JP4850526B2 - Method for producing metal glass alloy and method for producing metal glass alloy product - Google Patents
Method for producing metal glass alloy and method for producing metal glass alloy product Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims description 60
- 229910045601 alloy Inorganic materials 0.000 title claims description 60
- 229910052751 metal Inorganic materials 0.000 title claims description 57
- 239000002184 metal Substances 0.000 title claims description 55
- 239000011521 glass Substances 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- 239000005300 metallic glass Substances 0.000 claims description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000005266 casting Methods 0.000 description 19
- 125000004429 atom Chemical group 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 16
- 230000008025 crystallization Effects 0.000 description 16
- 230000001737 promoting effect Effects 0.000 description 12
- 238000005259 measurement Methods 0.000 description 6
- 150000004678 hydrides Chemical class 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 150000001247 metal acetylides Chemical class 0.000 description 5
- 150000004767 nitrides Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 2
- 239000013526 supercooled liquid Substances 0.000 description 2
- 229910017535 Cu-Al-Ni Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Description
非晶質相の比率が高い非鉄系金属ガラス合金の製造方法および金属ガラス合金製品の製造方法に関する。 The present invention relates to a method for producing a non-ferrous metallic glass alloy having a high amorphous phase ratio and a method for producing a metallic glass alloy product.
金属ガラス合金とは、ガラスのように元素の配列に規則性がない非晶質金属のことをいう。金属ガラス合金は、高い反発係数、高い強度、優れた鋳造性、および優れた耐腐食性といった特徴を有することにより、ゴルフクラブ、携帯電話のフレーム、腕時計のケーシング、圧力センサ、バネ材、および歯車などにその適用範囲が広がっている。 A metal glass alloy refers to an amorphous metal having no regularity in the arrangement of elements such as glass. Metallic glass alloys have characteristics such as high coefficient of restitution, high strength, excellent castability, and excellent corrosion resistance, so that golf clubs, mobile phone frames, watch casings, pressure sensors, spring materials, and gears The range of application is expanding.
ところで、Ｚｒ−Ｃｕ−Ａｌ−Ｎｉの四元金属ガラス合金を製造するため、従来から、当該四元金属原子を所定の配合率とすることが知られている（例えば、特許文献１）。しかし、特許文献１に記載された金属原子の成分割合で、真空溶解鋳造方法を用いて金属ガラス合金を製造しても、金属ガラス相に結晶が生じることが多く、金属ガラス合金の非晶質比率を高めることが困難であった。
本発明は、かかる問題点に鑑みてなされたものであり、その主たる目的は、非晶質相の比率が高い金属ガラス合金の製造方法を提供することにある。 This invention is made | formed in view of this problem, The main objective is to provide the manufacturing method of a metallic glass alloy with a high ratio of an amorphous phase.
請求項１に記載した発明は、「質量割合で、６６％以上６８％以下のジルコニウム（Ｚｒ）、２４．５％以上２６．５％以下の銅（Ｃｕ）、２．６％以上４．６％以下のアルミニウム（Ａｌ）、および２．９％以上４．９％以下のニッケル（Ｎｉ）の主要成分金属及び不可避的不純物からなる原料を用いる金属ガラス合金の製造方法であって、不可避的不純物は、１０ｐｐｍを超え２，０００ｐｐｍ未満の酸素（Ｏ）、１ｐｐｍを超え１５０ｐｐｍ未満の水素（Ｈ）、１０ｐｐｍを超え５００ｐｐｍ未満の窒素（Ｎ）、１０ｐｐｍを超え５００ｐｐｍ未満の炭素（Ｃ）、および１ｐｐｍを超え５００ｐｐｍ未満の鉄（Ｆｅ）のいずれか１種以上であることを特徴とする金属ガラス合金の製造方法。」である。
The invention according to claim 1 is described as follows: "Zirconium (Zr) of 66% to 68%, 24.5% to 26.5% copper (Cu), 2.6% to 4.6% by mass ratio". % or less of aluminum (Al), and a method for producing a metallic glass alloy using a material made of main components metallic and inevitable impurities 2.9% to 4.9% of nickel (Ni), inevitable impurities Is greater than 10 ppm less than 2,000 ppm oxygen (O), greater than 1 ppm less than 150 ppm hydrogen (H), greater than 10 ppm less than 500 ppm nitrogen (N), greater than 10 ppm less than 500 ppm carbon (C), and 1 ppm method for producing a metallic glass alloy, characterized in that at least one type of exceeding of less than 500ppm iron (Fe). "a.
請求項２に記載した発明は、「質量割合で、６６％以上６８％以下のジルコニウム（Ｚｒ）、２４．５％以上２６．５％以下の銅（Ｃｕ）、２．６％以上４．６％以下のアルミニウム（Ａｌ）、および２．９％以上４．９％以下のニッケル（Ｎｉ）の主要成分金属及び不可避的不純物からなる原料を用いる金属ガラス合金の製造方法であって、不可避的不純物は、１０ｐｐｍを超え１，０００ｐｐｍ以下の酸素（Ｏ）、１ｐｐｍを超え１００ｐｐｍ以下の水素（Ｈ）、１０ｐｐｍを超え４００ｐｐｍ以下の窒素（Ｎ）、１０ｐｐｍを超え４００ｐｐｍ以下の炭素（Ｃ）、および１ｐｐｍを超え４００ｐｐｍ以下の鉄（Ｆｅ）のいずれか１種以上であることを特徴とする金属ガラス合金の製造方法。」である。
The invention described in claim 2 is “by mass ratio, zirconium (Zr) of 66% to 68%, copper (Cu) of 24.5% to 26.5%, 2.6% to 4.6%. % or less of aluminum (Al), and a method for producing a metallic glass alloy using a material made of main components metallic and inevitable impurities 2.9% to 4.9% of nickel (Ni), inevitable impurities Is greater than 10 ppm and less than 1,000 ppm oxygen (O), greater than 1 ppm and less than 100 ppm hydrogen (H), greater than 10 ppm and less than 400 ppm nitrogen (N), greater than 10 ppm and less than 400 ppm carbon (C), and 1 ppm The manufacturing method of the metallic glass alloy characterized by being one or more of iron (Fe) exceeding 400 ppm and below. "
請求項３に記載した発明は、「原料を溶解することによって溶湯とし、溶湯を層流状態で鋳型に注入して鋳造すること」を特徴とする請求項１および２のいずれかに記載の金属ガラス合金の製造方法である。 The invention described in claim 3 is characterized in that “the molten metal is made by melting the raw material, and the molten metal is cast in a mold in a laminar flow state”. It is a manufacturing method of a glass alloy.
金属ガラスの製造方法としては、水焼入れ法、アーク溶解法、金型鋳造法、高圧射出成型法、吸引鋳造法、型締め鋳造法、および回転ディスク製線法などがあり、これらの方法を用いることによって、大型形状の金属ガラス合金（バルク金属ガラス）を製造できることが知られているが、これらの製造方法では、金属ガラス合金の非晶質相の比率を高めることが困難であった。 As methods for producing metal glass, there are a water quenching method, an arc melting method, a mold casting method, a high pressure injection molding method, a suction casting method, a mold clamping casting method, a rotating disk wire manufacturing method, and the like, and these methods are used. Although it is known that a large-sized metallic glass alloy (bulk metallic glass) can be produced by this, it is difficult to increase the ratio of the amorphous phase of the metallic glass alloy by these production methods.
これは、従来の製造方法において、金属ガラス合金の原料中に不可避不純物として含まれている酸素、水素、窒素、および炭素（以下、これら元素を「結晶化促進原子」と記載する。）と、これら結晶化促進原子と親和力の高い金属元素とが結合することによって生成された酸化物、水素化物、窒化物、および炭化物が、クラスター（結晶化するときに結晶の基となる、複数個の原子の集まり）化して結晶化の核となることで、金属ガラス中の結晶比率が高まることが原因である。 This is because oxygen, hydrogen, nitrogen, and carbon (hereinafter, these elements are referred to as “crystallization promoting atoms”) contained as inevitable impurities in the raw material of the metal glass alloy in the conventional manufacturing method, Oxides, hydrides, nitrides, and carbides formed by the combination of these crystallization promoting atoms and metal elements with high affinity are clustered (a plurality of atoms that form the basis of crystals when crystallizing). This is because the crystal ratio in the metallic glass is increased by forming a nucleus of crystallization.
そこで、発明者らは、請求項１および２に記載された金属ガラス合金の製造方法において「溶湯を層流状態で鋳型に注入して鋳造する」方法を用いることを特徴とする本発明に至った。 Accordingly, the inventors have reached the present invention characterized by using the method of “injecting and casting a molten metal into a mold in a laminar flow state” in the method for producing a metallic glass alloy according to claims 1 and 2. It was.
本発明によれば、金属ガラス合金が層流状態で鋳型に注入されることにより、金属ガラス合金に含有される結晶化促進原子と、これら結晶化促進原子と親和力の高い金属元素とが結合する確率が低くなり、金属ガラス中の酸化物、水素化物、窒化物、および炭化物がクラスター化して結晶化の核となる確率が著しく低減する。 According to the present invention, when a metallic glass alloy is injected into a mold in a laminar flow state, crystallization promoting atoms contained in the metallic glass alloy are bonded to metallic elements having high affinity with these crystallization promoting atoms. The probability is lowered, and the probability that the oxides, hydrides, nitrides, and carbides in the metal glass are clustered and become nuclei of crystallization is significantly reduced.
また、本発明に係る製造方法により得られた金属ガラス合金に過冷却液体温度域における高温塑性加工を施しても、金属ガラス合金中の酸化物、水素化物、窒化物、および炭化物がクラスター化する可能性が低い。 In addition, even when the metal glass alloy obtained by the production method according to the present invention is subjected to high temperature plastic working in the supercooled liquid temperature range, oxides, hydrides, nitrides, and carbides in the metal glass alloy are clustered. Less likely.
請求項４に記載した発明は、「請求項１および２のいずれかに記載の原料を溶解して溶湯とし、溶湯を層流状態で鋳型に注入して鋳造するのと同時に高温塑性加工し、または、溶湯を層流状態で鋳型に注入して鋳造した後に高温塑性加工する」金属ガラス合金製品の製造方法である。
The invention described in claim 4, "the claims 1 and 2 in either the melt by dissolving the raw material according to, high temperature plastic working simultaneously with the casting by injecting into a mold a molten metal in a laminar flow state Or, a molten glass is poured into a mold in a laminar flow state, casted, and then subjected to high-temperature plastic working. ”This is a method for producing a metal glass alloy product.
本発明によれば、非晶質相の比率が高い非鉄系金属ガラス合金を製造することができる。また、請求項３に記載した製造方法によれば、より非晶質相の比率が高い非鉄系金属ガラス合金を製造することができる。さらに、請求項４に記載した金属ガラス合金製品の製造方法によれば、高温塑性加工を施した後においても金属ガラス合金中の酸化物、水素化物、窒化物、および炭化物がクラスター化する可能性が低いことから、非晶質相の比率が高い金属ガラス合金製品を提供することができる。 According to the present invention, a non-ferrous metallic glass alloy having a high amorphous phase ratio can be produced. Moreover, according to the manufacturing method described in claim 3, a non-ferrous metallic glass alloy having a higher ratio of amorphous phase can be manufactured. Further, according to the method for producing a metal glass alloy product according to claim 4, oxides, hydrides, nitrides, and carbides in the metal glass alloy may be clustered even after high temperature plastic working. Therefore, it is possible to provide a metal glass alloy product having a high amorphous phase ratio.
本発明に係る金属ガラス合金の製造方法では、質量割合で、６６％以上６８％以下のジルコニウム（Ｚｒ）、２４．５％以上２６．５％以下の銅（Ｃｕ）、２．６％以上４．６％以下のアルミニウム（Ａｌ）、および２．９％以上４．９％以下のニッケル（Ｎｉ）を主要成分金属とし、１０ｐｐｍを超え２，０００ｐｐｍ未満の酸素（Ｏ）、１ｐｐｍを超え１５０ｐｐｍ未満の水素（Ｈ）、１０ｐｐｍを超え５００ｐｐｍ未満の窒素（Ｎ）、１０ｐｐｍを超え５００ｐｐｍ未満の炭素（Ｃ）、および１ｐｐｍを超え５００ｐｐｍ未満の鉄（Ｆｅ）のいずれか１種以上を不可避不純物として含有する原料が用いられる。このように不可避不純物として含まれる結晶化促進原子、および鉄の含有率を規定した理由について、以下に説明する。 In the method for producing a metallic glass alloy according to the present invention, zirconium (Zr) of 66% to 68%, copper (Cu) of 24.5% to 26.5%, 2.6% to 4% by mass. .6% or less of aluminum (Al) and 2.9% or more and 4.9% or less of nickel (Ni) as a main component metal, oxygen exceeding 10 ppm and less than 2,000 ppm (O), exceeding 1 ppm and less than 150 ppm Of hydrogen (H), more than 10 ppm and less than 500 ppm nitrogen (N), more than 10 ppm and less than 500 ppm carbon (C), and more than 1 ppm and less than 500 ppm iron (Fe) Raw materials are used. The reason why the crystallization promoting atoms contained as inevitable impurities and the content ratio of iron are specified will be described below.
結晶化促進原子について；結晶化促進原子の含有率についてそれぞれ下限を定めた理由は、商用的に入手可能な原料（実験室などでごく少量使用するために特別に精製された、結晶化促進原子の含有率が極端に小さい原料ではないもの。）に含まれる結晶化促進原子の含有率をこれ以下に抑えることは、実質的に困難だからである。一方、結晶化促進原子の含有率の上限を定めた理由は、この上限を超えた場合、結晶化が著しく進むことにより非晶質相が維持されないことが、後述する実験によって明らかになったからである。 Regarding crystallization promoting atoms; the reason for setting the lower limit for the content of crystallization promoting atoms is that the commercially available raw materials (crystallization promoting atoms specially purified for use in very small quantities in laboratories, etc.) This is because it is practically difficult to keep the content of the crystallization promoting atoms contained in the raw material in which the content of is not extremely low. On the other hand, the reason for setting the upper limit of the content of crystallization promoting atoms is that, when this upper limit is exceeded, it has become clear from experiments to be described later that the amorphous phase is not maintained due to remarkable progress of crystallization. is there.
鉄（Ｆｅ）について；鉄の含有率の下限を１ｐｐｍに定めた理由は、商用的に入手可能な原料に含まれる鉄の含有率をこれ以下に抑えることが実質的に困難だからであり、結晶化促進原子の含有率の下限を設定した理由と同じである。一方、鉄の含有率の上限を５００ｐｐｍと定めた理由は、まだ科学的に機構解明の途上であるが、この含有量を超えた場合、結晶化が著しく進むことにより非晶質相が維持されないことが、後述する実験によって明らかになったからである。 Regarding iron (Fe); the reason why the lower limit of the iron content is set to 1 ppm is that it is substantially difficult to keep the iron content contained in commercially available raw materials below this level. This is the same as the reason why the lower limit of the content rate of the chemical promotion atom is set. On the other hand, the reason why the upper limit of the iron content is set to 500 ppm is still in the process of elucidating the mechanism scientifically, but when this content is exceeded, the amorphous phase is not maintained due to remarkable crystallization. This is because it has been clarified by experiments described later.
次に、溶湯を層流状態で鋳型に注入して鋳造する方法について、具体的に説明する。 Next, a method for casting by injecting molten metal into a mold in a laminar flow state will be specifically described.
金属ガラス合金Ｘの溶湯を層流状態で鋳造することのできる鋳造装置１０は、図１に示すように、溶湯が注入されるキャビティ１２を内部に有する金型１４と、キャビティ１２の中央下部から鉛直下向きに延びる円筒状のスリーブ１６と、スリーブ１６の内部で摺動するプランジャーチップ１８と、一端がプランジャーチップ１８の下面に取り付けられている射出用ロッド２０と、油圧により射出用ロッド２０を鉛直方向に移動させるシリンダー２２と、スリーブ１６に入れた金属ガラス合金Ｘを加熱して溶湯にするためのスリーブヒータ２４と、金型１４の温度を１５０℃〜２５０℃の範囲内に保つための金型ヒータ２６とを備えており、キャビティ１２が、水平方向に延びるとともに、スリーブ１６の中心線に対して対称となる形状であることを特徴とする。
As shown in FIG. 1, a
そして、スリーブ１６の中に入れた金属ガラス合金Ｘがスリーブヒータ２４からの熱により溶解されるとともに、シリンダー２２により射出用ロッド２０が鉛直上向きに移動されることにより、プランジャーチップ１８も鉛直上向きに移動されて、溶解された金属ガラス合金Ｘがキャビティ１２内に射出される。
The metallic glass alloy X placed in the
このとき、プランジャーチップ１８が０．１ｍ毎秒ないし２ｍ毎秒の速度でスリーブ１６の内部を鉛直上向きに移動するようにシリンダー２２に送る圧油の量を調節することにより、スリーブ１６内で溶解された金属ガラス合金Ｘにおける乱流の発生を抑制し、溶湯の層流状態を維持しながら、溶湯を射出することができる。また、キャビティ１２の形状が水平方向に延びる形状であることにより、キャビティ１２の内部に射出された溶湯の流れを均一にすることができる。さらに、金型ヒータ２６により金型１４の温度を保持することにより、キャビティ１２に満たされる前に溶湯の温度が低下して、溶湯が固まることを防ぐことができるので、溶湯の流れを均一にすることができる。
At this time, the
なお、層流状態で鋳造加工をすることができるのであれば、鋳造装置１０を用いた鋳造加工に限定されることはなく、溶湯鍛造、傾倒鋳造、および重力鋳造など他の方法を用いても良い。
In addition, as long as casting can be performed in a laminar flow state, the present invention is not limited to casting using the
さらに、層流状態で鋳造加工をすることにより製造された金属ガラス合金は、過冷却液体温度域における高温塑性加工を行っても再び酸化物、水素化物、窒化物、および炭化物によりクラスター化する確率が低い。そのため、該金属ガラスの鋳造加工と同時、あるいは鋳造加工に引き続いて高温塑性加工を組み合わせることによって得られた金属ガラス合金製品は、過冷却温度域が広く、広い温度範囲で高温塑性加工をすることができるといった特徴を有する。 Furthermore, the probability that a metallic glass alloy produced by casting in a laminar flow state will be clustered again by oxides, hydrides, nitrides and carbides even after high temperature plastic working in the supercooled liquid temperature range. Is low. Therefore, metallic glass alloy products obtained by combining high-temperature plastic processing simultaneously with casting processing of the metallic glass or subsequent to the casting processing have a wide supercooling temperature range and high-temperature plastic processing over a wide temperature range. It has a feature that it can
本発明において不可避不純物の含有率の上限を規定した理由を構成する実験結果について説明する。 The experimental results constituting the reason for defining the upper limit of the content of inevitable impurities in the present invention will be described.
実験に供する金属ガラス合金を得るために、ジルコニウム、銅、アルミニウム、およびニッケルの含有率を前述した範囲に調整し、結晶化促進原子の含有率を変化させた多数種類の原料を溶製して金属ガラス合金を得た。 In order to obtain a metallic glass alloy to be used for the experiment, the content of zirconium, copper, aluminum, and nickel was adjusted to the above-mentioned range, and a large number of raw materials with varying contents of crystallization promoting atoms were melted. A metallic glass alloy was obtained.
表１に、結晶化促進原子の含有率をそれぞれ変化させた金属ガラス合金における非晶質比率を判定した結果を示す。 Table 1 shows the result of determining the amorphous ratio in the metallic glass alloys in which the content of crystallization promoting atoms was changed.
表１において、「○」は金属ガラス合金における非晶質比率が非常に大きいと判定される場合を示し、「△」は金属ガラス合金における非晶質比率が大きいと判定される場合を示している。そして、「×」は金属ガラス合金における非晶質比率が小さいと判定される場合を示している。 In Table 1, “◯” indicates a case where the amorphous ratio in the metal glass alloy is determined to be very large, and “Δ” indicates a case where the amorphous ratio in the metal glass alloy is determined to be large. Yes. And "x" has shown the case where it determines with the amorphous ratio in a metallic glass alloy being small.
表１に示すとおり、金属ガラス合金における酸素の含有率が２，０００ｐｐｍの場合、水素の含有率が１５０ｐｐｍの場合、窒素の含有率が５００ｐｐｍの場合、炭素の含有率が５００ｐｐｍの場合、および鉄（Ｆｅ）の含有率が５００ｐｐｍの場合において、金属ガラス合金における非晶質比率が大きいと判断される結果を得た。そして、酸素の含有率が１，０００ｐｐｍ以下、水素の含有率が１００ｐｐｍ以下、窒素の含有率が４００ｐｐｍ以下、炭素の含有率が４００ｐｐｍ以下、および鉄（Ｆｅ）の含有率が４００ｐｐｍ以下の範囲に規制することで、金属ガラス合金における非晶質比率が非常に大きいと判定される結果を得ることができた。 As shown in Table 1, when the oxygen content in the metallic glass alloy is 2,000 ppm, the hydrogen content is 150 ppm, the nitrogen content is 500 ppm, the carbon content is 500 ppm, and iron When the content rate of (Fe) was 500 ppm, the result that it was judged that the amorphous ratio in a metallic glass alloy was large was obtained. The oxygen content is 1,000 ppm or less, the hydrogen content is 100 ppm or less, the nitrogen content is 400 ppm or less, the carbon content is 400 ppm or less, and the iron (Fe) content is 400 ppm or less. By regulating, it was possible to obtain a result that the amorphous ratio in the metal glass alloy was determined to be very large.
金属ガラス合金における非晶質比率の判定は、金属ガラス合金のＸ線回折法（ＸＲＤ法；Ｘ−Ｒａｙ Ｄｉｆｆｒａｃｔｏｍｅｔｅｒ法）による測定結果に基づいて行った。この判定について具体的に説明するため、Ｘ線回折試験結果の例を図２に示す。図２に示された３種類の測定結果線（１）ないし（３）は、下から、「○」と判断される金属、「△」と判断される金属、および「×」と評価される場合の例を示している。 Determination of the amorphous ratio in the metal glass alloy was performed based on the measurement result of the metal glass alloy by the X-ray diffraction method (XRD method; X-Ray Diffractometer method). In order to specifically explain this determination, an example of an X-ray diffraction test result is shown in FIG. The three types of measurement result lines (1) to (3) shown in FIG. 2 are evaluated from the bottom as a metal judged as “◯”, a metal judged as “Δ”, and “x”. An example of the case is shown.
金属ガラス合金に結晶が存在すれば図２中の（ア）ないし（ウ）のような測定結果線にピークが生じる。そして、このピークの高さを基に合金中の結晶質比率を評価することができる。すなわち、ピークの高さが高いほど、金属ガラス合金に存在する結晶質比率が大きく、非晶質比率が小さいと評価することができる。以上より、測定結果線（３）における（ア）が最も高いピークであることから、測定結果線（３）に係る金属ガラス合金は、非晶質比率が小さいと評価することができる。 If a crystal exists in the metal glass alloy, a peak is generated in the measurement result line such as (a) to (c) in FIG. And the crystalline ratio in an alloy can be evaluated based on the height of this peak. That is, it can be evaluated that the higher the peak height, the larger the crystalline ratio present in the metal glass alloy and the smaller the amorphous ratio. From the above, since (a) in the measurement result line (3) is the highest peak, the metal glass alloy according to the measurement result line (3) can be evaluated as having a small amorphous ratio.
１０…鋳造装置
１２…キャビティ
１４…金型
１６…スリーブ
１８…プランジャーチップ
２０…射出用ロッド
２２…シリンダー
２４…スリーブヒータ
２６…金型ヒータ
DESCRIPTION OF
Claims (4)
前記不可避的不純物は、１０ｐｐｍを超え２，０００ｐｐｍ未満の酸素（Ｏ）、１ｐｐｍを超え１５０ｐｐｍ未満の水素（Ｈ）、１０ｐｐｍを超え５００ｐｐｍ未満の窒素（Ｎ）、１０ｐｐｍを超え５００ｐｐｍ未満の炭素（Ｃ）、および１ｐｐｍを超え５００ｐｐｍ未満の鉄（Ｆｅ）のいずれか１種以上であることを特徴とする金属ガラス合金の製造方法。 66% or more and 68% or less of zirconium (Zr), 24.5% or more and 26.5% or less of copper (Cu), 2.6% or more and 4.6% or less of aluminum (Al), and 2 by mass A method for producing a metallic glass alloy using a raw material comprising a main component metal of nickel (Ni) of 9.9% to 4.9% and unavoidable impurities,
The inevitable impurities include oxygen exceeding 10 ppm and less than 2,000 ppm (O), hydrogen exceeding 1 ppm and less than 150 ppm (H), nitrogen exceeding 10 ppm and less than 500 ppm (N), carbon exceeding 10 ppm and less than 500 ppm (C ), and manufacturing method of the metallic glass alloy, characterized in that 1ppm either one or more than 500ppm less than iron (Fe).
前記不可避的不純物は、１０ｐｐｍを超え１，０００ｐｐｍ以下の酸素（Ｏ）、１ｐｐｍを超え１００ｐｐｍ以下の水素（Ｈ）、１０ｐｐｍを超え４００ｐｐｍ以下の窒素（Ｎ）、１０ｐｐｍを超え４００ｐｐｍ以下の炭素（Ｃ）、および１ｐｐｍを超え４００ｐｐｍ以下の鉄（Ｆｅ）のいずれか１種以上であることを特徴とする金属ガラス合金の製造方法。 66% or more and 68% or less of zirconium (Zr), 24.5% or more and 26.5% or less of copper (Cu), 2.6% or more and 4.6% or less of aluminum (Al), and 2 by mass A method for producing a metallic glass alloy using a raw material comprising a main component metal of nickel (Ni) of 9.9% to 4.9% and unavoidable impurities,
The inevitable impurities include oxygen (O) exceeding 10 ppm and 1,000 ppm or less, hydrogen (H) exceeding 1 ppm and 100 ppm or less, nitrogen (N) exceeding 10 ppm and nitrogen (N) exceeding 10 ppm, carbon (C) exceeding 10 ppm and 400 ppm or less. ), and manufacturing method of the metallic glass alloy, characterized in that 1ppm either one or more than 400ppm or less iron (Fe).
当該溶湯を層流状態で鋳型に注入して鋳造するのと同時に高温塑性加工し、
または、当該溶湯を層流状態で鋳型に注入して鋳造した後に高温塑性加工する金属ガラス合金製品の製造方法。
A molten metal by dissolving the raw material of any of claims 1 and 2,
The molten metal is poured into a mold in a laminar state and cast at the same time as high-temperature plastic processing,
Or the manufacturing method of the metal glass alloy product which inject | pours the said molten metal into a casting_mold | template in a laminar flow state, casts, and then performs high temperature plastic processing.
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