_reactor content == preferably is 1. 1~30 atmosphere (called to expose the point to the money gas, and then through the orbital search method to heat the reaction, (four) or infrared The method is carried out = burning = to 4 phase (four) α point (10). C) or more, so that the rotation is caused by the powder transfer] and the surface modifier 2,: uniform, 'mouth, and exposed to the In the nitrogen-containing gas 3, therefore, ft::: not in the 'ash heating process', the surface modifier 2 can be as wide as the first two two, the formula and _ 1 react, and evenly = / Forming (4) High temperature pottery 1 layer 4 (for example, oxide, 垔 1 1 钱 钱 氧化物 ,), thus improving the uniformity of the ceramic layer 4 of the surface 15 201127747. For example, if the surface modifier is selected to be water, the water may directly react with the aluminum powder to form a ceramic layer of aluminum hydroxide or indirectly with the aluminum powder during heating. A reaction as shown in formula b is carried out to form a ceramic layer of alumina. 2[A1]-A1+6H20—2[Λ1]-Α1(0Η)3+3Η2..........(a) 2[A1]-A1(0H)3-^[A1]- Al2〇3+3H20......(b) If the surface modifier is selected from aluminum hydroxide, magnesium hydroxide, calcium hydroxide or barium hydroxide, during the heating process, The aluminum hydroxide, magnesium hydroxide, hydroxide or barium hydroxide will be respectively represented by formula c, formula d, formula e or formula f, and water and oxide are generated by thermal decomposition, and the water produced is As an active material, the aluminum powder is reacted with the aluminum powder to form a pottery layer of a hydroxide material; or further indirectly reacted with the powder to form a ceramic of alumina as shown in formula b Floor. Therefore, the aluminum oxide, magnesium hydroxide, calcium hydroxide or barium hydroxide can be used as a surface modifier to indirectly react with the aluminum powder to form the ceramic layer. Among them, the surface modifier is preferably selected from aluminum hydroxide. 2A1(0H)3 ^ Al2〇3 + 3H20.....................(c)

Mg(OH)2 ^ MgO + I-I20........................(d)

Ca(OH)2 CaO + H2〇..............................(e)

Ba(〇H)2 — BaO + H20.........................(f) If the surface modifier is selected as aluminum nitrate, Then, during the heating process, the aluminum nitrate will be as shown in the formula g, and the ruthenium 2 is generated by thermal decomposition, and the ruthenium 2 produced can be used as an active material to form a reaction with the powder as shown in the formula h. Oxidation of the material of the pottery layer. Therefore, using the nitric acid as a surface modification -] 6 - 201127747 plasmon can indirectly react with the aluminum powder to form the ceramic layer. 2Α1(Ν〇3)3 &quot;&quot;&quot;^ A]2〇3 + 6N〇2+3/2 〇2..................... (§) 2[Α1]-Α]+3/2 02 -&gt; [Al]-Al2N〇3......................(h Referring to FIG. 4 again, after the ceramic layer 4 is formed, as the temperature continues to rise to 660 ° C, even if the aluminum powder 1 is fused to form a molten aluminum crucible due to high temperature, the high temperature resistant ceramic The layer 4 still allows a gap between the dazzling aluminum crucibles to allow sufficient flow of the nitrogen-containing gas 3, thereby avoiding the occurrence of melting.

Please refer to Figure 5 again, until the temperature continues to rise above 660 ° C. 'The pottery layer 4 is broken due to the thermal expansion of the internal molten aluminum, and the molten state will overflow.' At this time, due to the inclusion The nitrogen gas 3 can flow sufficiently through the gaps 'and the temperature has reached the high temperature of the combustion synthesis reaction, so the nitrogen-containing gas 3 can be rapidly reacted with the molten aluminum to form a product of nitriding:) The ceramic layer 4 will also be completely nitrided with nitrogen to form the product of the aluminum nitride 5, as shown in Fig. 6, thereby increasing the overall conversion. Therefore, the present invention is uniformly mixed with the aluminum powder and the reaction sputum by the addition of the surface modifier, so that the surface modifier will react directly or indirectly with the (4) during heating, and uniformly The surface of the fun powder forms the layer of the temperature layer, which can avoid the occupationalization|g preparation method. First, the oxygen-containing gas is introduced into the table (4), and then the nitriding reaction is carried out to cause the wear. It is impossible to quit the flow of Shao powder and the unevenness of the ^ \ e knife cloth. However, the pottery layer formed by the invention will also be provided by the full amount of nitrogen to form Wei Huashao, so the nitrogen (10) finished product Oxygen content is not due to the surface modifier -17 — 201127747

The addition of D &quot;up to this&quot; completes the nitrided preparation process of the present invention, thereby increasing the conversion of aluminum argon. In addition, the reactant preparation step can be selectively carried out by the following treatments [especially, the volume occupied by the reactants in the container (4) total weight of the whole body/reactant stack) is higher than the peak; In order to avoid the decrease of the conversion rate, the reactant is preferably at least one of the following treatments: a diluent is mixed with the surface and the surface modifying agent as a wide reactant, and the diluent is high in melting point and does not participate in the reaction. ::Optional Free Nitrogen 丨N)Sale Qing 4), Nitriding Tai (3)N), Nitride Peng (BN), Carbonized Stone Xi (%), Oxidation Shao (5) Office ^ Huayin (Construction 'Dioxide Chin (10)) And the group of dioxotomy (10) = _ touch the powder, increase the gap between the shaft powder I to help absorb heat, the temperature should be too high. The riding agent accounts for _~8 of the total weight of the reactants by weight percentage, and is preferably a war. And (7) additionally placing at least one non-porous or porous junction on the reaction, and then selecting the reactant to be placed in the container, and the reaction needle can be added to increase the gap to the content. The circulation of the sister. The inner diameter of the saki is selected as 卜^, the::3__, the diameter of the perforation of the pipe wall is selected as = ??^, if the porous pipe is selected, the total area of the perforation is occupied by ^= The wall area is ~~· to enhance the nitrogen content (3) and the initiator is laid on the reactant. The initiator refers to the knife or gasification under Lvwenrong-'趟'乂 under 18—201127747 a compound, for example, a group consisting of a compound of free chemistry, such as ammonium chloride, a compound containing 1, (1, 4, 4), a halogen-containing fine powder, and a chain foil ball, to assist the reaction. The bismuth powder in the product produces combustion. # Before laying a layer of high temperature resistant isolation compound on the container, then the reaction, W ^ , placing the square; in the έ玄谷器, 'the isolation compound is located in the container and the reaction privately; ^ ^ people, between To help absorb heat and thus increase conversion rate. The isolating material can be selected from nitrides, oxides, carbides or other high temperature resistant materials. For example, the present invention selects aluminum nitride as the isolation compound. The aluminum nitride product is affected by the nitriding chain product formed by the combustion synthesis reaction between the isolating compound and the reactant. Purity. The barrier can be selected as non-porous or porous (four). In addition, in the heating and burning step S2, the column can be selectively treated, ^•, 甘+β±", &lt;丁广〇1%^, the content of the surface modifier is lower than the total weight of the reactant When the aluminum is under 0 U, the amount of the surface modifying agent is small, and the surface of the ceramic layer may not be formed after most of the crucible is formed. Therefore, it is preferred that the reactants start to react and cry an oxygen-containing gas. For example, oxygen or air, the vacuum withstand voltage is passed. °, the oxygen-containing gas is passed through the gap between the aluminum powder and the contact 'so that the oxygen-containing gas can be oxidized with the (10) to raise the ceramic layer of the ceramic powder to form an oxide layer of the ceramic material' to further Lifting the recharge degree; then turning off the oxygen-containing gas, and re-expanding the gas-containing gas to the vacuum pressure-resistant reactor, so that the layer coated with the ceramic layer is in the ancient and/or nitrogen-containing gas As described in the foregoing reaction mechanism, the ceramic enamel is also broken, so that the internal aluminum powder can sufficiently form an aluminum nitride product with the gas-containing gas. Therefore, the Tauman layer can be formed more uniformly on the surface of the powder by passing the oxygen-containing gas. As described above, the production of the aluminum nitride powder can be completed by the above-described reactant preparation step s] and the heating and burning step S2. The aluminum nitride product obtained by the completion of the reaction can be further ground into powdery particles for use as a further step. The following is an example of the preparation method of the aluminum nitride of the present invention under various conditions to verify that the present invention can greatly improve the production efficiency and conversion rate of aluminum nitride and simplify the process. Referring to Table 1, it is the spring reaction conditions of the seventh to seventh embodiments of the present invention. Taking the first embodiment as an example, 100 g of flake aluminum powder and 1 wt% of aluminum hydroxide (surface modifier) are first mixed as the reactant, and the diameter is 8 cm, the height is 9 cm, and the perforation rate is 15 〇/ A graphite crucible (container) of 0 is placed with a layer of aluminum nitride powder (high temperature resistant isolation compound) having a particle size of 〇·〗 3mm, and then a non-porous cylindrical aluminum foil (barrier layer) is placed in the graphite. In the event of a disaster, the reactant was placed in a cylindrical aluminum foil, and finally the aluminum nitride powder was uniformly filled between the cylindrical aluminum foil and the ruthenium graphite. The graphite crucible containing the reaction product is placed in the vacuum pressure-resistant reactor, and the vacuum is firstly applied to the crucible.] Taur (ton·) simultaneously passes the atmosphere of 3 atmospheres from the bottom and sides of the graphite crucible. (including nitrogen gas), heating with tungsten wire coil (heating wire) (voltage: 3 volts 'current: 28 amps), heating for about 30 seconds, combustion synthesis reaction is ignited, then turn off the tungsten wire coil power supply And the graphite is vented to the bottom of the air (oxygen-containing gas) for 1 minute, the air flow rate is 20 liter / min - 'then continuously continue to pass nitrogen to maintain the pressure in the vacuum withstand pressure reactor is 3 atm (recharged nitrogen pressure) ), the reaction is completed in about 60 seconds, and the 20 - 201127747 aluminum nitride product is obtained. After the aluminum nitride product 〆, ^ 〜 part is taken out, it is a light yellow loose powder limb 'this nitrogen gamma product is de-milled and determined by X-ray diffractometer (XRD), as shown in Figure 7, The middle arrow indicates the diffraction peak of Nitride, which is shown as aluminum nitride powder without flaws, α w &quot; a, ",, taste" and put a few grams of aluminum nitride powder into 15wt% Hydrochloric acid (HC1) solution is extracted from the residual aluminum in the wx, and the hydrogen is collected by the drainage and gas collection method, and the enthalpy is calculated by using the makeup 隹 丄 丄 丄 & 方 方 方 方 方 方 方 方 方 方 方 方 方 方 方 方 方 方The rate is about 99.96%, and the product is analyzed by the nitrous oxide analyzer to obtain an oxygen content of about 1515.5%. The process conditions of the second to seventh embodiments and the first yoke yoke are different. The seventh embodiment of the table of 'the towel' is heated by microwaves, and after heating, it is the same as the first embodiment. The remaining process conditions of the embodiments are the same as those of the first embodiment. As a result, it can be seen that the conversion rate of the first to seventh embodiments can reach 99.95% or more regardless of heating by a heating wire or heating by microwave, and the reproducibility is relatively high, and the oxygen content is high. Only 0.15%, and the overall reaction can be completed in only a few minutes, which can greatly improve the process efficiency and conversion rate. Table 1. Differences in reaction conditions of the first to seventh embodiments Example Jinlu powder modifier (wt% Perforation rate of container (%) Nitrogen pressure (atm) Heating method Recharge nitrogen pressure (atm) Conversion rate (wt%) Oxygen content (wt%)] 100g Flaky 1% aluminum hydroxide 15 A &gt; 30V: 28A Heating wire heating 3 99.96 0.15 2 100g flake 1% aluminum nitrate 15 3 25V, 28A heating wire heating 3 99.95 0.1 100g spherical 2% aluminum nitrate 15 3 30V: 28A heating wire heating 3 99.96 0.1 4 100g aluminum crumbs]% Aluminum hydroxide 15 30V: 28A heating wire heating 3 99.96 0.1 5 100g flakes]% calcium hydroxide 10 30 30V, 28A ' heating wire heating 4 99.96 0.15 6 100 〇 flakes 1% barium hydroxide 15 20 30V, 28A electricity Hot wire heating 20 99.96 0.15 201127747 Γ 钡---------^ !? 150g Sphere]% nitric acid 15 Λ 1000W [—4 ^ 1 Aluminum microwave 埶 3| 99^961 0.1 ——1 -- - a __ _ 8 to 10th embodiment and the process conditions of the first embodiment, the reed table 1 ', of which, the inverse of the 1Q embodiment An additional 30 wi% of the dopant was added to the solution, and the conditions of the (four) conditions and the results of the first embodiment were obtained. The cylindrical shape of the eighth to the third embodiment was: .96%' reproducibility was quite high. The oxygen content is also only. .2 2; = = The reaction can be completed in only minutes, which can greatly improve the process efficiency and conversion of the example aluminum powder 8 100g flakes 9 flakes 10 ]00g spherical 1% nitric acid | S_ — ]% hydrogen oxygen 1 % hydrogen oxygen

Modifier (wt%) Vessel wear rate (%) 10 Perforation rate of round-shaped box (%) Heating mode Air passage time (min) Conversion rate (wt%) Oxygen content (wt%) 50 30Y 40A heating wire heating 1.5 99.96 0.15 30 ----- 30V. 28A heating wire heating 2 99.96 0.2 20 — 35V: 28A heating wire heating 1 1 99.96 0.15 into the η and 12th embodiment and the process of the third embodiment The condition difference is listed; in Table 2, the remaining process conditions are the same as in the first embodiment. According to the results, the first embodiment is laid on the reactants, and the ampoule is used as a starter to help the reactants to burn; the 12th bakelite '33 powder, surface modifier and 2 5 wt% of nitriding|g (diluent) /, the same as 5 as the reactant to raise the gap between the aluminum powder particles. 201127747 The conversion rate of the two examples can reach 99.96%, the reproducibility is quite high, the oxygen content is only 0.2% or less, and the overall reaction can be completed in only a few minutes, which can greatly improve the process efficiency and conversion rate. Table 3, Differences in Reaction Conditions of the 11th and 2nd Embodiments Example Aluminum Powder Modifier Diluent Starter Heating Mode Air Passing Time (min) Conversion Rate (wt%) Oxygen Content (wt%) 11 L〇〇g flake 3m ice without ammonium chloride 30V; 30A electric heating wire T5^ 99.96 0.2 12 l〇〇g flake 3wt% hydrazine Ming 25wt% aluminum nitride no 30V, 28A heating wire heating 1 99.96 0.1

The difference of the process conditions of the thirteenth to fifteenth embodiments and the first embodiment is shown in Table 4, and the thirteenth to fifteenth embodiments are not heated until the electric heating wire is electrically heated for 30 seconds until the reactant is burned. The air is directly filled with nitrogen gas; wherein, in the fifteenth embodiment, a porous aluminum tube is separately placed in the reactants to facilitate gas passage. The remaining process conditions of the respective embodiments are the same as those of the first embodiment.

It can be seen from the results in Table 4 that in the 13th to 15th embodiments, the conversion rate can reach 99.96% or more, the reproducibility is quite high, the oxygen content is only less than %2%, and the overall reaction is only f minutes. Completed, can greatly improve process efficiency and conversion rate. Example: 丨明粉丨 modifier; device wear difference (wt°/〇) hole (%) rate 13 i〇〇g sheet 4% aluminum hydroxide 20 14 l〇 〇g flake 0.5% aluminum hydroxide 15

Non-porous I&quot; 10〇2 flake 30% aluminum hydroxide 30 ® ^ Ming Po &lt; ! rate (%) 1 pressure 1) heating method backfilling nitrogen pressure (atm) conversion rate (wt%) oxygen content (wt %) 30V, 28A heating wire heating 3 99.96 5T 30V, 35A heating wire heating 3 99.97 0.2 30V, 28A heating wire heating 2 99.96 0.15 ~ 23 201127747 Differences between the processing conditions of the 16th and 17th embodiments and the first embodiment In Table 5, and in the sixth and third embodiments, after heating the heating wire for 3 seconds until the reactant is burned, the air of the first embodiment (oxygen-containing gas) is replaced by oxygen into the vacuum. After the pressure-resistant reactor was charged, nitrogen gas was again charged, and the aluminum nitride powder laid in the sixteenth embodiment was 〇5 to 3 nm, and the rest of the process conditions were the same as in the first embodiment. It can be seen from the results in Table 5 that in the 16th and 17th embodiments, the conversion rate can reach 99.9% or more, the reproducibility is quite high, the oxygen content is only less than 3%, and the overall reaction takes only a few minutes. Can be completed, which can greatly improve process efficiency and conversion rate. Table 5, Example 16 Aluminum Powder_Modifier 16]00g j Wt% Hydrogen Oxide Sheet Aluminum 17 l〇〇g Twt%—Oxygen Flaky Aluminum Example Reaction Conditions Difference Initiator Nitrogen Pressure ( Atrn) Oxygen access time (seconds) Backfilled nitrogen pressure 1 Conversion force (atm) l (wt%) Oxygen content (wt%) &gt; t \ N 4 15 3 99.95 0.2 Ammonium chloride Γ~ 4 30 4 99.9 1 0.3 The difference between the process conditions of the eighth to twenty-first embodiments and the first embodiment is shown in Table 6. The other process conditions are the same as those of the third embodiment. Eight = Table 6 results show that the 18th to 2nd embodiment used aluminum Zhilida 20〇g or 35〇g 'conversion rate can still reach 99.96% high conversion rate reproduction twin phase ^ Still, the oxygen content is only less than 0.25%, and the overall reaction can be completed in only a few minutes. Therefore, the preparation method of the nitrogen contact in this case is that the reaction can be fully reacted for a large amount of reactants, and the gas can not be avoided. The disadvantage of the gap between the powders can increase the conversion rate. Oxygen content 201127747 (wt%) Pressure (atm) Into time (min) Gas pressure (atm) (wt%) (wt%) 18 200g Integrity 1% aluminum hydroxide Λ 30V: 28Α Heating wire heating 1 3 99.96 0.25 19 2〇〇g flake 2% aluminum hydroxide + 1% aluminum nitrate 3 35V: 30A heating wire heating · · 5 3 99.96 0.2 20 350g spherical 10% barium hydroxide 3 15V, 25A heating wire heating 1 3 99.96 0.15 21 350g spherical 5% aluminum nitrate 3 40V: 30A heating wire heating 2 3 99.96 0.15 In addition, the scanning electron microscope (SEM) results of the prepared aluminum nitride powder are shown in Annex 1. It can be clearly seen that there is still a gap between the formed nitriding powders, and it can be verified that in the process of the combustion synthesis reaction, the aluminum powder does have a gap between the aluminum powders for gas to pass, thereby achieving the effect of high conversion. Through the above various examples, the preparation method of the nitriding of the present invention can be clearly verified. By uniformly mixing the surface modifying agent with the aluminum powder, the high temperature resistant ceramic layer can be uniformly formed on the surface of the aluminum powder. The effect of avoiding the phenomenon of melting of aluminum is achieved, so that the aluminum powder can maintain a gap between the aluminum powder to fully flow through the surface of the aluminum powder, and fully react with the aluminum powder to increase the conversion rate of the aluminum nitride. Although the present invention has been disclosed in the above-described preferred embodiments, it is not intended to be used in the present invention. Any skilled person skilled in the art will be able to make various changes and modifications to the above-mentioned actual conditions. ^Technology of the stipulations of the stipulations of the stipulations of the stipulations of the invention. A 25 - 201127747 [Simple description of the figure] ^ Figure: Flow chart of the preparation method of the nitrogen (10) of the present invention. Fig. 2 is a schematic view showing the exposure of the ls powder and the surface modifying agent of the present invention to a nitrogen-containing gas. Figure 3: Schematic diagram of the present invention_surface forming a ceramic layer. Brother 4: The hair of the duck is melted _ wrapped in the Tao Jing layer _ schematic. Fig. 5 is a schematic view showing the cracking of the ceramic layer of the present invention due to high temperature. Figure 6: Schematic representation of the aluminum nitride product of the present invention. Figure 7: XRD pattern of nitriding prepared by the method of disproportionation. Attachment -: An SEM image of the U-form prepared by the preparation method of the present invention (10). &amp; [Description of main component symbols] Wenrong Rongzi production Lu nitrogenous body Aluminum nitride 1 Aluminum powder 2 Surface modifier 4 Ceramic layer

Claims (1)

201127747 VII. Patent application scope: 1. A method for preparing aluminum nitride, comprising: a reactant preparation step, uniformly mixing a powder and a surface modifier to form a reactant, and placing the reactant in a container; And a heating combustion step of exposing the reactants in the vessel to a nitrogen-containing gas and heating to a temperature above 660 ° C to burn the reactants. During the heating process, the surface modifier is The aluminum powder generates a surface modification reaction φ to form a ceramic layer on the surface of the I-lu powder, and the powder is combusted with the nitrogen-containing gas by combustion to form aluminum nitride. 2. The method for preparing aluminum nitride according to claim 1, wherein in the heating and burning step, the surface modifying agent directly reacts with the aluminum powder to form the ceramic layer. 3. The method for preparing aluminum nitride according to claim 1, wherein in the heating and burning step, the surface modifying agent indirectly reacts with the aluminum powder to form the ceramic layer. 4. The method for preparing aluminum nitride according to claim i, wherein in the heating and burning step, the surface modifying agent generates an active substance by thermal decomposition, and then transmits the active material and the aluminum powder. The surface is modified to form the Tauman layer. 5. A method for preparing a nitrided I-lu according to the scope of the patent application, wherein the group consisting of water, aluminum hydroxide, aluminum nitrate, magnesium hydroxide, calcium aroxide and barium hydroxide is used as the group. Surface modifier. The preparation method of the nitriding according to claim 1, wherein the surface modification is 0.1-27 to 201127747 to 30% by weight of the total weight of the reactant. 7. The preparation method according to the application of the patent scope 帛6, wherein the surface modifying agent is 5% by weight of the total weight of the reactant. 8. The method for preparing a gasification according to the scope of the patent application, wherein the aluminum powder and the surface modifying agent are uniformly mixed with a diluent to form the reactant. = Shen. The preparation method of the nitriding in the eighth paragraph of the patent scope, wherein the violation is made by nitriding (A1N), nitriding cerium (Si3N4.), nitriding (TiN nitriding (BN), niobium carbide ( As the diluent, a group consisting of sic), oxidized (Al2〇3), emulsified (ZK) 2), dioxin (Ti〇2), and cerium oxide (scratch) is used. - The preparation method of the nitriding according to the scope of the patent application 帛8, wherein the diluent accounts for _~ rib% of the total weight of the reactant by weight percentage]] In the preparation method of the nitriding, in the reactant compounding step, at least one aluminum tube is further disposed in the reactant. ''12. According to the preparation method of the nitriding according to the scope of the patent application, wherein the reactant preparation step, the initiator is laid on the reactant, and the initiator can be below 66 CTC. Decompose or gasify. The method for preparing nitriding 33 according to the invention of claim 4, wherein in the reactant compounding step, the reactant is placed in the container before the layer is separated from the container. Internally, the isolation: the system is between the container and the reactant. σ -28 - 201127747 14. The method for preparing aluminum nitride according to claim 13, wherein a barrier layer is further disposed between the isolation compound and the reactant. 15. The method for preparing aluminum nitride according to claim 1, wherein the pressure of the nitrogen-containing gas in the heating and burning step is 0.1 to 30 atm. The method for preparing aluminum nitride according to claim 1, wherein in the heating and burning step, after the reactant is burned, an oxygen-containing gas is brought into contact with the reactant, and the oxygen-containing gas is turned off. The nitrogen-containing gas is again brought into contact with the reactant. 17. The method for preparing aluminum nitride according to claim 1, wherein the nitrogen-containing system is selected from the group consisting of ammonia, nitrogen and air. 18. The method for preparing aluminum nitride according to claim 1, wherein the heating and burning step is performed by means of a heating wire, a microwave, a laser or an infrared ray. 19. The method for preparing aluminum nitride according to claim 1, wherein the heating and burning step forms a ceramic layer of an oxide, a hydroxide, a nitride or an oxynitride. —29 —