1246997 玖、發明說明： 【發明所屬之技術領域】 本發明是有關於一種氮化鋁之製造方法，尤指一種可形 成高品質，低成本的氮化鋁製造方法，達到具有生產快速， 易於1產’產品轉化率高，省能源，無公害污染等優點，並 可使其生成之氮化鋁產物疏鬆易磨，可易於進行後續之粉碎 研磨，進而可降低因研磨造成之不純物含量，達到增大生產 率’並降低生產成本之功效。 【先前技術】 氮化铭由於具有優越的熱傳導性（理論值：薦/mK)， 良好的電絕緣性，低熱膨脹率（4 3 ppm/K，财晶相近）， 良好的抗熱震性與良好的抗侵蝕性，近年來，已成為工業上 2重要的材料。它在許多高科技的4上極具應用潛力， 辨中包括有電子基板、積體電路封農材料、電子元件散教 製作=傳導複合材料、盛裝與處理熔融鹽或金屬之容器等 目二”製造氣化銘的方法，如氧化轉碳素還原氮 ^(日本仏卿）與銘粉直接氮化法（如美國船， ==:rck:’:，源，生產速率慢，製程 、成本而，以成夕年來，氮化銘之價格居高不下。 許多銘的價格居高不下，其市場規模-直_ 業界專豕預測之飛躍成長，而僅以小幅度地穩定成長 1246997 :、乂而成乎所有業界人士皆$忍為’氮化紹的價格若能大幅降 低（如降低30% )’則氮化銘的需求與使用必定大幅增加， 市場規模將會如預期的飛躍式成長。 由於目前工業上生產氮化銘的方法成本高，其降價的幅 度極為有限，欲大幅降低氮化銘的價格，唯一的途徑便是開 發高品質、低成本的製程方法； 其中目前合成氮化銘粉體之各方法與缺點為： (1) 氣相反應法：反應式為AlCh(g)+ 4NH3(g) AlN(s) + 3 NH4Cl(g)，操作溫度於900K至1500K，所需反應時間 要5小時以上，其產物形態包含結晶形與非晶形氮化鋁粉 體，一般產物之轉化率約為80%，生產成本高且產率小， 不適合工業生產。 (2) 有機金屬前驅物法：反應式為 R3AKD+ NHsCl) RsAlNHsCl)1246997 玖, the invention description: [Technical field of the invention] The present invention relates to a method for manufacturing aluminum nitride, in particular to a method for manufacturing high quality, low cost aluminum nitride, which has a fast production and is easy to be The product's high conversion rate, energy saving, pollution-free pollution, etc., and the aluminum nitride product produced by it can be loose and easy to be ground, and can be easily subjected to subsequent grinding and grinding, thereby reducing the content of impurities caused by grinding and increasing High productivity' and reduced production costs. [Prior Art] Niobium has excellent thermal conductivity (theoretical value: recommended / mK), good electrical insulation, low thermal expansion rate (4 3 ppm / K, similar to the crystal), good thermal shock resistance and Good corrosion resistance has become an important material in the industry in recent years. It has great potential in many high-tech 4s, including electronic substrates, integrated circuit sealing materials, electronic components for teaching and learning = conductive composite materials, containers for handling and processing molten salts or metals. The method of manufacturing gasification, such as oxidized carbon reduction nitrogen (Japan Yuqing) and Ming powder direct nitriding method (such as American ship, ==:rck: ':, source, slow production rate, process, cost In the coming year, the price of Ni Niming is high. Many Ming's prices are high, and its market size - straight _ industry-specific forecast of leap growth, but only a small stable growth of 1246997: In the eyes of all the industry, if the price of Nitrosamine can be greatly reduced (such as a 30% reduction), then the demand and use of Niobium must increase significantly, and the market scale will grow as expected. At present, the method of producing nitriding in the industry is costly, and the price reduction is extremely limited. The only way to greatly reduce the price of nitriding is to develop a high-quality, low-cost process method; The methods and disadvantages are as follows: (1) Gas phase reaction method: the reaction formula is AlCh(g)+ 4NH3(g) AlN(s) + 3 NH4Cl(g), the operating temperature is from 900K to 1500K, and the reaction time is required. For more than 5 hours, the product form includes crystalline and amorphous aluminum nitride powder, and the conversion rate of the general product is about 80%. The production cost is high and the yield is small, which is not suitable for industrial production. (2) Organic metal precursor method: The reaction formula is R3AKD+ NHsCl) RsAlNHsCl)
RaAINHsCI) R2A1NH2(1) +RH(g) R2A1NH2(1) -> RA1NH(1) +RH(g) RA1NH(1) AlN(s) +RH(g) 操作溫度於40OK至100OK，所需反應時間要i〇至240分 鐘，其產物主要為AIN，甲烷氣體裂解之碳沈積，必須再將 產物置於空氣中加熱除碳，可能導致氧含量增加。此外，此 法亦有成本高、產率低的問題，而不適合工業生產。 (3)氧化銘粉碳素還原氮化法：反應式為Al2〇3(s)+ N2(g) + 3C(s)-> 2AlN(s) +3C0(g)，操作溫度於 ΐ5〇〇κ至 2200K， · 所需反應時間5小時以上。 6 1246997 (4)金屬銘直接氮化法：反應式為2ai(s)+ N2(g)— 2AlN(s) ’操作溫度於ΐοοοκ至1500K，所需反應時間需5小時 以 1'1 U 〇 其中上述（3) # (4)之方法是目前工業上之主要生產 方法，金屬鋁直接氮化法有鋁熔聚的問題，很難以一次反應 獲得高純度氮化銘，因而常驗數次研磨再反應的程序，^ 必，在，溫下長時問操作，能量消耗極大；另外氧化在呂粉碳 素還原鼠化法，雖然可得_高純度的氮化紹，但是產物常 含l:&必須在含氧氣氛中將碳氧化去除，因此可能造 成含氧量提高’此外，此方法亦須在高溫長時 消耗亦大。 (5)燃燒合成法：此法與其他方法比較而言，是一種 新的陶瓷材料的合成方法， 田 燒反應來合成陶竞產品。它：行傳播燃 士 ΛΓ缺就以目前最新近開發之氮化1呂燃燒合成法而 :^點是（一）轉化率不夠高（如美國專利第5649278 號’最高僅達 99% )，（ _) ^ 649278 化率合下降、， C 一）不易1產，即較大量生產時，轉 羊曰下降（如杲國專利第564927 或燒結狀（如暴顾蜜y、一）產物為¥聚 研磨不易，L 9278號及㈣6,術，號）， 研愿不易亦即研磨時耗時 成雜質含量之描4 h 口磨球之耗損而造 貝各里之增加’目前所有現有之燃燒合成法皆有此問 7 1246997 【發明内容】 因此，本發明之主要目的仫 成本的氮魅製造方法，達到可形成高品質’低 產品轉化率高，生產成本低;能=快速’易於量產’ ’把源，無公害污染等優點。 物_目的係在於’並可使其生成之氮化紹產 物&鬆易磨，可易於進行後續之粉碎研磨，進而可降低因 研磨造成^純物含量，達到增大生錢率，並降低生產 成本之功效。 /為達上述之目的’本發明係一種氮化銘之製造方法， 係將原料崎先進行表面處理，㈣粉之表面生成一陶究 層，之後再將表面生成有㈣層之銘粉置於—氮氣氣氛 中，進行氮化反應而合成氮化紹；如此，可形成高品質， 低成本的氮化鋁製造方法，達到具有生產快速，易於量 產，產品轉化率高，省能源，無公害污染等優點，並可使 其生成之氮化鋁產物疏鬆易磨，可易於進行後續之粉碎研 磨，進而可降低因研磨造成之不純物含量，達到增大生產 速率，並降低生產成本之功效。 【實施方式】 士請參閱『第1〜4圖』所示，係本發明之燃燒合成反應 衣置示思圖、係本發明第1貫施例表面改質後之紹粉外觀型 悲不意圖、係本發明第丨實施例燃燒產物外觀型態示意圖、 係本發明第1實施例產物之XRD分析圖示意圖。如圖所示··本 發明係一種氮化鋁之製造方法，其係將原料鋁粉先進行表面 8 1246997 f理’而该原料紹粉可為顆粒狀、片狀 …呂含量需高於25wt%，係選自於—:条二？該原料 ，、-含銘合金銘粉或工業製造業：：：純銘 ^心二二粉面置::離…加熱或置於 層，又該原料_表面處理或氫氧化物 中，並加，、c—一方二^ (以紹粉重量為基準)進行加熱，使銘粉表二二2 = 另該原料銘粉表面處理之方法為將原料銘粉置:一:： 熱，高溫爐内可為空氣氣氛、氮氣氣氛或二 鼠耽之㈣’其加熱溫度與時間以避免_化，並能於财 二。、 g Cm且5亥加熱溫度為高於鋁熔點660°C至 C，該陶竞層為可為一氧化物、氣氧化物、氮化㈣氮至 人且Λ表η面處理後之原料銘粉’其氧化物或氣氧化 物層之^ 1為G.卜5 wt%，氮化物層其氮含量為〇卜5 石 wt%’氮、氧化物層其氮、氧總含量為〇1_5wt%，而以該表 面處理後之原料銘粉進行合成反應，該表面處理後之原料叙 粉可先與稀釋劑均混’該稀釋劑為高㈣且不參與化學反應 之物質，係為選自於A1N粉，Si3N4粉，TiN粉，卵粉，加粉二 wc粉，sic粉，ai2〇3粉’ Zr〇2粉，Ti〇2粉，抓粉，碳粉盘77鑽 粉及以前述化合物中以任何方式混合形成之該稀釋劑等 其中之一所形成；且該稀釋劑之用量佔該反應物整體重量之 0-80wt%，以0-30 wt%重量百分比為最佳，該表面處理後之 1246997 •以下刀解或氣化之化合物，係選自於一齒化錢鹽類、 合驗基之化合物、—含齒素之化合物及其中任二者、與 者等”中之-化合物所形成；該添加劑之添加量以佔反 應:粉體，量之(MO wt%為宜’另該表面處理後之原料銘粉 可先與㈣團均混，其中該㈣團係指使用小片料，做成 ?緻密、不拘形狀、大小為0·1-5·之團塊，而以0.2—2_為 取仏:^用！佔該反應物之Q —3G —，之後再將原料粉體置 於一氮氣氣氛中，加熱弓丨燃進行氮化反應而合成氮化紹，該 =成反應之氮氣操作壓力介於〇·卜3〇 atm，最佳之操作壓力 介於L 5-10 atm，且該所合成之氮化鋁產物為高度多孔且極 為疏’極容易研磨’如添加A1N粉該合成產物為氮化铭， 如添加其他粉體，其合成產物為含氮化鋁之複合材料。亦可 將原料粉體置入高溫爐、電熱爐或微波爐内，持續通入氮 氣’加熱反應物至氣化反應完全，且可進—步將氮化反應所 產生之產物在其冷卻後予以研磨至呈一粉體，該氮化反應係 採取下列步驟： (a) 將經由表面處理後之原料銘粉置入一盛裝容器中，· (b) 將步驟（a)所獲得之裝盛著反應物粉體的容器置於 一氮氣氣氛中，而該步驟中係將盛裝原料鋁粉的容器置 於耐局壓反應器所形成之一密室中，並抽空該密閉室 内空氣再回充氮氣於該密閉室内； (c)加熱位於該被填裝的容器内的反應物粉體至其自行 燃燒，該反應後產物轉化率可高於9〇%。 10 1246997 而當本發明於實施之使用時，首先將原料鋁粉進行表面 改貝處理’步驟為：取片狀铭粉（2mmximmx25um，氧含量〇· 1 wt%) 500 g置於1〇〇〇毫升之玻璃燒杯中，加入蒸餾水2〇〇毫 升後，在燒杯頂部覆蓋一多孔鋁箔，再將此燒杯置於加熱盤 上，控制加熱盤溫度維持2〇(rc，加熱至燒杯内水分完全蒸 發。待銘粉冷卻後，取出測其含氧量為1 wt %。將此表面改 貝後之銘粉置於一石墨製多孔掛禍容器中，其中銘粉與掛禍 内壁間並置放一層5mm厚之氮化鋁粉體，此氮化鋁粉直徑介 於〇·1-1mm之間，再於此鋁粉頂部置放5mm厚之起始劑，此起 始劑係由未經表面處理過之鋁粉均混〇· 5wt %之氯化銨粉體 所製成。如第1圖所示，將此坩堝容器丄〇置於一真空耐壓 反應器2内，而該真空耐壓反應器2外部係具有一壓力表 1、氮氣入口 4、溫度量測用熱電偶6、真空抽氣口 7、真 二4 8排氣口 9及鼠氣入口 1 1，調整高度使起始劑頂面 距離加熱鎢絲5之距離為4mm，然後關閉真空耐壓反應器 2，其中加熱用電極3與溫度量測用熱電偶6係在保持氣密 狀態下貫穿真空耐壓反應器2之壁並通向外側，使能自外部 進行必要的操作。 其次，利用真空抽氣口 7將此真空耐壓反應器2予以抽 八工至0· 1 t〇rr，然後經由氮氣入口 4回充氮氣至約， 如此抽真空一充氮氣反覆操作數次，以去除真空耐壓反應器 2内原存在之空氣，然後再將氮氣充入真空耐壓反應器2内 至、、々3atm，之後，打開電源，控制加熱功率為1，同時 、匕鼠氣入口 1 1，使氮氣由谷器底部通入，流經原料粉體 1246997 而自起始劑頂面流出，加熱約30秒即引燃反應，再經3〇秒即 關閉電源，反應進行中持續由容器底端通入氮氣，流量為5〇 Ι/min，同時使真空耐壓反應器2内之壓力維持在3 atm，引 燃至反應結束約1 〇分鐘； 第2圖係本發明第1實施例表面改質後之鋁粉外觀型 態，第3圖係本發明第1實施例燃燒產物外觀型態，其為一 片狀結構，尺寸與鋁粉相似。取產物〇 〇5克，以Lec〇公司之 TC-300氮氧分析儀分析得氧含量為〇 lwt %，燃燒產物經行 生式研磨機研磨後（轉速d〇〇rpm;球徑：5mm;時間：4〇 min)， 其平均粒徑為2_，取30 g倒入盛裝酸液（15wt% HC1 ; 2〇〇 笔升）之錐形瓶中，溶解殘餘之鋁，同時以排水集氣法收集 產生之氫氣，結果，無可量測到之氫氣產生，吾人將所有可 能之實驗誤差列入考慮，計算得轉化率應為99· 95%以上。 第4圖係本發明第1實施例產物之XRD分析示意圖，圖中顯示 皆為A—1N特性峰，無特性峰，此產物之顏色為黃色。 綜上所述，本發明係為一製程簡單，省能源，生產快速， 成本低、，產品性質優良之氮化鋁合成技術，同時能達到下列 現有方法無法達到之優點·· (1)與目則工業上之生產方法（即鋁粉直接氮化法及氧化 銘粉石反素還原氮化法）比較，本方法具有製程簡單，省能源， 生產快速，成本低的優點。 ί 2 )與現有燃燒合成法比較本發明方法使用之原料！呂粉， 係:，特殊處理’使得原料銘粉在進行氮化反應過程中不會 因南溫而炫融聚集，因此反應物可維持多孔狀態，氮氣容^ 1246997 補充’而達到高轉化率。 (3 )本發明方法之轉化率可達99. 9 :成法中之最高者(其他燃燒合成法最高綱：各種燃繞 可以I::法之產物極為疏鬆(手捏即碎)易於研磨， 1斤而之旎源與時間，亦即可增大增率，降 成本，同時降低因研磨造成之不純物污染。 -王產 (5)本發明方法易於大量生產之操作。 你杜清參閱『第5圖』所示，係本發明第2—7實施例之操作 :…、"果。如圖所不··其係為本發明第2-7實施例之操作 2與結果’實施例2_7其操作方式主要與實施例1同，不同 处：、、、改^於惺溫恒濕機中之加熱時間與溫度，這些改變 ^呂粉表面氧化之程度，其㈣改質後之氧含量、產物氧: 里、產物顏色與轉化率之結果如第5圖。 睛參閱『第6 ®』所示，係本發明第Η丨實施例之操作 條件與結果。如@所示··其係為本發明第8—u實施例之操作 條件與結果，實_8—⑽操作方式主要與實齡㈣，不 问處為改變鋁粉表面處理方式，該實施例8—n其表面處理方 弋為取3鋁粉體500克置入1〇〇〇1111之燒杯中，加入不同體積 之去離子水後，在燒杯頂部覆蓋一多孔鋁箔，再將此燒杯置 =加熱盤上，控制加熱盤溫度維持2〇(rc，加熱至燒杯内水 刀％全瘵發。其去離子水添加量、鋁粉改質後之氧含量、產 物氧含量、產物顏色與轉化率之結果如第6圖； 至於本發明之第12實施例係以Ca〇粉末2· 5克倒入150克 去離子水中，完全分散後，將此溶液倒入1〇〇〇毫升燒杯中， 1246997 之後再加500克原料鋁粉，再進行如實施例8之加熱表面改質 處理，其他操作條件與實施例丨相同；表面改質後之鋁粉含 氧量為1.3wt%，產物含氧量為〇.4wt%，外觀為片狀結構，顏 色為黃色，轉化率為99. 91%，XRD分析皆為氮化鋁特性峰。 睛參閱『第7圖』所示，係本發明第13_16實施例之操 作條件與結果。如圖所示：其係為本發明第13_丨6實施例之 操:條件與結果，實施例13_16其操作方式與條件為取不同 含量之CaO粉末倒入150克去離子水中，完全分散後，將此溶 液倒入1000毫升燒杯中，之後再加5〇〇克原料鋁粉，再進行 如實施例8之加熱表面改質處理，其他操作條件與實施例ι 同。 凊參閱『第8圖』所示，係本發明第17—2〇實施例之操 =條件與結果。如圖所示：其係為本發明第17—別實施例之 操作條件與結果，實施例17—2〇其操作方式與條件主要與實 施例13相同，不同處為表面處理時，水中添加不同之添加 劑，其產物氧含量、產物顏色與轉化率之結果如第8圖。 咕參閱『第9圖』所示，係本發明第21_24實施例之操 ^條件與結果。如圖、所示··其係為本發明第2卜24實施例之 操作條件與結果，貫施例21—24其操作方式與條件主要與實 鉍例1相同’不同處為鋁粉表面處理的方式。實施例21為將 鋁粕置於回溫爐内，在空氣氣氛中，以溫度6〇〇。匸加熱丨〇小 時’實施例22則為紹粉置於高溫爐内，在氮氣氣氛中，以溫 度600°C加熱1G小時，實施助與24則為將實施例21熱處理 後之銘粉再分別與2 wt%之Ca0與γ2〇3粉體均混，後續操作方 14 1246997 式與條件與實施例1同，其產物氧含量、產物顏色與轉化率 之結果如第9圖。 晴參閱『第1 〇圖』所示，係本發明第25—28實施例之 操作條件與結果。如圖所示：其係為本發明第25—28之實施 例γ為取用實施例1、2' 17與18合成之產物，使用氧化銘研 钵壓碎，再以手磨至—18〇 mesh，之後取此粉體3〇〇克，使用 研磨機（attritor)進行濕式研磨，其中使用之磨球為氧化 鍅磨球，直徑5mm，重1〇〇〇克，研磨液體為丙酮4〇〇毫升，轉 速50〇rpm，其研磨時間與粉體平均粒徑如第丄〇圖所示。 凊參閱『第1 1圖』所示，係本發明第29—34實施例之 操作條件與結果。如圖所示··其係為本發明第29—34實施例 j操作條件與結果，實施例29—34其操作方式與條件主要與 貫把例2 7相同’不同處為將實施例2 —7表面處理後之紹粉分 別置於控制氣氛高溫爐中進行氮化反應，#中溫度控制為 1200 C，加熱時間為10 hr，氮氣流率為工l/min。反應後 產物外觀仍維持片狀結構，此產物氧含量、顏色與轉化率之 結果如第1 1圖。 請參閱『第1 2圖』所示，係本發明第35_36實施例之 操^條件與結果。如圖所示：其係為本發明第35_36實施例 之才呆作條件與結果，實施例35_36其操作方式與條件主要斑 貫施例31相同，不同處為實施例35之加熱溫度為聽1加 熱時間為lGhr ’而實施例36加熱溫度為135代、加熱5 ，氣，率皆為2 l/min。產物外觀仍維持片狀結構，其產物 氧含量、產物顏色與轉化率之結果如第i 2圖。 15 1246997 請參閱『第1 3圖』所示，係本發明第37_38實施例之 操=條件與結果。如圖所示：其係為本發明第37_38實施例 之操作條件與結果，實施例37-38其操作方式與條件主要與 實施例4相同，不同處為實施例37為將實施例4表面處理後^ 鋁粉取3g，再置於控制氣氛微波加熱爐中進行氮化反應，其 中加熱功率為200 W、加熱1 hr，氮氣流率為！ 1/min‘f實施 例38其加熱功率為3〇〇 w、加熱〇 5匕，氮氣流率為〇 5 Ι/min。產物外觀仍維持片狀結構，產物氧含量、產物顏色 與轉化率之結果如第1 3圖。 至於本叙明之第3 9貫施例其操作方式與條件主要與實 轭例1相同，不同處為實施例39為將實施例丨表面處理後之鋁 粉置入一多孔鋁盤内，將此鋁盤置於一石墨製之多孔盤上， ，將此被盛裝之鋁盤及其底下之多孔盤置於實施例丨之反應 裔=，後續之操作步驟與實施例丨同。合成反應之產物外觀 型悲，為一片狀結構’其尺寸與原料鋁粉相似。取產物〇〇5 。克，以LeC0公司之TC_3〇〇氮氧分析儀分析得氧含量為〇15紂 % ’燃燒產物經行星式研磨機研磨後（轉速：4〇〇rpm;球徑： mm寸間· 2〇 min) ’其平均粒徑為5um，取30 g倒入盛裝 酸=(15wt% HC1 ; 2GG毫升）之錐形瓶中’溶解殘餘之紹， 同古時以排水斤集氣法收集產生之氫氣，由此收集之氫氣體積為 7毫升推异得轉化率為99. 92%，產物經分析顯示皆為 特性峰，無鋁特性峰，此產物之顏色為黃色。 〇明參閱『第1 4圖』所示，係本發明第40-47實施例之 #作條件與結果。如圖所示：其係為本發明㈣實施例 16 1246997 件與結果’實施例4G—47其操作方式與條件主要盥 後:二稀=處為了施勝47為將實施例1 團均、、曰彳1 = 粉、添加劑—氯化崎與銘箱 :=二_:，_製備方式為，先準 長刈cm見10 cm，厚度〇. 05 cm。取一外俨5 :二長度20 cm之圓桶狀物體以作為鋁製容器的模子，再； 剪好的銘箱包覆於該圓桶狀物體之側面 口之銘製容器、。 ㈣開 之乂將此鋁製谷器置於一石墨製之内凹狀多孔盤上，後續 21與實施例1同，其中氮化1呂粉粒度分佈為 拉占ιιΓ -銘/白團係使用條狀銘箱，長度40mm，厚度〇. 〇2随， 物：f成非緻密、不拘形狀，大小為〇.卜2随之團塊。產 外硯仍維持片狀結構，產物氧含量、產物顏色與轉 結果如第1 4圖。 “閱第1 5圖』所示’係本發明第48實施例之操作 :件與結果。如圖所示：其係為本發明第48實施例之操作條 與結果’實施例48其操作方式與條件主要與實施例！相 ^不同處為實施顯為使驗製容器且在已盛裝反應物之 奋益内再置入3根多孔铭管，多孔紹管管璧厚請5賴，直徑 咖，孔fe〇. 05-1 mm，孔面積50%。產物氧含量、產物顏色 與轉化率之結果如第1 5圖。 σ明參閱『第1 6圖』所示，係本發明第49-51實施例之 操=條件與結果。如圖所不··其係為本發明第Μ—Η實施例 之操作條件與結果，實施例49—51其操作方式與條件主要與 17 1246997 實施例1相同，不同處為原料鋁粉型態不同。實施例49係採 用長條狀紹絲，該鋁絲為工業廢鋁，長度1〇 —1〇〇mm，厚度 〇· 03mm ’ i度l-2mm ’實施例50-51係採用顆粒狀铭粉，實施 例50之鋁粉，其平均粒度為1〇//111，實施例51之鋁粉，其平均 粒度為30//m。表面處理後之鋁粉氧含量、產物氧含量、反應 物堆積密度、產物顏色與轉化率之結果如第1 6圖。 睛芩閱『第1 7圖』所示，係本發明第52—57實施例之 操作條件與結果。如圖所示··其係為本發明第52—57實施例 之操作條件與結果，實施例52,53,54,55,56,57其操作方式 與條件主要與實施例3,8，13，18,21，22相同，不同處為實施 例52-57係在反應物粉體與坩堝容器之底面及器壁間置放一 層氮化鋁粉；再於反應物粉體與氮化鋁粉之間置放一層或數 層厚度為0.0254mm鋁箔，置放此鋁箔除了可進一步提高轉化 率外還可使產物與原置放之氮化銘粉易於分離。其它操作方 式皆與第1實施例相同，產物氧含量、產物顏色與轉化率之 結果如第1 7圖。 至於本發明之第5 8實施例其操作方式與條件主要盘實 施例53相同，不同處為實施例58所採用之容器為銘製容器， 產物經XRD分析顯示皆為⑽特性峰，無|g特性峰，此產物之 顏色為黃色，轉化率大於99.95%。 惟以上所述者，僅為本發明之較佳實施例而已，當不能 以此㈣本發明實施之故，凡依本發㈣請專利範圍 及發明㈣㈣容所作之簡單料效變化 本發明專利涵蓋之範_。 '㈣屬 18 1246997 【圖式簡單說明】 第2圖 示意圖 第3圖 第4圖 第5圖 第6圖 第7圖 第8圖 第9圖 ★圖係、本&明之燃燒合成反應裝置示意圖。 係本發明第1實施例表面改質後之㈣外觀型蔑 > ^么月第1實施例燃燒產物外觀型態示意圖。 係本么明第1實施例產物之XRD分析示意圖。 係本發明第2—7實施例之操作條件與結果。 係本發明第8-11實施例之操作條件與結果。 係本發明第13-16實施例之操作條件與結果。 係本毛明第12 〇實施例之操作條件與結果。 二一係本發明第21-24實施例之操作條件與結果。 …貝心保忭條件與結果 係本發明第29-34實施例之操作條件與結果 係本發明第35-36實施例之操作條件與結澤 係本發明第37—38實施例之操作條件與結澤 係本發明第40—47實施例之操作條件與結澤 係本發明第48實施例之操作條件與結果。 係本發明第49-51實施例之操作條件與結澤 係本發明第52-57實施例之操作條件盥έ士連 元件標號對照】 '、、°弟 壓力表1 真空耐壓反應器2RaAINHsCI) R2A1NH2(1) +RH(g) R2A1NH2(1) -> RA1NH(1) +RH(g) RA1NH(1) AlN(s) +RH(g) Operating temperature from 40OK to 100OK, desired reaction The time is up to 240 minutes, the product is mainly AIN, carbon deposition of methane gas cracking, and the product must be placed in the air to heat and remove carbon, which may lead to an increase in oxygen content. In addition, this method has the problems of high cost and low yield, and is not suitable for industrial production. (3) Oxidation Ming powder carbon reduction nitridation method: the reaction formula is Al2〇3(s)+N2(g) + 3C(s)-> 2AlN(s) +3C0(g), the operating temperature is ΐ5〇 〇κ to 2200K, · The required reaction time is more than 5 hours. 6 1246997 (4) Metal direct nitriding method: the reaction formula is 2ai(s) + N2(g) - 2AlN(s) 'The operating temperature is ΐοοοκ to 1500K, and the required reaction time is 5 hours to 1'1 U 〇 The method of (3) # (4) above is the main production method in the industry at present, and the direct nitriding method of metal aluminum has the problem of aluminum fusion, and it is difficult to obtain high-purity nitriding by one reaction, and thus the grinding is performed several times. The process of re-reaction, ^ must, in the long-term operation under temperature, energy consumption is extremely large; in addition, the oxidation of the carbon powder in the Lu powder reduction ratification method, although the _ high-purity nitriding, but the product often contains l: & must be oxidized and removed in an oxygen-containing atmosphere, which may result in an increase in oxygen content. In addition, this method must also be consumed at high temperatures for a long period of time. (5) Combustion synthesis method: Compared with other methods, this method is a new synthesis method of ceramic materials, and the field reaction is used to synthesize Taojing products. It: the spread of the burning of the lack of fuel is based on the latest development of the recent nitriding 1 Lu combustion synthesis method: ^ point is (a) the conversion rate is not high enough (such as US Patent No. 5649278 'up to only 99%), ( _) ^ 649278 The rate of decline is lower, C 1) It is not easy to produce, that is, when the production is larger, the turn of the sheep is reduced (such as the patent of 564927 or the sintered form (such as the honey y, one). It is not easy to grind, L 9278 and (4) 6, surgery, No.), the research is not easy, that is, the time-consuming impurity content of the grinding is 4 h, the damage of the ball grinding ball is increased, and the existing combustion synthesis method is present. All of the above questions 7 1246997 [Summary] Therefore, the main purpose of the present invention is to produce a high-quality 'low product conversion rate, low production cost; can be = fast 'easy mass production' Take the source, pollution-free pollution and other advantages. The object is aimed at 'and can be used to produce the nitrided product & loose and easy to grind, which can be easily subjected to subsequent pulverization and grinding, thereby reducing the pure content caused by grinding, increasing the production rate and reducing production. The cost of the effect. For the purpose of the above-mentioned invention, the invention is a method for manufacturing a nitriding mold, which firstly performs surface treatment on the raw material, (4) a ceramic layer is formed on the surface of the powder, and then the (four) layer of the powder is formed on the surface. - Nitrogen atmosphere, nitriding reaction to synthesize nitrogen; so, can form a high-quality, low-cost aluminum nitride manufacturing method, to achieve rapid production, easy mass production, high product conversion rate, energy saving, pollution-free The advantages of pollution, etc., and the aluminum nitride product produced by the same can be loose and easy to be ground, and the subsequent pulverization and grinding can be easily performed, thereby reducing the impurity content caused by the grinding, increasing the production rate, and reducing the production cost. [Embodiment] Please refer to the "1st to 4th drawings", which is a schematic diagram of the combustion synthesis reaction coating of the present invention, which is the appearance of the powder after the surface modification of the first embodiment of the present invention. The schematic diagram of the appearance of the combustion product of the third embodiment of the present invention is a schematic diagram of the XRD analysis of the product of the first embodiment of the present invention. As shown in the figure, the present invention is a method for producing aluminum nitride, which is characterized in that the raw material aluminum powder is first subjected to a surface of 8 1246997, and the raw material of the raw material is granulated or flake-shaped. %, is selected from -: two? The raw material, - containing Ming alloy Ming powder or industrial manufacturing::: pure Ming ^ heart two two powder surface:: heated or placed in the layer, and the raw material _ surface treatment or hydroxide, and added , c-one two ^ (based on the weight of Shao powder) to heat, so that the Ming powder table 22 2 = Another method of surface treatment of the raw material powder is to set the raw material powder: one:: hot, high temperature furnace It can be air atmosphere, nitrogen atmosphere or two squirrels (four) 'the heating temperature and time to avoid _, and can be used in the second. , g Cm and 5 Hai heating temperature is higher than the melting point of aluminum 660 ° C to C, the pottery layer can be mono-oxide, gas oxide, nitride (tetra) nitrogen to human and the surface of the surface after the η surface treatment The powder 'its oxide or gas oxide layer ^ 1 is G. 卜 5 wt%, the nitride layer has a nitrogen content of 〇 5 5 stone wt% 'nitrogen, oxide layer, its total nitrogen and oxygen content is 〇1_5wt% And performing the synthesis reaction by using the surface-treated raw material powder, and the surface-treated raw material powder may be first mixed with the diluent. The diluent is high (four) and does not participate in the chemical reaction, and is selected from the group consisting of A1N powder, Si3N4 powder, TiN powder, egg powder, powdered two wc powder, sic powder, ai2〇3 powder 'Zr〇2 powder, Ti〇2 powder, powder, toner powder 77 drill powder and the above compounds Forming one of the diluents and the like formed by mixing in any manner; and the diluent is used in an amount of from 0 to 80% by weight based on the total weight of the reactant, preferably from 0 to 30% by weight, after the surface treatment 1246997 • The following compounded or gasified compound is selected from the group consisting of a toothed salt, a compound of the test group, a compound containing dentate and In the middle of the two, the compound, etc. - the compound is formed; the additive is added in the amount of the reaction: the powder, the amount (MO wt% is appropriate), the surface of the raw material after the surface treatment can be first and (4) The group is mixed, and the (four) group refers to the use of small pieces of material to make a dense, unconstrained shape, the size of 0·1-5·, and 0.2-2_ as the 仏: ^ use! Q - 3G -, then put the raw material powder in a nitrogen atmosphere, heating the bow to burn and carry out the nitriding reaction to synthesize the nitrogen, the reaction pressure of the nitrogen is 〇·卜3〇atm The optimal operating pressure is between L 5-10 atm, and the synthesized aluminum nitride product is highly porous and extremely sparsely 'very easy to grind'. If the A1N powder is added, the synthesized product is nitrided, such as adding other powder. The composite product is a composite material containing aluminum nitride. The raw material powder can also be placed in a high temperature furnace, an electric furnace or a microwave oven, and the nitrogen gas is continuously introduced to heat the reactants until the gasification reaction is complete, and the reaction can be carried out. The product produced by the nitridation reaction is ground to a powder after it is cooled, and the nitridation reaction system Take the following steps: (a) Place the surface-treated raw material powder into a container, (b) Place the container containing the reactant powder obtained in step (a) in a nitrogen atmosphere. In this step, the container containing the raw aluminum powder is placed in a chamber formed by the pressure-resistant reactor, and the air in the sealed chamber is evacuated and then backfilled with nitrogen in the sealed chamber; (c) heating is located in the filled chamber The reactant powder in the packed container is self-combusted, and the conversion rate of the product after the reaction can be higher than 9〇%. 10 1246997 And when the present invention is used in practice, the raw material aluminum powder is first subjected to surface modification treatment. The procedure is as follows: take a sheet of powder (2mmximmx25um, oxygen content 〇·1 wt%) 500 g in a 1 liter glass beaker, add 2 liters of distilled water, and cover a porous aluminum foil on the top of the beaker. The beaker was placed on a hot plate and the temperature of the heated pan was maintained at 2 Torr (rc) until the water in the beaker completely evaporated. After the powder is cooled, the oxygen content is taken to be 1 wt%. The surface powder after the surface modification is placed in a graphite porous container, in which a 5mm thick aluminum nitride powder is placed between the inner wall of the powder and the inner wall of the accident. The diameter of the aluminum nitride powder is 〇· Between 1-1mm, a 5mm thick initiator is placed on top of the aluminum powder. The initiator is made of aluminum powder which has not been surface treated and mixed with 5wt% ammonium chloride powder. . As shown in Fig. 1, the crucible vessel is placed in a vacuum pressure resistant reactor 2, and the vacuum pressure reactor 2 has a pressure gauge 1, a nitrogen inlet 4, and a thermocouple for temperature measurement. 6. The vacuum suction port 7, the true two 4 8 exhaust port 9 and the rat gas inlet 1 1 are adjusted so that the distance from the top surface of the initiator to the heated tungsten wire 5 is 4 mm, and then the vacuum withstand voltage reactor 2 is closed, wherein The heating electrode 3 and the temperature measuring thermocouple 6 are passed through the wall of the vacuum pressure-resistant reactor 2 while being kept in an airtight state, and are opened to the outside, so that necessary operations can be performed from the outside. Next, the vacuum pressure-resistant reactor 2 is evacuated to 0·1 t〇rr by using the vacuum suction port 7, and then nitrogen gas is recharged to about 30 via the nitrogen inlet 4, so that the vacuum is applied to the nitrogen gas for repeated operation several times. The original air in the vacuum pressure-resistant reactor 2 is removed, and then nitrogen gas is charged into the vacuum pressure-resistant reactor 2 to 、3 atm, and then the power is turned on to control the heating power to 1, and the squirrel gas inlet 1 1 The nitrogen gas is introduced from the bottom of the trough, flows through the raw material powder 1246997 and flows out from the top surface of the initiator, and is heated for about 30 seconds to ignite the reaction, and then the power is turned off after 3 seconds, and the reaction continues in the bottom of the container. Nitrogen was introduced into the end at a flow rate of 5 Torr/min while maintaining the pressure in the vacuum pressure-resistant reactor 2 at 3 atm and igniting until the end of the reaction for about 1 minute; FIG. 2 is the surface of the first embodiment of the present invention. The appearance of the modified aluminum powder is shown in Fig. 3. The appearance of the combustion product of the first embodiment of the present invention is a sheet-like structure having a size similar to that of aluminum powder. 5 g of the product was taken, and the oxygen content was analyzed by Lec〇 TC-300 nitrous analyzer to obtain 〇lwt%, and the combustion product was ground by a row mill (rotation speed d〇〇rpm; ball diameter: 5 mm; Time: 4〇min), the average particle size is 2_, take 30g into the conical flask containing the acid solution (15wt% HC1; 2〇〇 penliter), dissolve the residual aluminum, and use the drainage gas collection method The hydrogen produced is collected. As a result, there is no detectable hydrogen production. We consider all possible experimental errors, and the calculated conversion rate should be above 99.95%. Fig. 4 is a schematic view showing the XRD analysis of the product of the first embodiment of the present invention, which shows that both are A-1N characteristic peaks, no characteristic peaks, and the color of the product is yellow. In summary, the present invention is a simple aluminum nitride process, which is simple in process, energy-saving, fast in production, low in cost, and excellent in product properties, and can achieve the advantages that cannot be achieved by the following existing methods. (1) Compared with the industrial production method (ie, the direct nitriding method of aluminum powder and the oxidized melamine anti-reduction nitriding method), the method has the advantages of simple process, energy saving, rapid production and low cost. ί 2 ) Compare the raw materials used in the method of the present invention with the existing combustion synthesis method! Lu powder, system: special treatment, so that the raw material powder does not condense and aggregate due to the south temperature during the nitriding reaction, so the reactants can maintain a porous state, and the nitrogen gas capacity is 1246997 to achieve high conversion. (3) The conversion rate of the method of the present invention is up to 99. 9: the highest in the method of formation (the highest class of other combustion synthesis methods: various types of ignition can be I:: the product of the method is extremely loose (hand pinch), easy to grind, 1 jin and its source and time can also increase the rate of increase, reduce the cost, and reduce the impurities caused by grinding. - Wang (5) The method of the invention is easy to mass-produce operation. 5 shows the operation of the second to seventh embodiments of the present invention: ..., "fruit. As shown in Fig. 2, it is the operation 2 and the result of the second to seventh embodiments of the present invention. The operation mode is mainly the same as that of the first embodiment. The difference is: , , , and the heating time and temperature in the temperature and humidity machine, which change the degree of surface oxidation of the powder, and (4) the oxygen content after the modification, The results of product oxygen: product color and conversion rate are shown in Fig. 5. The eye is shown in "6th", which is the operating conditions and results of the third embodiment of the present invention. The operating conditions and results of the eighth embodiment of the present invention, the actual _8-(10) operation mode is mainly related to the actual age (four), regardless of The surface treatment method of the aluminum powder is as follows: in the embodiment 8-n, the surface treatment method is to take 500 g of aluminum powder into a beaker of 1〇〇〇1111, and after adding different volumes of deionized water, cover the top of the beaker. A porous aluminum foil, and then set the beaker to the heating plate, and control the temperature of the heating plate to maintain 2 〇 (rc, heated to the water knife in the beaker.) The amount of deionized water added, the oxygen after the modification of the aluminum powder The results of the content, the product oxygen content, the product color and the conversion rate are as shown in Fig. 6; as for the twelfth embodiment of the present invention, the Ca 〇 powder is 2.5 liters and poured into 150 g of deionized water, and after completely dispersing, the solution is prepared. Pour into a 1 ml beaker, add 1 246,997 and then add 500 g of raw aluminum powder, and then carry out the heating surface modification as in Example 8. The other operating conditions are the same as in the example; the surface modified aluminum powder contains The oxygen content is 1.3 wt%, the oxygen content of the product is 〇. 4 wt%, the appearance is a sheet-like structure, the color is yellow, and the conversion rate is 99.91%, and the XRD analysis is a characteristic peak of aluminum nitride. The figure shows the operating conditions and results of the 13th to 16th embodiments of the present invention. Shown: it is the operation of the 13th to 6th embodiments of the present invention: conditions and results, and the operation mode and condition of the embodiment 13_16 is that different amounts of CaO powder are poured into 150 g of deionized water, after being completely dispersed, The solution was poured into a 1000 ml beaker, and then 5 g of the raw material aluminum powder was added, followed by heating surface modification as in Example 8. The other operating conditions were the same as in the example. 凊 Refer to "Fig. 8" The invention is the operation condition and result of the embodiment 17-2 of the present invention. As shown in the figure: it is the operating condition and result of the 17th-other embodiment of the present invention, and the operation mode of the embodiment 17-2 The conditions were mainly the same as in Example 13, except that when the surface treatment was carried out, different additives were added to the water, and the results of the product oxygen content, product color and conversion rate are shown in Fig. 8.咕 Refer to Fig. 9 for the operation conditions and results of the 21st to 24th embodiments of the present invention. As shown in the figure, it is the operating conditions and results of the second embodiment of the present invention. The operation modes and conditions of the examples 21-24 are mainly the same as those of the actual example 1. The difference is the surface treatment of aluminum powder. The way. In Example 21, aluminum crucible was placed in a reheating furnace at a temperature of 6 Torr in an air atmosphere.匸 heating 丨〇 hours 'Example 22 is the Shao powder placed in a high temperature furnace, heated in a nitrogen atmosphere at a temperature of 600 ° C for 1G hours, the implementation of 24 and then the heat treatment of the Example 21 heat treatment It was mixed with 2 wt% of Ca0 and γ2〇3 powders, and the subsequent operation formula 14 1246997 was the same as that of Example 1, and the results of the product oxygen content, product color and conversion rate are shown in Fig. 9. Clear, as shown in the "Fig. 1", is the operating conditions and results of the 25th to 28th embodiments of the present invention. As shown in the figure: it is the embodiment of the 25th-28th invention of the present invention. γ is a product synthesized by using the examples 1, 2' 17 and 18, crushed by using oxidized mortar, and then hand-ground to -18〇. Mesh, after taking this powder 3 g, using a grinder (attritor) for wet grinding, wherein the grinding ball used is a cerium oxide ball, diameter 5 mm, weighs 1 gram, and the grinding liquid is acetone 4 〇 〇 ml, rotating at 50 rpm, the grinding time and the average particle size of the powder are shown in the figure.凊 Refer to the "Fig. 1 1" for the operating conditions and results of the embodiment 29-34 of the present invention. As shown in the figure, it is the operation condition and result of the embodiment j of the invention 29-34, and the operation mode and condition of the embodiment 29-34 are mainly the same as the case of the case 27. The difference is that the embodiment 2 is 7 The surface-treated powder is placed in a controlled atmosphere high temperature furnace for nitriding reaction. The temperature in # is 1200 C, the heating time is 10 hr, and the nitrogen flow rate is l/min. The appearance of the product after the reaction still maintained a sheet-like structure, and the results of the oxygen content, color and conversion of the product were as shown in Fig. 11. Please refer to the "Fig. 1 2" for the operation conditions and results of the 35th to 36th embodiments of the present invention. As shown in the figure: it is the condition and result of the embodiment of the 35th to 36th invention, and the operation mode and condition of the embodiment 35_36 are the same as the main example 31, and the difference is that the heating temperature of the embodiment 35 is 1 The heating time was lGhr' and the heating temperature of Example 36 was 135 generations, heating was 5, and the gas rate was 2 l/min. The appearance of the product still maintained a sheet-like structure, and the results of the product oxygen content, product color and conversion were as shown in Fig. 2. 15 1246997 Please refer to the "Fig. 1 3" for the operation and conditions and results of the 37th to 38th embodiments of the present invention. As shown in the figure: it is the operating conditions and results of the 37th to 38th embodiments of the present invention, and the operating modes and conditions of the embodiments 37-38 are mainly the same as those of the embodiment 4, except that the embodiment 37 is the surface treatment of the embodiment 4. After the aluminum powder is taken 3g, and then placed in a controlled atmosphere microwave heating furnace for nitriding reaction, wherein the heating power is 200 W, heating for 1 hr, nitrogen flow rate! 1/min'f Example 38 had a heating power of 3 〇〇 w, heating 〇 5 匕, and a nitrogen flow rate of 〇 5 Ι/min. The appearance of the product still maintained a sheet-like structure, and the results of product oxygen content, product color and conversion were as shown in Fig. 13. As for the 39th embodiment of the present description, the operation mode and conditions are mainly the same as those of the actual yoke example 1. The difference is that the embodiment 39 is to place the aluminum powder after surface treatment of the embodiment into a porous aluminum pan. The aluminum pan was placed on a porous disk made of graphite, and the aluminum pan and the porous disk underneath it were placed in the reaction of the embodiment. The subsequent operation steps were the same as in the examples. The product of the synthesis reaction is sorrowful in appearance and is in the form of a sheet-like structure whose size is similar to that of the raw material aluminum powder. Take the product 〇〇5.克, analyzed by LeC0 company's TC_3 〇〇 NOx analyzer, the oxygen content is 〇15纣% 'The combustion products are ground by the planetary grinder (rotation speed: 4〇〇 rpm; ball diameter: mm inch · 2〇min ) 'The average particle size is 5um, take 30g into the conical flask containing the acid = (15wt% HC1; 2GGml), 'dissolve the residue, and collect the hydrogen produced by the drainage method. The volume of hydrogen thus collected was 7 ml, and the conversion was 99.92%. The product was analyzed to show that it was a characteristic peak, and there was no peak of aluminum characteristic, and the color of the product was yellow. BRIEF DESCRIPTION OF THE DRAWINGS Referring to the "Fig. 14", the conditions and results of the 40th to 47th embodiments of the present invention are shown. As shown in the figure: it is the invention (4) embodiment 16 1246997 pieces and the result 'embodiment 4G-47 its operation mode and conditions are mainly after: two dilute = at the point of the wins 47 for the embodiment 1 group,曰彳1 = powder, additive - chlorinated sulphate and the name box: = two _:, _ preparation method is: first standard length 刈 cm see 10 cm, thickness 〇. 05 cm. Take a raft 5: a 20 cm long drum shape as a mold for the aluminum container, and a cut-out box to cover the side of the drum-shaped object. (4) After opening the aluminum granulator on a concave porous disk made of graphite, the subsequent 21 is the same as in the first embodiment, wherein the particle size distribution of the nitriding powder is la ιιΓ - Ming / white group Strip-shaped box, length 40mm, thickness 〇. 〇 2 with, object: f into non-dense, unconstrained shape, size is 〇. Bu 2 followed by a mass. The outer sputum still maintains a sheet-like structure, and the oxygen content of the product, the color of the product, and the result of the transformation are as shown in Fig. 14. The operation of the 48th embodiment of the present invention is shown in the following: FIG. 5 is an operation bar and a result of the 48th embodiment of the present invention. And the conditions are mainly different from the embodiment! The difference is that the implementation of the container is made and the three porous tubes are placed in the excitability of the contained reactants. The porous tube is thick and thin. , hole fe〇. 05-1 mm, pore area 50%. The results of product oxygen content, product color and conversion rate are shown in Figure 15. σ Ming see "Figure 16", which is the 49th of the present invention. The operation of the 51 embodiment is the condition and the result. As shown in the figure, it is the operating condition and result of the embodiment of the present invention, and the operation mode and condition of the embodiment 49-51 are mainly related to the embodiment 1 17246997. The same, different places are different types of raw aluminum powder. Example 49 is a long strip of used wire, the aluminum wire is industrial aluminum, length 1〇-1〇〇mm, thickness 〇·03mm 'i degree l-2mm 'Examples 50-51 are granulated powder, the aluminum powder of Example 50, having an average particle size of 1 Å//111, the aluminum powder of Example 51, The average particle size is 30 / / m. The results of aluminum powder oxygen content, product oxygen content, reactant bulk density, product color and conversion rate after surface treatment are shown in Figure 16. The eye is shown in Figure 17. The operating conditions and results of the examples 52-57 of the present invention are as shown in the drawings, which are the operating conditions and results of the examples 52-57 of the present invention, and examples 52, 53, 54, 55, 56 The operation mode and conditions of the 57 are mainly the same as those of the examples 3, 8, 13, 18, 21, 22, and the difference is that the examples 52-57 are placed between the bottom surface of the reactant powder and the crucible container and the wall. Aluminum nitride powder; one or more layers of 0.0254 mm aluminum foil are placed between the reactant powder and the aluminum nitride powder, and the aluminum foil can be placed in addition to further improving the conversion rate. The nitriding powder is easy to separate. The other operation modes are the same as in the first embodiment, and the results of the product oxygen content, product color and conversion rate are as shown in Fig. 17. As for the fifth embodiment of the present invention, the operation mode and conditions are mainly The disk embodiment 53 is the same, and the container used in the embodiment 58 is an inlaid container. XRD analysis showed that all of them were (10) characteristic peaks, no |g characteristic peaks, the color of this product was yellow, and the conversion rate was greater than 99.95%. However, the above is only the preferred embodiment of the present invention, when it is not possible (4) The reason for the implementation of the present invention is that the patent scope and invention (4) (4) of the present invention are subject to the simple material effect change. The invention covers the scope of the invention. [(4) is a genus 18 1246997 [simple description of the diagram] 3, Fig. 4, Fig. 5, Fig. 6, Fig. 7, Fig. 8 and Fig. 9 Fig. ★ Schematic diagram of the combustion synthesis reaction device of the system, the present & According to the first embodiment of the present invention, after the surface modification, (IV) Appearance type 蔑 > ^May month The first embodiment of the combustion product appearance pattern. A schematic diagram of XRD analysis of the product of the first embodiment is shown. The operating conditions and results of the second to seventh embodiments of the present invention. The operating conditions and results of the eighth to eleventh embodiments of the present invention. The operating conditions and results of the 13-16th embodiment of the present invention. The operating conditions and results of the 12th embodiment of the present invention. The operating conditions and results of the 21st-24th embodiment of the present invention. The conditions and results of the present invention are the operating conditions and results of the twenty-sixth to thirty-fourth embodiments of the present invention. The operating conditions and the embossing of the invention are in the thirty-38th embodiment of the present invention. The operating conditions and the results of the embodiment of the 40th to 47th embodiments of the present invention are the operating conditions and results of the 48th embodiment of the present invention. Operating Conditions and Knots of Embodiments 49-51 of the Invention The operating conditions of the 52-57th embodiment of the present invention are as follows: ',, ° ° Pressure gauge 1 Vacuum withstand pressure reactor 2
第1 〇 ®係、本發明第25-28實施例之操作條件與結果 第1 1圖 係本發明给〇n CM # A ^丨A 苐1 2圖 第1 3圖 第1 4圖 第1 5圖 第1 6圖 第1 7圖 1246997 氮氣入口 4 加熱鎢絲5 溫度量測用熱電偶6 真空抽氣口 7 真空計8 排氨口 9 坩堝容器10 氮氣入口 1 1The first 〇® system, the operating conditions and results of the 25th to 28th embodiments of the present invention, the first embodiment of the present invention is given to 〇n CM # A ^丨A 苐1 2 Figure 1 3 Figure 1 4 Figure 1 5 Figure 1 6 Figure 1 7 Figure 1246997 Nitrogen inlet 4 Heating tungsten wire 5 Thermocouple for temperature measurement 6 Vacuum suction port 7 Vacuum gauge 8 Ammonia port 9 坩埚 Container 10 Nitrogen inlet 1 1