JPH027919B2 - - Google Patents
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- Publication number
- JPH027919B2 JPH027919B2 JP18707885A JP18707885A JPH027919B2 JP H027919 B2 JPH027919 B2 JP H027919B2 JP 18707885 A JP18707885 A JP 18707885A JP 18707885 A JP18707885 A JP 18707885A JP H027919 B2 JPH027919 B2 JP H027919B2
- Authority
- JP
- Japan
- Prior art keywords
- composition
- crystal
- rod
- tungsten
- raw material
- 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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- 239000013078 crystal Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 20
- 229910052796 boron Inorganic materials 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000007791 liquid phase Substances 0.000 claims description 11
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000007790 solid phase Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007716 flux method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- -1 transition metal carbides Chemical class 0.000 description 2
- 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 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005162 X-ray Laue diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004907 flux Effects 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
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003658 tungsten compounds 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
本発明はタングステン・カーバイド（以下WC
と記載する）の結晶体の製造法、更に詳しくはフ
ローテイング・ゾーン法によるWCの結晶体の製
造法に関する。[Detailed description of the invention] Industrial application field The present invention is directed to tungsten carbide (hereinafter referred to as WC).
The present invention relates to a method for producing a crystalline body of WC (described as ), and more specifically to a method for producing a crystalline body of WC using a floating zone method.
WCは極めて高い温度（約2750℃）まで安定
で、高い硬度2000Kg／mm2）を有し、高い靭性を持
つているので、各種の超硬工具として広く実用に
供せられている。 WC is stable up to extremely high temperatures (approximately 2750°C), has a high hardness of 2000 kg/mm 2 ), and has high toughness, so it is widely used as a variety of carbide tools.
従来技術
従来のWC結晶体の製造法としては、
(1) コバルト金属浴にWCを溶解し、一定温度に
保つた後、徐冷し、弗硝酸などによりコバルト
金属を溶解除去するコバルト金属をフラツクス
として用いるフラツクス法。Conventional technology Conventional methods for producing WC crystals include: (1) Dissolving WC in a cobalt metal bath, keeping it at a constant temperature, cooling slowly, and dissolving and removing the cobalt metal using fluoronitric acid, etc. flux method used as
(2) WCを溶解したコバルト金属上面から浴を徐
冷すると共にWCの結晶を引上げるモデイフア
イド・チヨコラルスキー法がある。(2) There is a modified Czyochoralski method in which the bath is slowly cooled from the top of the cobalt metal in which WC is dissolved and the WC crystals are pulled up.
しかし、(1)の方法では一般に数mmの結晶しか得
られず、(2)の方法では１cm程度の結晶を得るのに
約１週間を要する問題点があつた。しかも(1)(2)は
いずれもフラツクス法であるため、フラツクス金
属やるつぼからの不純物の混入が避けられず、高
純度の結晶が得難い欠点があつた。 However, method (1) generally yields crystals only a few mm in size, and method (2) has the problem that it takes about a week to obtain crystals of about 1 cm. Moreover, since (1) and (2) are both flux methods, the contamination of impurities from the flux metal or crucible is unavoidable, making it difficult to obtain high-purity crystals.
一方、４族、５族遷移金属炭化物の大型単結晶
を得る方法としてフローテイング・ゾーン法（以
下FZ法と言う）が知られている。 On the other hand, a floating zone method (hereinafter referred to as FZ method) is known as a method for obtaining large single crystals of group 4 and group 5 transition metal carbides.
FZ法は第１図の概念図に示すように、目的と
する化合物の原料棒３の一部を例えば、高周波コ
イル７により加熱し、溶融帯６を形成させる。こ
の溶融帯６をはさんだ棒の両端をホールダー２で
保持し、一体に、上または下に移動させて結晶５
を成長させる方法である。図中１はシヤフト、４
は種子棒を示す。 In the FZ method, as shown in the conceptual diagram of FIG. 1, a part of a raw material rod 3 of a target compound is heated by, for example, a high frequency coil 7 to form a molten zone 6. Both ends of the rod sandwiching the melted zone 6 are held by the holder 2, and the rod is moved upward or downward as one unit to form the crystal 5.
It is a way to grow. In the diagram, 1 is the shaft, 4
indicates a seed rod.
この方法による４族、５族遷移金属炭化物の単
結晶育成においては、得られる結晶の組成を目的
の組成と一致させるために、溶融帯の組成を目的
固相組成と平衡共存する液相組成とする方法（特
許第1186975号）。また、育成中、溶融帯からの蒸
発により、溶融帯の組成が変化するのを防ぐた
め、これを補う目的で原料棒の組成を予め調整す
ることが行われている（特願昭55−37963号（特
開昭56−134599号）。 When growing single crystals of Group 4 and Group 5 transition metal carbides using this method, in order to match the composition of the resulting crystal with the target composition, the composition of the molten zone is adjusted to the liquid phase composition that coexists in equilibrium with the target solid phase composition. method (Patent No. 1186975). Additionally, in order to prevent the composition of the molten zone from changing due to evaporation from the molten zone during growth, the composition of the raw material rod is adjusted in advance to compensate for this (Japanese Patent Application No. 55-37963 No. (Japanese Unexamined Patent Publication No. 134599/1983).
発明の目的
本発明FZ法により大型のWC結晶体の製造法を
提供せんとするものである。OBJECT OF THE INVENTION It is an object of the present invention to provide a method for producing large WC crystals using the FZ method of the present invention.
発明の構成
本発明者らは前記目的を達成すべく、FZ法に
よりWC単結晶の育成を試みた。その結果、WC
の固相と平衡共存できるタングステンとカーボン
のみからなる液相組成は存在せず、そのような液
相組成と平衡共存するのは、カーボン欠損型の立
方晶WC（Ｃ−WC1-x）であることが分つた。Structure of the Invention In order to achieve the above object, the present inventors attempted to grow a WC single crystal using the FZ method. As a result, W.C.
There is no liquid phase composition consisting only of tungsten and carbon that can coexist in equilibrium with the solid phase of I found out something.
すなわち、タングステンとカーボンからのみな
る液相を用いる限り、FZ法ではWCの結晶体は育
成できないことが分つた。 In other words, it was found that the FZ method cannot grow WC crystals as long as a liquid phase consisting only of tungsten and carbon is used.
この問題点を解決すべく更に研究の結果、WC
は昇温に伴い、約2750℃で固相分解するが、固相
分解によつて生ずるＣ−WC1-xは僅か数10℃の昇
温で更に液相とカーボンに分解する。この場合、
何らかの元素または化合物を添加することによ
り、WCを安定化させ直接液相に分解させるよう
にすればFZ法の適用が可能になる。WCと類似の
結晶構造を持ち、高温まで安定なタングステン化
合物にW2B5があり、これはWCと同じくタング
ステンの積層が単純六方の構造をとり、ボロンの
数がWC中のカーボンに比し２倍であるWB2を変
形した構造であり、比較的組成範囲が広く、一致
溶融組成はWB〜2.3とされている。従つて、WCと
WB〜2.3の間には固溶関係が存在し、その組成比
に応じ、WCの多い方から順に固相分解、液相へ
の分解、一致溶融と移行する。すなわち、モル比
でWC：WB〜2.3＝１：0.06の組成比を持つ焼結体
を作り、これにFZ法を適用した結果、溶融帯の
移動に伴い、当初カーボンが多量に析出し、次い
でWCが単一層で析出することを究明した。 As a result of further research to solve this problem, WC
With increasing temperature, C-WC 1-x undergoes solid phase decomposition at about 2750°C, but C-WC 1-x produced by solid phase decomposition further decomposes into a liquid phase and carbon with a temperature increase of only a few tens of degrees Celsius. in this case,
The FZ method can be applied by adding some element or compound to stabilize WC and cause it to directly decompose into a liquid phase. W 2 B 5 is a tungsten compound that has a similar crystal structure to WC and is stable up to high temperatures. Like WC, the tungsten layer has a simple hexagonal structure, and the number of boron is compared to the carbon in WC. It has a structure that is a modified version of WB 2 , which is twice as large as WB 2, and has a relatively wide composition range, with a consistent melting composition of WB ~ 2.3 . Therefore, WC and
A solid solution relationship exists between WB and 2.3 , and depending on the composition ratio, the transition occurs from solid phase decomposition to liquid phase decomposition to liquid phase decomposition to coincident melting in descending order of WC. That is, as a result of making a sintered body with a molar ratio of WC:WB ~ 2.3 = 1:0.06 and applying the FZ method to this, a large amount of carbon precipitated at first as the molten zone moved, and then a large amount of carbon precipitated. It was found that WC precipitates in a single layer.
その時の溶融帯の組成はモル比でＷ：Ｃ：Ｂ＝
１：0.7：0.1であつた。この知見に基いて本発明
を完成した。 The composition of the molten zone at that time is the molar ratio W:C:B=
It was 1:0.7:0.1. The present invention was completed based on this knowledge.
本発明の要旨は、タングステン・カーバイド原
料棒の一部分を加熱して溶融帯を形成し、該溶融
帯を移動させてタングステン・カーバイドの結晶
体を製造する所謂フローテイング・ゾーン法によ
る製造法において、該溶融帯の組成をタングステ
ン・カーバイドの固相と平衡共存するタングステ
ン、カーボン及びボロンからなる液相組成とし、
結晶を育成することを特徴とするタングステン・
カーバイドの結晶体の製造法にある。 The gist of the present invention is to provide a manufacturing method using the so-called floating zone method in which a portion of a tungsten carbide raw material rod is heated to form a molten zone, and the molten zone is moved to manufacture a tungsten carbide crystal. The composition of the molten zone is a liquid phase composition consisting of tungsten, carbon and boron that coexist in equilibrium with a solid phase of tungsten carbide,
Tungsten, which is characterized by the ability to grow crystals.
In the method of manufacturing carbide crystals.
溶融帯域の組成は、WCの固相と平衡共存する
タングステン、カーボン及びボロンからなる液相
組成とする。そのためにはモル比で、Ｗ：Ｃ：Ｂ
＝１：（0.4〜1.0）：（0.03〜0.50）、望ましくは、
１：（0.6〜0.8）：（0.05〜0.30）であることが好ま
しい。この組成からずれると、結晶育成の初期段
階に、カーボン濃度の高低に応じ、Ｃまたは
W2CがWC相内に析出し、また、ボロン濃度の高
低に応じ過大なボロンが結晶に含まれるか、低い
とWC相の安定な成長ができなくなる。従つて、
前記の組成であることが好ましい。 The composition of the melting zone is a liquid phase composition consisting of tungsten, carbon, and boron that coexist in equilibrium with the solid phase of WC. For this purpose, the molar ratio is W:C:B
=1:(0.4~1.0):(0.03~0.50), preferably,
The ratio is preferably 1:(0.6-0.8):(0.05-0.30). If the composition deviates from this, depending on the carbon concentration, C or
W 2 C precipitates in the WC phase, and depending on the boron concentration, if too much boron is included in the crystal or too low, the WC phase cannot grow stably. Therefore,
Preferably, the composition is as described above.
原料棒としては、溶融帯から蒸発により失われ
るカーボン及びボロン、また溶融帯と結晶の間の
界面の分配により結晶に取り込まれるボロンを丁
度補うように原料棒に、カーボン及びボロンを含
有させた組成のものとするのがよい。その組成の
好ましい範囲はモル比でＷ：Ｃ：Ｂ＝１：（1.00
〜1.30）：（0.00〜0.20）、望ましくはＷ：Ｃ：Ｂ＝
１：（1.05〜1.20）：（0.01〜0.07）である。Ｃ濃度
が低過ぎると、WC結晶中にW2C相が析出し、ま
た高過ぎるとＣ相が析出し、結晶の質を低下させ
る。 The raw material rod has a composition in which carbon and boron are contained in the raw material rod to exactly compensate for the carbon and boron lost from the molten zone through evaporation, and the boron taken into the crystal by distribution at the interface between the molten zone and the crystal. It is better to make it the one of . The preferred range of its composition is W:C:B=1:(1.00
~1.30): (0.00~0.20), preferably W:C:B=
1:(1.05-1.20):(0.01-0.07). If the C concentration is too low, a W 2 C phase will precipitate in the WC crystal, and if it is too high, a C phase will precipitate, reducing the quality of the crystal.
Ｂ濃度が低過ぎると、十分な長さの溶融帯の移
動ができない間にWCの安定な成長ができなくな
り、またＢ濃度が高過ぎるとWC結晶内にボロン
が取り込まれるので望ましくない。しかし、その
組成は一定のものではなく、溶融帯移動速度、雰
囲気ガスの種類、及び圧力等の結晶育成条件によ
つて変化するので実験的に決めればよい。 If the B concentration is too low, stable growth of WC will not be possible while the molten zone cannot move for a sufficient length, and if the B concentration is too high, boron will be incorporated into the WC crystal, which is undesirable. However, the composition is not constant, and can be determined experimentally since it changes depending on the crystal growth conditions such as the moving speed of the molten zone, the type of atmospheric gas, and the pressure.
原料棒に相対し、溶融帯部をはさんで置かれる
種子棒の組成は、原料棒と同じでもまたは相違し
てもよく、また、W2C，WCの単結晶を用いて育
成する単結晶の方位を〔0001〕，〔10１０〕，〔11２
０〕等に平行にすることも可能である。 The composition of the seed rod placed opposite the raw material rod across the melted zone may be the same as or different from that of the raw material rod, and the composition of the seed rod may be the same as or different from that of the raw material rod . The direction of [0001], [1010], [112]
0], etc., is also possible.
本発明の方法を行う装置としては、例えば
ADL社製の高圧タイプの結晶育成炉が挙げられ、
この炉による結晶育成法を説明する。 As an apparatus for carrying out the method of the present invention, for example,
A high-pressure type crystal growth furnace made by ADL is mentioned.
The crystal growth method using this furnace will be explained.
直径約１cm、長さ10〜20cmの原料棒を上方に置
き、長さ３〜７cmの種子棒を下方に置き、該種子
棒の上に溶融帯部となる棒を置き、原料棒の下端
と接しさせる。前記溶融帯部となる棒は種子棒の
上部に置く方法のほか、種子棒自身を溶融帯の組
成と一致させてもよく、また、種子棒と原料棒の
間に必要量のＷ及びＢまたはＣ及びＢをはさみ、
この部分を溶融帯としてもよい。 A raw material rod with a diameter of about 1 cm and a length of 10 to 20 cm is placed above, a seed rod with a length of 3 to 7 cm is placed below, a rod that will become the melting zone is placed on top of the seed rod, and the lower end of the raw material rod and Let them come into contact with you. In addition to the method of placing the rod that becomes the molten zone above the seed rod, the seed rod itself may be made to match the composition of the molten zone, and the required amount of W, B or Scissor C and B,
This portion may be used as a melting zone.
この溶融帯部を例えば高周波加熱（光集光方式
でもよいし）して溶融帯を作り、その後、原料棒
及び種子棒を一体に、または異なる速度で下方に
移動させる。この移動によつてWC結晶が成長を
続ける。 This melting zone is heated, for example, by high frequency (light condensing method may be used) to form a melting zone, and then the raw material rod and the seed rod are moved downward together or at different speeds. This movement causes the WC crystal to continue growing.
この時の種子棒移動速度は、結晶成長が溶融体
の固化ではなく、溶融帯からのWCの析出による
ものであるから、おそい方が良く、0.5〜10mm／
ｈ、望ましくは１〜３mm／ｈとするのがよい。 The seed rod movement speed at this time should be 0.5 to 10 mm/
h, preferably 1 to 3 mm/h.
原料棒の移動速度は前記種子棒と同じ速度でも
よいが、溶融帯を安定に維持できる速度例えば種
子棒の移動速度の80〜90％であつてもよい。 The moving speed of the raw material rod may be the same speed as the seed rod, but it may also be a speed at which the molten zone can be stably maintained, for example, 80 to 90% of the moving speed of the seed rod.
また、原料棒、種子棒の上下関係を逆にし、上
方に移動するようにしてもよい。 Alternatively, the vertical relationship between the raw material rod and the seed rod may be reversed so that they move upward.
溶融帯の組成を均一に保つためには回転操作を
加えることが効果的である。即ち上下の棒を固定
したシヤフトを逆方向に回転させ、溶融帯部を混
合させる。その回転速度は通常５〜30rpm程度が
適当である。 Adding a rotation operation is effective in keeping the composition of the molten zone uniform. That is, a shaft to which upper and lower rods are fixed is rotated in opposite directions to mix the molten zone. The appropriate rotational speed is usually about 5 to 30 rpm.
結晶を育成する際の雰囲気は、ヘリウム、アル
ゴン等の不活性ガスの他、窒素、水素ガスであつ
てもよい。 The atmosphere for growing the crystal may be an inert gas such as helium or argon, or nitrogen or hydrogen gas.
雰囲気圧は大気圧（１×105Pa）でもよいが、
加圧雰囲気とすると、溶融帯からの成分の蒸発を
抑制するので有効である。しかし高過ぎると、対
流による熱損失が増大するので、通常２〜30×
105Pa、好ましくは３〜15×105Paであることが
適当である。 The atmospheric pressure may be atmospheric pressure (1×10 5 Pa), but
A pressurized atmosphere is effective because it suppresses evaporation of components from the molten zone. However, if it is too high, heat loss due to convection will increase, so it is usually 2 to 30 ×
10 5 Pa, preferably 3 to 15×10 5 Pa is suitable.
このようにして、約10時間溶融帯を移動する
と、直径８〜９mm、長さ30mm程度のWC単結晶を
育成することができる。 By moving the melt zone in this manner for about 10 hours, a WC single crystal with a diameter of 8 to 9 mm and a length of about 30 mm can be grown.
実施例 １
市販のWC原料粉（平均粒径0.7μm、全炭素
6.11wt％）を用い、WC1モルに対し、カーボン
（発光分析用）0.15モル、ボロン0.01モルの比で
全重量が100ｇとなるように秤量し、粘着剤とし
てアルコールに溶解した樟脳を適量加えて十分混
合した。これを乾燥した後、８×107Paでラバー
プレスを行い、直径12mm、長さ130mmの棒とした。
この棒を真空中2000℃において１時間焼結した。
得られた焼結棒は約直径10mm、長さ110mmで、密
度は90％程度であつた。この焼結棒を原料棒とし
た。Example 1 Commercially available WC raw material powder (average particle size 0.7 μm, total carbon
6.11wt%), weighed so that the total weight was 100g at a ratio of 0.15 mol of carbon (for luminescence analysis) and 0.01 mol of boron to 1 mol of WC, and added an appropriate amount of camphor dissolved in alcohol as an adhesive. Mixed thoroughly. After drying this, a rubber press was performed at 8×10 7 Pa to obtain a rod with a diameter of 12 mm and a length of 130 mm.
This bar was sintered in vacuum at 2000°C for 1 hour.
The obtained sintered rod had a diameter of about 10 mm, a length of 110 mm, and a density of about 90%. This sintered rod was used as a raw material rod.
一方種子棒として、WC1モルに対しタングス
テン0.41モル、ボロン0.05モルの比で、全重量が
40ｇとなるように、WC粉、Ｗ粉、アモルフアス
ボロン粉を秤量し、この混合物を原料棒と同じ条
件で焼結し、直径８mm、長さ50mmの種子棒とし
た。 On the other hand, as a seed rod, the total weight is 0.41 mol of tungsten and 0.05 mol of boron to 1 mol of WC
WC powder, W powder, and amorphous asboron powder were weighed to give 40 g, and this mixture was sintered under the same conditions as the raw material rod to form a seed rod with a diameter of 8 mm and a length of 50 mm.
原子棒を上方に、種子棒を下方に置き、両者の
間に、ボロン塊0.005ｇをはさんだ。 The atomic rod was placed above and the seed rod was placed below, and 0.005 g of boron mass was sandwiched between the two.
内径約16mm、２段各３回巻の高周波コイルを、
コイル上端にほぼ種子棒上端がくるようにセツト
し、加熱して溶融帯を形成した。そして上下棒を
逆方向に各15rpmで回転させ、種子棒を3.0mm／
ｈ、原料棒を2.7mm／ｈで、下方に移動させた。
雰囲気はHeガス８×105Paとした。 A high frequency coil with an inner diameter of approximately 16 mm and 2 stages of 3 turns each.
The seed rod was set so that the upper end of the seed rod was almost at the upper end of the coil, and heated to form a molten zone. Then, rotate the upper and lower rods in opposite directions at 15 rpm each, and rotate the seed rod by 3.0 mm/
h, the raw material rod was moved downward at a rate of 2.7 mm/h.
The atmosphere was He gas 8×10 5 Pa.
溶融帯移動開始と殆んど同時に、WC相の析出
が認められ、約10時間の移動により直径約９mm、
長さ30mmのWCの結晶体が得られた。 Almost simultaneously with the start of the molten zone movement, precipitation of the WC phase was observed, and after about 10 hours of movement, the WC phase became approximately 9 mm in diameter.
A WC crystal with a length of 30 mm was obtained.
得られた結晶体を粉末Ｘ線法によつて調べた結
果、WC単一相であることが確認された。反射ラ
ウエ法により結晶成長方向がほぼ〔11２０〕方向
に平行していることが分つた。また、結晶中のボ
ロンは化学分析の結果、300ppm（重量）と少な
く、高純度であることが分つた。 As a result of examining the obtained crystal by powder X-ray method, it was confirmed that it was a single WC phase. It was found by the reflection Laue method that the crystal growth direction was approximately parallel to the [1120] direction. Additionally, chemical analysis revealed that the boron content in the crystals was as low as 300 ppm (by weight), indicating high purity.
発明の効果
本発明の方法によると、従来FZ法ではWCの結
晶体の育成が不可能とされていたのを可能にし、
しかも良質大型の結晶体を極めて容易に製造し得
られる優れた効果を有する。Effects of the Invention According to the method of the present invention, it has become possible to grow WC crystals, which was previously considered impossible with the FZ method.
Moreover, it has an excellent effect in that high-quality, large-sized crystals can be produced extremely easily.
図面はFZ法の概念図である。
１：シヤフト、２：ホルダー、３：原料棒、
４：種子棒、５：結晶、６：溶融帯、７：高周波
コイル。
The drawing is a conceptual diagram of the FZ method. 1: Shaft, 2: Holder, 3: Raw material rod,
4: Seed rod, 5: Crystal, 6: Melt zone, 7: High frequency coil.
Claims (1)
加熱して溶融帯を形成し、該溶融帯を移動させて
タングステン・カーバイドの結晶体を製造する所
謂フローテイング・ゾーン法による製造法におい
て、該溶融帯の組成をタングステン・カーバイド
の固相と平衡共存するタングステン、カーボン及
びボロンからなる液相組成とし、結晶を育成する
ことを特徴とするタングステン・カーバイドの結
晶体の製造法。 ２ タングステン、カーボン及びボロンからなる
液相組成がモル比でＷ：Ｃ：Ｂ＝１：（0.4〜
1.0）：（0.03〜0.50）からなる液相組成である特許
請求の範囲第１項記載のタングステン・カーバイ
ドの結晶体の製造法。 ３ タングステン・カーバイド原料棒の組成比
を、予めタングステンに対するカーボン及びボロ
ンの割合を調整する特許請求の範囲第１項記載の
タングステン・カーバイドの結晶体の製造法。[Claims] 1. In a production method using the so-called floating zone method, in which a part of the tungsten carbide raw material rod is heated to form a molten zone, and the molten zone is moved to produce a tungsten carbide crystal. A method for producing a tungsten carbide crystal, characterized in that the composition of the molten zone is a liquid phase composition consisting of tungsten, carbon, and boron coexisting in equilibrium with the solid phase of tungsten carbide, and the crystal is grown. 2 The liquid phase composition consisting of tungsten, carbon and boron has a molar ratio of W:C:B=1:(0.4~
1.0): (0.03 to 0.50). 1.0): (0.03-0.50). 3. The method for producing a tungsten carbide crystal according to claim 1, wherein the composition ratio of the tungsten carbide raw material rod is adjusted in advance by adjusting the ratio of carbon and boron to tungsten.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18707885A JPS6247000A (en) | 1985-08-26 | 1985-08-26 | Production of crystal body of tungsten carbide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18707885A JPS6247000A (en) | 1985-08-26 | 1985-08-26 | Production of crystal body of tungsten carbide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6247000A JPS6247000A (en) | 1987-02-28 |
| JPH027919B2 true JPH027919B2 (en) | 1990-02-21 |
Family
ID=16199746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18707885A Granted JPS6247000A (en) | 1985-08-26 | 1985-08-26 | Production of crystal body of tungsten carbide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6247000A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10043792A1 (en) * | 2000-09-06 | 2002-03-14 | Starck H C Gmbh | Ultra-coarse, single-crystalline tungsten carbide and process for its manufacture; and carbide made from it |
| GB2509790B (en) * | 2013-03-27 | 2015-02-25 | Hardide Plc | Superabrasive material with protective adhesive coating and method for producing said coating |
-
1985
- 1985-08-26 JP JP18707885A patent/JPS6247000A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6247000A (en) | 1987-02-28 |
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