1343830 九、發明說明： 【發明所屬之技術領域】 . 本發明係有關於一種保護塗層塗佈方法，尤指一種長晶用坩鍋之保護 塗層塗佈方法。 【先前技術】 應用於太陽能電池之矽晶圓材料可分為單晶與多晶兩種，矽晶圓材料 於現在太陽能產業中市場佔有率高達90%。目前可利用CZ方式長單晶，或 φ 者利用DSS與HEM方法製造單方向柱狀多晶矽，上述長晶方法皆須使用陶 • 瓷坩鍋材料盛裝高溫液態矽金屬，一般坩鍋材料是採用熔融石英（Fused1343830 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a coating method for a protective coating, and more particularly to a coating coating method for a crucible for a long crystal. [Prior Art] The wafer materials used in solar cells can be divided into single crystal and polycrystalline. The wafer material has a market share of 90% in the solar industry. At present, CZ long crystals can be used, or φ can be used to fabricate unidirectional columnar polycrystalline germanium by DSS and HEM methods. The above crystal growth method must use ceramic ceramic crucible material to hold high temperature liquid bismuth metal, and the common crucible material is melted. Quartz (Fused
Quaratz)或石墨材料，當使用石墨坩鍋時，高溫矽金屬易與石墨反應生成 碳化矽，而影響到矽晶品質。另當使用熔融石英坩鍋時，亦會因石英坩鍋 内的玻璃相（Vitreous silica)在高溫過程漸漸轉變為結晶相 (Devitrification)，在坩鍋表面生成島狀的白矽石（Crist〇balite)，於長 晶過程中可能溶入矽熔湯，導致於矽凝固後生成差排。使用石英坩鍋所產 生的另一個問題是，當長晶溫度超過矽熔點時，石英坩鍋會因玻璃相軟化， 因而產生變形’所以常使用对熱石墨板支撐时銷。但是，由於高溫液蘇石夕 Φ 金屬會與石英坩鋼反應，生成氧化矽與氧，氧化矽會與耐熱石墨板起反應， ® 生成碳化矽與一氧化碳，而一氧化碳再與矽反應生成碳與氧化矽，而熔入 矽金屬的碳與氧，會對太陽能電池的轉換效率造成不利的影響，尤其是對 方向性柱狀多晶矽，其高溫矽金屬須於石英坩鍋中凝固，易因矽金屬與石 英坩鍋在高溫長時間發生界面反應，使得其矽金屬表面發生咬模現象’並 於降溫冷卻過程因膨脹係數的差異所形成的應力，造成坩鍋與鑄錠的破裂。 因此’一般常於石英掛銷内壁施加一層不與高溫石夕金屬反應的塗層， 利用此塗層以隔絕矽金屬與石英坩鍋的反應，並改善矽金屬與石英坩鍋咬 模問題。以前亦有許多文獻及專利述及不同的塗層材料與技術，最廣泛被 使用塗層材料是氮化石夕， 1 5 ^43830 如美國專利第4515755號，Shuitsu Matsuo提出以CVD氣相析出方式 彼覆一層氮化矽塗層於一石英坩鍋，塗層含有20%以上的p相或含8〇%以 上的α相，以避免高溫熔解矽金屬時，石英坩鋼中的氧溶入矽熔湯中進 而影響矽晶的性質。 另如美國專利第4741925號，Chaudhuri提出以化學沉積方式通入反應 式氣體在1250X形成α相氮化矽塗層，但此上述兩種鍍膜方式的增厚速度 很慢，且鍍膜設備昂貴，造成製程成本高’ 一般僅是應用在薄膜塗層。Quaratz) or graphite material, when using graphite crucibles, high-temperature niobium metal easily reacts with graphite to form niobium carbide, which affects the quality of twinning. In addition, when a fused silica crucible is used, the Vitreous silica in the quartz crucible is gradually converted into a crystalline phase (Devitrification) at a high temperature, and island-shaped chalk (Crist〇balite) is formed on the surface of the crucible. ), in the process of crystal growth may be dissolved into the sputum melt soup, resulting in the formation of poor sputum after solidification. Another problem with the use of quartz crucibles is that when the crystal growth temperature exceeds the melting point of the crucible, the quartz crucible will be deformed by the softening of the glass phase, so the pin is often used when supporting the hot graphite sheet. However, since the high-temperature liquid sulphide Φ metal reacts with quartz bismuth steel to form cerium oxide and oxygen, cerium oxide reacts with the heat-resistant graphite sheet, and ® forms cerium carbide and carbon monoxide, and carbon monoxide reacts with hydrazine to form carbon and oxidize.矽, and the carbon and oxygen melted into the base metal will adversely affect the conversion efficiency of the solar cell, especially for the directional columnar polycrystalline silicon, the high temperature bismuth metal must be solidified in the quartz crucible, easy to bismuth metal and The quartz crucible reacts at a high temperature for a long time, causing a bite phenomenon on the surface of the crucible metal, and the stress caused by the difference in the expansion coefficient during the cooling and cooling process causes cracking of the crucible and the ingot. Therefore, a coating which does not react with the high temperature stone metal is often applied to the inner wall of the quartz pin. This coating is used to isolate the reaction between the base metal and the quartz crucible, and to improve the problem of the base metal and the quartz crucible bite. In the past, there were many literatures and patents describing different coating materials and techniques. The most widely used coating material was Nitride Xi, 1 5 ^ 43830. For example, U.S. Patent No. 4515755, Shuitsu Matsuo proposed CVD gas phase precipitation. Coating a layer of tantalum nitride in a quartz crucible, the coating contains more than 20% of the p phase or more than 8% of the α phase, in order to avoid the high temperature melting of the base metal, the oxygen in the quartz tantalum steel melts into the crucible The soup in turn affects the nature of the twins. In addition, as in U.S. Patent No. 4,741,925, Chaudhuri proposes to form a α-phase tantalum nitride coating at 1250X by chemical deposition into a reactive gas, but the thickening speed of the above two coating methods is very slow, and the coating equipment is expensive, resulting in Process cost is high' is generally only applied to thin film coatings.
另如美國專利第5431869號，Kumar研究在長晶模具上塗佈含有機黏結 劑（如alcohol，esters, acetone, and benzene)與水的氮化矽漿體，以於 長晶模具形成一塗層，有效保護模具及使石夕錢易於脫模。另更於矽中加入 少量CaF2或CaCh，由於它不與純石夕反應，會被石夕推至模壁，可有效阻止 石夕液與模具間的反應’但由於鹵化物會侵钮氮化石夕塗層，在長時間長晶過 程易導致石夕中雜質含量提高。 另美國專利第6,165, 425號，Horst Lange使用氮化石夕粉末，其中氧含 量為0. 3至1. 5 wt%，鹼金屬（1-100 ppm)或鹼土族（1-100 ppm)、氟化 物（ 10-1000 ppm)、氣化物（30-1000 ppm)與碳含量（50-1500 ppm)控 制在最小量，其他金屬元素含量亦同，如Fe、Cr、Co、Ni、W、Ti等等》 其個別含量最好在1-100 ppm，此法適用於非鐵合金(Si、A1、Ge、Ti)的炫 解’尤其是石夕合金。同時為改善其塗層與掛锅結合度，可於其適當流體性 質下選擇加入organosilane、silicic acid esters、polyols、polyvinyl alcohols、acrylates 及水或水與 hydrophi 1 ic 溶劑 or 增厚劑(cei iui〇se 衍生物），然後再以塗刷或喷、Squirting、浸的方式製作塗層，之後，最 好在大於100X下乾燥，並於500至700T下燒結一段適當時間，以作脫g旨 燒結，但此專利並未詳細揭露其塗佈方法。 另美國專利第6491971號，Michael A Costantini提出坩銷用離模塗 層系統，使用氮化石夕加入Cellulose ether與去離子水(DI water)及消泡 劑’以高速搜拌混合，調至黏度為Zahn#2 60秒的漿體，利用商業用的喷 !343830 /畤 ％ /， 塗設備’均勻塗佈於掛鋼上’並經1095DC 3小時燒結，經 ’則量僅從89 Shore Α提南至95 Shore A，其缺點是燒結後塗層強度較弱， 坩鍋進矽料或移動過程，會因碰撞或到傷坩鍋產生塗層剝落，形成矽錠的 雜質。 此外，美國專利第6479108號，Alleppey V. Hariharant利用安定化 氧化結或 Magnesium zirconate (MgZr〇3)或 Barium zirconate (BaZr〇3)經 由向速電聚喷覆至石英时銷内外表面，由於陶究粉體在高溫熔解或軟化， 因而披覆在时鋼表面，作為隔絕炫融石夕與石英时鋼反應，以避免造成污染 早晶石夕或多㈣，但在錢喷f驗’由於高溫雜加熱石英賴使得溫 度大幅上升’會導致降溫過程_變化應力而有微歸。另外，實際運作 上對炫石夕量450公斤的財銷塗層，不易控制塗層均勻度與塗層厚度。 T. Buonassisi (Journal of Crystal Growth 287 (2006) 402 - 407) ，出有效降低多㈣長晶污染的方式有，如改錢切結構性質以減少長 晶過程氮切的分解(Decompositi〇n)與降低掛鋼表面積與體積比州如增 =鋼Size)。由以往專利文獻如美國專利第⑽泌號及美國專利第 _971號所述的氮化矽燒結溫度僅在5〇〇_1〇95χ =;燒結時’須加溫至祕戰，才會由_軸目= CU谷易獲得適當的陶曼強度，所以易於長升温·剝落或裂掉。 ㈣^改善氣化石夕塗層燒結體的陶£強度，可添加燒結促進劑與聚體黏結 d來提鬲其塗層強度，以利長晶製程。 . 【發明内容】 本务月之目的’在於提供一種長晶用㈣ 勾塗佈該t體於該_之_，並提升 層雜方法，可均 料與_鋼進行長晶時產生介面; 進而提昇長•钮沾氺σ玄 〜 。該長造後的咬模現象， ㈣材#的成。0率，以降低進行長晶的成本。 二達到上述之目的，本發明係為一種長晶用掛鋼之保護塗看塗佈方 7 ^43830 去:先取-肢鶴末及-助細，並加人水一縣劑及―;肖泡劑進行 搜拌為-Μ。當賴體具適當流動性後，預麟職，接著塗佈該毁體 至該购，以形成-保護塗層韻_，最後以高溫燒結祕護塗層。 【實施方式】 兹為使貴審查委員對本發明之結構特徵及所達成之功效有更進一步 之瞭解與<識’謹佐以I碰之實施例及配合詳細之說明，說明如後： 參閱第一圖，係本發明之—較佳實施例之流程示意圖。如圖所示， 本貫把例ir灰供種長晶用#鋼之保護塗層塗佈方法，於鋼之内壁开) 成—保護塗層，而該_之材質選自石英、氧⑽、氧化_、石,墨及其他 时鋼材料帽其-者。本貫施例之方法可均勾塗觸保護塗層於該掛鋼之 内壁，而雜護塗層可減少於進行長晶時，制_之長晶材料與該掛鋼 f生介面反應’其中該長晶材料選自仙⑽、脱、皿及其他長晶材料 擇其-者’且改善其鑄造後的咬模現象，進而提昇長晶材料之成品 以降低其製造成本。 本實施例所提供之方法係先執行步驟_，取一氣化石夕粉末及—助燒 &並加入水、—黏結劑及一消泡劑進行攙拌為一毁體，其中步驟训更 =含：先混合水、雜結劑及該消泡細城—溶液，接著加人該氮化石夕粉 =溶射’最後加人該助燒劑至已加人載化_末之該溶液中進行 見I七成Γ體。其巾綠化雜末與由水、！錄結劑及該肖泡劑所混合 =液之用置比為i : 4 ’該助燒劑之材料選自Be〇、_、⑽、Sr〇、咖、 、Y2Q3、祕及其他氧化物中擇其—者，其用量必須介於 。甘、6Wt/。之間，該黏結劑之材料選自隱、雜夜及魏乙自旨中擇其一 授拌速度由快至慢，以避免氮化石夕沉澱。 適當""動性後，先執行步驟SU，利用-特殊預熱爐預熱 然接^ 1之溫度維持於攝氏3Q度與攝氏5G度之間，以便進行㈣ 丁V驟S16 佈雜體至該職，並㈣塗佈該顏之厚度大In addition, as in U.S. Patent No. 5,431,869, Kumar studied coating a long-crystal mold with a tantalum nitride slurry containing an organic binder (such as alcohol, esters, acetone, and benzene) and water to form a coating on the crystal growth mold. It effectively protects the mold and makes Shi Xi Qian easy to demould. In addition, a small amount of CaF2 or CaCh is added to the crucible. Since it does not react with pure stone, it will be pushed to the mold wall by Shi Xi, which can effectively prevent the reaction between Shi Xi liquid and the mold. The eve coating, in the long-term crystal growth process, easily leads to an increase in the impurity content in Shi Xi. In U.S. Patent No. 6,165,425, Horst Lange uses a nitriding powder having an oxygen content of 0.3 to 1.5 wt%, an alkali metal (1-100 ppm) or an alkaline earth (1-100 ppm), fluorine. The compound (10-1000 ppm), vapor (30-1000 ppm) and carbon content (50-1500 ppm) are controlled to a minimum, and other metal elements are also the same, such as Fe, Cr, Co, Ni, W, Ti, etc. The individual content is preferably 1-100 ppm. This method is suitable for the non-ferrous alloy (Si, A1, Ge, Ti). At the same time, in order to improve the bonding degree between the coating and the hanging pot, organicsilane, silicic acid esters, polyols, polyvinyl alcohols, acrylates and water or water and hydrophi 1 ic solvent or thickener (cei iui〇) may be selected under appropriate fluid properties. Se derivative), and then coating by spraying or spraying, Squirting, dipping, and then preferably drying at more than 100X, and sintering at 500 to 700T for a suitable period of time for sintering. However, this patent does not disclose its coating method in detail. In addition to U.S. Patent No. 649,1971, Michael A Costantini proposed a die-coating system for the sale of slag, using Cellulose Ether and Deionized Water (DI water) and defoamer to mix at high speed and adjust to viscosity. Zahn#2 60 seconds of slurry, using a commercial spray! 343830 / 畤% /, coating equipment 'evenly coated on the steel' and sintered through 1095DC for 3 hours, the amount is only from 89 Shore Α To 95 Shore A, the disadvantage is that the strength of the coating after sintering is weak. When the crucible is fed or moved, the coating may peel off due to collision or damage to the crucible to form impurities of the crucible. In addition, U.S. Patent No. 6,479,108, Alleppey V. Hariharant utilizes a stabilized oxidized oxide or Magnesium zirconate (MgZr〇3) or Barium zirconate (BaZr〇3) to spray the inner and outer surfaces of the pin through the velocity electropolymer to the quartz. The powder melts or softens at high temperature, so it is coated on the surface of the steel. It acts as a steel to isolate the smelting stone and quartz when it is used to avoid causing pollution of the early crystal sill or more (four), but in the case of money spray Heating the quartz to make the temperature rise sharply 'will lead to the cooling process _ change the stress and have a slight return. In addition, in actual operation, it is difficult to control the uniformity of the coating and the thickness of the coating on the sales coating of 450 kilograms. T. Buonassisi (Journal of Crystal Growth 287 (2006) 402 - 407), there are ways to effectively reduce the growth of poly (tetra) crystals, such as changing the structure of the structure to reduce the decomposition of nitrogen in the process of crystal growth (Decompositi〇n) Reduce the surface area and volume ratio of the hanging steel to the state such as increase = steel size). The sintering temperature of tantalum nitride described in the prior patent documents, such as U.S. Patent No. (10) and U.S. Patent No. _971, is only 5 〇〇 1 〇 95 χ =; when sintering, it is necessary to warm up to a secret war. _ axis = CU Valley easy to obtain the appropriate Tauman strength, so it is easy to heat up, peel off or crack. (4) Improve the strength of the sintered body of the gasification stone coating, and add a sintering accelerator and a polymer bond d to enhance the coating strength to facilitate the growth process. [The content of the present invention] is to provide a long crystal (4) hook coating the t body in the _, and to enhance the layer impurity method, which can be used to form an interface with the _ steel for the growth of the crystal; Enhance the long • button dip 氺 玄 玄 ~. The shape of the mold after the long build, (four) material #. 0 rate to reduce the cost of performing long crystals. Secondly, to achieve the above purpose, the present invention is a kind of long-crystal coating with steel coating to see the coating side 7 ^ 43830 to: first take - limb crane and - help fine, and add people water a county agent and - "Shabu The agent is mixed into -Μ. When the body has proper fluidity, it is pre-stretched, and then the ruined body is coated to the purchase to form a protective coating, and finally the high-temperature sintering secret coating is applied. [Embodiment] In order to enable the reviewing committee to have a better understanding of the structural features and the effects achieved by the present invention, <study' BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic flow diagram of a preferred embodiment of the present invention. As shown in the figure, the ir ash is used to coat the long crystals with the protective coating method of # steel, and the inner wall of the steel is opened to form a protective coating, and the material of the _ is selected from the group consisting of quartz and oxygen (10). Oxidation _, stone, ink and other steel materials. The method of the present embodiment can be coated with a protective coating on the inner wall of the steel, and the hybrid coating can be reduced when the long crystal is formed, and the crystal growth material reacts with the steel interface. The crystal growth material is selected from the group (10), the decanter, the dish and other crystal growth materials to improve the mold biting phenomenon after casting, thereby improving the finished product of the crystal growth material to reduce the manufacturing cost thereof. The method provided in this embodiment firstly performs the step _, taking a gasification stone powder and a helper burning & and adding water, a binder and an antifoaming agent for mixing and smashing, wherein the step is more = : first mixing water, a mixture of the agent and the defoaming fine-solution, and then adding the nitriding stone powder = spraying 'the last addition of the co-firing agent to the added solution _ the end of the solution see I Seventy percent of the body. Its towel is green and mixed with water,! The recording agent and the foaming agent are mixed=the liquid is used in a ratio of i:4'. The material of the sintering aid is selected from the group consisting of Be〇, _, (10), Sr〇, coffee, Y2Q3, secret and other oxides. If you choose it, the amount must be between. Gan, 6Wt/. Between the materials of the binder is selected from the group consisting of hidden, midnight and Wei Yi. The mixing speed is from fast to slow to avoid precipitation of the nitrite. After appropriate "" dynamic, first perform step SU, use the preheating furnace of special preheating furnace to maintain the temperature between 3Q Celsius and 5G Celsius for (4) D-V-S16 cloth To the position, and (4) coating the thickness of the face
150μπι，持續至塗佈1 〜--.」之)轉換頁I 驟如，職—賴懸於該職之缝。錢執ϋ 之間。“结該保護塗層，其燒結溫度為攝氏麵度至攝氏_度 得控第二圓，為了避免漿體中的氮化碎粉末發生結團或沉搬， 為^卜該雜做剌_職合之麵之用量比 所:β八之、1 φ先添加部分氮化普末至由水、該黏結劑及該消泡劑 二2 1以形觸體，然而當該峨拌-娜1後，再執行 ㈣將w t加剩下的氮切粉末至爾體中，使該氮化補末均勾分佈 二二±。'後再依序進行步驟S14 ' S16、⑽。其中步驟S10所添加之 所^驟幻2所添加之氮化石夕粉末之總用量與由水、細吉劑及 ㈣泡劑所混合之溶液之用量比必鱗持丨：4。 做 。所而f實關彻―倾倾賴體於該職1，為了確保雜護塗層之 =„前，調整該偷之壓力大小、口徑大小及__之_， 使母-人遠貝搶所喷射之喷束形狀為橢圓形，該擔圓形之長度為4〇公分，兑 寬度為3公分與1Q公分之間’雜制該倾每次噴塗面積、喷盘 。侧咖綱在攝氏％ ^攝氏5G度之間，因此利用紅外線測溫搶量測該職溫度，以控制塗佈 於s玄掛銷之該保護塗層的厚度及其均勻性。 而本貫施例之方法主要使用氮化石夕粉末製成該保護塗層，該氮化石夕粉 末具有好的機械性質，熱震(Th咖丨shGck)、斷裂強度與高溫穩定性， 因此常驗喊零組件。但由於雜切粉末魅高，轉錄結，一般 若以大氣燒結法，則於燒結後會訂—些的·(ν_)，所⑽保護塗^ 之組織孔隙度較高。 曰 當該氮化⑽末被錢在長㈣_之保護塗層時，―般是以毁體塗 層方式披彳f，而«於騎贿難叙料為⑽_動_之間， 且因該保護塗層彼覆於該賴之内壁，其燒結溫度僅介於攝氏g⑻度與攝氏 1100度，娜護塗層燒結後的難度不似以熱壓成型的燒結體， 9 1343830 往往留下更多微小150μπι, continue until the coating 1 ~--.") conversion page I, for example, the job - hang in the seam of the job. Between money and stubbornness. "The protective coating is sintered at a temperature ranging from Celsius to Celsius to the second round. In order to avoid agglomeration or sinking of the nitrided powder in the slurry, The ratio of the amount of the surface is: β 八, 1 φ first add a portion of the nitrite to the water, the binder and the defoamer 2 21 to form the contact body, but when the 峨 mix-na 1 Then, (4) adding wt to the remaining nitrogen cut powder to the body, so that the nitriding complement is evenly distributed to the second and second ±. Then proceed to step S14 'S16, (10) sequentially, wherein step S10 is added The total amount of the nitriding powder added by the phantom 2 is the same as the amount of the solution mixed with water, fine kiln and (4) foaming agent: 。 所 所 所 所 所 所 所 所 所 倾In order to ensure that the pressure of the stealing coating, the size of the caliber and the ___, the shape of the spray of the mother-to-human fare is elliptical. The length of the circular shape is 4 cm, and the width is between 3 cm and 1 Q cm, and the spray area and the spray plate are mixed. The side ache is between Celsius % and 5 G Celsius, so the temperature is measured by infrared temperature measurement to control the thickness and uniformity of the protective coating applied to the s-hanging pin. The method of the present embodiment mainly uses the nitriding powder to make the protective coating. The nitriding powder has good mechanical properties, thermal shock (Thc丨shGck), breaking strength and high temperature stability, so the test is routine Shout the components. However, due to the high density of the miscellaneous cut powder, the transcriptional knot, generally in the case of the atmospheric sintering method, will be ordered after the sintering (v_), and the (10) protective coating has a high porosity. When the end of the nitriding (10) is covered by the long (four) _ protective coating, it is generally disguised as a destructive coating, and «between the bribe is difficult to tell (10)_moving_, and The protective coating covers the inner wall of the Lai, and the sintering temperature is only between g(8) degrees Celsius and 1100 degrees Celsius. The difficulty of sintering the Na-coating coating is not like that of a hot-pressed sintered body, and 9 1343830 often leaves more How tiny
’因此’降低此該保護塗層的功能， 嚴重時，甚至舍蚀彡呈_ 晶過程’會使得高溫·魏屬液， 保4塗層的空孔，渗穿人該保護塗肩 使得長晶後鑄件表φ發纽模問題，'Therefore, the function of the protective coating is lowered. In severe cases, even the etched 彡 crystal-forming process will make the high temperature · Wei liquid, the hole of the protective coating, and the protective coating shoulder to make the crystal growth After casting, the table φ is a new mold problem.
-般氮化石夕結構可以分為高溫穩定的沒相與低溫穩定相的〇相 = ，則燒結體的微結構為等軸狀晶粒，若該‘ 物、，》構3有較兩的仰’則燒結體的微結構為長柱狀晶粒，因此，粉末中 所含___會影響魏結密度。本實關所選狀氮切粉末之“ 相比例大於m，由該氮化矽粉末製成之該保護塗層具有良好的燒結密度。 此外’考量該助燒劑添加量_原料組成的影響，所以對於該助Μ 的添加量必搬量’且燒結後的該保護塗層中的助燒劑不會與高溫溶融ς 起化學反應。因此該助燒、纟讀之材料必縣擇於高溫自由紐⑪安定之陶 竟耐火材料，由Elligam Diagram_由能變化可知，該助燒劑之材料可選 擇BeO、MgO、CaO、SrO、BaO、Ti〇2、Zr〇2、、m、Ah〇3及其他不會與 石夕產生化學反狀氧化物t擇其-者，本實細所麵之魏劑材料為 Ah〇3、MgO或H)s，該助燒劑之添加量須介於丨的％與6的％之間，並配人少量 的石夕勝液或P麟其他黏結劑，提辆保護塗層燒結強度與其燒結後舰密 10 1343830 此外，就該保護塗層的燒結溫度選擇，一般氮化石 方式，其燒結溫度須達攝氏度與攝氏麵度之間，並維持高溫四小= 但對本實闕之方法而言加麟助制可提高低溫燒結強度， 以避免高溫燒結時賴材質結構變化所產生縮應力，因购受熱會發 生相艾化’轉變成trydinute and cristQbalite，同時伴隨著體積收縮， 所以邊保護塗層之燒結溫度須控制在i2〇〇<)c以内。 由上述可知，本發明所提供之掛鋼之保護塗層塗佈方法，本發明之方法 可均勾塗佈該保護塗層於該_之内壁，以避免長晶時之長晶㈣血物 鋼產生介面反應，並改善長㈣職生的咬模麟，進而料長晶材料之 成品率’以降低進行長晶之成本。 鉍上所述’本發明係實為一具有新賴性、進步性及可供產業利 符合我國專利法所規定之補申請要件無疑，爰依法提明 了 祈鈞局早曰賜准專利，至感為禱。 寻㈣6月’ —惟以上所述者，僅為本發明之—難實施_已，麵絲 =貫施之細’舉凡依本發明巾請專利範_述之形狀、構造、 神所為之均等變化與修飾，均應包括於本發明之申請專利範圍内。精 【圖式簡單說明】 第-圖：本發明之―較佳實施例之流程示意圖；以及 第二圖：本發明之另—較佳實施例之流裎示意圖。 【主要元件符號說明】 無- The nitridite structure can be divided into a high temperature stable phase and a low temperature stable phase of the 〇 phase =, then the microstructure of the sintered body is equiaxed grains, if the 'object," structure 3 has two 'The microstructure of the sintered body is long columnar grains. Therefore, the ___ contained in the powder affects the Wei junction density. In the case of the selected nitrogen-cut powder, the comparative coating is greater than m, and the protective coating made of the tantalum nitride powder has a good sintered density. In addition, the influence of the amount of the sintering aid on the composition of the raw material is considered. Therefore, the amount of the auxiliary additive must be increased, and the sintering aid in the protective coating after sintering does not chemically react with the high temperature melting. Therefore, the material for the combustion and reading is selected at a high temperature. New 11 stable ceramic refractory material, by Elligam Diagram_ from the change of energy, the material of the combustion aid can choose BeO, MgO, CaO, SrO, BaO, Ti〇2, Zr〇2, m, Ah〇3 And other materials that do not produce chemical anti-oxidation with Shi Xi, the material of the present agent is Ah〇3, MgO or H)s, and the amount of the sintering aid must be between 丨Between % and 6%, and a small amount of Shi Xisheng liquid or P Lin other binder, lifting the protective coating sintered strength and its sintered ship density 10 1343830 In addition, the sintering temperature of the protective coating is selected Generally, the nitriding method has a sintering temperature of between Celsius and Celsius and maintains a high temperature of four. Small = But for the method of the actual method, the support of the lining can improve the low-temperature sintering strength, in order to avoid the shrinkage stress caused by the change of the material structure during the high-temperature sintering, because the purchase of heat will occur in the phase of the transformation into the trydinute and cristQbalite, while With the volume shrinkage, the sintering temperature of the edge protective coating must be controlled within i2〇〇<)c. As can be seen from the above, the method for coating the protective coating of the steel provided by the present invention, the method of the present invention can be The protective coating is applied to the inner wall of the _ to avoid the interface reaction of the long crystal (four) blood steel in the long crystal, and improve the yield of the long (four) occupational students, and then the yield of the long crystal material is Reduce the cost of carrying out long crystals. The above-mentioned invention is a new application, progress and availability of industrial profits in line with the requirements of the Chinese Patent Law, no doubt, 提 提 提 提 提 早曰 曰 曰 专利 曰 四 四 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Shape, structure, god Equivalent changes and modifications are included in the scope of the patent application of the present invention. [Simplified description of the drawings] - Figure: Schematic diagram of the preferred embodiment of the present invention; and second diagram: another embodiment of the present invention - a schematic diagram of the flow of the preferred embodiment. [Description of main component symbols]