五 本發明係關於一種铭基複合材料之製造方法 工邮佳等優點，因此在航太 金屬基複合材料，以铭基複合材料 =:金製程…㈣程」兩大類，而= 造法」、「浸透法」及「複合鍀造法」 二種。其中，「粉末冶金製程」、「㈣鱗造法」及「产 2法」之生產成本較高且產品认寸及形狀受到較大的限 故難以進行大規模量產。以「複合禱造法」生產铭矣 複合材料雖可以避免上述之缺點，但其製程上添加補強^ 陶纽子時因渔潤性的問題，不易與銘湯均勾混合，且本 易除氣，故必須在眞空下操作”致使生產成本提高。 、本發明王要目的乃在於提供一種新的鋁基複合材料製 作万法，利用動態氧化製程，採劇烈捷持或再配合吹氣方 式使大量鋁湯和氧接觸，生成細微的氧化鋁，並隨即混入 鋁湯内。爲了避免新生成之氧化鋁與鋁湯間潤濕性不佳而 上浮形成『濕渣』，製程中並加入Ca、Mg等活性元素， 經濟部中央標準局員工消費合作社印製 一方面促進氧化物生成，另一方面亦可加強鋁湯與氧化鋁 間之潤濕性，使新生成的氧化鋁均勻分佈於鋁湯内。此創 新之動態氧化合成鋁基複合材料製程不僅效率高，製程溫 度亦在傳統鋁湯處理溫度範圍内（800 °C以下），爲一操作簡 易’適合量產，並且成本低、效率高之新製程。 本發明之另一目的在於提供一種鋁基複合材料之製造 本紙張尺度適用中國國家榡準（CNS ) Μ規格（2似別公楚） 2 2 B7 •、發明説明 以本= = =;?广基複合材㈣造 = 料。 含氧氣氛下攪拌，分金屬於 袈 化物均勻散佈於未被氧Q ^^成細小< 金屬氧 内之氣體。以及⑷㉔全奸。⑷除去金屬炫湯 冷卻。 b除金屬¥湯表面之浮渔，洗入鑄模内 1 丁 —銘或其合方法’其步驟包括舊 加 於 Λ — ^· '4- U Λ V 至屬熔湯。（b)在金屬熔湯内 4性物質’使其溶人金屬 拌’使部分金屬及高活性==小 經濟部中央標準局員工消費合作社印製 -銘vrr基複合材料之製造方法，其步驟包括：⑷將 其合金炫融’形成一金屬溶湯;⑻在氧化氣氛下一 A、:屬炫湯，—面投入一高活性物質於金屬溶湯表 使问活性質氧化形成氧化物並與金屬熔湯均勻混合； ⑷除去金屬料内 < 氣體；以及⑷自除金屬料表面之浮 渣，澆入鑄模内冷卻。 本紙張尺度適财國 A7 A7 經濟部中央標準局員工消費合作社印製 五、發明説明（3 ) "— 爲讓本發明之上述目的、特徵、和優點能更明顯易懂 ，下又特舉較佳實施例並配合所附的圖式作詳細説明如 下： 圖示之簡單説明： 第丨圖係經由掃描式電子顯微鏡（SEM)觀察萃取自 A1-〗0 /。Ca系統製得金屬基複合材料中之Ca〇顆粒型態； 第2圖係對第〗圖之Ca〇顆粒做Ca的線掃描X光分 散能量光譜圖；5. The present invention relates to a manufacturing method of Ming-based composite materials, such as good post and postal service. Therefore, in aerospace metal-based composite materials, Ming-based composite materials =: gold manufacturing process ... (iv) "the two major categories, and = manufacturing method", There are two types of "dipping method" and "compounding method". Among them, the "powder metallurgical process", "(iv) scale manufacturing method" and "production 2 method" have high production costs and large restrictions on product size and shape, which makes it difficult to mass-produce mass production. The production of Ming composite materials with the "composite prayer method" can avoid the above-mentioned shortcomings, but the process of adding reinforcement ^ Tao Niuzi is difficult to mix with the Ming soup due to the problem of fish wettability, and it is easy to degas Therefore, it is necessary to operate under the "air" to increase the production cost. The main purpose of the present invention is to provide a new method of making aluminum-based composite materials, using dynamic oxidation process, adopting vigorous support or combining with blowing method to make a lot of The aluminum soup comes into contact with oxygen to produce fine aluminum oxide, which is then mixed into the aluminum soup. In order to avoid the poor wettability between the newly generated aluminum oxide and the aluminum soup, it will float up and form a "wet slag". Ca and Mg are added in the process And other active elements, printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs, on the one hand, it promotes the formation of oxides, on the other hand, it also strengthens the wettability between the aluminum soup and alumina, so that the newly generated alumina is evenly distributed in the aluminum soup This innovative dynamic oxidation synthesis aluminum matrix composite material process not only has high efficiency, but also the process temperature is within the range of traditional aluminum soup processing temperature (below 800 ° C), which is suitable for easy operation. Production, low cost and high efficiency. Another object of the present invention is to provide an aluminum-based composite material manufacturing. This paper standard is applicable to China National Standard (CNS) Μ specifications (2 similar to other public Chu) 2 2 B7 • The description of the invention is based on this = = = ;? Broad-based composite material (made) = material. Stir under an oxygen-containing atmosphere, and divide the metal in the carcass uniformly dispersed in the un-oxygen Q ^^ into a small < metal oxygen gas. And ⑷㉔All rape. ⑷ Remove the metal dazzle soup and cool it. B In addition to the metal ¥ float on the surface of the soup, wash it into the mold 1 Ding-Ming or its combination method 'The steps include the old addition to Λ — ^ ·' 4- U Λ V is a molten soup. (B) In the molten metal soup, the four sex substances 'make it soluble in metal and mix it' to make some metals and high activity == printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs-Ming vrr based composite material The manufacturing method, the steps include: ⑷ melt the alloy to form a metal soup; ⑻ in the oxidizing atmosphere A ,: belongs to the dazzling soup, put a highly active substance on the surface of the metal soup to oxidize the active substance The oxides are mixed evenly with the metal melt; ⑷Remove In the material <gas; and ⑷ scum from the surface of the metal removal material, poured into the mold for cooling. The paper size is suitable for printing by the A7 A7 Ministry of Economic Affairs Central Standards Bureau employee consumer cooperatives. Fifth, invention description (3) "-In order to make the above-mentioned objects, features, and advantages of the present invention more obvious and understandable, the preferred embodiment and the accompanying drawings are described in detail as follows: A brief description of the drawings: Observe the type of Ca〇 particles in the metal matrix composites extracted from A1-〗 0 / .Ca system by scanning electron microscope (SEM); Figure 2 is a line scan of Ca of the particles in Figure〗 X-ray dispersion energy spectrum;
ύ··" J 第3圖係經由掃描式電子顯I微鏡（SEM)與Mg的線掃描 X光刀散旎量光譜分析萃取自A110% Mg系統製得金屬基 複合材料中之Mg〇顆粒； 第4圖係經由掃描式電子顯微鏡（SEM)觀察苹取自ύ ·· " J Figure 3 is the Mg〇 particles in the metal matrix composite material extracted from the A110% Mg system through the scanning electron microscope I (SEM) and the line scan X-ray knife dispersion spectrum analysis of Mg ; Figure 4 is observed via scanning electron microscope (SEM).
Al-10% Mg系統製得金屬基複合材料中之MgAi2〇4顆粒型 態；. 第：> 圖係對第4圖之MgAl204顆粒做Mg及A1的線掃 描X光分散能量光譜圖； 第6圖係依據本發明製程以八丨_〗〇% Ca系統製得金屬 基複合材料之X光繞射圖形，顯示Ca〇的存在； 第7圖係依據本發明製程以Ai_10%Mg系統製得金屬 基複合材料之X光繞射圖形，顯示Mg〇及MgAl2〇4的存 在； 第8圖係依據本發明製程以A1_! 〇% &及Ai 2〇〇/〇 Q 系統製得金屬基複合材料之耐磨耗性質測試，其酎磨耗性 (請先聞讀背面之注意事項再填寫本頁) 裝. 、π 表紙張尺度it财@ ®家蘇（CNS ) 經濟部中央樣準局員工消費合作社印製 A7 B7 五、發明説明（4 ) 質較母材者有大幅提昇之現象； 第9圖係依據本發明製程以αμ〇〇/0及Α1-20% Mg系统 製得金屬基複合材料之耐磨耗性質測試，其耐磨耗性質較 母材者有大幅提昇之現象； 第10圖係依據本發明製程以AM〇%Ca合金採動態氧 化法製得MMC之金相照片。 實施例 以粉末冶金法，擠壓鑄造法及浸透法製造金屬基複合 材料，因造價較高，且產品之形狀受較大限制，故工業化 量產之成本昂貴。複合鑄造法可避免上述方法之缺點，但 亦面臨濕潤性的問題無法克服。 習知以複合鑄造法生產鋁基複合材料之方法爲將鋁熔 融，並於熔融之金屬鋁内投入預先製備之陶瓷粒子或纖維 作爲補強材。然而製備好之陶瓷粒子或纖維表面會吸附氣 體，陶瓷粒子與熔融金屬鋁間之間因表面作用力不足，致 陶瓷粒子播法均勻分佈於鋁金屬相，是爲濕潤性問題。由 於濕鸦性問題，在喊粒子混人料之前，必須以複雜的 活化程序處理改善其與铭湯之親和力，且其粒徑通常必須 大於1 Ομπι，否則不易混入。 本發明之鋁基複合材料之製造方法將於底下以實施例 來詳細説明。 將鋁合金加熱至液相線以上溫度，此溫度依鋁合金液 相，泉不同而異，主要係指液相線以上之溫度至8⑻。C 間。 «I mt^ nn ·ϋ ^ ^^^^1 tm m \ Ji 0¾ 、-口 (請先閱·讀背面之注意事項再填寫本頁) 7Al-10% Mg system to obtain MgAi204 particle types in metal matrix composites ;. Figure: > Figure 4 is the line scan X-ray dispersion energy spectrum of MgAl204 particles in Figure 4 for Mg and A1; Fig. 6 is the X-ray diffraction pattern of the metal matrix composite material prepared by the eight-% 〇% Ca system according to the process of the present invention, showing the presence of Ca〇; Figure 7 is prepared by the Ai_10% Mg system according to the process of the present invention X-ray diffraction pattern of metal matrix composite material, showing the presence of Mg〇 and MgAl2〇4; Figure 8 is based on the process of the present invention with A1_! 〇% & and Ai 2〇〇 / 〇Q system made of metal matrix composite Abrasion resistance test of the material, its abrasion resistance (please read the notes on the back before filling in this page), install., Π sheet paper standard it financial @ ® 家 苏 （CNS） Ministry of Economic Affairs Central Bureau of Samples and Staff Consumption Printed by cooperatives A7 B7 5. Description of the invention (4) The quality is significantly improved compared with the base material; Figure 9 is based on the process of the present invention using αμ〇〇 / 0 and A1-20% Mg system made of metal matrix composites The abrasion resistance property test, the abrasion resistance property is greatly improved compared with the parent material; Figure 10 According to the process of the present invention in AM〇% Ca alloy oxidation method were adopted dynamic photomicrograph of MMC. Examples The production of metal matrix composite materials by powder metallurgy, squeeze casting and penetration methods is expensive due to the high cost and the shape of the product is greatly restricted. The compound casting method can avoid the shortcomings of the above methods, but also face the problem of wettability that cannot be overcome. The conventional method for producing aluminum-based composite materials by composite casting is to melt aluminum, and put previously prepared ceramic particles or fibers into the molten metal aluminum as a reinforcing material. However, the surface of the prepared ceramic particles or fibers will adsorb gas. The lack of surface force between the ceramic particles and the molten metal aluminum causes the ceramic particles to be evenly distributed in the aluminum metal phase, which is a problem of wettability. Because of the wet crow's sex problem, before calling the particles to mix with the material, complex activation procedures must be used to improve their affinity with Mingtang, and the particle size must usually be greater than 1 Ομπι, otherwise it is not easy to mix. The manufacturing method of the aluminum-based composite material of the present invention will be described in detail below with examples. The aluminum alloy is heated to a temperature above the liquidus. This temperature varies according to the aluminum alloy liquid phase and the spring. It mainly refers to the temperature above the liquidus to 8⑻. C room. «I mt ^ nn · ϋ ^ ^^^^ 1 tm m \ Ji 0¾ 、-口 (Please read first, read the notes on the back and fill in this page) 7
經濟部中央標率局員工潸費合作社印製 五、發明説明（5 ) 若以鋁之氧化物作爲補強之陶瓷粒子則毋須添加高活 性物質，將銘湯置於特定的氧化氣氛下挽掉，使銘湯内部 分鋁金屬氧化形成細微之三氧化二鋁顆粒。細微之三氧化 二鋁顆粒均勻地散佈於鋁湯内，不會有濕潤性的問題，且 三氧化二铭陶免顆粒之粒徑约可小至〇〇1叫〜卿^。此 製程操作溫度範圍在66〇至8〇〇c>c之間均可，其中以7扣 至770°C之溫度範圍最爲恰當。 、特定的含氧氣氛可爲空氣、氧氣、二氧化碳、水蒸氣 或上述各種氣體之組合。以上之氣體以直接通入铭湯内爲 較佳。 爲除去攪拌過程中攪入氣體所產生之氣泡，將援摔混 合均勻後之銘湯昇溫至稍高之溫度，使铭湯之黏度下降， 藉攪拌葉片以5至200轉/分鐘之速度緩慢援拌，使銘湯中 細小氣泡合併成較大氣泡並浮絲湯上層。接著以石墨管 通入氮氣或氬氣等惰性氣體，去聽湯中殘留之氣體。 最後趋除铭湯上層之浮渣，再倒入禱模内，冷卻製成 鋁基複合材料成品。 表成 若要在三氧化二铭外增加其他的補強陶免粒子，則可 於溶融之铭湯中添加高活性物質，此高活性物質可爲 Mg ’ T!，Nl，Cr，^及&之元素或其化合物，其中 乂 Ca Mg ’ Τι及Μη <活性較高，形成氧化物之速率較 快，故爲較佳之選擇，而又以Ca及峋爲最佳。 添加高活性物質後除三氧化二铭外另亦形成高活性物 質·^化物作爲補強之陶究粒子，如Mg〇，⑽， (請先閱.讀背面之注意事項再填寫本頁) 裝 訂 8 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（6)Printed by the staff cost cooperative of the Central Standardization Bureau of the Ministry of Economic Affairs 5. Description of the invention (5) If aluminum oxide is used as the reinforced ceramic particles, there is no need to add highly active substances, and the Mingtang is removed under a specific oxidizing atmosphere. Oxidize part of the aluminum metal in Mingtang to form fine aluminum oxide particles. The fine aluminum oxide particles are evenly distributed in the aluminum soup, there will be no wettability problems, and the particle size of the second oxide trioxide particles can be as small as 〇001 called ~ Qing ^. The operating temperature range of this process is between 66 ° and 800 ° C> c, and the temperature range of 7 ° to 770 ° C is the most appropriate. The specific oxygen-containing atmosphere may be air, oxygen, carbon dioxide, water vapor, or a combination of the above gases. It is better to directly pass the above gas into Ming Tang. In order to remove the bubbles generated by the stirring gas during the stirring process, the Ming Tang after mixing and mixing is heated to a slightly higher temperature, so that the viscosity of the Ming Tang decreases, and the stirring blade is slowly added at a speed of 5 to 200 rpm. Mix so that the small bubbles in the Ming Tang merge into larger bubbles and float the upper layer of the silk soup. Next, inert gas such as nitrogen or argon is passed through the graphite tube to listen to the remaining gas in the soup. Finally, the dross on the upper layer of Mingtang is removed, and then poured into the prayer mold, cooled to make the finished aluminum-based composite material. If it is necessary to add other reinforcing ceramic particles to the second oxide of trioxide, you can add a highly active substance to the melting soup of Ming. This highly active substance can be Mg 'T !, Nl, Cr, ^ and & Of the elements or their compounds, among them Ca Mg 'Τι and Mn < activity is higher, the rate of formation of oxides is faster, so it is the better choice, and Ca and glutamate are the best. After adding highly active substances, in addition to dioxin trioxide, highly active substances and chemical compounds are also formed as reinforcing ceramic particles, such as Mg〇, ⑽, (please read first. Read the precautions on the back and then fill out this page) Binding 8 A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (6)
NiO，Cr02，Mn02，Si02 等。 添加高活性物質之方法有兩種，一爲直接加入高活性 物質於鋁湯内，使其完全固溶，而固溶過程中合金元素並 未產生氧化反應。另一爲將合金元素置於鋁湯表面，使其 一面熔入鋁湯，一面藉高溫與空氣中之氧產生反應（氧化， 甚至燃燒），一面經由後續之攪拌動作均勻地攪入鋁湯之 中。此方法因高活性元素之氧化物新生成即攪入鋁湯中， 未於表面吸附氣體，故較不易產生濕潤性的問題。 高活性物質之例’其後續步驟與未添加高活性物質之 步驟相同，依序爲攪拌氧化（採合金元素置於鋁湯表面一面 氧化，一面攪入方法者，則此步驟之主要作用係在於使其 均勻淚合），除氣、舀去浮渣以及洗入轉模冷卻。 依據本發明製程’將Ca或Mg溶入鋁湯形成Al-Ca、 Al-Mg合金，再進行氧化反應，則所產生之ca〇、Mg〇 及MgAUO4顆粒均相當微細，約在〇 〇1_1〇μιη，但其生成 迷率較緩慢。若將Ca或Mg置於鋁湯上方，使·其一面溶入 铭湯，-面藉高溫#空氣中之氧產生氧化反應，並經由後 續之挽拌動作均勾地搜人銘湯之中。除氣後製得試片觀 察’發現系統中氧化物顆粒分俾均勻，包括㈤、峋〇、 MgAl2〇4等’其中顆粒較大者約可達μ，。此實施例所得 試片之氧化物顆粒經萃|後以掃描式電子顯冑鏡（sem)、 線掃描X光分散能量光譜(EDAX Line Scan)及χ光繞射儀 (XRD)分析，列轉第1圖至第7 a，其材料磨耗特性 顯示於第8圖及第9圖，第1〇圖係依據本發明製程以A1_ (請先閱讀背面之注意事項再填寫本頁) i裝. 訂 9NiO, Cr02, Mn02, Si02, etc. There are two methods for adding highly active materials. One is to directly add the highly active materials into the aluminum soup to make it completely solid solution, and the alloy elements do not produce oxidation reaction during the solid solution process. The other is to place the alloy elements on the surface of the aluminum soup, so that it melts into the aluminum soup on one side, reacts with the oxygen in the air by high temperature (oxidation, or even burns), and evenly stirs the aluminum soup through the subsequent stirring action in. In this method, oxides of highly active elements are newly formed, that is, they are stirred into the aluminum soup, and no gas is adsorbed on the surface, so the problem of wettability is less likely to occur. Examples of highly active substances' The subsequent steps are the same as the steps without adding highly active substances, followed by stirring oxidation (when alloying elements are placed on the surface of the aluminum soup and oxidized on one side, and the method is stirred on the other, the main role of this step is to Make it even tears), degassing, scooping off scum and washing into the rotating mold to cool. According to the process of the present invention, Ca or Mg is dissolved in an aluminum soup to form an Al-Ca, Al-Mg alloy, and then the oxidation reaction is performed, and the generated Ca〇, Mg〇 and MgAUO4 particles are quite fine, about 〇〇1_1〇 μιη, but its generation rate is relatively slow. If Ca or Mg is placed on top of the aluminum soup so that one side is dissolved in the Ming Tang, the surface will generate an oxidation reaction by the oxygen in the air at high temperature #, and will be searched into the Ming Tang through the subsequent mixing action. Observation of the test piece made after degassing found that the oxide particles in the system were evenly distributed, including ㈤, 峋 〇, MgAl2〇4, etc. where the larger particles can reach about μ. The oxide particles of the test piece obtained in this example were extracted and analyzed by scanning electron microscope (sem), line scanning X-ray dispersive energy spectroscopy (EDAX Line Scan) and χ-ray diffractometer (XRD). Figures 1 to 7a, the material wear characteristics are shown in Figures 8 and 9, Figure 10 is based on the process of the present invention to A1_ (please read the precautions on the back before filling this page) i installed. Order 9
A7 B7 五、發明説明（7 ) . 10%Ca合金採動態氧化法製得MMC之金相照片，顯示光 學顯微鏡可分辨之氧化物顆粒平均粒徑約5μπι，體積百分 比約12%，氧化物顆粒形狀大部分爲球狀或片狀，分佈尚 稱均勻。 雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明，任何熟習此項技藝者，在不脱離本發明之精 神和範圍内，當可作些許之更動與潤飾，因此本發明之保 護範圍當視後附之申請專利範圍所界定者爲準。 (請先閱讀背面之注意事項再填寫本頁) 丨裝 ,1Τ 經濟部中央標準局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公釐）A7 B7 5. Description of the invention (7). The metallographic photo of MMC prepared by dynamic oxidation of 10% Ca alloy shows that the average particle size of the oxide particles that can be resolved by the optical microscope is about 5μπι, the volume percentage is about 12%, and the shape of the oxide particles Most of them are spherical or flaky, and the distribution is still uniform. Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Anyone who is familiar with this skill can make some modifications and retouching without departing from the spirit and scope of the present invention. The scope of protection of the present invention shall be subject to the scope defined in the attached patent application. (Please read the precautions on the back and then fill out this page) 丨 Installed, printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This paper standard is applicable to China National Standard (CNS) Α4 specification (210X 297 mm)