TWI224985B - A method of casting for materials comprising an amorphous alloy matrix structure - Google Patents

A method of casting for materials comprising an amorphous alloy matrix structure Download PDF

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TWI224985B
TWI224985B TW91135228A TW91135228A TWI224985B TW I224985 B TWI224985 B TW I224985B TW 91135228 A TW91135228 A TW 91135228A TW 91135228 A TW91135228 A TW 91135228A TW I224985 B TWI224985 B TW I224985B
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alloy
amorphous
mold
water
casting
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TW91135228A
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TW200409684A (en
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Yu-Lom Lin
Rong-Ruey Jeng
Jium-Shyong Chem
Chien-Hung Yeh
Chung-Ping Chang
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Chung Shan Inst Of Science
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Abstract

This invention relates to a method of making amorphous alloy matrix structure materials by centrifugal casting. Particularly, the molten metal was forced into a water-cooled metal mold and solidified under a centrifugal force. In this method, the alloy is first melted via vacuum arc remelting (VAR) or induction skull melting (ISM) under either vacuum or protective atmosphere. The molten metal is then pressed into a water-cooled copper mold and rapidly solidify to form a bulk amorphous matrix. The advantages of this invention are that it can provide not only a high cooling rate but also a method of mass production. As a result, large and/or complicatedly shaped bulk amorphous matrix structure can be easily produced.

Description

1224985 五、發明説明(l) :-—-:- 產業上之利用範脅 古,日日=口金(或稱金屬玻璃、玻璃金屬)為一種具有 二,二強度、耐衝擊、财磨耗、财腐姓、低楊氏模數 曰二u I, 一些鐵系非晶質合金更具有優異之軟磁性質。非 料已應用於變壓器線圈、高爾夫球頭打擊面板、微 ,電f小齒輪、光學精密零件、防彈材料及民生3C產品 ^ 些研究學者發現非晶質基地與奈米(nano meter)析出相複合組織結構材料有著比純非晶相材料更 優異之機械性質,為一種未來極具潛力之材料。 現有較具產業運用價值之Zr/Ti/Cu/Fe系非晶質合 金,其熔融體仍需在5 °C〜100 °C/s以上的冷卻速率才能形 成非晶相,因受限於現有製程尚未建立適合複雜、大平面 或大尺寸零件之量化能力,故仍停留在學術研究或產品開 發階段’因此,開發一套適合量化特殊製程乃當務之急。 本發月即針對先前技術非晶合金製程能量限制而發展 出之一種鑄造方法,以ISM或VAR水冷銅坩堝加熱將合金熔 融,以高離心力加壓鑄造製程,依此技術約於15分鐘内即 可完成一爐次之澆鑄,若採用一爐次澆鑄多模穴,加上採 用水冷銅模可縮短模具冷卻時間,因此為一種可批次連續 鑄造之製程,具有量化能力。 本發明之離心鑄造,由於具有優異之急冷能力,故可 用以鑄造先前技術使用之所有非晶質合金系,包含具活性 之Zr/Ti系等之非晶質合金。以此方法可用以鑄造近於 100%非晶質合金或含部分結晶相之非晶質基地結構材料,1224985 V. Description of the invention (l): -——-:-Fan Yigu, industrial use, day = gold (or metal glass, glass metal) is a type with two or two strength, impact resistance, financial wear and tear, financial Rot surname, low Young's modulus is two u I, some iron-based amorphous alloys have excellent soft magnetic properties. Unexpected materials have been used in transformer coils, golf head strike panels, micro and electrical pinions, optical precision parts, bulletproof materials and 3C products for the people's livelihood. ^ Some researchers have found that amorphous bases are compounded with nanometer precipitation. Tissue structure material has more excellent mechanical properties than pure amorphous phase material and is a material with great potential in the future. For the existing Zr / Ti / Cu / Fe series amorphous alloys with more industrial application value, the molten body still needs to be cooled at a cooling rate of 5 ° C ~ 100 ° C / s to form the amorphous phase, due to the limitation of the existing The manufacturing process has not yet established a quantification capability suitable for complex, large flat or large-size parts, so it remains in the academic research or product development stage. Therefore, it is urgent to develop a special process suitable for quantification. This month is a casting method developed for the energy limitation of the amorphous alloy process of the prior art. The alloy is melted by heating ISM or VAR water-cooled copper crucibles, and the casting process is pressurized with high centrifugal force. According to this technology, it takes about 15 minutes. It can complete one-shot casting. If one-shot casting of multiple cavities is used, and the use of water-cooled copper molds can shorten the mold cooling time, it is a continuous continuous casting process with quantitative capabilities. The centrifugal casting of the present invention has excellent quenching ability, so it can be used to cast all amorphous alloy systems used in the prior art, including active amorphous alloys such as the Zr / Ti system. In this way, it can be used to cast nearly 100% amorphous alloys or amorphous base structural materials with partially crystalline phases.

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/:經由將非晶塊材加熱至適當溫度,使非晶基地析出奈 ^ 粒,製作出一種高韌性具有非晶/奈米晶複合組織材 ^,為一種創新之非晶質合金基地結構塊(板)材鑄造方 法’極具潛力及產業上之利用價值。 發明背景 非晶質合金為一固體但其原子結構排列類似液態物 夕,因其不具長程規律性之原子排列結構展現出具有許 夕異於結晶態合金的特殊性質,如高機械強度、高硬度、 良好抗蝕性、優異的光、電、磁特性以及抗耐磨性等。 自從Klement於1960首度以急冷凝固法合成^ —Si系的 非晶質相後’因受限於非晶相形成需極高之冷卻速率,因 此一直到1 970年代中期,Chen等學者才將Pd4QNi4()P2() (1976)和 Pd76Cu6Si18(1978)以低臨界冷卻速率(Critical Cooling Rate ’Rc)的水淬火方式(Water Quenching Method )分別製成直徑3mni和〇· 3mni厚的塊狀物。1988年 時’日本東北大學的井上明久教授首先發現Mg-Ln-ΤΜ(ΤΜ = 過渡金屬)非晶質合金的過冷液態區(Supercooled Liquid Region, ΔΤχ = Tx-Tg)達50K,過冷液態區之定義為結晶 化溫度(Tx)減掉玻璃轉換溫度(Tg)的溫度區間範圍,井上 教授並以非常低的Rc (臨界冷卻速率)合成Mg-Ln-TM塊狀 非晶質合金後,隨後幾年陸續發現特殊成份如Zr-A卜Ni、/: By heating the amorphous bulk material to an appropriate temperature, the amorphous base is precipitated with nano-particles, and a high-toughness amorphous / nanocrystalline composite structure material ^ is produced, which is an innovative amorphous alloy base structural block. The (plate) material casting method has great potential and industrial utilization value. BACKGROUND OF THE INVENTION Amorphous alloy is a solid but its atomic structure is similar to that of liquid materials. Because it has no long-range regularity, the atomic structure exhibits special properties different from crystalline alloys, such as high mechanical strength and high hardness. , Good corrosion resistance, excellent optical, electrical, magnetic properties and abrasion resistance. Since Klement first synthesized ^ —Si-based amorphous phase by the rapid condensation method in 1960, it was restricted by the formation of amorphous phase and required extremely high cooling rate. Therefore, scholars such as Chen did not apply it until the mid-1970s. Pd4QNi4 () P2 () (1976) and Pd76Cu6Si18 (1978) were made into water-quenching method (Critical Cooling Rate 'Rc) with a water quenching method (CQ). In 1988, Professor Akira Inoue of Tohoku University first discovered that the supercooled liquid region (ΔTχ = Tx-Tg) of Mg-Ln-TM (TM = transition metal) amorphous alloy reached 50K, and the supercooled liquid The zone is defined as the temperature range between the crystallization temperature (Tx) minus the glass transition temperature (Tg). After Inoue taught and synthesized the Mg-Ln-TM bulk amorphous alloy at a very low Rc (critical cooling rate), Special ingredients such as Zr-A and Ni,

Zr-Al-Cu、Zr-Al-Cu-Ni、Zr-Ti-Cu-Ni 和(Zr,Hf)-A1-Cu-Zr-Al-Cu, Zr-Al-Cu-Ni, Zr-Ti-Cu-Ni and (Zr, Hf) -A1-Cu-

Ni等合金系具寬廣ΔΤχ。加州理工學院的威廉強森教授亦Alloys such as Ni have a wide ΔΤχ. Professor William Johnson of California Institute of Technology

1224985 五、發明說明(3) 於1 993年發現在Zr-Ti-Be-TM合金系具寬廣在極低 之臨界冷卻速率即可形成非晶質合金,兩組學者亦可藉由 模壓鑄造法或壓鑄法等不同的製程技術,來製作塊狀非晶 材料。 塊狀非晶質合金雖可以上述方法成功製備,然經分析 其使用之製造參數,可發現仍存在需特殊製程設計及不適 合活性、複雜或大尺寸非晶質合金量化之缺失。 分析過去1 0年間塊狀非晶質成形方式不外乎(丨)水淬法·· 將合金置於石英管内加熱熔解後直接於水令急冷,形成棒 材,42)以冷模熔旋方式將合金置於石英管内以高週波感應 加熱熔解,以Ar加壓將熔融合金注入直立式旋轉銅滾輪 上’形成厚度約30 /zm之非晶箔帶;(3)以機械合金法製成非 晶粉末,再以冷均壓或熱均壓或滾壓方式成形;(4)真空上 吸法:將合金熔解靠大氣壓力差之壓力將合金垂直吸入金 屬模穴内急冷成型;(5)重力鑄造法:將熔融金屬液靠重力 注入金屬模具内急冷成型;(6 )以傳統之壓鑄法,將合金於 保護氣氣下以南週波方式將合金於陶究掛塌内嫁解後以油 壓將溶液押入金屬模内冷卻;(7)模壓成型法:將合金置於 下模以非消耗性電極加熱溶解後,下模水平移動至上模下 方與上模對準定位後,以鍛造方式加壓成型。 上述各種適合非晶塊材成型方式,都無法真正適合量 化製程’用以生產高品質、形狀複雜之大型非晶塊(板) 材’製程中均存在不利於大面積非晶塊(板)材量化問題, 1224985 五、發明說明(4) 例如以(1)水淬方式較適合製作非晶棒材,無量化能力; (2 )以冷模熔旋方式只是適合製作非晶箔帶,不具製作厚 $材旎力;(3 )以非晶粉末經冷均壓或熱均壓成型方式,因 需在結晶溫度以下加壓成型,因此形狀及製程能力受限, 不^製作形狀複雜、大尺寸塊(板)材,且成本昂貴,不適 合量化製程;(4 )以上吸法製作非晶塊材,因壓力差不大, 因此形狀複雜鑄件易造成鑄件產生冷接(c〇ld shut)紋及 形成局部結晶現象,不適合具大面積塊(板)材量化;(5)重 力鑄造方式:適於鑄造棒材,對於大平面或薄鑄件不易鑄 出完整形狀;(6)以壓鑄法或模壓成型法來製作非晶塊材, 雖可避免合金固化收縮時,在模壁與凝固層間產生一熱傳 效率低的空氣間隙層,降低模穴與熔液的熱傳效果,但此 兩種方法仍存在一些不利於活性金屬非晶相形成之因素, 例如s Zr/Τι系等具活性合金熔融金屬於澆鑄至銅模模穴 時,以傳統之壓鑄法成型,以高週波感應熔解方式將合金 於陶瓷坩堝中熔解,對於合金之清淨度不易掌控,同時對 於活性之Zr/Ti系合金會與坩堝材料反應,一些氧化物於 熔液中對於非晶相形成是不利的,通常以壓鑄法成型,只 有於合金熔解艙中以保護氣氛保護,當熔融金屬經流道^ 入模穴凝固時,容易造成金屬液局部氧化,因此對於非晶 塊(板)材之品質不易掌控。 模壓成型法雖於真空中或保護氣氛下熔解,較無上述 ς題,但由於係採用合金置於下模内熔解後,再將下模水 “移動至上模下方與上模對準定位後,以鍛造方式加壓成1224985 V. Description of the invention (3) In 1 993, it was discovered that Zr-Ti-Be-TM alloys can form amorphous alloys with a wide and extremely low critical cooling rate. Two groups of scholars can also use die casting method Or die-casting to produce bulk amorphous materials. Although the bulk amorphous alloy can be successfully prepared by the above method, but after analyzing the manufacturing parameters used, it can be found that there are still defects that require special process design and are not suitable for the quantification of active, complex, or large-sized amorphous alloys. The analysis of the bulk amorphous forming method in the past 10 years is nothing more than (丨) water quenching method. The alloy is placed in a quartz tube, heated and melted, and then quenched directly in water to form a bar. 42) Cold mold spinning method The alloy is placed in a quartz tube and melted by high frequency induction heating, and the molten alloy is injected into the upright rotating copper roller with Ar pressure to form an amorphous foil strip with a thickness of about 30 / zm; (3) made of non-aqueous foil by mechanical alloy method Crystal powder, and then formed by cold equalizing or hot equalizing or rolling; (4) vacuum suction method: melt the alloy by atmospheric pressure and draw the alloy vertically into the metal mold cavity for rapid cold forming; (5) gravity casting Method: Inject molten metal into the metal mold by gravity and quench it; (6) The traditional die-casting method is to dissolve the alloy in a ceramic slump under protective gas in a south frequency manner. The solution is pressed into the metal mold to cool; (7) compression molding method: the alloy is placed in the lower mold to be heated and dissolved by non-consumable electrodes, the lower mold is horizontally moved under the upper mold and aligned with the upper mold, and then press-molded by forging. . The above-mentioned various suitable amorphous block forming methods are not really suitable for the quantitative process 'for producing high-quality and large-sized large amorphous blocks (plates) materials' There are all kinds of amorphous blocks (plates) which are not good for large areas Quantitative problem, 1224985 V. Description of the invention (4) For example, (1) water quenching is more suitable for making amorphous rods without quantification ability; (2) cold mold fusion is only suitable for making amorphous foil strips, not for production Thick material strength; (3) The amorphous powder is formed by cold equalizing or hot equalizing. Due to the need for pressure molding below the crystallization temperature, the shape and process capability are limited. Do not make complex shapes and large sizes. Block (plate) material, which is expensive and not suitable for quantification process; (4) the above method is used to produce amorphous blocks, because the pressure difference is not large, so the complex shape of the casting is likely to cause cold shutting and The formation of local crystallization phenomenon is not suitable for quantification of large-area blocks (plates); (5) Gravity casting method: suitable for casting rods, it is not easy to cast a complete shape for large flat or thin castings; (6) by die casting or compression molding law The production of amorphous blocks can prevent the formation of an air gap layer with low heat transfer efficiency between the mold wall and the solidified layer when the alloy solidifies and shrinks, reducing the heat transfer effect of the mold cavity and the melt, but these two methods still exist. Factors that are not conducive to the formation of the amorphous phase of the active metal. For example, when molten metal with active alloys such as s Zr / Ti series is cast into the copper mold cavity, it is formed by traditional die casting method, and the alloy is applied to the ceramic crucible by high frequency induction melting. Medium melting is not easy to control the cleanliness of the alloy, and at the same time, the active Zr / Ti series alloy will react with the crucible material. Some oxides in the melt are not good for the formation of amorphous phases. They are usually formed by die casting. The alloy melting chamber is protected by a protective atmosphere. When the molten metal solidifies through the flow path ^ into the mold cavity, it is easy to cause local oxidation of the molten metal, so it is not easy to control the quality of the amorphous block (plate) material. Although the compression molding method melts in a vacuum or a protective atmosphere, there is no such problem, but because the alloy is placed in the lower mold and melted, the lower mold water is "moved under the upper mold and aligned with the upper mold. Pressurized by forging

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型,造成整個流程操作時間過長,易造成 會’也會因於下模直接將合金熔解加執, 品模穴部位溫度上升,會間接降低模穴部 更因係採用上下加壓方式成形,成形形狀 較適合於製作形狀簡單之非晶塊(板)材, 由於現今主要之非晶塊(板)材製程有 非均質成核機 會間接使下模成 位之激冷能力, 受到限制,因此 較無發展潛力。 上述缺失,雖然 分可製作達10mm 作形狀複雜、大 進展緩慢。針對 造方法,於真空 。將熔融金屬液 下凝固成形,是 形狀複雜之非晶Type, which causes the entire process to take too long to operate, which can easily cause the alloy to melt and add directly to the lower mold. The temperature rise in the cavity part of the product will indirectly reduce the cavity part. The formed shape is more suitable for making amorphous blocks (plates) with simple shapes. Due to the heterogeneous nucleation opportunities in the major amorphous block (plate) manufacturing processes today, the chilling capacity of the lower molds is indirectly limited, so it is limited. Less development potential. Although the above-mentioned defects can be made up to 10mm, the shape is complicated and the progress is slow. For manufacturing methods, vacuum. The molten metal is solidified and formed into a complex amorphous form

像Zr-Al-Ni-Cu 或Ti-Zr-Cu-Ni-B 等合金成 直徑以上之棒材,但因無法突破量化、製 面積能力限制,因此非晶合金之應用發展 上述缺失改進,本發明係採用一種離心鑄 中或保護氣氛下將合金溶融、堯鎊、凝固 澆注於水冷模具内,藉由強大離心力加壓 一種具有量化能力,且可以製作大尺寸、 質合金基地結構材料之成形方法。 發明技術内容Alloys such as Zr-Al-Ni-Cu or Ti-Zr-Cu-Ni-B are made of rods with a diameter larger than the diameter. However, due to the limitation of quantification and area capacity, the application and development of amorphous alloys are lacking. The invention uses a centrifugal casting or a protective atmosphere to melt, solidify, and solidify the alloy into a water-cooled mold, and presses a strong centrifugal force to pressurize a molding method that has a quantification ability and can produce large-sized, quality alloy base structural materials. . Summary of the Invention

本發明為一種離心鑄造製作非晶質合金基地結構材料 之成形方法,其特點為以離心力將熔融金屬液注入水冷金 屬模具内凝固成形。本發明之離心鑄造,係將合金熔融、 澆鑄、急冷凝固整個過程於真空艙内完成,合金於加熱溶 融後,澆注於高轉速之離心模具内,以高離心力瞬間將金 屬液壓入模穴内急冷凝固成形。 本發明使用之熱源係可以將合金熔解成為液態,熔融The invention is a method for forming an amorphous alloy base structural material by centrifugal casting, which is characterized in that a molten metal liquid is injected into a water-cooled metal mold by centrifugal force and solidified. The centrifugal casting of the present invention is to complete the entire process of melting, casting, and rapid solidification of the alloy in a vacuum chamber. After the alloy is melted by heating, it is poured into a high-speed centrifugal mold, and the metal is hydraulically injected into the mold cavity with high centrifugal force to rapidly condense. Forming. The heat source used in the present invention can melt the alloy into a liquid state and melt

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金屬液溫度大於炫點之加熱方式,且可以對熔融金屬液持 續加熱,提供熱量足以避免熔液於澆鑄前凝固,可以將熔 融金屬液内之核種以超溫完全重新熔解,避免非均質成核 或異質成核機會,以獲得全為非晶結構或高比率非晶基地 結構塊(板)材。一般使用之加熱方式,可為電漿加熱熔解 (Plasma melting)、電子束加熱熔解(Electr〇n beam melting)、電阻加熱、真空電弧熔解(Vacuum arc remelting)或採感應殼式熔解(Inducti〇n skuU melting)法或真空感應熔解法(Inducti〇n fflelting)。 各種加熱法使用之掛堝可為石墨、陶瓷或採用殼式銅 坩堝加熱方式。對於Zr/Ti/Cu基等活性合金之熔解,以採 用水冷式銅坩堝能夠獲得較高清淨度金屬熔液,亦可避免 溶融金屬與掛蜗材料反應,尤其以感應殼式熔融法將合金 於真空或惰性乳氣下加熱溶融,可以輕易將合金溶融夜體 加熱超過熔點50 °C以上,可以鑄造複雜大平面塊(板)材, 降低因澆溫過低造成成品不完整或冷接情形,亦可有效抑 制高溫熔融合金於坩堝内或於澆鑄過程產生異質成核或非 均質成核機會,有利於非晶質相之形成,更因採用非消耗 性水冷銅掛禍,不易與合金反應,為一非常適合如 系等活性高之合金熔解製程。 本發明之離心鑄造係採用水平式離心鑄造方式,離心 轉速至少為50rpm以上。較高之轉速可獲得較大之加壓能 力,可於瞬間將金屬液完全填充於模穴内,適於鑄造複雜 或大面積之塊(板)材,可有效避免鑄件冷接紋產生,同時The heating method of the molten metal temperature is higher than the dazzling point, and the molten metal liquid can be continuously heated, providing enough heat to prevent the molten metal from solidifying before casting. It can completely re-melt the nucleus in the molten metal liquid at excessive temperature, and avoid heterogeneous nucleation. Or heterogeneous nucleation opportunities to obtain all amorphous structures or high-rate amorphous base structure blocks (plates). Generally used heating methods can be Plasma melting, Electron beam melting, Resistance heating, Vacuum arc remelting, or Induction shell melting. skuU melting) method or vacuum induction melting method (Inductioon fflelting). The hanging pot used for various heating methods can be graphite, ceramic or shell copper crucible heating method. For the melting of Zr / Ti / Cu-based active alloys, water-cooled copper crucibles can be used to obtain higher purity metal melts, and the reaction of molten metals with snail materials can also be avoided. Especially, the alloys are melted by induction shell melting. Heating and melting under vacuum or inert milk can easily heat the molten alloy body above the melting point above 50 ° C. It can cast complex large flat blocks (plates) to reduce the incompleteness or cold connection of the finished product due to low pouring temperature. It can also effectively suppress the occurrence of heterogeneous nucleation or heterogeneous nucleation opportunities in the crucible or during the casting process of the high-temperature molten alloy, which is beneficial to the formation of amorphous phases. It is also difficult to react with the alloy due to the use of non-consumable water-cooled copper. It is a very suitable melting process for alloys with high activity. The centrifugal casting of the present invention adopts a horizontal centrifugal casting method, and the centrifugal rotation speed is at least 50 rpm or more. Higher speed can obtain greater pressurizing capacity, which can fill the metal cavity completely in the mold instantly. It is suitable for casting complex or large-area block (plate) material. It can effectively avoid the cold welding of the casting.

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1224985 五、發明說明(8) [實例一]:(ISM加熱熔解製程) 母合金錠熔製:以真空電弧溶解爐(yacuum Arc Reme 11 i ng ’ VAR )進行每一爐溶解量約6 〇 〇克,依重量百 分比將純錯(99% )、純鋁(99· 9% )、純鎳(99% )、 純銅(99.5% )或Al-2%Sc合金(99·9% )料秤重,置於 水冷銅掛堝内抽真空至PiO-sTorr後,在高氬氣氛下熔 融,為使合金完全均勻,熔解料凝固後翻轉再熔解,如此 重複進行至少七次以上,完成&5,11()1^5(:113()(&1;%)母合金 錠熔製。 非晶合金板材鑄造:(1 )離心模具:離心模具上下模使 用熱傳導性甚佳之無氧銅製作,每模模穴尺寸為板材4 片,尺寸為50mm*100mm*3mm (2)熔解鑄造··取 Zr55Al1GNi5Cu3G (at%)合金狡秤重約3000公克,置於ISM真 空爐感應式水冷銅坩堝内,抽真空達l.〇*l〇-3T〇rr後,通 高氬將真空度調整為1· ΪΜΟ—Τογγ,以電力將合金熔融, 待合金熔融加熱約2分鐘後,在1秒内快速澆鑄於2〇〇rpm高 轉速銅模内,約1 5分鐘後經凝固冷卻後取出板材。為瞭解 所縳造之板材是否為非晶合金,本實例採用X-ray繞射結 構分析來做初步鑑定,結果如第一圖所示板片試樣的X一 ray繞射圖,從繞射圖可知大部份均為非晶質基地僅有小 部份結晶繞射峰出現,本實驗所採用之金屬模雖為低轉速 及無水冷裝置,但以超大體積之銅質材料製作模具,以低 轉速即可獲得足夠之成形離心力及能夠瞬間達到吸熱能 力。 、1224985 V. Description of the invention (8) [Example 1]: (ISM heating and melting process) Master alloy ingot melting: Vacuum arc melting furnace (yacuum Arc Reme 11 in ng 'VAR) is used to dissolve each furnace at about 600. Grams, pure wrong (99%), pure aluminum (99 · 9%), pure nickel (99%), pure copper (99.5%) or Al-2% Sc alloy (99 · 9%) according to weight percentage After being vacuumed to PiO-sTorr in a water-cooled copper hanging pot, it is melted in a high argon atmosphere. In order to make the alloy completely homogeneous, the molten material is solidified and then re-melted. This is repeated at least seven times. Complete & 5, 11 () 1 ^ 5 (: 113 () (&1;%) mother alloy ingot melting. Amorphous alloy sheet casting: (1) Centrifugal mold: The upper and lower molds of the centrifugal mold are made of oxygen-free copper with excellent thermal conductivity. The size of each mold cavity is 4 plates with a size of 50mm * 100mm * 3mm. (2) Melting and casting · Take Zr55Al1GNi5Cu3G (at%) alloy cunning weight and weigh about 3000 grams, and place it in an ISM vacuum furnace induction water-cooled copper crucible. After evacuating to 1.0 × * 10-3 Torr, the vacuum degree was adjusted to 1 · ΪΜΟ—Τογγ by passing high argon, and the alloy was melted by electric power. After about 2 minutes of melting and heating, it is quickly cast into a 200rpm high-speed copper mold in 1 second, and the plate is taken out after solidification and cooling after about 15 minutes. In order to understand whether the bound plate is an amorphous alloy, this The example uses X-ray diffraction structure analysis for preliminary identification. The results are shown in the X-ray diffraction pattern of the plate sample shown in the first figure. From the diffraction pattern, it can be seen that most of them are amorphous bases and only small. Some crystal diffraction peaks appear. Although the metal mold used in this experiment is a low-speed and water-free device, the mold is made of a large volume of copper material. At low speed, sufficient forming centrifugal force can be obtained and heat absorption can be achieved instantly. ability. ,

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非晶質合金板材熱分析結果如第二圖所示,Tg、Tx(Qn set)分別為693· 43K及773· 02K,從此二個溫度求出ΔΤχ約 為80Κ,顯示以此方法製作之非晶質合金具有寬廣之過冷 液悲區間’此溫度區間一般用來衡量當溫度超過破璃轉換 溫度Tg時,玻璃相之穩定性,ΑΤχ值愈大代表過冷液艘之 熱穩定性愈佳,愈容易於過冷液態區間内成形,例如以精 密模具超塑成形方式,可將非晶質合金板材製成特殊形狀 之零件。The results of the thermal analysis of the amorphous alloy sheet are shown in the second figure. The Tg and Tx (Qn set) are 693 · 43K and 773 · 02K, respectively. From these two temperatures, ΔΤχ is about 80K. Crystalline alloys have a wide supercooled liquid sad interval 'This temperature interval is generally used to measure the stability of the glass phase when the temperature exceeds the glass transition temperature Tg. The larger the ATx value, the better the thermal stability of the supercooled liquid vessel. , The easier it is to form in the supercooled liquid region, for example, the superplastic forming method of precision molds can be used to make amorphous alloy plates into parts with special shapes.

[實例二]:(VAR加熱熔解製程) 母合金錠熔製同實例一製程,非晶合金板材鑄造:(j ) 離心模具:離心模具上模及下模使用熱傳導性甚佳之無氧 銅製作,上下銅模内設有循環水冷卻管路,每模板材4 片’模穴最大尺寸為50mm*100mm*3mm (2)溶解鑄造:將[Example 2]: (VAR heating and melting process) The melting process of the master alloy ingot is the same as that of Example 1. Casting of amorphous alloy sheet: (j) Centrifugal mold: The upper and lower molds of the centrifugal mold are made of oxygen-free copper with excellent thermal conductivity. There are circulating water cooling pipes in the upper and lower copper molds. The maximum size of 4 mold cavities is 50mm * 100mm * 3mm. (2) Dissolution casting:

Zr55Al1GNi5Cu3。(at%)母合金錠秤重約6〇〇克,置於var爐水 冷銅坩堝内,分別以機械幫浦及擴散幫浦抽真空達5· 〇*1〇 5Torr後’通高純度氬氣將真空度調整為uwpToR,加 熱將合金熔融,待合金完全熔融持續加熱約2· 5分鐘後,Zr55Al1GNi5Cu3. (At%) The master alloy ingot weighs about 600 grams and is placed in a water-cooled copper crucible in a var furnace. It is evacuated with a mechanical pump and a diffusion pump to 5.0 · 1.05 Torr. The vacuum degree is adjusted to uwpToR, and the alloy is melted by heating. After the alloy is completely melted and continuously heated for about 2.5 minutes,

於0.5秒内快速澆鑄κ150〇Γρπι高轉速水冷銅模内 約1〇分 鐘後經凝固冷卻後取出板材。試片x — ray結構繞射分析結 果如第三圖所示,由X-ray繞射圖可知大部份均為非晶質 基^,僅有小部份結晶繞射峰出現。將經11^丫繞射分析後 之試片以微差掃瞄熱分析結果如第四圖所示,Tg、Tx( on set)分別為709·3Κ&799Κ,從此二個溫度求出ΔΤχ約為Quickly cast κ150〇Γρι in a high-speed water-cooled copper mold in 0.5 seconds in about 0.5 seconds. After solidification and cooling, the plate was taken out. The diffraction analysis results of the test piece x-ray structure are shown in the third figure. From the X-ray diffraction pattern, it can be seen that most of them are amorphous, and only a small number of crystalline diffraction peaks appear. The thermal analysis results of the test strip after the 11 ^ diffraction analysis are shown in the fourth figure, and the Tg and Tx (on set) are 709.3K and 799K, respectively. From these two temperatures, the ΔΤχ approx. for

1224985 五、發明說明(10) 89· 7K,以此方法製作之板材,可獲得寬廣之過冷液態區 間,顯示以此法製作板材之過冷液體熱穩定性良好。 以實例二方法製作之3mm厚試片於適當位置取約10mm X 1 Omm正方形試片,將試片沿厚度方向之表層磨掉1· 5 mm 後,以1%氫氟酸腐蝕液將試片腐蝕1秒,於光學顯微鏡下 觀察其金相組織,如第五圖所不’試片為具非晶相基地及 少量1 0 /z m以下之微小結晶相複合結構組織。1224985 V. Description of the invention (10) 89 · 7K. The plate produced by this method can obtain a wide supercooled liquid area, which shows that the supercooled liquid produced by this method has good thermal stability. Take a 3mm thick test piece made in the method of Example 2 and take about 10mm X 1 Omm square test piece at an appropriate position. After grinding the surface layer of the test piece in the thickness direction by 1.5mm, use 1% hydrofluoric acid etching solution to test the test piece. After being etched for 1 second, the metallographic structure was observed under an optical microscope. As shown in the fifth figure, the test piece was a composite structure with a microcrystalline phase base and a small amount of 10 / zm or less.

ZhsAligNigCu3〇 (at% )合金以VAR溶解方式離心鱗造 (1500rpm)板片所得之成品如第六圖所示,成品尺寸為 5 0mm X 100mm X 3mm(厚),所鑄出板片之形狀完整,且表面光 度良好。 [比較例一] (一)非晶 其製程為 後,通高 例_、二 方式加熱 融持續加 内,板材 否為非晶 步鑑定, 基地,但 液於澆铸 鑄出完整 質合金以傳統之重力鑄造製作: 以機械幫浦及擴散幫浦抽真空達5.0*10-3 Torr 純度氬氣將真空度調整為1·7*1〇-1 Torr,取實 使用之 Zr55Al10Ni5Cu3。母合金鑄錠3〇〇克以VAR 將合金於水冷銅掛禍内加熱炼融,待合金完全溶 熱約2· 5分鐘後,於0· 5秒内快速澆鑄於水冷銅模 尺寸為50 mm *100 mm *3 mm。為瞭解所鑄造之板材是 合金,本比較例採用X-ray繞射結構分析來做初 結果如第七圖所示,從繞射圖可知部份為非晶質 存在高比例之結晶相。採用重力铸造方式,金屬 過程無加壓力量,因此對於大平面或薄鑄件不易 形狀來,發展受限。The finished product of the ZhsAligNigCu3〇 (at%) alloy centrifugally scaled (1500rpm) plate by VAR dissolving method is shown in the sixth figure. The finished product size is 50mm X 100mm X 3mm (thick). The shape of the cast plate is complete. , And the surface brightness is good. [Comparative Example 1] (I) Amorphous, its process is as follows, the high-passing example _, two methods of heating and melting continue to add, whether the plate is amorphous step identification, base, but the liquid-casting casts a complete alloy in the traditional way Gravity casting production: Vacuum the mechanical pump and diffusion pump to 5.0 * 10-3 Torr purity argon to adjust the vacuum to 1.7 * 1〇-1 Torr, and use the actual Zr55Al10Ni5Cu3. 300 g of master alloy ingot was heated and smelted in water-cooled copper with VAR. After the alloy was completely dissolved for about 2.5 minutes, it was quickly cast in water-cooled copper molds within 0.5 seconds. The size was 50 mm. * 100 mm * 3 mm. In order to understand that the casted plate is an alloy, this comparative example uses X-ray diffraction structure analysis as the initial result. As shown in the seventh figure, it can be seen from the diffraction pattern that the part is amorphous and there is a high proportion of crystalline phase. With gravity casting, the metal process has no pressurizing force, so it is not easy to shape for large flat or thin castings, and its development is limited.

第15頁 1224985 五、發明說明(11) 综上所述,本發明為一種非晶質合金基地結構材料之 離心鑄造方法,於真空中或保護氣氛下將合金熔融、澆 鑄、凝固,熔融金屬於水冷模具内,藉由強大離心力加壓 下凝固成形,是一種具有量化能力,且可以製作大尺寸、 形狀複雜並具非晶質合金基地結構塊(板)材之成形方法。 離心鑄造法與比較例之重力鑄造法相比較,以離心缚造製 作之板材可獲得更高比例之非晶質相,尤其以水冷铜模配 合離心鑄造,以VAR或ISM之水冷銅坩堝熔融澆鎢,可用以 鑄造如Ti/Zr等高活性合金,以此法製作非晶質合金基地 結構材料乃屬首先創作,且極具產業上利用價值,誠 份符合發明專利申請之要件,又本創作於申請前並未 見於任何刊物及公開使用之情事,故乃依專利法 已 文提出申請。 &定#Page 15 1224985 V. Description of the invention (11) In summary, the present invention is a centrifugal casting method of amorphous alloy base structural material. The alloy is melted, cast, and solidified in a vacuum or in a protective atmosphere. In a water-cooled mold, solidifying and forming under the pressure of a strong centrifugal force is a forming method that has quantification ability and can produce large-sized, complex shapes and amorphous alloy base structural blocks (plates). Compared with the gravity casting method of the comparative example, the centrifugal casting method can obtain a higher proportion of amorphous phase in the plate made by centrifugal casting, especially using a water-cooled copper mold with centrifugal casting, and VAR or ISM water-cooled copper crucibles for molten tungsten casting. It can be used to cast highly active alloys such as Ti / Zr, and this method is used to make amorphous alloy base structure materials. It is the first creation and has great industrial use value. It is in good faith that it meets the requirements of the invention patent application. Before the application, it did not appear in any publications and public use, so the application was made in accordance with the patent law. & 定 #

第16頁 1224985 圖式簡單說明 第一圖:以ISM熔解洗鑄Zr55 A l1()Ni5Cu3()合金離心鍚造 (200rpm)板片試樣的X-ray繞射圖。 第二圖:以181!熔解澆鑄21*55八110?^5(:113()合金離心鑄造 (20 0rpm)板片試樣DSC熱分析圖。 第三圖:以VAR熔解澆鎊Zr55Al1()Ni5Cu3(l合金離心鑄造 (150〇rpm)板片試樣的X-ray繞射圖。 第四圖:以VAR溶解洗鑄Zr55Al10Ni5Cu3()合金離心鑄造 (1500rpm)板片試樣DSC熱分析圖。 第五圖:以VAR熔解澆鑄Zr55Al10Ni5Cu3()合金離心鑄造 (1 50 Or pm)板片金相組織。 第六圖:以¥人1?溶解洗鑄21*55人1101^5〇113()合金離心鑄造 ( 1 500rpm)板片之實體成品圖。 第七圖:以VAR熔解澆鑄Zr55Al1QNi5Cu3Q合金重力鑄造板片試 樣的X-ray繞射圖。Page 16 1224985 Brief description of the diagram The first picture: X-ray diffraction pattern of Zr55 A l1 () Ni5Cu3 () alloy centrifugally fabricated (200rpm) plate sample by ISM melting and washing. The second picture: DSC thermal analysis chart of 21 * 55 eight 110? ^ 5 (: 113 () alloy centrifugal casting (200 rpm) plate casting with 181! Melting. The third picture: Zr55Al1 () casting with VAR melting X-ray diffraction pattern of Ni5Cu3 (1 alloy centrifugally cast (150 rpm) plate sample. Fourth figure: DSC thermal analysis chart of Zr55Al10Ni5Cu3 () alloy centrifugally cast (1500 rpm) plate sample dissolved and washed with VAR. Fifth image: Zr55Al10Ni5Cu3 () alloy centrifugal casting (1 50 Or pm) sheet metallographic structure is cast by VAR. Sixth image: 21 * 55 person 1101 ^ 5〇113 () alloy is dissolved and washed with ¥ person 1? Centrifugal casting (1,500 rpm) sheet of the solid finished product. Figure 7: X-ray diffraction pattern of Zr55Al1QNi5Cu3Q alloy gravity cast sheet sample cast by VAR melting.

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Claims (1)

^24985 _請專利範圍 l一種非晶寶合金基地結構材料之鑄造方法,复 為以離心力將熔融金屬液注入水冷之金屬模^内·’ 於非晶相形成臨界冷卻速率急速凝固成形,其製程包同 括: (1)將合金錠置於坩堝内,於真空或保護氣體中以 加熱或感應加熱方式使合金錠熔融;(2)將熔融金 間澆注於50rpm以上轉速預先通水冷卻之金屬模具屬内噼 持續離心加壓及通水冷卻直至合金固化成形。 2·如申請專利範圍第丨項之鑄造方法,其中金屬模具 咼熱傳導係數銅金屬製作。 木用 3·如申請專利範園第丨項之鑄 口。拄魅;芯1 屬模具與成 抑接觸面至少一面設有水冷流路裝置。 4·如t請專利範圍第1項之鑄造方法,其中非晶質合合其 地結構材料中之非曰哲軟脚 σ、基 竹γ <非日日質基地佔整體艘積比率至少3 〇 %以上^ 24985 _Please patent scope l A casting method of amorphous precious alloy base structural material, which is a method of injecting molten metal liquid into a water-cooled metal mold by centrifugal force. ^ 'Formation of a critical cooling rate in the amorphous phase, rapid solidification forming, and its manufacturing process Including: (1) Placing the alloy ingot in a crucible and melting the alloy ingot by heating or induction heating in a vacuum or a protective gas; (2) Pouring molten gold between 50 rpm and above the metal cooled by water in advance The inner mold of the mold is continuously centrifugally pressurized and cooled with water until the alloy is solidified. 2. The casting method according to item 丨 of the patent application scope, wherein the metal mold is made of copper metal with a thermal conductivity coefficient. Wood use 3. For example, the gate of the patent application No. 丨. Charm; core 1 belongs to the mold and the contact surface of at least one side is provided with a water-cooled flow path device. 4. If the casting method of item 1 of the patent scope is requested, wherein the non-crystalline and soft-feeling σ, the basic bamboo γ < non-Japanese-Japanese quality base in the amorphous structure material is at least 3 〇% or more
TW91135228A 2002-12-05 2002-12-05 A method of casting for materials comprising an amorphous alloy matrix structure TWI224985B (en)

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US11504763B2 (en) 2020-11-26 2022-11-22 Industrial Technology Research Institute Aluminum alloy wheel and method for manufacturing the same

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TWI621485B (en) * 2016-11-07 2018-04-21 財團法人金屬工業研究發展中心 Metal casting method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11504763B2 (en) 2020-11-26 2022-11-22 Industrial Technology Research Institute Aluminum alloy wheel and method for manufacturing the same

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