JPH0364479B2 - - Google Patents
Info
- Publication number
- JPH0364479B2 JPH0364479B2 JP9136487A JP9136487A JPH0364479B2 JP H0364479 B2 JPH0364479 B2 JP H0364479B2 JP 9136487 A JP9136487 A JP 9136487A JP 9136487 A JP9136487 A JP 9136487A JP H0364479 B2 JPH0364479 B2 JP H0364479B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium carbide
- single crystal
- titanium
- zone
- composition
- 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.)
- Expired
Links
- 239000013078 crystal Substances 0.000 claims description 38
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 23
- 239000010936 titanium Substances 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 18
- 239000012535 impurity Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007716 flux method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明はフローテイングゾーン法（以下FZ法
と言う）による炭化チタン単結晶の育成法に関す
る。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for growing titanium carbide single crystals by the floating zone method (hereinafter referred to as the FZ method).
炭化チタンは融点（3100℃）、硬度（ビツカー
ス硬度3000Kg／mm2）が高く、各種の超硬工具や表
面保護材として広く実用に供されている。最近で
は電子材料への応用が検討され、仕事関数
（3.25eV）が低く、耐イオン衝撃に強く、かつ化
学的にも安定であるので、電子エミツター材、特
にフイールドエミツター材としての利用が検討さ
れている。フイールドエミツター材としては単結
晶が用いられ、大型で高純度の良質の単結晶を得
ることが重要である。 Titanium carbide has a high melting point (3100° C.) and hardness (Vickers hardness 3000 Kg/mm 2 ), and is widely used in various cemented carbide tools and surface protection materials. Recently, its application to electronic materials has been considered, and as it has a low work function (3.25eV), is resistant to ion bombardment, and is chemically stable, its use as an electron emitter material, especially a field emitter material, is being considered. has been done. A single crystal is used as the field emitter material, and it is important to obtain a large, highly pure, and high quality single crystal.
従来技術
従来の炭化チタン単結晶の育成法としては、フ
ラツクス法、気相法、アークベルヌーイ法、FZ
法が知られている。その中でも大型単結晶を育成
するにはFZ法が適している。Conventional technology Conventional methods for growing titanium carbide single crystals include flux method, gas phase method, arc Bernoulli method, and FZ method.
The law is known. Among them, the FZ method is suitable for growing large single crystals.
従来のFZ法による炭化チタン単結晶の育成に
おいては、供給焼結棒として高密度の炭化チタン
粉末焼結体が用いられている。この方法による
と、育成された単結晶には0.05〜0.5重量％のタ
ングステン、0.03重量％程度の窒素不純物の混入
をさけ得なかつた。このタングステン不純物はフ
イールドエミツターとして使用する場合、放射さ
れる電子ビームの特性に悪影響を与える欠点があ
つた。また、この単結晶には多結晶体の厚さ約１
mmの皮が存在し、中心部の結晶部分も最大４度方
位のずれたサブグレインよりなる品質の悪いもの
しか得られない欠点があつた。 In the conventional FZ method for growing titanium carbide single crystals, a high-density titanium carbide powder sintered body is used as a supply sintering rod. According to this method, the grown single crystal was unavoidably contaminated with 0.05 to 0.5% by weight of tungsten and about 0.03% by weight of nitrogen impurities. When used as a field emitter, this tungsten impurity has the disadvantage of adversely affecting the characteristics of the emitted electron beam. In addition, this single crystal has a polycrystalline thickness of about 1
There was a peel of 1 mm in diameter, and the crystalline part in the center was of poor quality and consisted of subgrains that were misoriented by up to 4 degrees.
発明の目的
本発明は前記の従来法における欠点を解消せん
とするものであり、その目的は高純度で良質の炭
化チタン単結晶を育成する方法を提供するにあ
る。OBJECTS OF THE INVENTION The present invention aims to eliminate the drawbacks of the conventional methods described above, and its purpose is to provide a method for growing highly pure and high quality titanium carbide single crystals.
発明の構成
本発明者らは前記目的を達成すべく研究の結
果、チタン金属粉末と炭素粉末の直接反応による
炭化チタンの合成と、その際発生する高い反応熱
を利用して焼結も同時に行つた炭化チタン焼結棒
は高純度である。しかし、その密度は40〜45％と
低く、初期融帯の形成が困難であるため、従来
FZ法における供給結晶棒としては使用されてい
なかつた。Structure of the Invention As a result of research to achieve the above object, the present inventors have synthesized titanium carbide by direct reaction between titanium metal powder and carbon powder, and simultaneously performed sintering using the high reaction heat generated at the time. The ivy titanium carbide sintered rod is of high purity. However, its density is low at 40 to 45%, making it difficult to form an initial melting zone.
It was not used as a feed crystal rod in the FZ method.
本発明者らはこれを利用すべく、初期融帯形成
材として炭化チタン単結晶、炭化チタン融帯の固
化物または65％以上の高密度炭化チタンを用いて
初期融帯を形成し、融帯移動を行うときは、前記
高純度で低密度の炭化チタン焼結体が供給焼結棒
が使用し得られること。また得られる炭化チタン
単結晶はタングステン等の金属不純物は含まれ
ず、窒素不純物は従来の1/10以下と、純度の高い
ものとなり、かつ結晶棒の周囲には殆ど多結晶体
の皮は存在せず、またサブグレインの密度が２×
102／cmと従来の値の半分となることを知見し得
た。この知見に基づいて本発明を完成した。 In order to utilize this, the present inventors formed an initial melt zone using a titanium carbide single crystal, a solidified titanium carbide melt zone, or a high-density titanium carbide of 65% or more as an initial melt zone forming material. When moving, the high-purity, low-density titanium carbide sintered body can be obtained by using a supply sintered rod. In addition, the resulting titanium carbide single crystal does not contain metal impurities such as tungsten, and has a high purity with nitrogen impurities less than 1/10 of conventional ones, and there is almost no polycrystalline skin around the crystal rod. Also, the subgrain density is 2×
It was found that the value was 10 2 /cm, which is half of the conventional value. The present invention was completed based on this knowledge.
本発明の要脂は、
フローテイングゾーン法による炭化チタン単結
晶の育成において、供給焼結棒として、チタンと
炭素の直接反応により炭化チタンの合成と焼結を
同時に行い得られた焼結棒を用い、初期融帯形成
材として、炭化チタン単結晶、炭化チタン融帯の
固化物または65％以上の高密度炭化チタンを用い
て初期融帯を形成し、融帯移動を行い単結晶を育
成することを特徴とする炭化チタン単結晶の育成
法にある。 The essential feature of the present invention is to use a sintered rod obtained by simultaneously synthesizing and sintering titanium carbide through a direct reaction between titanium and carbon as a supplied sintered rod during the growth of titanium carbide single crystals by the floating zone method. The initial melting zone is formed using a titanium carbide single crystal, a solidified titanium carbide melting zone, or a high-density titanium carbide of 65% or more as the initial melting zone forming material, and the melting zone is moved to grow a single crystal. A method for growing a titanium carbide single crystal is characterized by the following.
本発明の方法を詳述すると、金属チタン粉末と
して市販の100メツシユより細い粉末を、炭素粉
末として黒鉛粉末または予め脱ガスを行つたカー
ボンブラツクを用いる。 To explain the method of the present invention in detail, a commercially available powder finer than 100 mesh is used as the metallic titanium powder, and graphite powder or carbon black which has been degassed in advance is used as the carbon powder.
炭化チタンは広い不定比組成領域（Ｃ／Ti＝
0.55〜0.97）を持つため、所定の組成になるよう
に、チタンと炭素を秤量し、少量の有機溶媒例え
ばアセトンと共に混合した後、ゴム袋につめ、こ
れを室温において静水圧加圧を行つて圧粉体を形
成する。この成形体の一端を真空中または不活性
ガス雰囲気中で800℃以上に加熱したヒーターを
接触させ、チタンと炭素の自己燃焼反応を起こさ
せ焼結体を作る。この際、組成が多少ずれるた
め、例えばＣ／Ti＜0.8の組成領域ではチタンが
少なくなり、Ｃ／Ti＞0.9の組成領域では炭素が
失われるため、厳密に焼結体の組成を制御するに
は、焼結体の組成分析を行い、配合組成と焼結組
成の対応を行うことが好ましい。 Titanium carbide has a wide non-stoichiometric composition range (C/Ti=
0.55 to 0.97), titanium and carbon are weighed and mixed with a small amount of an organic solvent, such as acetone, to give the desired composition, then packed in a rubber bag and subjected to isostatic pressure at room temperature. Form a green compact. One end of this molded body is brought into contact with a heater heated to 800°C or higher in a vacuum or inert gas atmosphere to cause a self-combustion reaction between titanium and carbon, creating a sintered body. At this time, the composition will deviate slightly, for example, titanium will decrease in the composition region of C/Ti < 0.8, and carbon will be lost in the composition region of C/Ti > 0.9, so it is difficult to strictly control the composition of the sintered body. It is preferable that the composition of the sintered body be analyzed and the blended composition and sintered composition be matched.
単結晶育成はFZ法の育成炉を用いる。第１図
はFZ法育成炉の概念図で、１は上軸、１′は下
軸、２はホルダー、３は炭化チタン焼結棒、３′
は初期融帯形成用材、４は育成した炭化チタン単
結晶、５は融帯、６は高周波ワークコイルを示
す。 A FZ method growth furnace is used for single crystal growth. Figure 1 is a conceptual diagram of the FZ method growth furnace, where 1 is the upper shaft, 1' is the lower shaft, 2 is the holder, 3 is the titanium carbide sintered rod, and 3'
Reference numeral 4 indicates a material for forming an initial melting zone, 4 indicates a grown titanium carbide single crystal, 5 indicates a melting zone, and 6 indicates a high frequency work coil.
前記の方法で得られた炭化チタン焼結棒を上部
軸の３にセツトし、その下部に炭化チタン単結
晶、炭化チタン融帯の固化物または65％以上の高
密度炭化チタンの初期融帯形成材をホルダー２に
より固定支持する。初期融帯形成材の端を高周波
ワークコイル６から高周波を発生させ誘導加熱に
より溶融させ、融帯５を形成し、該融帯と炭化チ
タン焼結棒３をゆつくり下方に移動させて結晶を
育成する。 The titanium carbide sintered rod obtained by the above method is set at 3 on the upper shaft, and a titanium carbide single crystal, a solidified titanium carbide melt zone, or an initial melt zone of 65% or more high-density titanium carbide is formed at the bottom. The material is fixedly supported by a holder 2. The end of the initial melt zone forming material is melted by induction heating by generating high frequency waves from a high frequency work coil 6 to form a melt zone 5, and the melt zone and titanium carbide sintered rod 3 are slowly moved downward to form crystals. Cultivate.
この時の融帯５及び供給焼結棒の移動速度は
0.2〜10cm／ｈが適当である。雰囲気はアルゴン
やヘリウム等の不活性ガスが用いられる。これは
蒸発の抑制と、RFコイル間及びコイルと試料間
の放電を抑制する作用をする。 At this time, the moving speed of the melting zone 5 and the supplied sintered rod is
0.2 to 10 cm/h is appropriate. An inert gas such as argon or helium is used as the atmosphere. This functions to suppress evaporation and discharge between the RF coils and between the coil and the sample.
本方法を実施するに当たり、初期融帯の組成を
得ようとする単結晶と共存する液相組成となるよ
うに、上、下軸に固定された試料の間に炭素また
はチタンの円盤をはさみ、この円盤と初期融帯形
成材を溶かすことにより、液相を形成させる。そ
のためには予備実験を行い、供給焼結棒の蒸発に
よる組成変化を確かめておき、初期融帯と供給焼
結棒の組成を制御する。 To carry out this method, a disk of carbon or titanium is sandwiched between the samples fixed on the upper and lower shafts so that the liquid phase composition coexists with the single crystal whose initial melting zone composition is to be obtained. By melting this disk and the initial melt zone forming material, a liquid phase is formed. To this end, a preliminary experiment is conducted to confirm the composition change due to evaporation of the supplied sintered rod, and the initial melting zone and the composition of the supplied sintered rod are controlled.
これにより、育成中、融帯の組成が壱定に保た
れ、均一な目的組成を持つ単結晶が育成し得られ
る。 As a result, the composition of the melt zone is kept constant during growth, and a single crystal having a uniform target composition can be grown.
実施例
TiC0.96単結晶の育成
TiC0.96単結晶の育成には、融帯の組成をＣ／
Ti＝1.3に供給焼結棒の組成をＣ／Ti＝0.98に制
御する必要があることを予備実験により確かめ
た。Example Growth of TiC 0.96 single crystal To grow TiC 0.96 single crystal, change the composition of the melt zone to C/
It was confirmed through preliminary experiments that it is necessary to control the composition of the sintered rod supplied to Ti=1.3 to C/Ti=0.98.
供給焼結棒の作成
325メツシユのチタン金属粉と脱ガスしたカー
ボンブラツク粉末をＣ／Ti＝0.99となるようにア
セトン中で混合した後、直径11φのゴム袋につめ
円柱状とした。これを100MPaの静水圧加圧を行
い圧粉体とし、その一端を真空中で、1300℃のヒ
ーターに接触させ、自己燃焼反応を起こさせて炭
化チタンの合成と焼結を同時に行わせた。得られ
た焼結棒は直径約0.9cm、長さ15cmであつた。Preparation of supplied sintered rod Titanium metal powder of 325 mesh and degassed carbon black powder were mixed in acetone so that C/Ti = 0.99, and then packed into a rubber bag with a diameter of 11φ and shaped into a cylinder. This was subjected to hydrostatic pressure of 100 MPa to form a green compact, and one end of the green compact was brought into contact with a heater at 1300°C in a vacuum to cause a self-combustion reaction to simultaneously synthesize and sinter titanium carbide. The obtained sintered rod had a diameter of about 0.9 cm and a length of 15 cm.
単結晶の育成
前記の方法で得られた焼結棒を、FZ育成炉の
上軸のホルダーを介して固定し、下軸にはTiC単
結晶を固定し、両者の間に炭素円盤をはさんだ。
不活性ガス雰囲気となし高周波加熱により、TiC
単結晶と炭素円盤を加熱して初期融帯を形成させ
た。融帯形成後、下軸を下方へ２cm／ｈの速度で
移動させ、上軸は4.4cm／ｈの速度で下方へ移動
させて融帯へ送り込むことによつて単結晶を育成
させた。Growth of single crystal The sintered rod obtained by the above method was fixed through a holder on the upper shaft of the FZ growth furnace, a TiC single crystal was fixed on the lower shaft, and a carbon disk was sandwiched between the two. .
By using an inert gas atmosphere and high-frequency heating, TiC
A single crystal and a carbon disk were heated to form an initial melt zone. After the melt zone was formed, the lower shaft was moved downward at a speed of 2 cm/h, and the upper shaft was moved downward at a speed of 4.4 cm/h to feed into the melt zone, thereby growing a single crystal.
得られた結晶は直径約0.9cm、長さ４cmで、分
析の結果は、始端部、中央部、終端部の炭素はそ
れぞれ19.17，19.34，19.37重量％であり、組成に
して、Ｃ／Ti＝0.946，0.956，0.958であつた。ま
た得られた単結晶には多結晶体の皮は存在せず、
非常に良質の単結晶であつた。 The obtained crystal had a diameter of about 0.9 cm and a length of 4 cm, and the analysis results showed that the carbon content in the starting, central, and terminal parts was 19.17, 19.34, and 19.37% by weight, respectively, and the composition was C/Ti= They were 0.946, 0.956, and 0.958. In addition, the obtained single crystal does not have a polycrystalline skin,
It was a very high quality single crystal.
発明の効果
本発明の方法によると、供給焼結棒として低密
度であるため、使用されなかつたチタンと炭素の
直接反応により炭化チタンの合成と焼結と同時に
行い得られた焼結棒を使用可能とし、得られる炭
化チタン単結晶は不純物のないものとなし得ると
共に、多結晶体の皮も存在せず、かつサブグレイ
ンのない高品質のものとなし得る。これによりフ
イールドエミツターとして使用する場合も放射さ
れる電子ビームの特性を悪影響を与えない等の優
れた効果を有する。Effects of the Invention According to the method of the present invention, a sintered rod obtained by simultaneously synthesizing and sintering titanium carbide through the direct reaction of unused titanium and carbon due to its low density is used as the supplied sintered rod. The titanium carbide single crystal obtained can be free of impurities, have no polycrystalline skin, and can be of high quality without subgrains. As a result, even when used as a field emitter, it has excellent effects such as not adversely affecting the characteristics of the emitted electron beam.
第１図はFZ法の概念図である。
１：上軸、１′：下軸、２：ホールダー、３：
炭化チタン焼結棒、３′：初期融帯形成用材、
４：育成した炭化チタン単結晶、５：融帯、６：
高周波ワークコイル。
Figure 1 is a conceptual diagram of the FZ method. 1: Upper axis, 1': Lower axis, 2: Holder, 3:
Titanium carbide sintered rod, 3': material for forming initial melting zone,
4: Grown titanium carbide single crystal, 5: Melting zone, 6:
High frequency work coil.
Claims (1)
結晶の育成において、供給焼結棒として、チタン
と炭素の直接反応により炭化チタンの合成と焼結
を同時に行い得られた焼結棒を用い、初期融帯形
成材として、炭化チタン単結晶、炭化チタン融帯
の固化物または65％以上の高密度炭化チタンを用
いて初期融帯を形成し、融帯移動を行い単結晶を
育成することを特徴とする炭化チタン単結晶の育
成法。1. In growing titanium carbide single crystals using the floating zone method, a sintered rod obtained by simultaneously synthesizing and sintering titanium carbide through a direct reaction between titanium and carbon is used as a supplied sintered rod to form an initial melting zone. Carbonization is characterized by forming an initial melt zone using a titanium carbide single crystal, solidified titanium carbide melt zone, or high-density titanium carbide of 65% or more as the material, and growing a single crystal by moving the melt zone. A method for growing titanium single crystals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9136487A JPS63256598A (en) | 1987-04-14 | 1987-04-14 | Growth method of titanium carbide single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9136487A JPS63256598A (en) | 1987-04-14 | 1987-04-14 | Growth method of titanium carbide single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63256598A JPS63256598A (en) | 1988-10-24 |
| JPH0364479B2 true JPH0364479B2 (en) | 1991-10-07 |
Family
ID=14024327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9136487A Granted JPS63256598A (en) | 1987-04-14 | 1987-04-14 | Growth method of titanium carbide single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63256598A (en) |
-
1987
- 1987-04-14 JP JP9136487A patent/JPS63256598A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63256598A (en) | 1988-10-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |