JPH0660326B2 - Amorphous coating and method for producing the same - Google Patents
Amorphous coating and method for producing the sameInfo
- Publication number
- JPH0660326B2 JPH0660326B2 JP60037206A JP3720685A JPH0660326B2 JP H0660326 B2 JPH0660326 B2 JP H0660326B2 JP 60037206 A JP60037206 A JP 60037206A JP 3720685 A JP3720685 A JP 3720685A JP H0660326 B2 JPH0660326 B2 JP H0660326B2
- Authority
- JP
- Japan
- Prior art keywords
- amorphous
- base material
- layer
- explosive
- metal
- 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
- 238000000576 coating method Methods 0.000 title claims description 24
- 239000011248 coating agent Substances 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000463 material Substances 0.000 claims description 79
- 239000002360 explosive Substances 0.000 claims description 59
- 239000000843 powder Substances 0.000 claims description 47
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
- 238000004880 explosion Methods 0.000 claims description 19
- 230000035939 shock Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 61
- 229910052802 copper Inorganic materials 0.000 description 36
- 239000010949 copper Substances 0.000 description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 35
- 229910000831 Steel Inorganic materials 0.000 description 24
- 239000010959 steel Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 20
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 9
- 238000005530 etching Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000005304 joining Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 230000005484 gravity Effects 0.000 description 5
- 239000002932 luster Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 4
- 239000002178 crystalline material Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000001475 halogen functional group Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000005300 metallic glass Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
- Pressure Welding/Diffusion-Bonding (AREA)
- Ceramic Products (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、鉄系、銅系、ステンレス等の金属製の母材表
面に半導体、金属等のアモルファス層を一体に形成した
アモルファス被覆体に関するもので、例えば回転駆動軸
の回転応力（トルク）を検出するトルクセンサとして用
いて有効である。TECHNICAL FIELD The present invention relates to an amorphous coating body in which an amorphous layer such as a semiconductor or a metal is integrally formed on the surface of a base material made of a metal such as iron, copper or stainless. It is effective when used as a torque sensor that detects the rotational stress (torque) of the rotary drive shaft, for example.
金属等のアモルファスは、従来の結晶質の金属に比較し
て、その硬度・耐摩耗性・化学耐蝕性・磁気特性などの
優れた特性を有する点から、最近広い範囲の用途が研究
され、例えば磁気ヘッド・トルクセンサ等の磁性材料と
して応用研究が注目されている。Amorphous materials such as metals have recently been researched in a wide range of applications because they have excellent characteristics such as hardness, wear resistance, chemical corrosion resistance, and magnetic characteristics as compared with conventional crystalline metals. Applied research is attracting attention as a magnetic material for magnetic heads and torque sensors.
金属のアモルファスはスパッター法、気相化学反応法、
メッキ法、溶融物質の超急冷法により製造されており、
なかでもアモルファス金属薄帯は遠心法、双ロール法、
単ロール法により、溶融した金属を連続的に冷却回転体
上に噴出して急冷凝固して製造されている。しかし、そ
の方法により得られるアモルファスの薄帯は、厚さがせ
いぜい数百ミクロン程度のリボン状のものである。この
アモルファスの薄帯は、例えば特開昭５７−２１１０３
０号（U.S.No.4414855）、特開昭５８−９０３４号等に
開示される様に、トルクセンサの磁歪材料として利用研
究されている。尚、トルクセンサとは、トルク（回転応
力）の加わる駆動軸の表面に磁歪材料を接着させ、付加
されるトルクに応じて前記磁歪材料の磁気特性が変化す
る度合を検出して、駆動軸に加えられたトルクを測定す
るものである。Amorphous metal is sputter method, gas phase chemical reaction method,
Manufactured by plating method and ultra-quenching method of molten material,
Among them, the amorphous metal ribbon is a centrifugal method, a twin roll method,
It is manufactured by a single roll method, in which molten metal is continuously jetted onto a cooling rotator and rapidly solidified. However, the amorphous ribbon obtained by the method has a ribbon-like shape with a thickness of at most several hundreds of microns. This amorphous ribbon is disclosed in, for example, JP-A-57-21103.
No. 4 (US Pat. No. 4,414,855) and Japanese Patent Application Laid-Open No. 58-9034 have been used and studied as a magnetostrictive material for torque sensors. A torque sensor means that a magnetostrictive material is adhered to the surface of a drive shaft to which torque (rotational stress) is applied, and the degree to which the magnetic characteristic of the magnetostrictive material changes according to the applied torque is detected, It measures the applied torque.
ところが、上述の様に磁歪材料として用いられるアモル
ファスの薄帯は、その駆動軸の表面にエポキシ等の接着
剤、あるいははんだ付けなどによって接着されている。
このため駆動軸とアモルファス薄帯とん接着強度が弱
く、駆動軸もしくは薄帯に応力が作用した時、又は雰囲
気温度が変化した時には、アモルファスの薄帯が前記軸
表面から剥離する、あるいはその接着・接合状態が不安
定となり磁歪材料としての特性が低下し、正確な特性を
検出することができなくなるといった問題点を有してい
る。However, as described above, the amorphous ribbon used as the magnetostrictive material is adhered to the surface of the drive shaft with an adhesive such as epoxy or soldering.
Therefore, the adhesive strength between the drive shaft and the amorphous ribbon is weak, and when the drive shaft or the ribbon is stressed or when the ambient temperature changes, the amorphous ribbon peels off from the surface of the shaft, or its adhesion. -There is a problem in that the bonding state becomes unstable and the characteristics of the magnetostrictive material deteriorate, making it impossible to detect accurate characteristics.
さらに金属等のアモルファス層を金属の母材表面にスパ
ッタ法、メッキ法等によって製造する方法もあるが、こ
れらはアモルファス層が十分強固に接着されていないた
め、上述と同様の問題を有しているとともに、その製造
速度がきわめて遅いことも問題である。Further, there is a method of producing an amorphous layer of a metal or the like on the surface of a metal base material by a sputtering method, a plating method, or the like, but these have the same problems as described above because the amorphous layer is not firmly adhered. In addition, the production speed is extremely slow, which is also a problem.
このようにアモルファス層が母材表面上に強固に接着・
接合されていないが故に、非晶質の優れた磁歪特性が十
分発揮されていないと同時に、耐久性の問題が解決され
ていないのが現状である。In this way, the amorphous layer firmly adheres to the surface of the base material.
Since they are not joined, the excellent amorphous magnetostrictive characteristics are not sufficiently exhibited, and at the same time, the problem of durability has not been solved.
本発明者らは上記問題点を鑑みるとともに、一方におい
て、爆発圧接の原理を利用してアモルファス成形体を成
形することに着目して種々の実験検討も繰り返した。In view of the above problems, the present inventors have repeated various experimental studies focusing on molding an amorphous compact by utilizing the principle of explosive pressure welding.
爆薬の爆発によって生ずる瞬間的な高エネルギーを固体
金属の接合に利用する、いわゆる爆発圧接法は既に公知
であり、この方法をアモルファスの粉体に適用した例も
僅かながら知られている。例えば特開昭５９−７４３３
号に開示される様に、筒状金属容器にアモルファスの粉
体を充填し、その容器の周囲を爆薬によって爆発させ、
圧搾により前記アモルファスの粉体を一体に成形する方
法が考案されている。ところが、前記方法によって成形
されるアモルファスの成形体は、成形体全体がアモルフ
ァスであるため高価なものとなる。すなわち、金属等の
アモルファスはその製造方法が特殊なものであるが故
に、その粉体自体の価格が高くなる。またアモルファス
の耐摩耗性・耐蝕性・磁歪特性を利用するものにおいて
は、その成形体の内部はアモルファスであることは必ず
しも必要ではなく、むしろその成形体の表面にあるアモ
ルファス層が重要となるのに対して、上記方法で成形し
た成形体は、その成形体内部もアモルファスであるため
に一層高価なものとなる。さらに上記方法で成形した成
形体はアモルファスの粉末の充填される量及び厚み等に
応じて、その成形条件を適宜制御する必要があり、本発
明者らの実験研究によると、アモルファスの粉末の充填
される量の多いもの程、その成形後のアモルファス成形
体にはクラック、切裂、巣が発生し易い。これは筒状容
器内のアモルファスの粉体に外周より加えられる衝撃波
が、中央に向かって進みそのエネルギーが中央部にて集
中した後、その二次現象として希薄波が発生するため、
その中央において巣が発生し易い。The so-called explosive pressure welding method, which utilizes the instantaneous high energy generated by the explosion of explosives for joining solid metals, is already known, and a few examples of applying this method to amorphous powder are also known. For example, JP-A-59-7433
As disclosed in No. 1, a cylindrical metal container is filled with amorphous powder, and the periphery of the container is exploded with explosives,
A method of integrally molding the amorphous powder by pressing has been devised. However, the amorphous molded body molded by the above method is expensive because the entire molded body is amorphous. That is, the price of the powder itself is high because the manufacturing method of the amorphous material such as metal is special. Also, in the case of utilizing the wear resistance, corrosion resistance and magnetostriction characteristics of amorphous, it is not always necessary that the inside of the molded body is amorphous, but rather the amorphous layer on the surface of the molded body becomes important. On the other hand, the molded body molded by the above method becomes more expensive because the inside of the molded body is amorphous. Furthermore, it is necessary to appropriately control the molding conditions of the molded body molded by the above method according to the amount and thickness of the amorphous powder to be filled. The larger the amount of the formed material, the more easily cracks, cuts, and cavities occur in the amorphous molded body after molding. This is because a shock wave applied to the amorphous powder in the cylindrical container from the outer periphery advances toward the center and its energy is concentrated in the center part, and then a rare wave is generated as a secondary phenomenon,
A nest is likely to occur in the center.
本発明者らはさらに上記の点を検討した結果、金属製の
母材表面に半導体、金属等のアモルファスの粉末を層状
に強固に接合したアモルファス被覆体を製造するという
考えに至ったのである。そこで本発明者らは前述の爆発
圧接法によるアモルファス被覆体の製造を種々試験し
た。このときのアモルファス被覆体は、母材となる円柱
状シャフトや平板状のプレートの表面にアモルファスの
粉体を、種々の爆発圧力、爆発速度等の加工条件を変更
して、層状に接合して得られるものであった。この加工
後の被覆体のうち、アモルファスの粉体が母材表面に緻
密な一体層として接合されたものを選択して、その軸方
向に垂直な断面において光学顕微鏡によって観察したと
ころ、その被覆体のアモルファスの被覆層には割れ、フ
ラック等の欠陥の観察されない、かつ母材とアモルファ
スの被覆層との境界面にはその境界面の観察されない良
好な被覆体であった。As a result of further studying the above points, the present inventors have come to the idea of producing an amorphous coating body in which amorphous powders of semiconductors, metals, etc. are firmly bonded in layers to the surface of a metal base material. Therefore, the present inventors have variously tested the production of the amorphous coating by the above-mentioned explosion pressure welding method. At this time, the amorphous coating is formed by layering amorphous powder on the surface of a cylindrical shaft or a flat plate, which is a base material, by changing the processing conditions such as various explosion pressures and explosion speeds. It was obtained. Of the coated bodies after this processing, one in which amorphous powder was bonded to the surface of the base material as a dense integral layer was selected and observed with an optical microscope in a cross section perpendicular to the axial direction. No defects such as cracks and flacks were observed in the amorphous coating layer of No. 1 and no boundary surface was observed at the interface between the base material and the amorphous coating layer.
ところが、これらの被覆体の母材つまりシャフトやプレ
ートに、応力を加える、すなわちシャフトの場合はその
表面がねじれる様に応力を加えたところ、あるものは極
めて小さい回転応力でシャフト表面からアモルファス被
覆層が剥離し、またあるいものは大きな回転応力でもそ
の剥離が発生しなかった。そこで、その剥離が発生しな
かった被覆体のシャフト表面付近及びその被覆層を観察
したところ、シャフト表面の近傍に、アモルファスの粉
体の一部が結晶化した結晶部が存在した、あるいはアモ
ルファス部分と結晶部とが混在した層−接合層の存在が
確認された。すなわち、母材とアモルファスの層とが強
固に接合されたアモルファス被覆体を得るには、母材の
表面近傍において母材とアモルファス層とを金属接合す
る接合層が存在していること、を本発明者らは発見して
本発明に考え至ったのである。However, when stress is applied to the base material of these coverings, that is, the shaft or plate, that is, in the case of a shaft, the surface is twisted. Peeled off, and in some cases the peeling did not occur even with a large rotational stress. Then, when observing the shaft surface of the coating body where the peeling did not occur and its coating layer, there was a crystal part in which a part of the amorphous powder was crystallized near the shaft surface, or an amorphous part. The existence of a layer-junction layer in which the crystal part and the crystal part were mixed was confirmed. That is, in order to obtain an amorphous coating body in which the base material and the amorphous layer are firmly bonded, a bonding layer for metal-bonding the base material and the amorphous layer is present near the surface of the base material. The inventors of the present invention discovered and came to the present invention.
すなわち本発明のアモルファス被覆体は、金属製の母材
と、アモルファスとなり得る組成の金属が少なくとも一
部結晶化して前記母材の表面５０〜２５０μｍに形成さ
れた接合層と、前記接合層と接合して形成された非晶質
のアモルファス層とを具備し、前記接合層によって前記
母材とアモルファス層とが金属結合により接合している
ことを特徴とする。That is, in the amorphous coating body of the present invention, a metal base material, a bonding layer in which a metal having a composition that can be amorphous is at least partially crystallized and formed on the surface 50 to 250 μm of the base material, and the bonding layer is bonded. And an amorphous amorphous layer formed by the above, wherein the base material and the amorphous layer are bonded by a metal bond by the bonding layer.
またその製造方法は、金属製の母材の表面から隔てて金
属製容器を設け、この容器内に前記母材表面と接触する
ようにアモルファスの粉体を充填し、前記容器の外部か
ら前記容器の表面に沿って容器に平行な方向での進行速
度が２０００〜５０００ｍ／ｓｅｃで進行する衝撃波を
負荷し、前記容器を前記母材の表面に高速で推進して前
記アモルファスの粉体の表面を塑性変形させてアモルフ
ァスの粉体の間の空隙を押し潰し、その変形及び圧縮エ
ネルギーによって粉体相互を接合すると共に、該接合さ
れたアモルファスの粉体のアモルファス層と前記母材と
が、母材表面５０〜２５０μｍで前記アモルファスの粉
体の少なくとも一部が溶解して結晶化した接合層を介し
て接合されたアモルファス被覆体の製造方法。Further, the manufacturing method thereof, a metal container is provided apart from the surface of the metal base material, and an amorphous powder is filled in the container so as to be in contact with the surface of the base material, and the container is provided from the outside of the container. A shock wave traveling at a traveling speed of 2000 to 5000 m / sec in a direction parallel to the surface of the container is loaded, and the container is propelled to the surface of the base material at high speed so that the surface of the amorphous powder is The voids between the amorphous powders are plastically deformed to crush the voids, and the powders are bonded to each other by the deformation and compression energy, and the amorphous layer of the bonded amorphous powders and the base material are base materials. A method for producing an amorphous coating body, in which at least a part of the amorphous powder is dissolved and crystallized at a surface of 50 to 250 μm through a bonding layer.
ここでは、接合層が存在するメカニズム及びそれらと接
合強度の関係について説明する。Here, the mechanism of the bonding layer and the relationship between them and the bonding strength will be described.
母材表面の近傍に接合層が存在することによって、母材
とアモルファス層との接合強度が向上する、その理由に
ついて本発明者らは次の様に考える。The present inventors consider the reason why the bonding strength between the base material and the amorphous layer is improved by the presence of the bonding layer near the surface of the base material as follows.
すなわち前記容器の外部から前記母材の表面に向かって
高エネルギー衝撃波が加えられると、前記容器内のアモ
ルファスの粉体同士はその界面において高エネルギーで
衝突して、その界面温度は上昇するが、その衝撃波の作
用は瞬時であるため、各粉体界面に発生する熱は各粉体
内に吸収され、アモルファスの粉体全部が結晶化するま
での温度にはならない。しかし、粉体の界面の熱は、そ
の界面のアモルファスを一時溶解後、超急冷させるの
で、各粉体の界面の表面が相互に融合或いは圧接して金
属接合するものと考える。That is, when a high-energy shock wave is applied from the outside of the container toward the surface of the base material, the amorphous powder particles in the container collide with each other with high energy at the interface, and the interface temperature rises, Since the action of the shock wave is instantaneous, the heat generated at the interface of each powder is absorbed in each powder and does not reach the temperature until the entire amorphous powder is crystallized. However, the heat of the interface of the powders causes the amorphous of the interface to be temporarily melted and then rapidly cooled, so that it is considered that the surfaces of the interfaces of the powders are fused or pressure-contacted with each other to cause metal bonding.
また、母材表面の近傍にあるアモルファスの粉体は、前
記加工に伴う衝撃圧力によって母材表面に衝突する。そ
の際、母材表面とアモルファス粉体の母材に近い部分は
強烈な塑性変形を受け、それによって発生した熱が前記
アモルファスの粉体と母材表面とを部分的に一時溶解さ
せる。この表面近傍で溶解したアモルファス及び母材の
熱エネルギーは、母材の表面よりその内部で伝達される
ので、前記溶解した部分は急冷却される。ところが、こ
の冷却速度はアモルファス化するに必要な超急冷却速度
（１０-4〜１０-6℃／ｓｅｃ）よりも小さいため、前記
溶解した部分はアモルファスとはならずに一部、もしく
は全部が結晶化し、母材表面の近傍で接合層となる。こ
のように母材表面の近傍のアモルファスの粉体が一旦溶
解し、再結晶化する際に金属製の母材と母材表面の近傍
に存在するアモルファスの粉体とが融合或いは圧接して
接合されているものと考えられる。このため、母材とア
モルファス層が一体に接合して接合強度の強いアモルフ
ァス被覆体が得られる。Further, the amorphous powder in the vicinity of the surface of the base material collides with the surface of the base material due to the impact pressure associated with the processing. At that time, the surface of the base material and the portion of the amorphous powder near the base material undergo intense plastic deformation, and the heat generated thereby partially temporarily melts the amorphous powder and the surface of the base material. The heat energy of the amorphous material and the base material melted near the surface is transferred from the surface of the base material to the inside thereof, so that the melted portion is rapidly cooled. However, since this cooling rate is lower than the ultra-rapid cooling rate (10 −4 to 10 −6 ° C./sec) required for making amorphous, the melted portion does not become amorphous, but a part or all of it is formed. It crystallizes and becomes a bonding layer near the surface of the base material. In this way, when the amorphous powder near the surface of the base material is once melted and recrystallized, the metal base material and the amorphous powder existing near the surface of the base material are fused or pressure-bonded to each other. It is thought to have been done. Therefore, the base material and the amorphous layer are integrally bonded to each other to obtain an amorphous coating body having high bonding strength.
本発明の実施例について説明する。 Examples of the present invention will be described.
第３図は、実施例１〜５及び比較例１〜５の製造方法の
態様を示す図である。FIG. 3 is a figure which shows the aspect of the manufacturing method of Examples 1-5 and Comparative Examples 1-5.
図中符号１は、円柱状の金属母材、２は母材１の軸方向
の中央にてその表面と接触するように充填されるアモル
ファスの粉体、３は母材１の両端部に設けられる環状の
２つの鋼栓で、一方の鋼栓３には排気用の空気流路４
（直径２mm）が形成され、流路４は排気用銅管９（外径
８mm、内径６mm）と連通している。５は銅管で、その内
部には母材１、アモルファスの粉体２、鋼栓３が配置さ
れており、これらを以下被衝撃体と称する。被衝撃体の
両端の部分にて、母材１、鋼栓３、銅管５の各隙間は銅
ロウで密封されるとともに、空気流路４と排気用銅管９
も銅ロウによって気密状態でロウ付けされている。この
状態で銅管５を３００℃にまで昇温し３０分間保持し、
被衝撃体中の粉体２の空気を排気用銅管９より排気す
る。このときロータリー式真空ポンプで１０-2ｔｏｒｒ
の真空℃にした後銅管９をつぶして真空密封状態にす
る。この状態の被衝撃体は、銅管７の中心軸に沿って配
置され、その被衝撃体の外周を爆薬６が包み込んでい
る。銅管７は、爆薬６の形状を保つと共に爆発の際に安
定した状態で爆発が進行する為に使用されるものであ
る。６号電気雷管８は、爆薬６を起爆するために爆薬６
の表面に取付けられており、その取付け方法は粘着テー
プで固定する。もしくは爆薬６が可塑性のものであれば
爆薬６に挿入する。In the figure, reference numeral 1 is a cylindrical metal base material, 2 is an amorphous powder filled so as to come into contact with the surface of the base material 1 at the center in the axial direction, and 3 is provided at both ends of the base material 1. Of two annular steel plugs, one of which is an air passage 4 for exhaust.
(Diameter 2 mm) is formed, and the flow path 4 communicates with the exhaust copper pipe 9 (outer diameter 8 mm, inner diameter 6 mm). Reference numeral 5 denotes a copper tube in which a base material 1, amorphous powder 2, and a steel stopper 3 are arranged, and these are hereinafter referred to as an impacted body. The gaps between the base material 1, the steel plugs 3, and the copper pipes 5 are sealed with copper solder at both ends of the impacted body, and the air passage 4 and the exhaust copper pipe 9 are provided.
Is also brazed in an airtight state by copper brazing. In this state, the temperature of the copper tube 5 is raised to 300 ° C. and kept for 30 minutes,
The air of the powder 2 in the impacted body is exhausted from the exhaust copper tube 9. At this time, 10 -2 torr with rotary vacuum pump
After the temperature is set to the vacuum temperature of 2 ° C., the copper tube 9 is crushed to make a vacuum sealed state. The impacted body in this state is arranged along the central axis of the copper tube 7, and the explosive 6 surrounds the outer periphery of the impacted body. The copper tube 7 is used to maintain the shape of the explosive 6 and to allow the explosion to proceed in a stable state during the explosion. No. 6 electric detonator 8 uses explosives 6 to detonate explosives 6.
It is attached to the surface of, and the attachment method is fixed with adhesive tape. Alternatively, if the explosive 6 is plastic, insert it into the explosive 6.
実施例１ 母材１としてステンレス鋼丸棒（ＳＵＳ３１６、直径１
８mm、長さ１２０mm）を用い、アモルファスの粉体２に
は組成Ｆｅ65、Ｃｏ15、Ｂ15、Ｓｉ5（幅５０mm、外径
２６mm、内径１８mm）を粒径１４０メッシュ以下で、充
填密度3.２６ｇ／cm3で充填する。尚、このアモルファ
スの粉体の密度は7.３２ｇ／cm3（アルキメデス法によ
って測定）であったので、その充填比率は４4.５％であ
る。各々の鋼栓３は、３５mm、外径２６mm、内径１８mm
のものを用いた。銅管５には、長さ１２０mm、外径３０
mm、内径２６mmを銅管７には長さ２００mm、外径６０m
m、内径５３mmを用い、爆薬６は長さ２００mm、外径５
３mm、総量４９０ｇで、比重1.３８ｇ／cm3となった。
図の構成で爆薬６を爆発させた場合、使用した爆薬は３
２００ｍ／ｓｅｃの爆発速度で爆発するものを使用し
た。Example 1 A stainless steel round bar (SUS316, diameter 1 as base material 1)
8 mm, length 120 mm), and amorphous powder 2 has composition Fe 65 , Co 15 , B 15 , and Si 5 (width 50 mm, outer diameter 26 mm, inner diameter 18 mm) with a grain size of 140 mesh or less and a packing density of 3 Fill with .26 g / cm 3 . Since the density of this amorphous powder was 7.32 g / cm 3 (measured by Archimedes method), the filling ratio was 44.5%. Each steel plug 3 has 35mm, outer diameter 26mm, inner diameter 18mm
I used the one. The copper tube 5 has a length of 120 mm and an outer diameter of 30.
mm, inner diameter 26 mm, copper tube 7 length 200 mm, outer diameter 60 m
m, inner diameter 53mm, explosive 6 length 200mm, outer diameter 5
When the total weight was 3 mm and the total amount was 490 g, the specific gravity was 1.38 g / cm 3 .
If you explode explosive 6 in the configuration shown, the explosive used is 3
The thing which exploded at an explosion speed of 200 m / sec was used.
上記の条件にて爆薬６を爆発させたところ、被衝撃体の
最外層を構成する銅管５は、アモルファスの粉体２の充
填された部分においてその外径が２5.４mm乃至２7.２mm
迄圧縮され（爆発前の外径は３０mm）た。この銅管５を
旋盤によって完全に取り除いてアモルファス層の外径が
均一になるまで切削したところ、外径２2.１mm、幅９８
mmの金属光沢を有する美麗な表面の被覆体が得られた。When the explosive 6 is exploded under the above conditions, the outer diameter of the copper tube 5 forming the outermost layer of the impacted body is 25.4 mm to 27.2 mm in the portion filled with the amorphous powder 2.
It was compressed up to 30 mm in outer diameter before explosion. When this copper tube 5 was completely removed by a lathe and cut until the outer diameter of the amorphous layer became uniform, the outer diameter was 22.1 mm and the width was 98.
A beautiful surface coating with a metallic luster of mm was obtained.
実施例１によって得られた被覆体の物性について説明す
る。The physical properties of the coated body obtained in Example 1 will be described.
この被覆体の断面において最外周の部分の硬度測定をし
たところ、大部分がビッカース硬度Ｈｖ＝８１０〜９１
０程度で、同一組成のアモルファス合金リボンとほぼ同
程度の値を示したので、均一のアモルファス層が形成さ
れていることが判った。ところが、ステンレス丸棒１の
表面に幅（厚さ）５０〜１００μｍの部分すなわち母材
表面の近傍に形成される接合層部分においてのみ、Ｈｖ
＝１０００〜１１００程度の値を示すことがわかった。When the hardness of the outermost portion of the cross section of this cover was measured, most of it was Vickers hardness Hv = 810-91.
At about 0, the value was almost the same as that of the amorphous alloy ribbon having the same composition, so it was found that a uniform amorphous layer was formed. However, only in the part of the width (thickness) of 50 to 100 μm on the surface of the stainless round bar 1, that is, in the joining layer part formed near the surface of the base material, Hv
It was found that the value was about 1000 to 1100.
さらにその断面を研磨してナイタール腐食液でエッチン
グしたところ、被覆体の大部分は金属光沢を保持してい
たが、その接合部のみが黒く変色した。When the cross section was further polished and etched with a Nital etchant, most of the coating retained metallic luster, but only the joints turned black.
そこで、被覆体を長さ１０mmに切断し、内部のステンレ
ス棒のみをワイヤーカット加工によって取り除いてリン
グ状の被覆層のみにした後、それを結晶カッターによっ
て幅３mm、長さ１０mmに切断した。そして、そのナイタ
ールエッチングによって黒化するステンレス棒側の面
（接合層）を、またナイタールエッチングしても金属光
沢を保つ外周側の部分（アモルファス層）を、各々Ｘ線
回析によって分析した結果、前者は結晶化を示すピーク
が強く、わずかにアモルファスを示すハローパターンが
観察されたが、後者はアモルファスを示すハローパター
ンのみとなった。さらに、それらをＥＰＭＡにより組成
分析した結果、両者ともアモルファス合金粉体とほぼ同
様の組成を示した。このことから、接合部はアモルファ
ス合金粉体が一部又は大部分結晶化して形成された接合
層であり、被覆体のその外側の部分はアモルファス状態
を保持したアモルファス合金層となっていることがわか
った。これを第１図に示す。Therefore, the coated body was cut into a length of 10 mm, and only the inner stainless rod was removed by wire cutting to form only a ring-shaped coated layer, which was then cut with a crystal cutter into a width of 3 mm and a length of 10 mm. Then, the surface of the stainless steel rod side which is blackened by the nital etching (bonding layer) and the portion of the outer peripheral side which retains metallic luster even after the nital etching (amorphous layer) were analyzed by X-ray diffraction. As a result, the former had a strong crystallization peak and a halo pattern showing a slight amorphous was observed, whereas the latter had only a halo pattern showing an amorphous. Further, as a result of compositional analysis of them by EPMA, both showed almost the same composition as the amorphous alloy powder. From this, it can be said that the joint portion is the joint layer formed by partially or mostly crystallizing the amorphous alloy powder, and the outer portion of the covering body is the amorphous alloy layer that maintains the amorphous state. all right. This is shown in FIG.
第１図は、後述する爆発加工によって製造されたアモル
ファス被覆体の母材表面の付近を、ナイタールでエッチ
ングした後の状態での顕微鏡写真で、その倍率は１００
倍である。FIG. 1 is a photomicrograph of a state in which the vicinity of the base material surface of an amorphous coating body produced by explosion processing described later is etched with nital, and the magnification is 100.
Double.
なお、接合層が形成される原因としては、爆発成形にお
いて生じる衝撃力はステンレス棒表面近傍では外周部
（アモルファス層の）に比べて高くなるため、その付近
のアモルファス合金粉末が溶融接合し、その表面近傍に
沿って結晶化したものと考えられる。The reason why the bonding layer is formed is that the impact force generated in the explosive molding is higher in the vicinity of the surface of the stainless steel rod than in the outer peripheral portion (of the amorphous layer). It is considered to have crystallized along the vicinity of the surface.
なお、ここでエッチングによる顕微鏡観察について説明
する。加工後のアモルファス被覆体を、その母材表面の
近傍が露出する様にその軸方向に垂直な平面において、
切断砥石で切断して研磨した後、その断面をナイタール
によってエッチングして顕微鏡で観察した。このナイタ
ールは、９０ccのエチルアルコール（９６％含有品でそ
の他４％の水分を含む）と１０ccの硝酸（密度1.４０）
とを混合した混合液である。この液で一般の結晶質の金
属をエッチングして観察すると、第１図に撮影された母
材の様な模様となるが、これは金属の結晶質特有の模様
で一般に観察される。The microscope observation by etching will be described here. After processing the amorphous coating, in a plane perpendicular to the axial direction so that the vicinity of the surface of the base material is exposed,
After cutting with a cutting grindstone and polishing, the cross section was etched with Nital and observed with a microscope. This nital is 90 cc of ethyl alcohol (96% content and 4% water content) and 10 cc of nitric acid (density 1.40).
It is a mixed liquid obtained by mixing and. When a general crystalline metal is etched with this solution and observed, the pattern looks like the base material photographed in FIG. 1, but this is generally observed as a pattern peculiar to the crystalline metal.
しかしながら、従来においては、結晶質に存在する粒
界、転位、空孔、格子欠陥などの欠陥を観察する方法と
して前述のようなエッチングによる観察は用いられてい
るが、非晶質の物質に関しては用いられていないのが現
状である。すなわち、非晶質の物質は、その原子配列に
規則性がないが故に、全体として均質であり、硬度、耐
蝕性、磁気特性などの特性が結晶質と比較して優れたも
のと考えられている。このため、もともと欠陥の集合体
と考えられている非晶質の物体を、エッチングによって
観察しようとする試みはなされていなかった。However, conventionally, the observation by etching as described above has been used as a method for observing defects such as grain boundaries, dislocations, vacancies, and lattice defects existing in a crystalline material. It is currently not used. That is, since an amorphous substance has no regularity in its atomic arrangement, it is considered to be homogeneous as a whole, and the properties such as hardness, corrosion resistance, and magnetic properties are superior to those of crystalline substances. There is. Therefore, no attempt has been made to observe an amorphous object originally considered as an aggregate of defects by etching.
ところが、本発明者らがアモルファス被覆体に上述の観
察を行ったところ、母材表面の近傍には比較的大きな面
積の黒い層状の存在が確認された。これは、非晶質に比
較して耐蝕性の劣る部分が存在するアモルファス被覆体
を、ナイタールによってエッチングすると、両者の耐蝕
性の相違によって、非晶質に比較して耐蝕性の劣る部分
が腐食されて黒く変化して観察されるものと考えられる
ので、その黒い部分は非晶質より耐蝕性の劣る結晶質あ
るいは酸化物と考えられる。However, when the present inventors made the above observation on the amorphous coating, it was confirmed that a black layer having a relatively large area was present near the surface of the base material. This is because when an amorphous coating that has a portion with inferior corrosion resistance compared to amorphous is etched with nital, the portion with inferior corrosion resistance compared to amorphous corrodes due to the difference in corrosion resistance between the two. It is considered that the black portion is observed and changed to black, and therefore the black portion is considered to be crystalline or oxide having poorer corrosion resistance than amorphous.
また、本発明者らは、エッチング液としてナイタールを
用いたが、強酸性のエッチング液、例えば塩酸、硫酸等
を含むエッチング液によっても前述と同様の観察が期待
されるので、強酸性のエッチング液による非晶質の観察
は、その非晶質中に微量の結晶質もしくは結晶質に相当
する部分が存在するかどうかを判定するには極めて有効
な判定方法である。特に非晶質中に極微量の結晶質が存
在するもの、例えば前述の被覆層の様なものを全体が均
一の非晶質であるかどうかを観察する場合は、Ｘ線およ
び電子線回折検査結果よるも手がるにかつ簡単に判定が
できるので上述の方法は工業的に有効なものになる。Further, although the present inventors have used nital as an etching solution, the same observations as described above are expected with a strongly acidic etching solution, for example, an etching solution containing hydrochloric acid, sulfuric acid, etc. The observation of an amorphous material by means of is an extremely effective judgment method for judging whether or not a trace amount of crystalline material or a portion corresponding to crystalline material exists in the amorphous material. Especially when observing whether or not a very small amount of crystalline material exists in an amorphous material, such as the above-mentioned coating layer, whether or not the entire material is homogeneous, X-ray and electron diffraction The above method is industrially effective because the result can be determined easily and easily.
アモルファス被覆体のアモルファス層の比重を測定した
結果、同一組成のリボンの密度の９５％以上に達し、極
めて高密度に接合していることがわかった。As a result of measuring the specific gravity of the amorphous layer of the amorphous coating, it was found that the density reached 95% or more of the ribbon having the same composition, and the bonding was extremely high.
以上のように、アモルファス合金粉体が高密度に強固に
接合してアモルファス合金層を形成するためには、ステ
ンレス棒の表面にアモルファス合金粉体が溶融結晶化し
た接合層が存在することが必要で、それによってアモル
ファス合金層とステンレス棒とが極めて強固に接合して
いる。As described above, in order to form the amorphous alloy layer by strongly bonding the amorphous alloy powder with high density, it is necessary that the joining layer in which the amorphous alloy powder is melted and crystallized is present on the surface of the stainless steel rod. As a result, the amorphous alloy layer and the stainless steel rod are bonded extremely firmly.
なお、具体的にその剥離強度の測定について説明する。The measurement of the peel strength will be specifically described.
円柱状のシャフト（径２2.１mm、長さ１２０mm）のシャ
フトの中央部にアモルファス層（厚さ2.５mm、幅５０m
m）が形成されたアモルファス被覆体を用いて、そのシ
ャフトの一端を回転しないように固定支持し、その他端
にシャフトの軸と垂直となるように長さ１ｍの強固な棒
を固定し、その棒の先端に荷重を付加して、シャフトに
回転トルクを与えた。これを以下付加トルク（kg・ｍ）
と言う。An amorphous layer (thickness: 2.5 mm, width: 50 m) in the center of the cylindrical shaft (diameter: 22.1 mm, length: 120 mm)
m) is used, one end of the shaft is fixed and supported so that it does not rotate, and a solid rod with a length of 1 m is fixed to the other end so as to be perpendicular to the axis of the shaft. A load was applied to the tip of the rod to give a rotational torque to the shaft. This is the following additional torque (kg ・ m)
Say
このとき、アモルファス層が母材表面と一体に接合され
ていると、付加トルク量に応じた歪み量がアモルファス
層に発生する。この歪み量に応じてアモルファス層の磁
歪量が変化する。これを利用してアモルファス層の表面
近傍に非接触にて励磁コイル、検出コイルを設置し、励
磁コイルに通電することによってアモルファス層を励磁
し、それを検出コイルによって電圧に変換して検出する
と、その歪み量に比例した出力電圧が得られる。（以上
はトルクセンサの原理でもある）。ここで母材表面とア
モルファス層との接合において、アモルファス層が全て
剥離すると、検出コイルからの検出電圧が減少して零に
なる。ところが、部分的に剥離が発生した場合は、必ず
しも零にならないので、ここでは検出コイルからの検出
電圧の減少量が３０％を超えたとき、アモルファス層が
母材表面から剥離したものと見做し、この時の付加トル
クを最大付加トルクとして測定した。At this time, if the amorphous layer is integrally joined to the surface of the base material, a strain amount corresponding to the additional torque amount is generated in the amorphous layer. The magnetostriction amount of the amorphous layer changes according to this distortion amount. By utilizing this, an exciting coil and a detecting coil are installed in the vicinity of the surface of the amorphous layer in a non-contact manner, the amorphous layer is excited by energizing the exciting coil, and the detecting coil converts the voltage into a voltage, which is detected. An output voltage proportional to the amount of distortion can be obtained. (The above is also the principle of the torque sensor). Here, when the amorphous layer is completely peeled off at the joining of the base material surface and the amorphous layer, the detection voltage from the detection coil decreases and becomes zero. However, when partial peeling occurs, it does not always become zero. Therefore, when the reduction amount of the detection voltage from the detection coil exceeds 30%, it is considered that the amorphous layer is peeled from the surface of the base material. Then, the additional torque at this time was measured as the maximum additional torque.
したがって最大付加トルクを測定することによって、ア
モルファス層が母材表面から剥離したかどうか、すなわ
ち剥離強度を検出することができる。Therefore, by measuring the maximum applied torque, it is possible to detect whether or not the amorphous layer has peeled from the surface of the base material, that is, the peel strength.
上述の方法によって、第１図に示した被覆体（実施例
１）を測定した結果、接合層の厚さは５０〜１００μ、
最大付加トルクは２５kg・ｍであった。As a result of measuring the covering body (Example 1) shown in FIG. 1 by the above method, the thickness of the bonding layer was 50 to 100 μm,
The maximum applied torque was 25 kg · m.
比較例１ 実施例１の実験を繰返した。ただし、爆薬の外径を４２
mmとし、爆薬周囲を包囲する銅管の内径もそれに合わせ
て４２mmのものとした。装填された爆薬の量は２６５
ｇ、実質的な装填比重は実施例１の場合と変わらなかっ
た。Comparative Example 1 The experiment of Example 1 was repeated. However, the outer diameter of the explosive is 42
mm, and the inner diameter of the copper tube surrounding the explosive was 42 mm in accordance with it. The amount of explosive loaded is 265
g, the substantial loading specific gravity was the same as in Example 1.
実施例１の場合と同様にして、爆薬を爆発させたとこ
ろ、被衝撃体の外径はアモルファスの部分で２6.２mm乃
至２8.７mmに迄絞られていたが、旋盤で銅管の部分を切
削除去したところ、焼結は不十分で所々に巣が認めら
れ、切断してステンレス鋼とアモルファスの接合部分を
検査した結果、アモルファスが結晶化している部分は少
なく、接合境界にまばらに認められる程度であり、部分
的に接合していない箇所が認められた。実施例１と本比
較例の差は爆薬の量の差のみであり、本比較例で接合が
不十分な理由は爆発圧力が不足した結果、接合境界での
温度上昇が不十分で、その為接合が十分に達成されず、
温度上昇が接合に十分な場合に認められるアモルファス
粒の結晶化が認められなかったものと考えられる。When the explosive was exploded in the same manner as in Example 1, the outer diameter of the impacted body was narrowed to 26.2 mm to 28.7 mm in the amorphous portion, but the portion of the copper pipe was turned by the lathe. After cutting and removal, sintering was insufficient and cavities were found in some places. As a result of cutting and inspecting the joint part of stainless steel and amorphous, there are few amorphous parts crystallized and sparsely observed at the joint boundary The degree was small, and some areas were not joined. The difference between Example 1 and this comparative example is only the difference in the amount of explosive, and the reason why joining is insufficient in this comparative example is that the temperature rise at the joining boundary is insufficient as a result of insufficient explosion pressure. Joining is not fully achieved,
It is considered that the crystallization of the amorphous grains, which was observed when the temperature rise was sufficient for joining, was not observed.
実施例２から実施例５ 実施例１と同様にしてアモルファス合金粉体を焼結しつ
つ金属の丸棒に接合する実験を行った。第１表にこれら
の実施条件と結果を示す。Example 2 to Example 5 In the same manner as in Example 1, an experiment was conducted in which the amorphous alloy powder was sintered and joined to a metal round bar. Table 1 shows these execution conditions and results.
比較例２から比較例５ 実施例２から４の実験を第１表中の爆薬の条件だけを第
２表に記載するように変えて行った。表中の比較例の番
号は、それぞれ実施例の番号に対応し、爆薬の条件以外
は対応する実施例と同じである。 Comparative Example 2 to Comparative Example 5 The experiments of Examples 2 to 4 were carried out by changing only the explosive conditions in Table 1 as described in Table 2. The numbers of the comparative examples in the table correspond to the numbers of the examples, respectively, and are the same as the corresponding examples except the explosive conditions.
以上の比較例からも明らかなように、本発明に於いても
要件であるアモルファス層と金属母材との接合部でのア
モルファスの結晶化した層−接合層が、強固な接合に是
非必要であり、それには爆薬の爆発速度が２０００ｍ／
ｓｅｃ以上、５０００ｍ／ｓｅｃ以下である必要がある
ことも理解される。更に、爆薬の爆発速度のみならず、
爆薬の量、ひいては被衝撃体に加えられる圧力の量が少
なくても良好な接合が得られないことも分る。 As is clear from the above comparative examples, the amorphous crystallized layer-bonding layer at the bonding portion between the amorphous layer and the metal base material, which is also a requirement in the present invention, is absolutely necessary for strong bonding. There is an explosive explosive speed of 2000m /
It is also understood that it should be not less than sec and not more than 5000 m / sec. Furthermore, not only the explosive velocity of explosives,
It can also be seen that good bonding cannot be obtained even if the amount of explosive, and hence the amount of pressure applied to the impacted body, is small.
本発明に於いて使用出来る爆薬の種類と量は、現在工業
的に利用出来る爆薬の種類が極めて多い為、具体的に説
明することが非常に困難である。しかし、当業者であれ
ば、本発明明細書を参考にして２、３の実験を行うだけ
で容易に爆薬の種類と量を選択、設定出来る。The types and amounts of explosives that can be used in the present invention are extremely difficult to explain in detail because there are so many types of explosives that can be industrially used at present. However, those skilled in the art can easily select and set the type and amount of explosive by only performing a few experiments with reference to the present specification.
実施例６ 実施例１の実験を繰返した。ただし、被衝撃体の構成は
実施例１と等しくしたが、爆発圧力を負荷する為の爆薬
の配置を第４図のように変更した。第４図において、
１′から９′迄は実施例１の１から９の各々に対応する
が、１０′は新しく加わった要素で、この場合外径５０
mm、内径４６mm、長さ１４０mmの銅管を用いた。また、
７′の銅管も配置の変更に応じて外径７６mm、内径６８
mm、長さ２００mmののもとし、爆薬６′は銅管７と銅管
１０′の間に環状に充填し、その雷管側の部分を銅管１
０′から５０mm延長して環状の爆薬６′の端の空間を厚
さ２０mmの円板状の爆薬で埋め、反対側は銅管１０′か
ら１０mm延長した形状とした。使用した爆薬の種類は実
施例１で使用したものと同じものとした。その結果、充
填された爆薬の量は３６５ｇとなった。Example 6 The experiment of Example 1 was repeated. However, the structure of the impacted body was the same as in Example 1, but the arrangement of the explosive for loading the explosion pressure was changed as shown in FIG. In FIG.
1'to 9'corresponds to each of 1 to 9 of the first embodiment, but 10 'is a newly added element, in this case an outer diameter 50
A copper tube having an inner diameter of 46 mm, an inner diameter of 46 mm and a length of 140 mm was used. Also,
The 7'copper tube also has an outer diameter of 76 mm and an inner diameter of 68 depending on the layout change.
mm, length 200 mm, the explosive 6'is annularly filled between the copper tube 7 and the copper tube 10 ', and the portion on the side of the detonator is the copper tube 1
The space at the end of the annular explosive 6'which is extended by 50 mm from 0'is filled with a disc-shaped explosive having a thickness of 20 mm, and the opposite side is extended by 10 mm from the copper pipe 10 '. The type of explosive used was the same as that used in Example 1. As a result, the amount of explosive charged was 365 g.
実施例１と同様にして爆薬を爆発させたところ、銅管１
０′は周囲の爆薬が爆発速度３２００ｍ／ｓｅｃで爆発
した結果、銅管１０′の内側に高速で投射され、被衝撃
体の最外層を構成する銅管５′の表面に配管８′の端か
ら衝突して行った。銅管１０′が銅管５′の表面に衝突
する点の爆発進行方向への移動速度は、爆薬の爆発速度
と等しく３２００ｍ／ｓｅｃであった。When the explosive was exploded in the same manner as in Example 1, copper tube 1
No. 0'is projected at a high speed inside the copper tube 10 'as a result of the explosives in the surrounding area exploding at an explosion speed of 3200 m / sec, and the end of the pipe 8'on the surface of the copper tube 5'that constitutes the outermost layer of the impacted body Went from a collision. The moving speed of the point at which the copper tube 10 'collides with the surface of the copper tube 5'in the explosion proceeding direction was 3200 m / sec, which is equal to the explosive explosive speed.
被衝撃体は、銅管１０′が被衝撃体の外層に被さった状
態で回収され、旋盤で銅管１０′と銅管５′を切削除去
したところ、アモルファスは巣やクラックがない、美麗
な金属光沢を持った表面状況を示し、接合境界では８０
乃至１２０μｍ幅の結晶化したアモルファスを伴って巣
やクラック、非接合部分を伴わない安全な接合状態で接
合していることが認められた。The impacted body is collected with the copper tube 10 'covering the outer layer of the impacted body, and the copper tube 10' and the copper tube 5'are removed by cutting with a lathe. It shows the surface condition with metallic luster, 80 at the joint boundary.
It was confirmed that the crystals were joined together in a safe joined state without cavities, cracks, and non-joined portions with the crystallized amorphous having a width of 120 μm.
本実施例の場合は、実施例１と同様な被衝撃体により少
ない爆薬量による衝撃を負荷して同様な効果を得ている
が、これは被衝撃体表面から離して同心円状に設けた環
状の爆薬の内面に接する銅管が、爆薬の爆発圧力によっ
て管の内側に高速で収縮し、被衝撃体の表面に衝突する
際、爆薬量を同一とした場合、爆薬の爆発圧力が直接被
衝撃体の表面に負荷される場合より高い圧力を発生する
からである。In the case of the present embodiment, a similar impact is obtained by applying an impact with a small amount of explosive to the impacted body similar to that of Example 1, but this is an annular shape provided concentrically apart from the surface of the impacted body. When the copper tube in contact with the inner surface of the explosive contracts at high speed inside the tube due to the explosive pressure of the explosive and collides with the surface of the impacted object, if the explosive amount is the same, the explosion pressure of the explosive is directly This is because it produces a higher pressure than when it is applied to the surface of the body.
本実施例６で作ったものは実施例１のものと同様、８０
〜１２０μｍの一部結晶化した接合層が存在し、その剥
離強度も２５kg・ｍ程度で良好に接合した被覆体であっ
た。比較例３のものの剥離強度を調べたところ、最大付
加トルクは１kg・ｍ程度の強度であった。なお、接合不
良の比較例２、４、５のものは測定不能であった。The thing made in this Example 6 is the same as that of Example 1, and
There was a partially crystallized bonding layer of ˜120 μm, and the peel strength was about 25 kg · m, which was a well bonded coating. When the peel strength of Comparative Example 3 was examined, the maximum applied torque was about 1 kg · m. It should be noted that in Comparative Examples 2, 4, and 5 with poor bonding, measurement was impossible.
比較例６ 実施例６と同様な実験繰返した。ただし、使用した爆薬
は、実施例６で使用したものと同形状で比重1.６５ｇ／
cm3、爆発速度７８００ｍ／ｓｅｃのもの６１５ｇとし
た。実施例６と同様にして爆薬を爆発させたところ、被
衝撃体はばらばらに分離して回収することが出来なかっ
た。これは、爆発速度が高過ぎる為に負荷された衝撃圧
力が破壊的に働き、有効に焼結と接合が行えなかったも
のと考えられる。Comparative Example 6 The same experiment as in Example 6 was repeated. However, the explosive used had the same shape as that used in Example 6 and a specific gravity of 1.65 g /
cm 3 and explosion speed of 7800 m / sec were 615 g. When the explosive was exploded in the same manner as in Example 6, the impacted bodies could not be separated and collected. It is considered that this is because the applied impact pressure acts destructively because the explosion speed is too high, and sintering and joining cannot be effectively performed.
実施例７ 第５図に示すように長さ１５０mm、幅８０mm、厚さ９mm
のＳＳ４１鋼板の片面を研磨加工によって面粗さ1.５Ｓ
に仕上げ、その面を上向けにして側面は幅１５mm、厚さ
１mm、長さ４６２mmのアルミニウム板を巻きつけて鋼板
の上面側に６mmの幅ではみ出させ、その部分を枠として
Ｆｅ７５、Ｂ１５、Ｓｉ１０（各重量５）の組成で、＃
１４０から＃２２０の範囲の粒が６０重量％、＃１００
０以下の粒が４０重量％混合されたアモルファス２４２
ｇを上面が平らで枠の上端と一致するようにして充填
し、その上を長さ１５０mm、幅８０mm、厚さ１mmのアル
ミニウム板で覆った。Example 7 As shown in FIG. 5, length 150 mm, width 80 mm, thickness 9 mm
One side of SS41 steel plate of No.1 has a surface roughness of 1.5S by polishing
Finish, and with the side facing up, the side surface is wrapped with an aluminum plate having a width of 15 mm, a thickness of 1 mm, and a length of 462 mm, and the steel plate is protruded on the upper surface side with a width of 6 mm. With the composition of Si10 (5 weight each),
60% by weight of particles in the range of 140 to # 220, # 100
Amorphous 242 in which 40% by weight or less of particles are mixed
g was filled so that the upper surface was flat and coincided with the upper end of the frame, and it was covered with an aluminum plate having a length of 150 mm, a width of 80 mm and a thickness of 1 mm.
一方、長さ１７０mm、幅１００mm、厚さ２mmの鋼板の上
に長さ１７０mm、幅１００mm、厚さ１５mmの比重1.６５
ｇ／cm3で爆発速度７８００ｍ／ｓｅｃを載せたもの
を、鋼板の下面がアモルファスの上面を覆ったアルミニ
ウムの上面に鋼板とアルミニウム板の長手方向が１２°
の角度で向かい合い、かつ鋼板とアルミニウムの短い方
の辺が接するようにし、離れた方の辺は全体を地上に置
いた際に地面から木片で支えて角度を維持するようにし
た。また、アルミニウム枠とアルミニウム板及びＳＳ４
１鋼板の継目は塩化ビニールのテープと油粘土でシール
してその一部から銅管差込み、内部を真空に引けるよう
にした。On the other hand, a specific gravity of 1.65 with a length of 170 mm, a width of 100 mm and a thickness of 15 mm on a steel plate with a length of 170 mm, a width of 100 mm and a thickness of 2 mm.
An explosion rate of 7800 m / sec at g / cm 3 was applied to the upper surface of aluminum with the lower surface of the steel plate covering the amorphous upper surface, and the longitudinal direction of the steel plate and the aluminum plate was 12 °.
The steel plate and the aluminum have short sides facing each other at an angle of, and the distant side is supported by a piece of wood from the ground when the whole is placed on the ground to maintain the angle. In addition, aluminum frame and aluminum plate and SS4
The seam of 1 steel plate was sealed with vinyl chloride tape and oil clay, and a copper tube was inserted from a part of it so that the inside could be evacuated.
第５図は、その実施状況を示す断面図で、１″はＳＳ４
１鋼板、２″はアモルファス、５″は覆いのアルミニウ
ム板、６″は爆薬、８″は６号電気雷管、９″は真空引
き用の外径８mm、内径６mm、長さ２００mmの銅管、１
０″は厚さ２mmの鋼板、ａはアルミニウムの枠、ｂは被
衝撃体を真空にする際のシール用塩化ビニールテープと
油粘土、ｃは爆薬と厚さ２mmの鋼板を指示する木片、ｄ
は地盤を示す。FIG. 5 is a cross-sectional view showing the implementation state, where 1 ″ is SS4.
1 steel plate, 2 ″ amorphous, 5 ″ cover aluminum plate, 6 ″ explosive, 8 ″ electric detonator No. 6, 9 ″ vacuum evacuating outer diameter 8mm, inner diameter 6mm, length 200mm copper tube, 1
0 ″ is a steel plate with a thickness of 2 mm, a is an aluminum frame, b is a vinyl chloride tape and oil clay for sealing when the impacted object is evacuated, c is a piece of wood indicating an explosive and a steel plate with a thickness of 2 mm, d
Indicates the ground.
爆薬を起爆したところ、厚さ２mmの鋼板は下方に平均速
度１９００ｍ／ｓｅｃで飛ばされ、アルミニウム板の表
面に衝突した。爆発が始まった位置から反対側の端へ鋼
板とアルミニウム板の衝突する点が移動して行く速度
は、４３００ｍ／ｓｅｃであった。その結果、爆薬によ
って飛ばされた鋼板、アルミニウム板、アモルファス及
びＳＳ４１鋼板は強固に一体となって接合された。全体
を各材料を重ね合わせた面に直角な断面で切断したとこ
ろ、最上層の鋼板とカバーのアルミニウム板は波状の境
界で接合され、アルミニウム板は約0.５mmの厚さにわた
ってアモルファスの粒の間にめり込んでアモルファスと
接合し、アモルファスは金属光沢を持った、巣が認めら
れない状態で焼結していた。更に、アモルファスとＳＳ
４１鋼板は研磨してナイタール腐食液で腐食して光学顕
微鏡によって観察したところ、幅１００μｍから２５０
μｍのアモルファスが結晶化した結晶境界を伴って境界
に空隙やクラックが存在しない状態で接合していた。When the explosive was detonated, a steel plate having a thickness of 2 mm was blown downward at an average velocity of 1900 m / sec and collided with the surface of the aluminum plate. The speed at which the point where the steel plate and the aluminum plate collide moved from the position where the explosion started to the opposite end was 4300 m / sec. As a result, the steel plate, aluminum plate, amorphous, and SS41 steel plate blown off by the explosive were firmly and integrally joined. When the whole was cut in a cross section perpendicular to the surface where the materials were overlapped, the uppermost steel plate and the aluminum plate of the cover were joined at a wavy boundary, and the aluminum plate had a thickness of about 0.5 mm and was composed of amorphous grains. It was embedded in the gap and joined with the amorphous material, and the amorphous material had metallic luster and was sintered in a state where no cavities were observed. Furthermore, amorphous and SS
41 steel plate was polished, corroded with a Nital corrosive liquid, and observed by an optical microscope.
Along with the crystal boundaries in which μm amorphous was crystallized, the bonding was performed in the state where there were no voids or cracks at the boundaries.
なお、前記実施例１と同様にＸ線回折で調べたところア
モルファス層がハローパターンを示し、接合層において
回折ピークが観察された。When examined by X-ray diffraction as in Example 1, the amorphous layer showed a halo pattern, and a diffraction peak was observed in the bonding layer.
上述の実施例６、７によって得られた被覆体の特性は、
実施例１で分析した結果と同様であった。The characteristics of the coatings obtained according to Examples 6 and 7 above are as follows.
The results were the same as those analyzed in Example 1.
比較例７ 実施例７の実験を繰返した。ただし、爆薬を上面に載せ
た厚さ２mmの鋼板は被衝撃体の上方に１５mm離して平行
に設置してから爆薬をその一端から爆発させた。その結
果、厚さ２mmの鋼板は下方に１９００ｍ／ｓｅｃの速度
で飛ばされ、アルミニウムのカバーの表面に衝突した。
爆薬が爆発を開始した側から反対側へ鋼板とアルミニウ
ム板の衝突する点が移動して行く速度は、爆薬の爆発速
度と等しく７８００ｍ／ｓｅｃであった。Comparative Example 7 The experiment of Example 7 was repeated. However, a steel plate having a thickness of 2 mm with an explosive placed on the upper surface was placed 15 mm above the impacted body in parallel, and then the explosive was exploded from one end thereof. As a result, the steel plate having a thickness of 2 mm was blown downward at a speed of 1900 m / sec and collided with the surface of the aluminum cover.
The speed at which the point where the steel plate and the aluminum plate collide moved from the side where the explosive started to explode to the opposite side was 7800 m / sec, which was the same as the explosive speed.
その結果、爆薬に接していた鋼板と被衝撃体はらばらに
なり、まとまった形で回収することは出来なかった。As a result, the steel plate and the impacted body that were in contact with the explosives fell apart and could not be collected in a cohesive form.
以上述べたように、母材表面と接触する様にアモルファ
スの粉体を充填し、その粉体を衝撃波によって、母材表
面に高速で推進させることによって、母材の表面に、均
一で高密度のアモルファス層を成形することが可能にな
るとともに、母材表面近傍に形成された接合層を介して
母材とアモルファス層がきわめて強固に接合されるよう
になる。As described above, the amorphous powder is filled so as to come into contact with the surface of the base material, and the powder is propelled at high speed by the shock wave to the surface of the base material, so that the surface of the base material is uniformly and densely packed. The amorphous layer can be molded, and the base material and the amorphous layer can be bonded very firmly through the bonding layer formed near the surface of the base material.
第１図は実施例１におけるアモルファス被覆体の接合層
付近の金属組織を示す顕微鏡写真、第２図はその顕微鏡
写真の模式図、第３図は実施例１〜５および比較例１〜
５の製造方法を示す断面図、第４図は実施例６および比
較例６の製造方法を示す断面図、第５図は実施例７およ
び比較例７の製造方法を示す断面図を示す。 １…金属製母材，２…アモルファスの粉体，５…金属製
容器である銅管，６…爆薬。FIG. 1 is a micrograph showing a metal structure in the vicinity of the bonding layer of the amorphous coating in Example 1, FIG. 2 is a schematic diagram of the micrograph, and FIG. 3 is Examples 1-5 and Comparative Examples 1- 1.
5 is a sectional view showing the manufacturing method of Example 5, FIG. 4 is a sectional view showing the manufacturing method of Example 6 and Comparative Example 6, and FIG. 5 is a sectional view showing the manufacturing method of Example 7 and Comparative Example 7. DESCRIPTION OF SYMBOLS 1 ... Metal base material, 2 ... Amorphous powder, 5 ... Copper tube which is a metal container, 6 ... Explosive.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 井村 徹 愛知県名古屋市千種区東山元町６−１ (56)参考文献 特開 昭60−194085（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toru Imura 6-1, Higashiyamamotomachi, Chikusa-ku, Nagoya-shi, Aichi (56) Reference JP-A-60-194085 (JP, A)
Claims (4)
金属が少なくとも一部結晶化して前記母材の表面５０〜
２５０μｍに形成された接合層と、前記接合層と接合し
て形成された非晶質のアモルファス層とを具備し、前記
接合層によって前記母材とアモルファス層とが金属結合
により接合していることを特徴とするアモルファス被覆
体。1. A base material made of metal and a metal having a composition capable of becoming amorphous are at least partially crystallized, and the surface 50 to 50
A bonding layer formed to have a thickness of 250 μm, and an amorphous amorphous layer formed by bonding with the bonding layer, wherein the bonding layer bonds the base material and the amorphous layer by metal bonding. An amorphous coating characterized by:
ングすると黒色化して観察される特許請求の範囲第１項
記載のアモルファス被覆体。2. The amorphous coating according to claim 1, wherein the bonding layer is observed to be black when it is etched by an acidic corrosive liquid.
を設け、この容器内に前記母材表面と接触するようにア
モルファスの粉体を充填し、前記容器の外部から前記容
器の表面に沿って容器に平行な方向での進行速度が２０
００〜５０００ｍ／ｓｅｃで進行する衝撃波を負荷し、
前記容器を前記母材の表面に高速で推進して前記アモル
ファスの粉体の表面を塑性変形させてアモルファスの粉
体の間の空隙を押し潰し、その変形及び圧縮エネルギー
によって粉体相互を接合すると共に、該接合されたアモ
ルファスの粉体のアモルファス層と前記母材とが、母材
表面の近傍で前記アモルファスの粉体の少なくとも一部
が溶解して結晶化した５０〜２５０μｍの厚さの接合層
を介して接合されたアモルファス被覆体の製造方法。3. A metal container is provided separately from the surface of a metal base material, and an amorphous powder is filled in the container so as to come into contact with the surface of the base material. 20 along the surface in the direction parallel to the container
A shock wave traveling at 00-5000 m / sec is loaded,
The container is propelled to the surface of the base material at a high speed to plastically deform the surface of the amorphous powder to crush the voids between the amorphous powders, and the powders are bonded to each other by the deformation and compression energy. At the same time, the amorphous layer of the joined amorphous powder and the base material are joined together in a thickness of 50 to 250 μm in which at least a part of the amorphous powder is melted and crystallized in the vicinity of the surface of the base material. A method for producing an amorphous coating body bonded via a layer.
る衝撃波である特許請求の範囲第３項記載のアモルファ
ス被覆体の製造方法。4. The method for producing an amorphous coating according to claim 3, wherein the shock wave is a shock wave generated by explosion of explosive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60037206A JPH0660326B2 (en) | 1985-02-25 | 1985-02-25 | Amorphous coating and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60037206A JPH0660326B2 (en) | 1985-02-25 | 1985-02-25 | Amorphous coating and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61195905A JPS61195905A (en) | 1986-08-30 |
| JPH0660326B2 true JPH0660326B2 (en) | 1994-08-10 |
Family
ID=12491110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60037206A Expired - Lifetime JPH0660326B2 (en) | 1985-02-25 | 1985-02-25 | Amorphous coating and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0660326B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2533529B2 (en) * | 1987-04-20 | 1996-09-11 | 日本油脂株式会社 | Amorphous metal-metal composite and method for producing the same |
| JPS648219A (en) * | 1987-06-29 | 1989-01-12 | Nippon Oils & Fats Co Ltd | Amorphous metal-metal composite and its production and amorphous metal-metal composite torque sensor using said composite |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS597433A (en) * | 1982-07-07 | 1984-01-14 | Asahi Chem Ind Co Ltd | Forming method of amorphous forming body |
| US4490329A (en) * | 1983-09-08 | 1984-12-25 | Oregon Graduate Center For Study And Research | Implosive consolidation of a particle mass including amorphous material |
| JPH0641636B2 (en) * | 1984-03-14 | 1994-06-01 | 日本電装株式会社 | Method for forming amorphous coating |
-
1985
- 1985-02-25 JP JP60037206A patent/JPH0660326B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61195905A (en) | 1986-08-30 |
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