九 發明說明： 【發明所屬之技術領域】 程，其係在陶 先預成形為一特定 •本發明係在提供一種超塑性陶瓷之新製 曼卷體間置入可形成玻璃相之化合物， %狀坧體，再經第一次熱處理讓陶f v 並成Am 、嗛闹无叔體粒界形成玻璃相 塑·Η I 你坂喝相軟化的溫度下 過〖生加工，進一步定型，然後再以第二士古 又 ^且成轉化成為陶瓷基材料之微結構組織。在、 4::鐵一樣先製作成特定形狀儲存，使用時:塑性加 马所需之形狀。 灯！丨王刀口 【先前技術】 下，l超塑性。啊物仙⑼是指在應力的作用 大的的：_。一般金屬材枓大都具有很 的雜抑里，可塑性加工製成各種 趨二前機械材料的應用有從金屬材料擴展 = 特性，極具潛力，但是陶㈣料脆而㈣優異 的缺點，使其在機械材上的應較限。"…加工 近年來發現陶兗在略低於燒結溫度的 塑性的特徵，這些研究始於19 性，〜、有超 是這•超塑= 強化陶t(ZTC)的研究。但 m陶竟的塑性變形量受到晶大小、形狀及加 工條件的限制很大，目前超塑性陶瓷體的微結構通常有下 列三個限制條件： (1) 晶粒微細（fine grain size):晶粒粒徑要小於1 // Π1以下。 (2) 等轴晶粒（equiaxed grains):晶粒形狀成等軸之 圓球狀。 (3) 穩定的晶粒大小（stability of fine grain size):在加工溫度下，晶粒不會成長或改變外形。 【發明内容】 爰此’有鑑於目前對於超塑性陶瓷體受限的條件甚 多’使陶瓷的超塑性性質亦不盡理想。 本發明主要係為一種超塑性陶瓷之新製程，其係有下 述步驟： (1) 在陶瓷粉體間置入可形成玻璃相之化合物 (2) 成形為一特定形狀坯體 (3) 第一次熱處理形成玻璃相和緻密化坯體 (4) 塑性加工 (5) 第二次加熱處理使玻璃組成陶瓷化 上述之陶究粉體係為氧化物、氣化物、碳化物、碗化 物或其化合物之任意比例混合物。 上述之玻璃相為單一組成。 上述之玻璃相為氧化物、氮化物、碳化物、硫化物或 其化合物之任意比例混合物。 ^37985 上述之玻璃相材料包括氧化石夕（Si〇〇、氧化紹⑽ J、氧化填⑽5)及氧化蝴⑽3)、氧化鎂（Mg〇)、 $ ^卸（Μ)、氧化鐘（U2〇)、氧化鑭（La2〇3)、氧化 錄（_)、氧化錄（Sb2〇5)、氧化组（⑽）、氧化絡 r2〇3)、氧化鋇（_、氧化約⑽）、氧化錄（㈣）、 氣化錄（⑽）、氧化鋅（ZnQ)、氧化銅（⑽）、氧化 錫（Sn〇2)、氧化錯（pb〇)和氧化鐵（^必、^◦ 一 組成或其組合。 上述之第一次加熱處自包括結晶化、擴散進入陶瓷 ，、緻密化、退火、與陶瓷相反應形成化合相和相變化之 單一手段或其組合。 上述之第二次加熱處理係使玻璃組成進入陶瓷基材 料之晶粒、晶界或晶格結構中之單一方式或其組合。土 上述之可形成玻璃相之化合物，係為醇鹽、氨鹽、草 酸鹽、擰檬酸鹽、玻璃粉、有機酸鹽和無機酸鹽。 上述之成升> 方式包括模壓、射出、擠出、泥毁成步、 刮刀加工、冷均壓加工。 上述之使玻璃組成陶瓷化的微結構，包括形成複合陶 瓷材料。 σ 本發明具有下列之優點： 1.本發明係利用玻璃相在特定溫度下產生的粘性流 體做超塑性加工。在製備過程中，先在晶界產生所需玻= 相，並將生坯燒結成緻密素坯，再利用玻璃相在〜π Τ疋溫度 1337985 下產生的粘性流體做超塑性加工，定型出所需形狀，最後 再經商溫熱處理成將玻璃轉化成陶竞相，—方面在晶粒間 (粒界）存在一些玻璃相，可使晶粒在熔融液相的潤滑下促 進塑性流動，提高塑性變形量，可以達到超塑性加工目 的’另一方面玻璃相轉化成最終的陶瓷相，減少粒界存在 玻璃相對陶瓷體的高溫機械性質之負面影響。 2.本發明之超塑性陶瓷體的原料和製程條件要求不 • 1¾ ’主要的塑性成形機構是《熔融玻璃相在晶界潤滑，減少 晶粒間摩擦’可降低晶粒大小和形狀對塑性變形量的影 響’使原料選擇更具多樣性，來源更廣，加上可以在低應 力下完成變形’不需在較高加工溫度下進行，晶粒不會成 長或改變外形，減低技術難度和設備要求，使製程更具競 爭力。 【實施方式】 首先，如第一圖所示，本發明主要係為超塑性氧化鋁/ • 富紐紅柱石複合陶瓷之製程，其係具有下述步驟： 1.在陶瓷粉體間置入可形成玻璃相之化合物：以溶膠 凝膠法（α - AI2O3粉末與酒精及四乙基氧矽在球磨筒中混 合’然後加入NHWH混合’ pH值為11· 5〜13，使四乙基氧 石夕水解。）將非晶質Si〇2經水解均勻分散於AI2O3粉末外 層’調整水分和黏度，以利後需成形；上述該陶瓷粉體係 為氧化物、氮化物、破化物、硫化物或其化合物之任意比 - 例混合物’而玻璃相為單一組成，係為氡化物、氮化物、 8 …/985 反化物4化物或其化合物之任意比例混合物；其玻璃相 之材料包括氧切（Si〇2)、氧化銘（A·)、氧化峨（p 2〇5)及氧化蝴（B2〇3)、氧化鎂（Mg〇)、氧化卸（κ2〇)、 •氧化鋰（Li2〇)、氧化鑭（La2〇3)、氧化鎳（Ni0)、氧化 録（制5)、氧化组（Ta2〇5)、氧化鉻（Cn〇3)、氧化鋇 (BaO)、氧化約（Ca〇)、氧化總、氧化始、 氧化鋅（ZnO)、氧化鋼（Cu〇)、氧化錫（Sn〇2)、氧化 •錯（Pb〇)和氧化鐵（Fe2〇3、Fe〇)單一組成或其組合，上 述可形成玻璃相之化合物，係為醇鹽、氨鹽、草酸鹽、檸 檬酸鹽、玻璃粉、有機酸鹽和無機酸鹽。 2·成形為一特定形狀坯體：將坯料捏練後送入擠出 機’以成形條棒狀’於乾燥後定型，成形方式包括模壓、 射出、擠出、泥聚成形、刮刀加工、冷均壓加工。 3. 第一次加熱處理讓陶瓷粉體粒界形成玻璃相並成 為緻密化坯體（素坯）：先將生坯在13〇〇〇c 〜14〇〇<^燒結成 φ 素链’此溫度除了形成玻璃相’所形成的玻璃相可幫助緻 密化’燒成是以每分鐘5〇C的升溫速度，在空氣中加溫至 所需溫度’持溫完畢後爐冷；加熱處理使玻璃組成進入陶 瓷基材料之晶粒、晶界或晶格結構中之單一方式或其組 合；而加熱處理之方法包括有結晶化、擴散進入陶瓷相、 緻密化、退火、與陶瓷相反應形成化合相和相變化之單一 手段或其組合。 4. 塑性加工：非晶質si〇2高溫會產生黏性流，Al2〇3粉 9 1337985 粒藉此再排列而大量塑性變形。在製備過程中，利用素坯 於1200°C〜1300°C產生的粘性流做超塑性加工。 5.第二次加熱處理使玻璃組成陶瓷化：再經1500°C以 上熱處理成氧化鋁/富鋁紅柱石複合陶瓷，使玻璃組成陶 瓷化，而使玻璃組成陶瓷化的微結構，包括形成複合陶瓷 材料；高溫之超塑性行為測定是使用高溫萬能材料試驗 機。Cross head移動速度為每分鐘0. 5mm，支點間距離 為40mra，符合ASTM F417標準的三點彎曲法測試。 【圖式簡單說明】 第一圖係為本發明之製程步驟示意圊。 第二圖係為本發明第一實施例以溶膠凝膠法添加的素坯 樣品之超塑性變形的照片。 【主要元件符號說明】Nine inventions: [Technical field to which the invention pertains] The process is preformed into a specific one in the ceramics. The present invention is a compound in which a glass phase can be formed between a new body of a superplastic ceramic. The corpus callosum, after the first heat treatment, make the ceramic fv into Am, noisy, no unbody body grain boundary to form a glass phase plastic Η I 坂 坂 软化 soft phase of the 〖 raw processing, further shaping, and then The second stone is transformed into a microstructure of ceramic-based materials. In the case of 4:: iron, it is first stored in a specific shape, and when used: plastically adds the shape required by the horse. light!丨王刀口 [Prior Art] Under, l superplastic. Ah (9) refers to the role of stress in the big: _. In general, most of the metal materials have a lot of impurities, and the plasticity processing is made into various kinds of pre-two mechanical materials. The application of metal materials is extended from the metal material = characteristic, which has great potential, but the ceramic (four) material is brittle and (four) excellent shortcomings make it The mechanical material should be limited. "...Processing In recent years, it has been found that the pottery is characterized by a plasticity slightly lower than the sintering temperature. These studies began with 19, and there is super. This is the study of superplastic = reinforced pottery t (ZTC). However, the plastic deformation of m ceramics is greatly limited by the crystal size, shape and processing conditions. At present, the microstructure of superplastic ceramics generally has the following three restrictions: (1) Fine grain size: crystal The particle size should be less than 1 // Π1 or less. (2) Equivalent grains: The grain shape is equiaxed in a spherical shape. (3) Stable of fine grain size: At processing temperatures, grains do not grow or change shape. SUMMARY OF THE INVENTION [In view of the current limited conditions for superplastic ceramic bodies, the superplastic properties of ceramics are also less than ideal. The invention is mainly a new process of superplastic ceramics, which has the following steps: (1) placing a compound capable of forming a glass phase between ceramic powders (2) forming a green body of a specific shape (3) One heat treatment to form a glass phase and a densified body (4) Plastic processing (5) Second heat treatment to ceramize the glass composition The above ceramic system is an oxide, a vapor, a carbide, a bowl or a compound thereof Mixture of any ratio. The above glass phase is a single composition. The above glass phase is a mixture of oxides, nitrides, carbides, sulfides or compounds thereof in any ratio. ^37985 The above glass phase materials include oxidized stone (Si〇〇, oxidized (10) J, oxidized (10) 5) and oxidized (10) 3), magnesium oxide (Mg 〇), $ ^ unloaded (Μ), oxidized clock (U2 〇 ), lanthanum oxide (La2〇3), oxidation record (_), oxidation record (Sb2〇5), oxidation group ((10)), oxidized complex r2〇3), yttrium oxide (_, oxidation about (10)), oxidation record ( (4)), gasification recorded ((10)), zinc oxide (ZnQ), copper oxide ((10)), tin oxide (Sn〇2), oxidized error (pb〇) and iron oxide (^, ^ ◦ a composition or a combination thereof The first heating described above is a single means or a combination thereof including crystallization, diffusion into the ceramic, densification, annealing, reaction with the ceramic phase to form a combined phase and phase change. The second heat treatment described above makes the glass a single mode or a combination thereof which constitutes a grain, a grain boundary or a lattice structure of a ceramic-based material. The above-mentioned compound which forms a glass phase is an alkoxide, an ammonium salt, an oxalate, a citrate, Glass powder, organic acid salt and inorganic acid salt. The above-mentioned liters include: molding, injection, extrusion, mud Step-by-step, doctor blade processing, cold pressure equalization processing. The above-described microstructure for ceramizing glass, including forming a composite ceramic material. σ The present invention has the following advantages: 1. The present invention utilizes a glass phase to be produced at a specific temperature. The viscous fluid is superplasticized. In the preparation process, the desired glass = phase is produced at the grain boundary, and the green body is sintered into a dense green body, and then the viscous fluid produced by the glass phase at a temperature of ~π Τ疋 1137798 is used. Superplastic processing, shaping the desired shape, and finally by heat treatment to convert the glass into Tao Jing phase, there are some glass phases between the grains (grain boundary), which can make the crystal grains under the lubrication of the molten liquid phase. Promote plastic flow and increase the amount of plastic deformation, which can achieve the purpose of superplastic processing. On the other hand, the glass phase is transformed into the final ceramic phase, which reduces the negative influence of the high temperature mechanical properties of the glass on the ceramic body. The raw material and process conditions of the plastic ceramic body are not required. • The main plastic forming mechanism is that the molten glass phase is lubricated at the grain boundary to reduce intergranular friction. It can reduce the influence of grain size and shape on the amount of plastic deformation. 'The choice of raw materials is more diverse, the source is wider, and the deformation can be completed under low stress. No need to carry out at higher processing temperatures, the grains will not Growth or change of shape, reduce technical difficulty and equipment requirements, make the process more competitive. [Embodiment] First, as shown in the first figure, the present invention is mainly superplastic alumina / • Fu New andalusite composite ceramic The process has the following steps: 1. Inserting a compound capable of forming a glass phase between the ceramic powders: a sol-gel method (mixing α-AI2O3 powder with alcohol and tetraethyl oxon in a ball mill barrel) and then adding NHWH mixed 'pH value of 11. 5~13, so that tetraethyloxohydrate is hydrolyzed.) The amorphous Si〇2 is uniformly dispersed in the outer layer of AI2O3 powder by hydrolysis to adjust the moisture and viscosity, so as to form the above; The ceramic powder system is any mixture of oxides, nitrides, broken compounds, sulfides or compounds thereof, and the glass phase is a single composition, which is a telluride, a nitride, a 8 ... / 985 derivative a mixture of any ratio of its compounds; its glass phase materials include oxygen cut (Si〇2), oxidized (A·), cerium oxide (p 2〇5), and oxidized butterfly (B2〇3), magnesium oxide (Mg〇) ), oxidative unloading (κ2〇), • lithium oxide (Li2〇), yttrium oxide (La2〇3), nickel oxide (Ni0), oxidation recording (manufacturing 5), oxidation group (Ta2〇5), chromium oxide (Cn 〇3), barium oxide (BaO), oxidation (Ca〇), total oxidation, oxidation start, zinc oxide (ZnO), oxidized steel (Cu〇), tin oxide (Sn〇2), oxidation • wrong (Pb〇 And a single composition of iron oxide (Fe2〇3, Fe〇) or a combination thereof, the above-mentioned compound capable of forming a glass phase, which is an alkoxide, an ammonium salt, an oxalate, a citrate, a glass powder, an organic acid salt, and an inorganic Acid salt. 2. Forming into a specific shape of the blank: the billet is kneaded and sent to an extruder to form a strip in the shape of a rod, which is shaped after molding, including molding, injection, extrusion, mud forming, scraping, and cold. Pressure equalization processing. 3. The first heat treatment causes the ceramic powder grain boundary to form a glass phase and becomes a densified green body (green body): firstly, the green body is sintered at 13〇〇〇c ～14〇〇<^ into a φ-chain This temperature can help to densify in addition to the glass phase formed by the formation of the glass phase. 'The firing is at a heating rate of 5 ° C per minute, and is heated to the desired temperature in the air. 'The furnace is cooled after the temperature is maintained; the heat treatment makes The glass composition enters a single mode or a combination of crystal grains, grain boundaries or lattice structures of the ceramic-based material; and the heat treatment method includes crystallization, diffusion into the ceramic phase, densification, annealing, and reaction with the ceramic phase to form a combination A single means of phase and phase change or a combination thereof. 4. Plastic processing: Amorphous si〇2 will produce viscous flow at high temperature, and Al2〇3 powder 9 1337985 will be rearranged and deformed in a large amount. In the preparation process, the viscous flow generated by the green body at 1200 ° C to 1300 ° C is used for superplastic processing. 5. The second heat treatment ceramizes the glass composition: heat treatment at 1500 °C or higher to form alumina/mullite composite ceramics, tempering the glass composition, and constituting the ceramized microstructure of the glass, including forming a composite Ceramic materials; high temperature superplastic behavior is measured using a high temperature universal material testing machine. The cross head moves at a speed of 0.5 mm per minute, and the distance between the fulcrums is 40 mra, which is in accordance with the ASTM F417 standard three-point bending test. BRIEF DESCRIPTION OF THE DRAWINGS The first figure is a schematic diagram of the process steps of the present invention. The second figure is a photograph of the superplastic deformation of the sample of the green body added by the sol-gel method in the first embodiment of the present invention. [Main component symbol description]