JPH0476353B2 - - Google Patents
Info
- Publication number
- JPH0476353B2 JPH0476353B2 JP19411588A JP19411588A JPH0476353B2 JP H0476353 B2 JPH0476353 B2 JP H0476353B2 JP 19411588 A JP19411588 A JP 19411588A JP 19411588 A JP19411588 A JP 19411588A JP H0476353 B2 JPH0476353 B2 JP H0476353B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium carbide
- single crystal
- melt
- weight
- single crystals
- 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
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- 238000000034 method Methods 0.000 claims description 38
- 239000013078 crystal Substances 0.000 claims description 36
- 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 29
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 11
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000723346 Cinnamomum camphora Species 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229960000846 camphor Drugs 0.000 description 2
- 229930008380 camphor Natural products 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
- 238000005530 etching Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- WTKKCYNZRWIVKL-UHFFFAOYSA-N tantalum Chemical compound [Ta+5] WTKKCYNZRWIVKL-UHFFFAOYSA-N 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
本発明は融液法による炭化チタン単結晶の育成
法の改良に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an improved method for growing titanium carbide single crystals by a melt 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せられている。最近
では炭化チタンの格子定数（4.328Å）が耐環境
素子材料などとして注目されている炭化ケイ素の
格子定数（4.3596Å）に近く、かつ高温で安定な
ことから、その基板結晶としての利用も検討され
ている。そのためには大型で高品質な単結晶が要
望されている。 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, the lattice constant of titanium carbide (4.328 Å) is close to that of silicon carbide (4.3596 Å), which is attracting attention as a material for environmentally resistant devices, and is stable at high temperatures, so its use as a substrate crystal is also being considered. has been done. For this purpose, large-sized, high-quality single crystals are required.
従来技術
従来の炭化チタン単結晶の育成法としては、溶
液法、気相法、固相法、融液法が知られている。
その中で、大型単結晶を育成するには融液法が適
している。融液法としては引き上げ法、アークベ
ルヌイ法、フローテイングゾーン法があるが、高
品質の単結晶を育成するにはフローテイングゾー
ン法が適している。Prior Art As conventional methods for growing titanium carbide single crystals, a solution method, a gas phase method, a solid phase method, and a melt method are known.
Among them, the melt method is suitable for growing large single crystals. Melt methods include the pulling method, the Ark-Bernoulli method, and the floating zone method, but the floating zone method is suitable for growing high-quality single crystals.
融液法による炭化チタン単結晶の育成法におい
ては、従来単結晶の育成が容易なように高純度の
炭化チタン原料が用いられてきた。しかし、この
方法で育成された単結晶中には多くの欠陥（例え
ば粒界密度で103cm／cm2）が存在する欠点があつ
た。 In the method of growing titanium carbide single crystals using the melt method, high-purity titanium carbide raw materials have conventionally been used to facilitate the growth of single crystals. However, the single crystal grown by this method has a disadvantage in that there are many defects (eg, grain boundary density of 10 3 cm/cm 2 ).
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、その目的は炭化チタン単結晶
中の欠陥（特に粒界密度）を少なくし、大型で良
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。Purpose of the Invention The present invention aims to eliminate the drawbacks of the conventional methods described above, and its purpose is to reduce defects (particularly grain boundary density) in titanium carbide single crystals and to produce large, high-quality titanium carbide single crystals. It is to provide a method to cultivate.
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、融液法によつて炭化チタン単結晶を育成する
に際し、炭化チタンに対しタンタルまたはニオブ
もしくはそれらの混合物を0.2〜10重量％含有さ
せて出発原料として使用すると、単結晶中の中心
部分で粒界がなくなり全体における粒界密度が
102cm／cm2と従来の値（103cm／cm2）より１桁も少
なく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。Structure of the Invention As a result of research to achieve the above object, the present inventors found that when growing titanium carbide single crystals by the melt method, 0.2 to 10% by weight of tantalum or niobium or a mixture thereof is added to titanium carbide. When used as a starting material, grain boundaries disappear at the center of the single crystal and the overall grain boundary density decreases.
It was found that this value was 10 2 cm/cm 2 , which is one order of magnitude lower than the conventional value (10 3 cm/cm 2 ). The present invention was completed based on this knowledge.
本発明の要旨は、炭化チタン単結晶を融液法に
よつて育成する方法において、0.2〜10重量％の
タンタルまたはニオブもしくはそれらの混合物を
含有させた炭化チタンを出発原料として使用する
ことを特徴とする炭化チタン単結晶の育成法にあ
る。タンタルまたはニオブもしくはこれらの混合
物が0.2重量％より少なく、また10重量％を超え
ると、共に粒界密度がふえる。従つて、0.2〜10
重量％の範囲であることが必要である。 The gist of the present invention is a method for growing titanium carbide single crystals by a melt method, characterized in that titanium carbide containing 0.2 to 10% by weight of tantalum, niobium, or a mixture thereof is used as a starting material. A method for growing titanium carbide single crystals. When tantalum or niobium or a mixture thereof is less than 0.2% by weight and exceeds 10% by weight, the grain boundary density increases. Therefore, 0.2 to 10
It is necessary that the amount is within the range of % by weight.
本発明の方法を大型で高品位の単結晶が育成し
易いフローテイングゾーン法（以下FZ法と言う）
によつて図面に基づいて実施態様を説明する。 The method of the present invention is called the floating zone method (hereinafter referred to as FZ method), which facilitates the growth of large, high-quality single crystals.
An embodiment will be described based on the drawings.
第１図はFZ法育成炉の概念図で、１は上軸、
１′は下軸、２，２′はホルダー、３は焼結棒、
３′は初期融帯形成用材、４は育成した単結晶、
５は融帯、６は高周波ワークコイルを示す。 Figure 1 is a conceptual diagram of the FZ method growth furnace, where 1 is the upper axis;
1' is the lower shaft, 2 and 2' are the holders, 3 is the sintered rod,
3' is the initial melt zone forming material, 4 is the grown single crystal,
5 indicates a melting zone, and 6 indicates a high frequency work coil.
炭化チタン粉末にタンタルまたはニオブ粉末を
0.2〜10重量％混合し、これに結合剤として少量
の樟脳を加えてラバープレス（1000Kg／cm2）によ
り圧粉棒を作る。この圧粉棒を真空中または不活
性ガス雰囲気中で2000℃に加熱して焼結棒を得
る。この際焼結棒の組成を厳密に制御するには、
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。 Add tantalum or niobium powder to titanium carbide powder
Mix 0.2 to 10% by weight, add a small amount of camphor as a binder, and make a powder rod using a rubber press (1000 kg/cm 2 ). This compacted powder rod is heated to 2000° C. in a vacuum or in an inert gas atmosphere to obtain a sintered rod. At this time, in order to strictly control the composition of the sintered rod,
It is preferable to perform a composition analysis of the sintered body and to correspond between the blended composition and the sintered composition.
得られた焼結棒３を上軸１にホルダー２を介し
てセツトし、その下部に初期融帯形成用材３′と
して炭化チタン単結晶または焼結棒をホルダー
２′を介して固定支持する。次に初期融帯形成用
材３′の端を高周波ワークコイル６からの誘導加
熱により溶融させ融帯５を形成させ、上軸１と下
軸１′をゆつくり下方に移動させて結晶を育成す
る。 The obtained sintered rod 3 is set on the upper shaft 1 via a holder 2, and a titanium carbide single crystal or a sintered rod is fixedly supported under the upper shaft 1 as an initial melting zone forming material 3' via a holder 2'. Next, the end of the initial melt zone forming material 3' is melted by induction heating from the high frequency work coil 6 to form a melt zone 5, and the upper shaft 1 and the lower shaft 1' are slowly moved downward to grow crystals. .
その時の育成速度は0.2〜５cm／ｈ、好ましく
は0.7〜２cm／ｈである。雰囲気は数気圧のアル
ゴン、ヘリウム等の不活性ガスが用いられる。こ
れは蒸発の抑制と高周波ワークコイル間及び該コ
イルと試料間の放電を抑制する作用をする。 The growth rate at that time is 0.2 to 5 cm/h, preferably 0.7 to 2 cm/h. The atmosphere is an inert gas such as argon or helium at several atmospheres. This has the effect of suppressing evaporation and electric discharge between the high frequency work coil and between the coil and the sample.
本発明の方法を実施するには、前記のフローテ
イングゾーン法に限らず、融液から引き上げるこ
とによる引き上げ法、アークベルヌイ法及びゾー
ンレベリング法（上下軸に固定された試料間に炭
素または金属円板をはさみ、この円板と初期融帯
形成材を溶かし融帯を形成させる。）によつても
行うことができる。 In order to carry out the method of the present invention, the method is not limited to the above-mentioned floating zone method, but also the pulling method by lifting from the melt, the Ark Bernoulli method, and the zone leveling method (a carbon or metal circle between the samples fixed on the upper and lower axes). This can also be done by sandwiching a plate and melting the disc and the initial melting zone forming material to form a melting zone.)
実施例１ TiC0.95の単結晶の育成
TiC0.95単結晶の育成には融帯組成をＣ／Ti＝
1.3、供給焼結棒の組成をＣ／Ti＝1.02に制御す
るのがよいことを予備実験で確かめた。Example 1 Growth of single crystal of TiC 0.95 To grow single crystal of TiC 0.95 , the melt zone composition was changed to C/Ti=
1.3. Preliminary experiments have confirmed that it is best to control the composition of the supplied sintered rod to C/Ti = 1.02.
炭化チタン粉末に３原子％の炭素粉及び0.5重
量％のタンタル粉末を添加し混合後、結合剤とし
て樟脳を少量加えて再び混合した。この混合物を
直径10φのゴム袋に詰め円柱状にし、これを1000
気圧でラバープレスして圧粉体を得た。この圧粉
体を黒鉛サセプターに納め、真空中2000℃で加熱
して焼結体を得た。 After adding and mixing 3 atomic % carbon powder and 0.5 weight % tantalum powder to titanium carbide powder, a small amount of camphor was added as a binder and mixed again. This mixture was packed into a rubber bag with a diameter of 10φ and made into a cylinder shape, and this was
A green compact was obtained by rubber pressing at atmospheric pressure. This green compact was placed in a graphite susceptor and heated in vacuum at 2000°C to obtain a sintered body.
これをFZ育成炉の上軸にホルダーを介して固
定し、下軸には炭化チタン単結晶＜100＞を固定
し、両者の間に炭素円盤（約0.1ｇ）を挟んだ。
育成炉に７気圧のヘリウムを充填後、高周波加熱
によりTiCと黒鉛円盤を溶かし初期融帯を形成
し、1.5cm／ｈで下方に移動させて＜100＞方向に
単結晶を育成した。 This was fixed to the upper shaft of the FZ growth furnace via a holder, a titanium carbide single crystal <100> was fixed to the lower shaft, and a carbon disk (approximately 0.1 g) was sandwiched between the two.
After filling the growth furnace with helium at 7 atm, the TiC and graphite disks were melted by high-frequency heating to form an initial melt zone, and the single crystal was grown in the <100> direction by moving downward at 1.5 cm/h.
得られた炭化チタン単結晶は、直径09cm、長さ
６cmで、分析の結果、始端部、中央部、終端部の
炭素含量はそれぞれ19.32，19.25，19.37重量％で
あり、組成にしてＣ／Ti＝0.955，0.951，0.958で
あつた。タンタルは結晶中に均一に分布してお
り、濃度は炭化チタンの蒸発のため少し増加し、
0.53重量％であつた。単結晶中の粒界密度は
（100）面をエツチングして測定した結果、200
cm／cm2でタンタルを含有させない場合のそれに比
較して一桁近く低くなつた。 The obtained titanium carbide single crystal had a diameter of 09 cm and a length of 6 cm, and as a result of analysis, the carbon contents at the starting end, center, and end were 19.32, 19.25, and 19.37% by weight, respectively, and the composition was C/Ti. = 0.955, 0.951, 0.958. Tantalum is uniformly distributed in the crystal, and the concentration increases slightly due to the evaporation of titanium carbide,
It was 0.53% by weight. The grain boundary density in a single crystal was measured by etching the (100) plane, and was found to be 200
cm/cm 2 was nearly an order of magnitude lower than that in the case without tantalum.
実施例２ TiC0.95単結晶の育成
出発物質は炭化チタン粉末に３原子％の炭素粉
及び0.5重量％のニオブ粉末を添加混合して作製
した。Example 2 Growth of TiC 0.95 single crystal A starting material was prepared by adding and mixing 3 atomic % carbon powder and 0.5 weight % niobium powder to titanium carbide powder.
単結晶の育成は実施例１と同様の手順により行
つた。 The single crystal was grown using the same procedure as in Example 1.
得られた炭化チタン単結晶は、直径0.9cm、長
さ６cmで、分析の結果、始端部、中央部、終端部
の炭素含量はそれぞれ、19.20，19.21，19.30重量
％であり、組成にしてＣ／Ti＝0.948，0.948，
0.945であつた。 The obtained titanium carbide single crystal had a diameter of 0.9 cm and a length of 6 cm, and as a result of analysis, the carbon content at the starting end, center, and end was 19.20, 19.21, and 19.30% by weight, respectively, and the composition was C. /Ti=0.948, 0.948,
It was 0.945.
ニオブは結晶中に均一に分布しており、濃度は
炭化チタンの蒸発のため約２％増加し、0.51重量
％であつた。単結晶中の粒界密度は、（100）面を
エツチングして測定した結果、250cm／cm2で、ニ
オブを含有させない場合のそれに比較して一桁近
く低くなつた。 Niobium was uniformly distributed in the crystals and the concentration increased by about 2% due to evaporation of titanium carbide to 0.51% by weight. The grain boundary density in the single crystal was measured by etching the (100) plane and was found to be 250 cm/cm 2 , which is nearly an order of magnitude lower than that in the case where niobium is not included.
発明の効果
本発明の方法によると、炭化チタン単結晶中の
欠陥を少なくし、大型で良質の炭化チタン単結晶
を育成することができる。Effects of the Invention According to the method of the present invention, defects in a titanium carbide single crystal can be reduced and a large-sized and high-quality titanium carbide single crystal can be grown.
第１図はFZ法の概念図である。
１……上軸、１′……下軸、２，２′……ホルダ
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, 2'... Holder, 3... Titanium carbide sintered rod, 3'... Initial melting zone forming material, 4... Grown titanium carbide single crystal, 5
...Fluid zone, 6...High frequency work coil.
Claims (1)
方法において、0.2〜10重量％のタンタルまたは
ニオブもしくはそれらの混合物を含有させた炭化
チタンを出発原料として使用することを特徴とす
る炭化チタン単結晶の育成法。 ２ 融液法がフローテイングゾーン法である特許
請求の範囲第１項の方法。[Claims] 1. In a method for growing titanium carbide single crystals by a melt method, titanium carbide containing 0.2 to 10% by weight of tantalum or niobium or a mixture thereof is used as a starting material. Characteristic method for growing titanium carbide single crystals. 2. The method according to claim 1, wherein the melt method is a floating zone method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19411588A JPH0244100A (en) | 1988-08-03 | 1988-08-03 | Growth method of titanium carbide single crystal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19411588A JPH0244100A (en) | 1988-08-03 | 1988-08-03 | Growth method of titanium carbide single crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0244100A JPH0244100A (en) | 1990-02-14 |
| JPH0476353B2 true JPH0476353B2 (en) | 1992-12-03 |
Family
ID=16319172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19411588A Granted JPH0244100A (en) | 1988-08-03 | 1988-08-03 | Growth method of titanium carbide single crystal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0244100A (en) |
-
1988
- 1988-08-03 JP JP19411588A patent/JPH0244100A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0244100A (en) | 1990-02-14 |
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