JPH03115109A - Boron nitride powder - Google Patents
Boron nitride powderInfo
- Publication number
- JPH03115109A JPH03115109A JP1250765A JP25076589A JPH03115109A JP H03115109 A JPH03115109 A JP H03115109A JP 1250765 A JP1250765 A JP 1250765A JP 25076589 A JP25076589 A JP 25076589A JP H03115109 A JPH03115109 A JP H03115109A
- Authority
- JP
- Japan
- Prior art keywords
- boron nitride
- powder
- sintering
- nitride powder
- sintered
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 49
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000843 powder Substances 0.000 title claims abstract description 36
- 238000005245 sintering Methods 0.000 claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000012298 atmosphere Substances 0.000 abstract description 9
- 229920000877 Melamine resin Polymers 0.000 abstract description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004438 BET method Methods 0.000 abstract description 5
- 229910021538 borax Inorganic materials 0.000 abstract description 3
- 239000004328 sodium tetraborate Substances 0.000 abstract description 3
- 235000010339 sodium tetraborate Nutrition 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000000465 moulding Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- -1 alkaline earth metal borate Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000013001 point bending Methods 0.000 description 3
- 238000001272 pressureless sintering Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は窒化硼素（以下、ＢＮと記す）粉末、更に詳し
くは焼結特性の優れた窒化硼素粉末に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to boron nitride (hereinafter referred to as BN) powder, and more particularly to boron nitride powder with excellent sintering properties.
窒化硼素は白色の粉末で、特に六方晶の物は黒鉛と同じ
層状構造で熱伝導性、電気絶縁性、潤滑性、耐熱性及び
耐蝕性に優れた特性を持うている。Boron nitride is a white powder, especially the hexagonal crystal, which has the same layered structure as graphite and has excellent properties such as thermal conductivity, electrical insulation, lubricity, heat resistance, and corrosion resistance.
また、焼結体は、機械加工が可能であるため、これらの
性質を生かして多岐な用途に用いらている。Further, since sintered bodies can be machined, they are used in a wide variety of applications by taking advantage of these properties.
しかしながら、従来製造販売されてきた窒化硼素は難焼
結性であるため、窒化硼素焼結体を製造するにはアルカ
リ土類金属化合物等の焼結助剤を多量に添加し、ホット
プレスを使用して圧力を加えて加熱する方法がとられて
きた。However, the boron nitride that has been manufactured and sold conventionally is difficult to sinter, so in order to manufacture boron nitride sintered bodies, a large amount of sintering aids such as alkaline earth metal compounds are added and hot pressing is used. A method of applying pressure and heating has been used.
（本発明が解決しようとする問題点）
従来の窒化硼素焼結体の製造では前述の様に焼結助剤を
多量に加え、なおかつホットプレスを使用して高温高圧
処理が必要であるため生産性の向上が困難であり製造コ
ストが非常に高くなる。また、大型の焼結体を得ようと
しても、特殊な設備であるため制限があり任意の大きさ
の物を得ることも困難であった。また、ホットプレスの
様な焼結方法を用いるにしても窒化硼素は焼結が困難で
あるためアルカリ土類金属化合物の様な焼結助剤を添加
する必要が有るため焼結助剤を均一に混合するためのコ
ストもかかっていた。(Problems to be Solved by the Invention) In the conventional production of boron nitride sintered bodies, as mentioned above, a large amount of sintering aid is added and high-temperature and high-pressure treatment using a hot press is required. It is difficult to improve the properties and the manufacturing cost becomes very high. Furthermore, even if an attempt was made to obtain a large-sized sintered body, there were limitations due to the use of special equipment, and it was difficult to obtain a sintered body of any desired size. In addition, even if a sintering method such as hot pressing is used, it is difficult to sinter boron nitride, so it is necessary to add a sintering aid such as an alkaline earth metal compound, so the sintering aid must be uniformly distributed. There was also the cost of mixing the
従来のホットプレスによるコスト高を改良するために、
窒化硼素を常圧で焼結する方法が近年検討され、例えば
（１）特開昭６２−１２３０７０号ではＢ粉末を１重量
％以上、ＫＯ−ＢｓＯｓ （Ｘはアルカリ土類金属）の
粉末０．５〜７０重量％を含有してなる混金粉末を成形
後、還元窒化雰囲気で焼結せしめることを特徴とする窒
化ボロン系焼結体の製造方法が、（２）特開昭６３−４
０７６９号ではＢｚＯｓとアルカリ土類金属酸化物およ
び又はアルカリ土類金属フン化物を含有する大方晶系窒
化硼素を不活性雰囲気中で加熱して得られた高結晶性生
成物を用いて成形し常圧焼結する方法が、（３）特開昭
６３−３０３８６２号では結晶子の大きさＬｃが１００
〜２５０Å、ＢＮ純度９０〜９７重量％のＢＮ粉末原料
に焼結助剤としてＢｅ、Ｍｇ、 Ｃａ、 Ｓｒ、 Ｂａ
の硝酸塩１種または２種以上を加えて、液体分散媒体中
で混合し、該混合物を成形し、該成形体を常圧Ｎ２雰囲
気下で焼成することを特徴とするＢＮ焼結体の製造方法
が、（４）特開平１−１３１０６５号にはアルカリ土類
金属はう酸塩を２〜４０重量％含有してなり相対密度が
６５％以上であることを特徴とする常圧焼結窒化硼素成
形体が、（５）特開平１−１７２２７１号には窒化硼素
９０〜９９重■％とアルカリ土類金属酸化物の１種若し
くは２種以上１〜ｌＯ重量％とを含む混合粉末を１ ＝
１０ｔ／ｃｍ”の加圧下に成形し、非酸化性雰囲気中１
〜７６０ｔｏｒｒの減圧若しくは常圧下乃至１０ｋｇｆ
／ｃＩＩ＋”以下の加圧下１４５０〜１８００°Ｃで焼
結することを特徴とする窒化硼素焼結体の製造方法の記
述がある。しかしながら、いずれの場合も焼結助剤を添
加する必要があるが、この焼結助剤の添加は添加量が不
適当だと強度が低くなり、混合が不十分だと強度のばら
つきが大きくなる等の問題があった。このため秤量、混
合を精密に行うために多くの時間を要し、また焼結晶の
強度もホットプレス品に比べ非常に小さい等十分に改良
された方法とはなっていなかった。また、焼結助剤のコ
ストもかかっていた。In order to improve the high cost caused by conventional hot pressing,
In recent years, a method of sintering boron nitride under normal pressure has been studied. For example, (1) JP-A No. 62-123070 discloses that B powder is 1% by weight or more and KO-BsOs (X is an alkaline earth metal) powder is sintered in an amount of 1% by weight or more. A method for producing a boron nitride-based sintered body is disclosed in (2) JP-A-63-4, which comprises molding a mixed metal powder containing 5 to 70% by weight and then sintering it in a reducing nitriding atmosphere.
In No. 0769, a highly crystalline product obtained by heating macrogonal boron nitride containing BzOs and an alkaline earth metal oxide and/or an alkaline earth metal fluoride in an inert atmosphere is used to form the product. The pressure sintering method is disclosed in (3) JP-A No. 63-303862, in which the crystallite size Lc is 100.
Be, Mg, Ca, Sr, Ba as sintering aids to the BN powder raw material with ~250 Å and BN purity of 90 to 97% by weight
A method for producing a BN sintered body, which comprises adding one or more types of nitrates, mixing in a liquid dispersion medium, molding the mixture, and firing the molded body under a normal pressure N2 atmosphere. However, (4) JP-A-1-131065 discloses a pressure-sintered boron nitride containing 2 to 40% by weight of an alkaline earth metal borate and having a relative density of 65% or more. (5) JP-A-1-172271 discloses a mixed powder containing 90 to 99% by weight of boron nitride and 1 to 10% by weight of one or more alkaline earth metal oxides.
It was molded under a pressure of 10t/cm" and molded in a non-oxidizing atmosphere.
~760torr reduced pressure or normal pressure to 10kgf
There is a description of a method for manufacturing a boron nitride sintered body characterized by sintering at 1450 to 1800°C under pressure of /cII+'' or less.However, in either case, it is necessary to add a sintering aid. However, there are problems with adding this sintering aid, such as if the addition amount is inappropriate, the strength will be low, and if mixing is insufficient, the strength will vary widely.For this reason, weighing and mixing must be done precisely. This method was not sufficiently improved, as it took a lot of time and the strength of the sintered crystals was much lower than that of hot-pressed products.Additionally, the cost of sintering aids was high.
（問題点を解決するための手段〕
本発明者らは今般上述の問題点を解決し、焼結助剤無添
加で常圧焼結が可能であり、また焼結体強度も従来知ら
れている常圧焼結体より大きくなる窒化硼素粉末につい
て観音研究した結果、結晶子の大きさが４０〜１５０人
で、比表面積が１５０〜３００ ｍ”７ｇ、酸素含有量
が４〜ｌＯ重量％である窒化硼素粉末であれば、焼結助
剤が無添加で常圧焼結が可能であること、また焼結体強
度も大きくなる事を見いだし本発明を完成するに到った
。(Means for Solving the Problems) The present inventors have now solved the above-mentioned problems, and have realized that pressureless sintering is possible without the addition of sintering aids, and that the strength of the sintered body is higher than previously known. As a result of Kannon research on boron nitride powder, which is larger than the pressureless sintered body, the crystallite size is 40 to 150, the specific surface area is 150 to 300 m''7g, and the oxygen content is 4 to 10% by weight. We have completed the present invention by discovering that with a certain boron nitride powder, atmospheric pressure sintering is possible without the addition of sintering aids, and that the strength of the sintered body is increased.
即ち、本発明は、結晶子の大きさが４０〜１５０人で、
比表面積が１５０〜３００ ｍ”１ｇ、酸素含有量が４
〜１０重量％である焼結助剤無添加で常圧焼結が可能な
窒化硼素粉末に関する。That is, in the present invention, the crystallite size is 40 to 150,
Specific surface area is 150-300 m”1g, oxygen content is 4
The present invention relates to boron nitride powder that can be sintered under normal pressure without adding a sintering aid of up to 10% by weight.
本発明を更に詳細に説明する。 The present invention will be explained in more detail.
本発明でいう結晶子の大きさとは結晶子のＣ軸方向の平
均厚み（Ｌｃ）で日本学術振興会第１１７委員会法によ
って測定する事が出来る。この値が４０人未満の窒化硼
素の場合は窒化硼素粉末の空気中での安定性が低くなる
ので好ましくなく、１５０人を越える場合は焼結性が低
下し、焼結体強度が向上しないので好ましくない。The size of crystallites in the present invention refers to the average thickness (Lc) of crystallites in the C-axis direction, which can be measured by the method of the 117th Committee of the Japan Society for the Promotion of Science. If this value is less than 40 for boron nitride, the stability of the boron nitride powder in the air will decrease, which is undesirable. If it exceeds 150, the sinterability will decrease and the strength of the sintered body will not improve. Undesirable.
また比表面積とは、いわゆる吸着法（ＢＥＴ法）によっ
て測定された値で、この値が３００ｍ”１ｇより大きい
窒化硼素の場合は窒化硼素粉末の空気中での安定性が低
くなるので好ましくなく、１５０ｍ”／ｇ以下の場合は
焼結性が低下し、焼結体強度が向上しないので好ましく
ない。In addition, the specific surface area is a value measured by the so-called adsorption method (BET method), and if this value is larger than 300m"1g for boron nitride, the stability of the boron nitride powder in the air will be low, so it is not preferable. If it is less than 150 m''/g, the sintering properties will deteriorate and the strength of the sintered body will not improve, which is not preferable.
また酸素含有量とはインパルス炉抽出法（例えば酸素窒
素同時分析装置ＬＥＣＯ社ＴＣ１３６型）などで測定さ
れた値で、この値が１０重世％を越える窒化硼素の場合
は焼結体の高温強度が低下するため好ましくなく、４重
量％未満の場合は焼結性が低下し、焼結体強度が向上し
ないので好ましくない。In addition, the oxygen content is the value measured by the impulse furnace extraction method (for example, using an oxygen-nitrogen simultaneous analyzer LECO TC136 model), and in the case of boron nitride where this value exceeds 10%, the high-temperature strength of the sintered body is If the amount is less than 4% by weight, the sinterability will decrease and the strength of the sintered body will not improve, which is not preferable.
また、常圧焼結が可能であるとは、上記の結晶子の大き
さ、比表面積、酸素含有量の窒化硼素粉末をカルシア等
の焼結助剤を添加せずにスリップキャスト法やプレス成
型法で成型し、成型物を窒素、アルゴン、アンモニア、
水素、もしくはこれらの混合ガス雰囲気の大気圧下で１
５００″Ｃ以上に加熱することにより焼結体となること
を意味する。Also, the fact that pressureless sintering is possible means that boron nitride powder with the above crystallite size, specific surface area, and oxygen content is formed by slip casting or press molding without adding a sintering aid such as calcia. molded product using nitrogen, argon, ammonia,
1 under atmospheric pressure in a hydrogen or mixed gas atmosphere
This means that a sintered body is formed by heating to 500″C or higher.
また、成型助剤無添加とは成型時のバインダー、分散剤
、滑剤等焼結助剤以外の物の無添加は意味しない。Furthermore, the term "no molding aid added" does not mean no addition of substances other than sintering aids such as binders, dispersants, lubricants, etc. during molding.
上述の様な常圧焼結が可能な窒化硼素を得る方法として
は（１）硼砂とメラミンとの混合物を不活性ガス雰囲気
にて７５０°Ｃ以上に加熱する方法（特開昭４７−２７
２００号に記述）、（２）硼砂とメラミンとの混合物を
不活性ガス雰囲気で６５０〜１１００°Ｃに加熱した後
、得られた反応生成物を洗浄液のＰＨが１以下となるま
で希鉱酸で洗浄し、ついで、洗浄液のｐＨが５〜７にな
るまで水洗する方法（特開昭６１−６３５０５号に記述
）、（３）はう酸アンモニウムと尿素、メラミンまたは
グアニジンとの混合物を６５０〜１１００°Ｃに加熱す
る方法（特開昭６１−２９５２１１号に記述）、（４）
無水硼酸及び硼酸塩類から選ばれた１種以上の硼素化合
物とＮｌｌ！基を有する有機化合物との混合物を耐熱性
の蓋付き容器に入れ、不活性ガスまたは還元性ガスを流
通させることなく該蓋付き容器を加熱する方法（特開昭
６４−１８９０７号）等がある。Methods for obtaining boron nitride that can be sintered under pressure as described above include (1) a method of heating a mixture of borax and melamine to 750°C or higher in an inert gas atmosphere (Japanese Patent Laid-Open No. 47-27
200), (2) After heating the mixture of borax and melamine to 650 to 1100°C in an inert gas atmosphere, the resulting reaction product is heated with dilute mineral acid until the pH of the cleaning solution becomes 1 or less. (described in JP-A No. 61-63505); (3) a mixture of ammonium oxalate and urea, melamine or guanidine; Method of heating to 1100°C (described in JP-A-61-295211), (4)
One or more boron compounds selected from boric anhydride and borates and Nll! There is a method in which a mixture with an organic compound having a group is placed in a heat-resistant lidded container and the lidded container is heated without passing an inert gas or reducing gas (Japanese Patent Application Laid-open No. 18907/1983). .
以上のいずれの方法を用いても、加熱温度と加熱時間を
調整することにより特許請求範囲の物性と同等の物性の
窒化硼素を得ることが出来る。No matter which of the above methods is used, boron nitride having physical properties equivalent to those claimed in the claims can be obtained by adjusting the heating temperature and heating time.
また、以上の例示した以外の方法であっても、製造条件
を調整して特許請求範囲の物性と同等の物性とした窒化
硼素であるならば、本特許に含まれる。Further, even methods other than those exemplified above are included in this patent as long as the manufacturing conditions are adjusted to produce boron nitride with physical properties equivalent to those in the claims.
以下実施例にて本発明を説明するが、実施例において部
及び％は、特記する以外は重量基準を表す。The present invention will be explained below with reference to Examples, in which parts and percentages are by weight unless otherwise specified.
実施例１
（窒化硼素粉末の製造）
内容積１２の蓋つきアルミナ製るつぼに、粉砕した無水
硼砂１８０ｇ及びメラミン３４０ｇの混合物を入れた後
、そのるつぼを電気炉に入れ、電気炉中に毎分４００
ｍの割合で窒素ガスを流しながら、るつぼを電気炉で９
００℃で５時間加熱した。 反応後、窒素ガス雰囲気中
で一晩放冷し、反応生成物をビーカーの中に入れ、さら
に５％塩酸をビーカー中の反応生成物に加え、洗浄とデ
カンテーションを繰り返し、洗浄後の９８を１以下とし
た後、約３０分間攪拌し、デカンテーションの後、イオ
ン交換水を加え、攪拌とデカンテーションを繰り返し、
洗浄後のｐＨを６とした後、濾別した。さらに、沈殿物
をメタノールで２回洗浄した後、減圧で１００℃で２時
間乾燥して窒化硼素粉末を得た。Example 1 (Production of boron nitride powder) A mixture of 180 g of crushed anhydrous borax and 340 g of melamine was placed in an alumina crucible with a lid having an internal volume of 12, and then the crucible was placed in an electric furnace, and the crucible was heated every minute in the electric furnace. 400
The crucible was heated in an electric furnace while flowing nitrogen gas at a rate of 9 m.
The mixture was heated at 00°C for 5 hours. After the reaction, leave to cool overnight in a nitrogen gas atmosphere, put the reaction product into a beaker, add 5% hydrochloric acid to the reaction product in the beaker, repeat washing and decantation, and remove the washed 98. 1 or less, stir for about 30 minutes, decant, add ion exchange water, repeat stirring and decantation,
The pH after washing was adjusted to 6, and then filtered. Further, the precipitate was washed twice with methanol and then dried under reduced pressure at 100° C. for 2 hours to obtain boron nitride powder.
得られた窒化硼素のＬｃは９２Å、ＢＥＴ法による比表
面積は２１０ｇ”／ｇ 、含有酸素量は６．２％であっ
た。The Lc of the obtained boron nitride was 92 Å, the specific surface area by BET method was 210 g''/g, and the amount of oxygen contained was 6.2%.
（焼結）
次にこの窒化硼素粉末を焼結助剤無添加で１ ｔｏｎ／
ＣＩｌ！の圧力で一軸プレス成型した。得られた予備成
型体を黒鉛るつぼに入れ、窒化硼素粉を埋め粉にして窒
素雰囲気にて１７５０’Ｃで１時間焼結した。(Sintering) Next, add this boron nitride powder to 1 ton/min without adding any sintering aids.
CIl! Uniaxial press molding was carried out at a pressure of The obtained preform was placed in a graphite crucible, filled with boron nitride powder, and sintered at 1750'C for 1 hour in a nitrogen atmosphere.
この焼結体の比重は１．７で、３点曲げ強度の測定結果
は常温で４ ｋｇ／ｒａｍ”と、焼結助剤無添加であっ
ても十分に焼結しており、強度も高いものが得られた。The specific gravity of this sintered body is 1.7, and the three-point bending strength measurement result is 4 kg/ram'' at room temperature, indicating that it is sufficiently sintered and has high strength even without the addition of sintering aids. I got something.
実施例２
（窒化硼素粉末の製造）
内容積１Ｎの蓋つきアルミナ製るつぼに、粉砕した無水
四硼酸アンモニウム４０ｇ及び尿素１３０ｇの混合物を
入れた後、そのるつぼを電気炉に入れ、電気炉中に毎分
４００ Ｉｄの割合で窒素ガスを流しながら、るつぼを
電気炉で１０００°Ｃで５時間加熱した。Example 2 (Manufacture of boron nitride powder) A mixture of 40 g of crushed ammonium tetraborate anhydride and 130 g of urea was placed in an alumina crucible with a lid having an internal volume of 1N, and then the crucible was placed in an electric furnace. The crucible was heated in an electric furnace at 1000° C. for 5 hours while flowing nitrogen gas at a rate of 400 Id/min.
反応後、窒素ガス雰囲気中で一晩放冷し、反応生成物を
ビーカーの中に入れ、イオン交換水を加え、攪拌とデカ
ンテーションを行い、濾別した９さらに、沈殿物をメタ
ノールで２回洗浄した後、減圧で１００℃で２時間乾燥
して窒化硼素粉末を得た。 得られた窒化硼素のＬｃは
１１０Å、ＢＥＴ法による比表面積は２００ｍ”／ｇ
、含有酸素量は５．１％であった。After the reaction, the reaction product was left to cool overnight in a nitrogen gas atmosphere, the reaction product was placed in a beaker, ion-exchanged water was added, stirring and decantation were performed, and the precipitate was filtered out. After washing, it was dried under reduced pressure at 100° C. for 2 hours to obtain boron nitride powder. The obtained boron nitride has an Lc of 110 Å and a specific surface area of 200 m”/g by BET method.
, the oxygen content was 5.1%.
（焼結）
次にこの窒化硼素粉末を焼結助剤無添加で１ ｔｏｎ／
ｃｌＩ″の圧力で一軸プレス成型した。得られた予備成
型体を黒鉛るつぼに入れ、窒化硼素粉を埋め粉にして窒
素雰囲気にて１７５０℃で１時間焼結した。(Sintering) Next, add this boron nitride powder to 1 ton/min without adding any sintering aids.
Uniaxial press molding was carried out at a pressure of ``clI''.The obtained preform was placed in a graphite crucible, filled with boron nitride powder, and sintered at 1750°C for 1 hour in a nitrogen atmosphere.
この焼結体の比重は１．６で、３点曲げ強度の測定結果
は常温で３．７ｋｇ／ａｓ”と、焼結助剤無添加であっ
ても十分に焼結しており、強度も高いものが得られた。The specific gravity of this sintered body is 1.6, and the measurement result of the three-point bending strength is 3.7 kg/as'' at room temperature, indicating that it is sufficiently sintered even without the addition of sintering aids, and the strength is also high. I got something expensive.
実施例３
（窒化硼素粉末の製造）
原料ホウ素化合物として粉末状の無水ホウ砂４０２ｇと
原料含窒素化合物として粉末状のメラミン５０４ｇをよ
く混合しくＮ／Ｂ原子比・３．０） 、この混合物を内
容積２１のアルミナ製ルツボに入れ、このルツボを台車
に乗せた状態で内部温度が約８００°Ｃに保持されたブ
タン燃焼方式トンネルキルンに該台車を送り込み、キル
ン内の滞留時間が約４時間になるように台車速度を制御
し、上記ルツボを加熱した。トンネルキルンから取り出
された台車上のルツボを放冷後粉末状の内容物を取り出
し、次いでこの粉末を濃度３％の硫酸水溶液及びイオン
交換水で洗浄後、１２０℃で４時間乾燥して窒化硼素の
粉末を得た。Example 3 (Manufacture of boron nitride powder) 402 g of powdered anhydrous borax as a raw material boron compound and 504 g of powdered melamine as a raw material nitrogen-containing compound were thoroughly mixed (N/B atomic ratio 3.0), and this mixture was prepared. The crucible was placed in an alumina crucible with an internal volume of 21 cm, and the crucible was placed on a cart and the cart was sent to a butane combustion tunnel kiln whose internal temperature was maintained at approximately 800°C, and the residence time in the kiln was approximately 4 hours. The crucible was heated by controlling the cart speed so that After leaving the crucible on the cart taken out from the tunnel kiln to cool, the powdered contents were taken out, and the powder was washed with a 3% sulfuric acid aqueous solution and ion-exchanged water, and then dried at 120°C for 4 hours to form boron nitride. powder was obtained.
得られた窒化硼素粉末のＬｃは６７Å、ＢＥＴ法による
比表面積は２７０＋ｗ”／ｇ 、含有酸素量は７．３％
であった。The obtained boron nitride powder has an Lc of 67 Å, a specific surface area of 270+w”/g by the BET method, and an oxygen content of 7.3%.
Met.
（焼結）
次にこの窒化硼素粉末を焼結助剤無添加で１．５ｔｏｎ
／ｃｍ”の圧力で一軸プレス成型形した。得られた予備
成型体を黒鉛るつぼに入れ、窒化硼素粉を埋め粉にして
窒素雰囲気にて１７００℃で１時間焼結したこの焼結体
の比重は１．８．３点曲げ強度の測定結果は常温で５
ｋｇ／−一〇あり、焼結助剤無添加であっても十分に焼
結して、強度も高いものが得られた。(Sintering) Next, add 1.5 tons of this boron nitride powder without adding any sintering aids.
The obtained preformed body was placed in a graphite crucible, filled with boron nitride powder, and sintered at 1700°C for 1 hour in a nitrogen atmosphere.The specific gravity of this sintered body was 1.8. The measurement result of 3-point bending strength is 5 at room temperature.
kg/-10, and even without the addition of a sintering aid, it was sufficiently sintered and a product with high strength was obtained.
比較例１
市販の窒化硼素粉末（六方晶、純度９９％、比表面Ｍｉ
７ｍ”／ｇ）を焼結助剤無添加で１．５ｔｏｎ／ｃｍ”
の圧力で一軸プレス成型した。得られた予備成型体を黒
鉛るつぼに入れ、窒化硼素粉を埋め粉にして窒素雰囲気
にて１７５０°Ｃで１時間焼結した。Comparative Example 1 Commercially available boron nitride powder (hexagonal crystal, purity 99%, specific surface Mi
7 m”/g) to 1.5 ton/cm” without adding sintering aids.
Uniaxial press molding was carried out at a pressure of The obtained preform was placed in a graphite crucible, filled with boron nitride powder, and sintered at 1750° C. for 1 hour in a nitrogen atmosphere.
得られた物は焼結しておらず、密度、強度とも測定不能
であった。The obtained product was not sintered, and neither density nor strength could be measured.
（発明の効果）
窒化硼素焼結体の製造にはホ・７トブレス法が一般的で
あり、常圧焼結法も最近では研究されてきた。しかしな
がら窒化硼素はＨ焼結法であるため焼結助剤の添加は不
可避であった。 しかるに本発明の窒化硼素粉末は焼結
助剤無添加であっても常圧焼結が出来るため、生産性が
非常に高く製造コストが低減し、窒化硼素成型体の用途
拡大に大きく寄与する事と思われる。(Effects of the Invention) The Ho-7 press method is commonly used to produce boron nitride sintered bodies, and the pressureless sintering method has also been studied recently. However, since boron nitride is produced using the H sintering method, the addition of a sintering aid is unavoidable. However, since the boron nitride powder of the present invention can be sintered under normal pressure even without the addition of sintering aids, productivity is extremely high, manufacturing costs are reduced, and this greatly contributes to expanding the applications of boron nitride molded bodies. I think that the.
Claims (1)
３００ｍ＾２／ｇ、酸素含有量４〜１０重量％である焼
結助剤無添加で常圧焼結が可能な窒化硼素粉末。1) Crystallite size 40-150 Å, specific surface area 150-150 Å
Boron nitride powder having a particle size of 300 m^2/g and an oxygen content of 4 to 10% by weight, which can be sintered under normal pressure without the addition of a sintering aid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1250765A JP2845983B2 (en) | 1989-09-28 | 1989-09-28 | Boron nitride powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1250765A JP2845983B2 (en) | 1989-09-28 | 1989-09-28 | Boron nitride powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03115109A true JPH03115109A (en) | 1991-05-16 |
| JP2845983B2 JP2845983B2 (en) | 1999-01-13 |
Family
ID=17212711
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1250765A Expired - Lifetime JP2845983B2 (en) | 1989-09-28 | 1989-09-28 | Boron nitride powder |
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| Country | Link |
|---|---|
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Cited By (4)
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|---|---|---|---|---|
| JP2008001536A (en) * | 2006-06-20 | 2008-01-10 | Osaka Univ | Aluminum nitride-boron nitride composite powder and method for producing the same |
| WO2013046784A1 (en) * | 2011-09-27 | 2013-04-04 | 日立化成株式会社 | Inorganic nitride particles, epoxy resin composition, semi-cured resin composition, cured resin composition, resin sheet, heat-generating electronic component, and method for producing inorganic nitride particles |
| WO2013081061A1 (en) * | 2011-11-29 | 2013-06-06 | 三菱化学株式会社 | Aggregated boron nitride particles, composition containing said particles, and three-dimensional integrated circuit having layer comprising said composition |
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1989
- 1989-09-28 JP JP1250765A patent/JP2845983B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008001536A (en) * | 2006-06-20 | 2008-01-10 | Osaka Univ | Aluminum nitride-boron nitride composite powder and method for producing the same |
| WO2013046784A1 (en) * | 2011-09-27 | 2013-04-04 | 日立化成株式会社 | Inorganic nitride particles, epoxy resin composition, semi-cured resin composition, cured resin composition, resin sheet, heat-generating electronic component, and method for producing inorganic nitride particles |
| JP2013082883A (en) * | 2011-09-27 | 2013-05-09 | Hitachi Chemical Co Ltd | Composition, b-stage sheet, prepreg, cured product of the composition, laminate, metal substrate, wiring board, and method of producing the composition |
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| WO2013081061A1 (en) * | 2011-11-29 | 2013-06-06 | 三菱化学株式会社 | Aggregated boron nitride particles, composition containing said particles, and three-dimensional integrated circuit having layer comprising said composition |
| JP2013241321A (en) * | 2011-11-29 | 2013-12-05 | Mitsubishi Chemicals Corp | Aggregated boron nitride particle, composition containing aggregated boron nitride particle, and three-dimensional integrated circuit having layer comprising composition |
| JP2015006985A (en) * | 2011-11-29 | 2015-01-15 | 三菱化学株式会社 | Boron nitride aggregated particle, composition containing boron nitride aggregated particle, and three-dimensional integrated circuit having layer comprising the composition |
| US9822294B2 (en) | 2011-11-29 | 2017-11-21 | Mitsubishi Chemical Corporation | Agglomerated boron nitride particles, composition containing said particles, and three-dimensional integrated circuit having layer comprising said composition |
| US10400151B2 (en) | 2011-11-29 | 2019-09-03 | Mitsubishi Chemical Corporation | Agglomerated boron nitride particles, composition containing said particles, and three- dimensional integrated circuit having layer comprising said composition |
| JP2021102537A (en) * | 2019-12-25 | 2021-07-15 | デンカ株式会社 | Hexagonal boron nitride powder, method for producing the same, cosmetic and method for producing the same |
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|---|---|
| JP2845983B2 (en) | 1999-01-13 |
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