JPH0243715B2 - TANKETSUSHONOSEIZOHO - Google Patents
TANKETSUSHONOSEIZOHOInfo
- Publication number
- JPH0243715B2 JPH0243715B2 JP26853284A JP26853284A JPH0243715B2 JP H0243715 B2 JPH0243715 B2 JP H0243715B2 JP 26853284 A JP26853284 A JP 26853284A JP 26853284 A JP26853284 A JP 26853284A JP H0243715 B2 JPH0243715 B2 JP H0243715B2
- Authority
- JP
- Japan
- Prior art keywords
- single crystal
- polycrystal
- polycrystalline
- crystal
- hours
- 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 - Lifetime
Links
- 239000013078 crystal Substances 0.000 claims description 65
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000032683 aging Effects 0.000 description 11
- 229910000859 α-Fe Inorganic materials 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000002159 abnormal effect Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006061 abrasive grain Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Description
（産業上の利用分野）
本発明は、多結晶体の均一な単結晶化に関する
もので、特にVTR等の磁気ヘツドに有用な単結
晶フエライト等の製造法に関するものである。
（従来の技術）
従来、単結晶の製造法として、本出願人は特開
昭55−162496号公報において固相反応法による単
結晶製造方法を開示した。この製造法では、種と
なる単結晶と多結晶体の接合面を鏡面研磨した
後、塩酸、硝酸を接合面に介在させて接合し、直
ちに加熱して多結晶体を単結晶化していた。
（発明が解決しようとする問題点）
上述した製造法においては、ブリツジマン法等
の単結晶製造法と比べて大量生産が可能で単結晶
製品が安価となる等の利点があるが、多結晶体全
体が均一な単結晶になりにくく、種単結晶の貼付
不良等に起因する多結晶体の結晶の異常成長が認
められる場合があつた。そのため、単結晶の収率
が低いと共に大きな単結晶が得られない欠点があ
つた。
第２図ａ，ｂはそれぞれ典型的な不良の例を示
す斜視図で、１は種単結晶、２は多結晶体、３は
バツクダミー、４は異常結晶成長部、５は生成さ
れた単結晶部を示している。なお、第２図ａは種
単結晶の貼付が不十分のために発生する異常結晶
成長を、また第２図ｂは多結晶体２の材料が悪い
ために発生する異常結晶成長を示している。
本発明の目的は、上述した不具合を解消して、
種貼付不良等に起因する結晶の異常成長を防止し
て、収率よく大きな単結晶部を得ることができる
単結晶部の製造法を提供しようとするものであ
る。
（問題点を解決するための手段）
本発明の単結晶部の製造法は、多結晶体と単結
晶とを接触して加熱することにより、単結晶を多
結晶体方向に結晶成長させて単結晶を得る方法に
おいて、多結晶体と単結晶の接合面を鏡面研磨
し、その鏡面研磨面間に酸を介在させて多結晶体
と単結晶を接合し、多結晶体と単結晶とを接合し
た状態で相対湿度70％以上の雰囲気に少なくとも
２時間以上保持した後、加熱して多結晶体を単結
晶化することを特徴とするものである。
（作用）
種となる単結晶と多結晶体との接合面に強酸を
塗布すると、ある一定条件下では接合面に極く薄
い金属塩の層が生成する。本発明では、この金属
塩の層により単結晶と多結晶体を強固に接合した
状態で加熱して単結晶を得るのが最も望ましい。
本発明者等が種々検討の結果、上述した状態を
達成し望ましい単結晶を得るためには、単結晶と
多結晶体を接合後少なくとも70％以上の相対湿度
中で２時間以上エージングすると良いことがわか
つた。ここで、相対湿度70％以上で２時間以上の
エージングが必要であるのは、この条件を満たさ
ないと望ましい接合が達成できず、種貼付不良等
に起因する結晶の異常成長を防止することができ
ないためである。
（実施例）
以下、本発明を実施例に基づき詳細に説明す
る。本発明の単結晶の製造法は、多結晶体であれ
ばどのような組成のものにでも適用できるが、実
際に好適に使用されるものとしては以下のような
組成があげられる。
(Field of Industrial Application) The present invention relates to uniform single crystallization of polycrystalline materials, and particularly to a method for producing single crystal ferrite useful for magnetic heads such as VTRs. (Prior Art) Conventionally, as a method for producing a single crystal, the present applicant disclosed a method for producing a single crystal using a solid phase reaction method in Japanese Patent Application Laid-open No. 162496/1983. In this manufacturing method, the joint surfaces of the seed single crystal and the polycrystalline body are polished to a mirror surface, and then hydrochloric acid and nitric acid are interposed between the joint surfaces to join them, and the polycrystalline body is immediately heated to turn the polycrystalline body into a single crystal. (Problems to be Solved by the Invention) The above-mentioned manufacturing method has advantages over single-crystal manufacturing methods such as the Bridgeman method, such as being able to mass-produce and making single-crystal products cheaper. It was difficult to form a uniform single crystal as a whole, and there were cases in which abnormal growth of polycrystalline crystals was observed due to poor attachment of the seed single crystal. Therefore, the yield of single crystals was low and large single crystals could not be obtained. Figures 2a and 2b are perspective views showing typical examples of defects, respectively, where 1 is a seed single crystal, 2 is a polycrystalline body, 3 is a back dummy, 4 is an abnormal crystal growth part, and 5 is a produced single crystal. It shows the part. Furthermore, Fig. 2a shows abnormal crystal growth that occurs due to insufficient attachment of the seed single crystal, and Fig. 2b shows abnormal crystal growth that occurs due to poor material of polycrystalline body 2. . The purpose of the present invention is to solve the above-mentioned problems,
It is an object of the present invention to provide a method for producing a single crystal part that can prevent abnormal growth of crystals due to poor seed attachment, etc., and can obtain a large single crystal part with good yield. (Means for Solving the Problems) The method for manufacturing a single crystal part of the present invention is to grow the single crystal in the direction of the polycrystal by contacting and heating the polycrystal and the single crystal. In the method of obtaining crystals, the joint surfaces of a polycrystalline body and a single crystal are mirror-polished, and an acid is interposed between the mirror-polished surfaces to join the polycrystalline body and the single crystal, and the polycrystalline body and the single crystal are joined together. The method is characterized in that the polycrystalline material is kept in an atmosphere with a relative humidity of 70% or more for at least 2 hours or more, and then heated to convert the polycrystalline material into a single crystal. (Function) When a strong acid is applied to the bonding surface between the seed single crystal and the polycrystal, under certain conditions an extremely thin layer of metal salt is formed on the bonding surface. In the present invention, it is most desirable to obtain a single crystal by heating the single crystal and the polycrystal in a state in which the metal salt layer firmly bonds the single crystal to the polycrystal. As a result of various studies, the present inventors have found that in order to achieve the above-mentioned state and obtain a desirable single crystal, it is advisable to age the single crystal and polycrystal for at least 2 hours in a relative humidity of at least 70% or more after joining. I understood. Here, aging for 2 hours or more at a relative humidity of 70% or higher is necessary because unless these conditions are met, desired bonding cannot be achieved and abnormal growth of crystals due to poor seed attachment etc. can be prevented. This is because it cannot be done. (Examples) Hereinafter, the present invention will be described in detail based on Examples. Although the method for producing a single crystal of the present invention can be applied to polycrystals of any composition, the following compositions can be mentioned as those that are actually preferably used.
【表】
まず、上述したような組成の多結晶体ブロツク
を準備し、その接合面をダイヤモンド砥粒で鏡面
研磨する。一方、種として同一の大きさの接合面
をもつ同一組成の単結晶を準備し、同様にその接
合面を鏡面研磨する。その後、両接合面に塩酸、
硝酸等の強酸を滴下し、単結晶と多結晶体を接合
した。このとき、結晶成長しない多結晶体からな
るダミー材を準備して、多結晶体に関して単結晶
と対向する面に鏡面研磨後強酸を介して接合する
と、単結晶化のためにより好適である。次に、上
述した方法で得られた接合体を、相対湿度70％以
上、好ましくは80％以上の雰囲気中に２時間以
上、好ましくは５時間以上保持する。その後、接
合体を多結晶体において不連続な結晶粒子の成長
の起る温度未満の温度に加熱して、多結晶体全体
を単結晶化する。
実施例 １
純度99.9％の炭酸マンガンを焙焼して得られた
酸化マンガンと、純度99.9％の酸化亜鉛および酸
化第二鉄を原料とし、その組成がMn Ｏ＝31モ
ル％、Zn Ｏ＝16.5モル％、Fe2O3＝52.5モル％で
あり不純物としてSiO20.01％以下、TiO20.05％
以、、CaO0.005％以下、Na2O0.003％以下である
調合物を成形し、平衡酸素分圧下で1320℃、４時
間焼成してマンガン亜鉛フエライト多結晶体を得
た。
このフエライト多結晶体と、そのフエライト多
結晶体とほぼ同一組成を有する高圧ブリツジマン
法で製造されたフエライト単結晶とより、10×30
×５mmと10×30×0.5mmの板を切り出し、それぞ
れの接合面をダイヤモンド砥粒を用いて研磨し
た。その後、その接合面に6Nの塩酸を塗布し、
多結晶フエライト板と単結晶フエライト板とを重
ね合わせた。さらに、結晶成長しない多結晶フエ
ライトよりなるダミー材を準備し、多結晶フエラ
イトに関して単結晶フエライトの接合面と反対側
に、同様にして研磨後塩酸を介して接合した。
このフエライト接合体に対して、後述する第１
表に示すようにエージング時間とエージングの際
の雰囲気条件（気中の相対湿度）とを変化させて
エージングを行なつた。エージング後この接合体
を窒素雰囲気中において1250℃で30分間加熱した
後、フエライト多結晶体の不連続な結晶粒子成長
の起る1360℃未満の温度である1350℃で15時間保
持し、固相反応を生起させて本発明による単結晶
体を得た。結果を完全に単結晶化したものの出現
率（％）で第１表に示す。[Table] First, a polycrystalline block having the composition described above is prepared, and its joint surface is mirror-polished with diamond abrasive grains. On the other hand, a single crystal with the same composition and a bonding surface of the same size is prepared as a seed, and the bonding surface is mirror-polished in the same manner. Then, apply hydrochloric acid to both joint surfaces.
A strong acid such as nitric acid was dropped to join the single crystal and polycrystal. At this time, it is more suitable for single crystallization to prepare a dummy material made of a polycrystalline material that does not grow crystals, and to bond the surface of the polycrystalline material facing the single crystal with a strong acid after mirror polishing. Next, the bonded body obtained by the method described above is maintained in an atmosphere with a relative humidity of 70% or more, preferably 80% or more for 2 hours or more, preferably 5 hours or more. Thereafter, the joined body is heated to a temperature lower than the temperature at which discontinuous crystal grain growth occurs in the polycrystalline body, thereby converting the entire polycrystalline body into a single crystal. Example 1 Manganese oxide obtained by roasting manganese carbonate with a purity of 99.9%, zinc oxide and ferric oxide with a purity of 99.9% are used as raw materials, and the composition is Mn O = 31 mol%, Zn O = 16.5 Mol%, Fe 2 O 3 = 52.5 mol%, impurities include SiO 2 0.01% or less, TiO 2 0.05%
Thereafter, a composition containing 0.005% or less of CaO and 0.003% or less of Na 2 O was molded and fired at 1320° C. for 4 hours under equilibrium oxygen partial pressure to obtain a manganese-zinc ferrite polycrystalline body. A 10×30
×5 mm and 10 × 30 × 0.5 mm plates were cut out, and the joint surfaces of each were polished using diamond abrasive grains. Then, apply 6N hydrochloric acid to the joint surface,
A polycrystalline ferrite plate and a single-crystalline ferrite plate were stacked on top of each other. Furthermore, a dummy material made of polycrystalline ferrite, which does not undergo crystal growth, was prepared and bonded to the polycrystalline ferrite on the side opposite to the bonding surface of the single-crystal ferrite after polishing in the same manner using hydrochloric acid. For this ferrite bonded body, the first
Aging was carried out by changing the aging time and the atmospheric conditions (relative humidity in the air) during aging as shown in the table. After aging, this bonded body was heated at 1250°C for 30 minutes in a nitrogen atmosphere, and then held at 1350°C for 15 hours, which is a temperature below 1360°C at which discontinuous crystal grain growth of ferrite polycrystals occurs, to form a solid phase. A reaction occurred to obtain a single crystal according to the present invention. The results are shown in Table 1 as the appearance rate (%) of completely single crystals.
【表】
また、第１表の結果により、エージング雰囲気
（相対湿度）、エージング時間と良品率の関係を第
１図に示す。第１表および第１図から明らかなよ
うに、本発明の範囲であるエージング時間２時間
以上、好ましくは５時間以上で、エージング雰囲
気が気中相対湿度70％以上範囲のものは、種貼付
不十分等に起因する多結晶フエライトの異常成長
が少く良好な結果が得られている。
（発明の効果）
以上詳細に説明したところから明らかなよう
に、本発明の単結晶の製造法によれば、多結晶体
全体が完全の単結晶化した単結晶を収率よく得る
ことができる。また、大きな単結晶を得ることが
できると共に多結晶体を単結晶化する収率を向上
させることができる。さらに、本発明方法により
得られたフエライト単結晶はVTR用磁気ヘツド
として好適に使用できる。[Table] Based on the results shown in Table 1, the relationship between aging atmosphere (relative humidity), aging time, and non-defective product rate is shown in FIG. As is clear from Table 1 and Figure 1, the aging time within the scope of the present invention is 2 hours or more, preferably 5 hours or more, and the aging atmosphere is in the atmospheric relative humidity range of 70% or more, without seed attachment. Good results have been obtained with less abnormal growth of polycrystalline ferrite caused by crystallization. (Effects of the Invention) As is clear from the detailed explanation above, according to the method for producing a single crystal of the present invention, a single crystal in which the entire polycrystalline body is a complete single crystal can be obtained in good yield. . Furthermore, it is possible to obtain large single crystals and to improve the yield of single crystallization of polycrystals. Furthermore, the ferrite single crystal obtained by the method of the present invention can be suitably used as a magnetic head for a VTR.
第１図は本発明のエージング雰囲気（相対湿
度）エージング時間と良品率の関係を示すグラ
フ、第２図ａ，ｂはそれぞれ典型的な不良の例を
示す斜視図である。
１……種単結晶、２……多結晶体、３……バツ
クダミー、４……異常結晶成長部。
FIG. 1 is a graph showing the relationship between the aging atmosphere (relative humidity) and aging time of the present invention and the non-defective product rate, and FIGS. 2a and 2b are perspective views showing typical examples of defects, respectively. 1... Seed single crystal, 2... Polycrystalline body, 3... Back dummy, 4... Abnormal crystal growth part.
Claims (1)
により、単結晶を多結晶体方向に結晶成長させて
単結晶を得る方法において、 多結晶体と単結晶の接合面を鏡面研磨し、その
鏡面研磨面間に酸を介在させて多結晶体と単結晶
を接合し、多結晶体と単結晶とを接合した状態で
相対湿度70％以上の雰囲気に少なくとも２時間以
上保持した後、加熱して多結晶体を単結晶化する
ことを特徴とする単結晶の製造法。 ２ 前記多結晶体と単結晶の接合体を、相対湿度
80％以上の雰囲気に５時間以上保持することを特
徴とする特許請求の範囲第１項記載の単結晶の製
造法。[Claims] 1. A method for obtaining a single crystal by growing the single crystal in the direction of the polycrystal by contacting and heating the polycrystal and the single crystal, comprising: The surfaces are mirror-polished, the polycrystal and single crystal are bonded by interposing acid between the mirror-polished surfaces, and the bonded polycrystal and single crystal are placed in an atmosphere with a relative humidity of 70% or more for at least 2 hours. 1. A method for producing a single crystal, which comprises holding the polycrystal as a single crystal by heating the polycrystal. 2. The polycrystalline and single crystal bonded body is heated at relative humidity.
2. The method for producing a single crystal according to claim 1, wherein the single crystal is maintained in an atmosphere of 80% or more for 5 hours or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26853284A JPH0243715B2 (en) | 1984-12-21 | 1984-12-21 | TANKETSUSHONOSEIZOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26853284A JPH0243715B2 (en) | 1984-12-21 | 1984-12-21 | TANKETSUSHONOSEIZOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61146779A JPS61146779A (en) | 1986-07-04 |
| JPH0243715B2 true JPH0243715B2 (en) | 1990-10-01 |
Family
ID=17459820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26853284A Expired - Lifetime JPH0243715B2 (en) | 1984-12-21 | 1984-12-21 | TANKETSUSHONOSEIZOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0243715B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6048394A (en) * | 1997-08-14 | 2000-04-11 | Competitive Technologies Of Pa, Inc. | Method for growing single crystals from polycrystalline precursors |
| US7208041B2 (en) | 2000-02-23 | 2007-04-24 | Ceracomp Co., Ltd. | Method for single crystal growth of perovskite oxides |
| US8202364B2 (en) | 2002-10-11 | 2012-06-19 | Ceracomp Co., Ltd. | Method for solid-state single crystal growth |
-
1984
- 1984-12-21 JP JP26853284A patent/JPH0243715B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61146779A (en) | 1986-07-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |