A(i B6 五、發明説明（—） 改良之陶瓷焊接方法 (請先閲讀背面之注意事項再填寫本页一 本發明爲陶瓷焊接方法及有關技術之改良，尤其是有關在該方法使用之 粉末成份物筲組合之粒度大小爲特徵者。 本發明亦提供一供陶瓷焊接卞法使用之改良物質组合。 陶瓷焊接方法早已用於修補練焦壚、玻璃瀘及同類物等，如英國專利 402 203號，L330、894號及2_〇35、524號，瑞典專利102挪號，陶党焊接 方法通常包含在一物質組合之輸運氣體中以混合粉末方式輸送至一喷搶， 粉末粒子在喷搶内摻入含氧氣體後從喷搶射出一表面上，其中該-混合粉末 一部份與氧反應發出熱量引致該混合粉末其他部份與其本身及與該表面作 最少部汾融合以達成焊接》 這用於陶瓷焊接方法之典型物質組合爲一对熔氧化物及金屬與/或類金 ‘屬粒子之混合粉末，用於以陶瓷焊接方法化成耐熱物質之物質組合及方法 見於英國專利2,154,228號，211〇,2〇〇號及2，l7〇，m號，， 以上各種性質已括近似粒度大小及粒度分配 .訂· 英國專利2，17〇，191號説明該耐熔粒子與可氧化金屬粒子之粒度特徵，其 主要申請專利範圍爲①耐熔轾子之平均粒度—定大於可氧化粒子之平均粒 度，及②耐熔粒子之大小幅度必須高於某一最低點，其中㈠已見於先前專 利’如英國專利1，33〇,894號即列出耐炫粒子與可氧化粒子之最大平均粒度 分别爲5〇0微米（microns)及5〇微米，英國專利以爪说號説明較廣粒度分配 .線. 使粒子大小幅度較高有利於形成耐久之焊接，比使用較爲均句粒度分配之 耐炫粒子形成之焊接減少多孔性及裂縫。 由英國專利2，17〇，191號所揭示之方法及物質组合使用而得之好處，茲發 現以利用比該專利f·吏爲一致粒度分配之耐熔粒子可形成高品質及耐久之 耐火材料，尤有進者，除去耐熔粒子之粗糙部份有助於該組合物流通於輸 :送系統，可使焊接成品更爲光滑，及減少非用於焊接之輸送物質之比率， :消除耐溶粒子之細粒部份亦有助於物質流動，更有助於減少播作時飄浮空 :氣中之硅石塵份量，及減少在反應區内之浮塵，因而減少非用於焊接之輸 f 4 (210X297X^1) 213894 經濟部中央標準局印製 A 6 A、發明説叫（二） 送物質之比率，增強可氧化粒子之發熱反應使該等反應不受抑制如石塵之 使用於地下礦坑滅火者。 英國專利2,154,228號及2,110,200號揭示之组合物包含不燃性耐火材料及可 發熱氧化物質，後者具有平均粒度低於50微米及包含矽與鋁，其中鋁達到 總重量百分之十二，英國專利2,154,228號則揭含鋁量最少爲總重量百分之 一。在上述專利各實施例中揭示之矽鋁混合物與耐熔氧化粒子並用，該粒 子含有一種或多種礦物質如二氧化鈷、氧化鎂、礬石、矽石、矽線石、矽 酸鉛等，所有上述專利之特點在可製成適當選擇之耐熔粒子作爲焊接修補 組合物，使與受處理之耐火材料底質最爲近似。 陶瓷焊接方法廣用於修補以矽耐熔塊爲面料之煉焦瀘，備後上該組合物 即該焊接粉末包含鋁、矽及矽石粒子之混合物，英國專利2,154, 228號舉出 修補煉焦壚之組合物含有鋁百分之一，矽百分之十二，矽石百分之八十 七，以重φ計算。 在煉焦壚中其矽耐熔塊並非百分之一百純矽石，在複合氧化耐火材料分 子中含有其他物質爲小量之銘、鐵及鈣等雜質。較佳焊接粉末之矽石成份 係與上述相同晶粒及化學結構之碾碎矽耐火材料。 使用一種包含百分之一重量之鋁、矽及碾碎矽石耐火材料之焊接粉末混 合物不一定能造出與获石物質組合物完全相配，該化學上不相配，加上所 使用之焊接粉末混合物由喷槍射出之物質周邊流失及因其不被容納於修補 部份之熱範圍内不致不能形成修補成品一部份，該流失物質主要爲耐火材 料，如此使用鋁於焊接粉末中尤其是重量最少爲百分之一，結果爲頚著較 高量之鋁氧化在焊接修補本身而較低量在矽石耐火材物質中。 再者發現以鋁，矽及矽石粉末混合物造成之焊接可能含有一部份矽金 屬，有些專家認爲其對焊接成品之品質及耐久性有害，紂整個方法之效能 有影響。 應注意者爲在修補煉焦瀘時耐火材料溫度在末端可能爲800 ·(：甚至1200 °C，在瀘中央則超過，雖然使用鋁在焊接粉末混合物中可以在較低溫度助 長良好焊接開始，但在較高溫度例如1200 ·(〇及以上則可能引致高及不良之 肀4(210X297公沒） (^) 請先閲讀背面之注意事項再填寫本頁) •笟. •線· 經濟部中央標準局印免 A6 B6 五、發明説明（ 三） 反應速率以致反應區軟塊層過度加熱，變成低黏度及易流動，在此現象發 生時改正焊接施用變得困難，因該射出焊接粉末椎進速率逼使软塊層擴散 及在周邊變形而產生多孔及不平表而之不良焊接品質。 本發明目的之一爲提供改良之陶瓷焊接方法及其組合物。 本發明另一目的爲提供一種使用於陶瓷焊接方法之組合物係可以使該焊 接修補材料與耐火材物質有較佳之化學配合者。 本發明又一目的爲提供一種使用於陶瓷焊接方法之組合物係可以在較高 溫度使用，例如最少800 ·〇底質溫度而不致有如使用含鋁組合物所造成之 變形及不良焊接品質者。 本發明第一方面提供一改良之陶瓷焊接方法，係以一含有耐熔粒子及可 氧化金屬粒子之混合物從喷搶與含氧氣體射在一表面上使可氧化粒子作發 熱反應以達成該混合物其他粒子與本身及該表面起碼作部份融合而形成焊 接，其特徵爲該耐熔粒子之調和平均粒度（如下述）爲介於300與1000微米 之間，及該耐炫粒子之粒度範園擴展因子（Size range spread facfor)(如下 述）爲介於0.4與1.1之間。 該調和平均粒度定義爲 £CW;/S〇 其中wi爲物質在i分之一粒度級之百分率或重量，及Si爲i分之一粒度級 之平均粒度。 該粒度範園擴展因子定義爲： 2(G80-G20) F(G)=- G80 十 G20 其中G80表示耐熔粒子之80%粒度，G20表示耐熔粒子20%粒度，及％ 粒度〃表示之耐熔粒子重量之百分比。可由具有該粒度網孔之篩子通過。 Λ調和平均粒度〃（Harmonic mean size) —詞可用於敛述粒子粒度分配，因 該詞已屬週知，在陶瓷焊接過程中化學反應係依賴表面者，是以調和平均 粒度定義爲一平均表面面積之粒子之直徑。 可氧化金屬粒子需要幼細才可助長與氧作反應係一普速常識，實際上此 甲 4(210X297 公发） 請先閲讀背面之注意事項再填寫本頁) *裝· •訂· 21389 ί Α6 Β6 五、發叫说明Ο ) 種商用金屬粒子最大粒度爲125微米（俚其粒度分fc紙至超微粒大小）普 遍被使用且極滿意。 本發明之第二方面提供一種陶瓷焊接用之物質组合物，該組合物含有耐 熔粒子與可氧化金屬粒子之混合物，其特徵爲耐熔粒子之調和平均粒度係 介於300與1000微米之間，其耐熔粒子之粒度範圍擴展因子係介於0.4與1.1 之間。 較佳之组合物包含耐熔氧化粒子及矽粉末之混合物，矽爲該混合物之唯 一基本形式成分。 用於本發明之耐熔氧化物以矽石較佳，存在於組合物之矽粉末可以爲組 合物總重量最少百分之十至百分之十八。而以百分之十二至百分之十六爲 較佳。 本發明之陶瓷焊接方法及組合物在以下實施例中説明： 實施例1 一種組合物包含一種以百分之八十四重量之碾碎矽石耐熔材料與百分之: 十六重量之基本形式矽粉末製成之混合物，該耐熔材料之粒子粒度爲最大 2公分最小25〇微米平均爲75〇微米，該耐熔材料之調和平均粒度爲600微 米，粒度範圍擴展因子爲〇.95，矽之粒度最大爲125微米，其平均粒度爲26 微米》 該混合物以英國專利2,173、ns號（附註）所敘述之機器及方法在i〇〇(TC 下噴在矽石耐熔碑上，粉末係利用55〇NL/min之氧化氣體流率及1:2之空氣 /氧氣（Air/Oxygen)比例以6〇kg/hr速度輸送，粉末從19inm直徑之喷哑射出， 喷咀距離耐熔材料底質75-100mm » 該混合物自動燃點造出一良好焊接，牢固黏貼底質及具有與底質近似之 物理及化學特敬。 該焊接經化學分析顯示礬石（alumina)含量爲2.1%，而主磚内之典型値爲 1.5 〜2% » {請先聞讀背面之注意事項再填寫本頁) 甲 4(210Χ 297乂沒） {Τ'] 2ί3Βί·'ΐA (i B6 V. Description of the invention (—) Improved ceramic welding method (please read the precautions on the back and then fill in this page. This invention is an improvement of the ceramic welding method and related technologies, especially related to the powder used in the method The particle size of the combination of ingredients is characteristic. The present invention also provides an improved material combination for the ceramic welding method. The ceramic welding method has long been used to repair the coke, glass and similar materials, such as British Patent 402 203 No., L330, 894 and 2_〇35, 524, Swedish Patent No. 102 No., Tao Dang welding method usually involves transporting a mixed powder in a transport gas of a material combination to a spray, powder particles are sprayed After mixing with oxygen-containing gas, a surface is ejected from the spray, where a part of the mixed powder reacts with oxygen to emit heat, which causes the other parts of the mixed powder to fuse with itself and with the surface to achieve minimum welding. 》 The typical material combination for ceramic welding method is a pair of fused oxide and mixed powder of metal and / or metalloid particles, which is used to form ceramic welding method. The material combination and method of thermal materials are shown in British Patent Nos. 2,154,228, 2110, 2000 and 2,170, m. The above properties include approximate particle size and particle size distribution. Order · British Patent 2,17. , No. 191 describes the particle size characteristics of the refractory particles and oxidizable metal particles, and its main patent application scope is ①the average particle size of the refractory zizi-must be greater than the average particle size of the oxidizable particles, and ②the size range of the refractory particles must be Above a certain minimum point, which has been seen in previous patents such as British Patent No. 1,33〇, 894, which lists the maximum average particle size of glare-resistant particles and oxidizable particles as 500 micrometers (microns) and 50. Micron, the British patent uses claws to indicate a wider particle size distribution line. Making the particle size range higher is beneficial to the formation of durable welds, which reduces porosity and cracks compared to welds formed with glare particles with a more uniform particle size distribution. The benefits derived from the combination of the methods and substances disclosed in British Patent No. 2,17〇, 191 have found that the use of refractory particles with a consistent particle size distribution than the patent f · li can form high quality And durable refractory materials, especially those that remove the rough parts of the refractory particles to help the combined logistics flow through the delivery: delivery system, which can make the welded product smoother and reduce the transportation of materials not used for welding Ratio,: The elimination of the fine particles of the soluble particles also helps the material flow, and it also helps to reduce the floating air during sowing: the amount of silica dust in the air and the floating dust in the reaction zone, thus reducing the non-use Welding output f 4 (210X297X ^ 1) 213894 Printed by the Central Bureau of Standards of the Ministry of Economic Affairs A 6 A. The invention is called (2) The ratio of the material to be sent to enhance the heat-generating reaction of the oxidizable particles so that these reactions are not suppressed like stone dust It is used in fire extinguishers in underground mines. The compositions disclosed in British Patent Nos. 2,154,228 and 2,110,200 include non-combustible refractory materials and exothermic oxidizing substances, the latter having an average particle size of less than 50 microns and containing silicon and aluminum, wherein the aluminum reaches a total weight of 100 Twelfth, British Patent No. 2,154,228 discloses that the aluminum content is at least 1% of the total weight. The silicon-aluminum mixture disclosed in the embodiments of the above patents is used in combination with refractory oxide particles, which contain one or more minerals such as cobalt dioxide, magnesium oxide, alumite, silica, sillimanite, lead silicate, etc. The features of all the above patents are that the refractory particles can be made into a proper selection as a welding repair composition, so that it is the most similar to the treated refractory substrate. The ceramic welding method is widely used for repairing coke-making lubricating fabrics made of silicon refractory blocks. After the preparation of the composition, the welding powder contains a mixture of aluminum, silicon and silica particles. British Patent No. 2,154, 228 cites the repair of coking coke. The composition contains 1% aluminum, 12% silicon, and 87% silica, calculated by weight φ. In the coking furnace, the silicon refractory lumps are not 100% pure silica, and the composite oxidized refractory molecules contain small amounts of impurities such as Ming, iron, and calcium. The silica component of the preferred welding powder is a crushed silicon refractory with the same grain and chemical structure as described above. The use of a welding powder mixture containing one percent by weight of aluminum, silicon and crushed silica refractory material may not necessarily produce a complete match with the composition of the obtained stone material, which is not chemically compatible, plus the welding powder used The mixture around the material ejected by the spray gun is lost and cannot be formed into a part of the repaired product because it is not contained in the heat range of the repaired part. The lost material is mainly refractory material, so the use of aluminum in the welding powder, especially the weight At least 1%. The result is that the aluminum oxide is oxidized in a higher amount in the welding repair itself and in a lower amount in the silica refractory material. Furthermore, it was found that the welding caused by the mixture of aluminum, silicon and silica powder may contain a part of silicon metal. Some experts believe that it is harmful to the quality and durability of the welding product, and it affects the performance of the entire method. It should be noted that the temperature of the refractory material may be 800 at the end when repairing the coking luke (: even 1200 ° C, which is exceeded in the center of the lube. Although the use of aluminum in the welding powder mixture can promote a good welding start at a lower temperature, but At a higher temperature such as 1200 · (〇 and above may cause high and bad Yu 4 (210X297 public) (^) Please read the precautions on the back before filling out this page) • 笟. • Line · Central Standards of the Ministry of Economic Affairs Bureau Print Exemption A6 B6 V. Description of the invention (3) The reaction rate is such that the soft layer in the reaction zone is overheated and becomes low viscosity and easy to flow. It is difficult to correct the welding application when this phenomenon occurs, because the injection of the welding powder vertebral penetration rate Force the soft block layer to diffuse and deform in the periphery to produce porous and uneven surface and poor welding quality. One of the objects of the present invention is to provide an improved ceramic welding method and its composition. Another object of the present invention is to provide a ceramic for use The composition of the welding method can make the welding repair material and the refractory material have better chemical coordination. Another object of the present invention is to provide a ceramic The composition of the welding method can be used at a higher temperature, such as a minimum of 800 · 〇 substrate temperature without causing the deformation and poor welding quality caused by the use of the aluminum-containing composition. The first aspect of the present invention provides an improved ceramic welding The method is to use a mixture containing refractory particles and oxidizable metal particles from spraying and oxygen-containing gas on a surface to make the oxidizable particles react with heat to achieve other particles of the mixture and themselves and the surface at least as part Fusion to form a weld, characterized by the harmonic mean particle size of the refractory particles (as described below) between 300 and 1000 microns, and the size range spread facfor of the glare-resistant particles (as described below) ) Is between 0.4 and 1.1. The blended average particle size is defined as £ CW; / S〇 where wi is the percentage or weight of the substance in the one-in-one particle size class, and Si is the average particle size in the one-in-one particle class The particle size range expansion factor is defined as: 2 (G80-G20) F (G) =-G80 10 G20 where G80 represents 80% particle size of refractory particles, G20 represents 20% particle size of refractory particles, and% particle size 〃 represents The percentage of the weight of the refractory particles. It can be passed through a sieve with a mesh of this size. ΛHarmonic mean size 〃 (Harmonic mean size) — The word can be used to summarize the particle size distribution, because the word is well known in the ceramic welding process The chemical reaction depends on the surface, which is defined as the diameter of the particles with an average surface area. The oxidizable metal particles need to be fine to promote the reaction with oxygen. It is a common sense. 210X297 Public issue) Please read the precautions on the back before filling out this page) * Package • Order 21389 ί Α6 Β6 5. Calling instructions Ο) The maximum size of commercial metal particles is 125 microns Ultrafine particle size) is commonly used and very satisfactory. The second aspect of the present invention provides a material composition for ceramic welding, which contains a mixture of refractory particles and oxidizable metal particles, characterized in that the fused particles have an average particle size between 300 and 1000 microns The expansion factor of the refractory particle size range is between 0.4 and 1.1. The preferred composition contains a mixture of refractory oxide particles and silicon powder, and silicon is the only basic form of the mixture. The refractory oxide used in the present invention is preferably silica. The silicon powder present in the composition may be at least 10% to 18% of the total weight of the composition. And 12% to 16% is better. The ceramic welding method and composition of the present invention are described in the following examples: Example 1 A composition contains a crushed silica refractory material with a weight of 84% and a base of 16% by weight In the form of a mixture of silicon powder, the particle size of the refractory material is a maximum of 2 centimeters and a minimum of 25 microns and an average of 75 microns, the blended average particle size of the refractory material is 600 microns, and the particle size range expansion factor is 0.95 The maximum particle size of silicon is 125 micrometers, and the average particle size is 26 micrometers. The mixture is sprayed on silica refractory monument under the machine and method described in British Patent No. 2,173, ns (note) under i〇〇 (TC It uses the oxidizing gas flow rate of 55〇NL / min and the air / oxygen ratio of 1: 2 at a rate of 60kg / hr. The powder is ejected from the 19-in.m diameter spray matte and the nozzle is away from the refractory material Substrate 75-100mm »The mixture automatically ignites to create a good weld, which firmly adheres to the bottom and has physical and chemical specialities similar to the bottom. The analysis of the weld by chemical analysis shows that the content of alumina is 2.1%, and Typical in the main brick 1.5 ~ 2% »{Note Please read the back of smell and then fill the page) A 4 (210Χ 297 qe no) {Τ '] 2ί3Βί ·' ΐ
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五、發明説明（玉J 作爲比較，以一種用82.5%重量之碾碎矽石耐火材料，16%之基本形式 矽粉末及1.5 %鋁製成之混合物爲上述過程喷在矽石耐火材料磚上，該焊 接結果經化學分析顯示礬石含量爲5.7%，其像石成分與主磚内之典型値 1·5〜2%大有差别。 上述結果確定以本發明所用之組合物焊接之含量只有試驗焊接含量之一 半 實施例2 如實施例1配製之組合物，但該混合物含有Η %重量基本形式之矽及86 %重量之碾碎矽耐火材料，其他方面與實施例1相同„ 在相同環境下將該混合物喷在矽石耐火材料磚上，結果焊接及主底質均 顯示礬石含量與實施例1所得者接近β尤有進者，以來發明之电合 焊接之基本矽不含量明顯低於用先前技術造成者。 實施例3 茲重覆實施例1之實驗，但用一組合物其中含有耐熔粒子混合物其粒 介於1賴與25〇micr〇m微米之間調和平均粒度爲侧micr〇m及粒 ^届 爲0.6 °結果焊接工作之燃點及控制均順利，完成一原密耐久之焊接。 實施例4 。茲進一·步以前述實施例所用之組合物作不同溫度實驗， C及12〇〇 C ,實驗在煉焦破現場進行以建立施用本發明之 00 :斤有實驗皆獲得良好結果，即粉末燃點容易，谭接順利G到㈡焊 (請先閱讀背面之注意事項再填寫本页) 經濟部中央摞準局邙裝 公 7 9 2 X 10 2 /IV 4 甲V. Description of the invention (Jade J As a comparison, a mixture of 82.5% by weight of crushed silica refractory material, 16% basic form silicon powder and 1.5% aluminum was sprayed on the silica refractory brick for the above process The chemical analysis of this welding result shows that the content of alumite is 5.7%, and its stone composition is significantly different from the typical value of 1.5-5% in the main brick. The above results confirm that the content of the composition used in the present invention is only One-and-a-half of the test soldering content Example 2 The composition prepared as in Example 1, but the mixture contains 5% by weight of silicon in basic form and 86% by weight of ground silicon refractory, otherwise the same as Example 1 in the same environment Next, the mixture was sprayed on the silica refractory bricks. The welding and main substrates showed that the content of alumina was close to that obtained in Example 1. β is especially advanced. The basic silicon content of the electro-welded welding has been significantly lower since the invention. Example 3 The experiment of Example 1 is repeated, but the composition contains a mixture of refractory particles whose particles are between 1 μm and 25 μm. mi cr〇m and grains are 0.6 °. The result is that the ignition point and control of the welding work are smooth, and an original dense and durable welding is completed. Example 4. Here is a step-by-step experiment of different temperatures with the composition used in the previous example, C And 12〇〇C, the experiment was carried out at the coking and breaking site to establish the application of the present invention 00: Jin You experiments have obtained good results, that is, the powder ignition point is easy, Tan Tan smoothly G to ㈡ welding (please read the notes on the back before filling (This page) The Ministry of Economic Affairs, Central Bureau of Pre-Examination, 7 9 2 X 10 2 / IV 4 A