經濟部中央榡準局印裝 219354 A6 ___ B6 五、發明説明（ ) 發明背景 陶变/破璃複合基板係以破璃爲基材,並於其中分散以陶瓷 微粒填充物。破璃為基板之主成份，基板之基本性質受玻璃種類及其成份 之影響；而陶瓷填充物係用以改變或増強基板之物理或化學特性，故可斿 調整玻璃組成及陶瓷填充物之種類及比例以改變陶瓷/玻璃之特性，以滿 足不同需要。例如電子構裝之多晶片棋組m〇du7asj用之多層 陶究基板~w7t7'7ayer ceramic substrate),以陶变/破璃複合基板製作 時，可遴用低介電常數，低熱膨脹係數之玻璃，如硼矽睃玻璃，以配合陶 究填充物如非晶質二氣化矽（fiysec/ s/77.ca)，堇音石（corc/7.eri.ie),鎂橄 欖石（forsierKe)，氣化鋁等，並藉由破璃與陶瓷填充物比例之調整，使 基板可在S如〜J⑽(TC燒結圾密，如此可選用熔點低並具低電阻之金屬如 金、銀、銅等爲線路導體，製成低介電常數，且熱膨脹係數接近矽晶片之 多層式陶变基板，達成高石夕晶月密度構裝，高佈線密度•的 density)及T靠度，並減少訊號在基板傳輸之延遲及產生之雜訊，以符合 大锢電腦系統及超級電腦之設計需求。 在記錄媒體硬式礙碟機方面，以陶究/破璃複合基板製作磁碟X基板 時，可利用玻璃在高溫軟化時攤平之特性以得到高平坦度之基板，再於破 璃基材中添加橄細陶究顆粒，拋光後自然於表面形成數十至數百埃之微小 高低起伏。故以此製程可裴得高硬度，高平整度，且有逋當表面紋理 itexturd之硬碟基板，且可簡化硬碟月之製程，増加硬碟密度，符合高 記愫容量磁碟；i之需求。 也可利用低热膨脹係數及良好耐熱衝擊等特性之破璃如堋矽睃玻璃， 鋁矽睃玻璃，並配以高機械強度及高熱傳導率之陶瓷填充物如氣化鋁，破 化妙或H化料製成内含加熱線路之加熱板、加熱狀遠紅外_射器等 〇 陶究/破瑞複合基板因有以上優點’故有廣泛應用承力；然此系統因 有天生機械強度不足的弱點，故其應用範面受到限制。 甲4(210X 297公发） ί請先閲讀背面之注意事項再瑱寫本页) it A6 B6 219354 五、發明説明（，丨 陶瓷或玻璃材料因其脆性之閼係，當其表面有裂缝或刮痕等表面缺陷 並處於張應力（tensWe stress)狀況時，表面缺陷極易向内成長而導致 陶变體之破壌。玻璃或陶瓷典哩強化方法即於表面產生一|錄應力 (compressive stress)，以抑制表面裂缝之成長。此時，欲使表面裂缝成 長，需要額外张應力以超越此表面壓縮應力方可，因之，陶瓷體之強度得 提高。 本發明以前，於破璃表面形成壓縮應力的技術有下列5種：J離子交 換法，2.熱回火法ft/jenna? ie/^er7·/^) ; 3.表面結晶控制法；壓合法 na/nfnaiej ; 5.表面被復法。茲分別簡述如下： J.離子交換法 本法是將擬被強化物品浸入融炫的里類中，使物品表面的離子與里 類中之離子進行離子交換。因強化機構與溫度範園之不同，此法吁分為 一類。第一類之處理溫度在應變點（stra/n p0/n~以下，以融盥中離子 半#較大的離子取代待強化試月中離子半徂较小的離子。此為一般平板 破璃之強化方法。例如以_離子取代玻璃中之勤離子，因奸離子傲積較 大，進入破璃後於破璃表面產生一摩縮應力。設定熱處理潘度於慮變點 以下’是避免玻璃材料產生流變Hew)，導致恩绮應力衰減。 第一類之處理溫度在應變點溫度以上，以較小離子半徑的離子取代較大 半徑之離子。如以鋰離子取代坡璃中之餉離子。因鋰破璃較鈷玻璃熱膨 脹係數小，故於冷卻遇程中，含鋰離子的表層產生一壓縮應力，玻璃板 得以強化。離子交換法因發展较早，技術成熟，處理物品不限玻璃，結 晶體亦可，故應用甚廣。惟其缺點為薄物髅產生變形，熱處理後氩類附 著表面，容易造成污染，且無法強化内含元件及線路之物品，如陶变構 哼 裝基板。美國專利J於破璃成形後，以離子交換法將表面的鈉 | 離子以鋰離子取代之，後續熱處理中，於破璃表面產生々石英固溶體 I 結晶，而造成表面熱膨脹係數較小，冷卻後產生壓缩應力，而使表面得 f W強化。 甲 4(210X2972 潑) 請先閱讀背面之注意事項再填寫本頁) •裝· 一 4 - 219354 A6 B6 經濟部中央標準局印敦 五、發明說明（) 熱回火法 本法係於破璃成形後，當破璃仍在高溫時吹風冷卻至應力消除黠 (TlmieaHng Temperaiurej，此時表面冷卻較快，體積收縮量較大，迫 使仍停留在较高溫之内層產生流變，故外層不致於有張應力形成，再W 较低之冷卻速率冷卻之，因表面溫度較低，冷卻至室溫後收縮量較小， 而内層之收縮量較大，故於表面產生壓缩應力，而此時表層溫度巳低於 應力消除點，壓缩應力不易衰減，故吁達到強化效果。这也是一般強化 玻璃常使用的方法，基本上此法僅逋用於玻璃或富含玻璃的簡易形狀物 品。其侵點是方法簡單，成本低；缺點是：僅用於玻璃或富含玻璃 的物品；僅能處理形狀簡軍且厚之物品；控制不易、易變形； 高溫使用時，強化效果自動消失，工作溫度範圍較小。 >3.表面結晶控制法 此法逋用於可結晶之玻璃或玻璃陶变，利用物理或化學方法，或僅 利用成份控剎，使物品於成形後再熱處理時表面結晶狀況與内部不同， 造成熱膨脹係數較低之表面，於冷卻後表面產生壓縮應力而強化。 美國專利利用SO?氣體與玻璃物品反應，於表面溶出鋰 離子’造成表面成份與内部不同，於後續熱處理時，表面完全結晶，内 部部份結晶，因熱膨脹係數不同，冷卻時於表面產生靨縮應力而強化。 美國專利4,2_ZS，5J2利用後續結晶熱處理處於高溫狀況，破璃表面 因易揮發物質如ZnO, b〇, S0205, L7·/»，及f等之揮發而使表面與内 部成伤有差異，結晶行爲因之不同，表面之私膨肤係數较小，冷卻後查 生壓縮應力而為之強化。 表面結晶控制法最大缺點為控制不易，物品變異性大，可靠性差， 且處理步驊多，變因多，成本高。另外，可用此法之材質成份範圍狭小 ^應用範圓小。 4·壓合法 此法爲先製作熱膨脹係數不同的玻璃薄月，再組合熱膨脹係數不同 甲 4(210X297 公发） -5 - 請先閲讀背面之注意事項再填寫本頁) _装· •線· 219354 A6 B6 經洚部中央榡準局印製 五、發明説明（，1 之薄；ί，加溫至玻璃軟化黠以上，再以壓力壓成—體，造成熱膨脹係數 较小的表層，冷卻後之表層產生壓縮應力致使強化。美國專利3,549,440 爲一例。此法之優點為容易以破璃薄月之成份及厚度控制強化層之厚度 與壓縮應力之大小。因此專利係先製作玻璃板再進行壓合，且處理溫度 高達J35(TC，故無法在其中製作電子元件或網印(Screen PrhiingJ線 路，如玻璃片太薄，則厚度均勻性不良，故無法踅作薄的強化玻璃板。 5.表面被復法 本法係於燒結後之物體表面上，以CM (化學氣相j或溅鍍 等方法鍍以低熱膨脹係數材料，處理時需加溫，處理後冷 卻時於物雅表面形成>#縮應力而強化之。美國專利4,7SJ,970爲一例。 其強化物品主要是氣化鋁或玻璃陶究基板。鍍層是二氣化矽或金屬氮化 物0镀層厚度自200埃至2橄米。其優點爲可以很薄的強化層強化物品 ，且可強化内含元件及線路的陶变基板。缺點為強化層的厚度無法太厚 f無法超過數微米），無法忍受表面刮傷，應用範園很受限制。 综上所述，幾種先前技術均係先將原料加熱至熔點以上，使其熔化爲 流體，再將此熔融物冷卻並做成玻璃平板或物品，再將其做表面處理，以 形成表面壓縮應力以強化之。或再以熱膨脹係數不同之破璃於高溫與之綦 屡，以達表面形成靨縮應力之目的。 除熔化後再冷卻成形製做破璃成品外，亦可以玻璃粉末或玻璃及陶究 混合粉末，利用粉體成形技術f如刮刀成形、乾壓成形、擠出成形、射出 成形等）做成所需形狀之生胚體，再將此生胚體置於遠较熔融溫度烏低之 溫度中燒結，製作緻密化之陶变/玻璃複合材料或物品。例如以玻璃為基 材，並加入陶变填充物之電子構装用多層陶瓷基板。惟一般皆無法達到高 強度，通常強度僅達J50〜Ja⑽Pa左右。強度不足爲以燒結製成陶瓷/玻 璃衬料之重要缺點。 請先閲讀背面之注意事項再瑱寫本頁} •訂. .線. 甲 4(2l〇X297i'海） -6 - 經濟部中央橾準局印裂 219354 A6 ___B6 五、發明説明（ ) 發明目的 本發明人因鑑於目前陶变/玻璃複合材料或物品強化方法之缺點，經 長時間實驗研究，乃發明一改良方法。 緣是’本發明之主要目的在提供一種強化方法，能大幅提高原材質基 板強度，且製程簡旱，控制容易，成本低。 本發明之另一目的在提供一種強化方法，可大幅増加強化層厚度，且 強化層厚度控制容易。 本發明之次一目的在提供一種強化方法，可以製作強化内有線路及電 子元件之多層陶究線路板。 本發明之再一目的在提供一種強化方法，適用之玻璃及陶变種類及比 率範固廣大，應用範面大。 本發明之詳細說明 烏使责審査委员能更加了解本發明之實體内容、特微及功效，茲詳 細說明如后： 本發明所用"陶瓷/玻璃"一詞係指以玻璃爲基材，另添加其他陶瓷 或玻璃微細粉末填充物（fiHer)所說成之複合材料。填充物 係用以強化玻璃基材或改變其物理或化學性質。填充物之重量比例可爲 〜，當其爲0時，即為破璃材料。 本發明之製程係先將玻璃及陶瓷粉末成形做成生胚，再燒結使之級密 化。粉體製備及生胚成形時，即需配製數種粉末配方，此等不同配方之粉 末做成生胚並燒結後，具有不同之熱膨脹係數，此等熱膨脹係數可由各個 別組成粉雅之物化特性推算求得’也可實際量測燒結後物品之熱膨联係數 而得。 本發明之強化原理係將於燒結後會具不同熟膨脹係數之生胚，在成形 時疊壓一起，並適當安排其成形步驟，使熱膨脹係數较小者在外層，熱膨 脹係數较大者在中間，形成多層結構。將此破璃結構高溫熱處理時，由於 甲 4(210X297 公发） 諳先閲讀背面之注意事項再填寫本頁) •装· •線· A6 B6 219354 五、發明說明（） {請先聞讀背面之注意事項再填寫本頁} 玻璃之軟化及流變，試；j因燒結緻密而勒結成一整體。在地結溫度時，因 玻璃可以流變消除應力，燒結完成後，試月開始降溫，當溫度低於玻璃軟 化點時，則材料因熱膨脹係數不同產生之應力即不易消除，在後續降溫時 ，因外層之熟膨躲;係數較小，故收箱量較小，而中間層因熱膨脹係數較大 ，收縮量較大，外層因受中間層收缩之拉力產生恭缩應力，可阻擋裂缝之 前進，產生強化效果。 本發明之強化原理可應用於任何由粉體成形做成生胚，再燒結成產品 之所有製程及產品。基本原則為於生胚成形時，將熱膨脹係數较小之材料 成形於外層0而產品強度増加之多少則依材料未強化前本身之強度、表面 壓缩應力層之厚度、表面層與中間層材料熱膨脹係數之差異、材料内所含 缺陷之大小及多少等而定。惟不論此等因素有何改變，只要表面存 在有靨縮應力層，即能増加成品之強度。 本發明特別逋合於強化平板，尤其是多層陶究基板（T/t77t7*-7ayer Ceramic substrate八而此多層陶变基板可用於多層陶变構裝（仙/玄7,7ayer Ceramic Pac/rage)或具有電磁屏蔽 f£7eciT〇-mag/7eiic sMe7c/7.ng)之硬 式後碟基板（hard disc substrate) 〇 本發明之強化方法包括下列各步驟： J.將兩種以上經燒結後具有不同熱膨脹係數之破璃粉末或玻璃與陶瓷之混 合粉末、溶則、黏結則、分散則、塑化則及其他添加則分別混合成兩種 以上均勻衆料or s7/pJ〇 玻璃粉末之主要成份爲二氣化矽、氧化硼，鹼金屬氣化物， 例如：A/a/，《20，Li20等，鹼土金屡氣化物含咐0，Ca0，及SaO等 ，及其他金屬氣化物如 P60, /Vi2〇3，及仙2〇5 經濟部中央標準局印- 等。 陶瓷粉末則包括：氣化鋁（W)、錤橄欖石(Yorsier/trej、石英、 二氧化# iZrOp、氮化鋁（/I7/V)、氪化硼、堇音石（cordieritrej、 二氧化鈦Π·?·%)、破化矽（S/Cj、氮化矽（5/ /V4>)、氧化鎂（《gCM，或 甲 4(210X297 公餐） —8 — 219354 A6 B6 濟 部 中 央 標 準 Μ 印 五、發明説明（) 非晶質二氣化矽（fused siHca)。 玻璃或陶变粉末之平均粒度吁在心』〜忉.0“7"之間，而以0.5〜 4/χ m爲佳0 溶剌可爲水，甲笨 fto7uene)、正丁酵 M-iJiviancW)、G 醇（et/ianoU 、甲醇 Onethano^、甲 G酮ethy7 fcetonej、甲基異丁基酮 7.so/jutW Jteionej、三氣G垸（frycWoro ei/janeJ、丙酮 (acetone)、異丙酵 f/so-propa/7〇7J 〇 勒結則可為聚已烯縮丁醛Ηη_κ7 Suiyra7, /Ψβ)、聚G烯醇 h/7y7 /17co/7〇7, ΖΨ/U、肀基纖維素（Wet外7 ceHtWoseJ、G基 鐵維素（^ί7»/7 ceNWosehJl肀基丙嫌跋甲S旨 fp〇7ymei/7_K7 methacry7ate，PWW/1J、忠Cj基丙燦跋甲 s旨（/?〇7y et/jy7 mei/7acry7ateJ 、致甲基丙燦歧met/jacrj^7_c acid)、或其他壓克力高分子 (acrylic resins) 〇 塑化則吁以是呔睃二辛喃（Zh-ociyi /j/?i/ia7aie, flOPj、呔政二丁 S旨P/jt/7a7ate, 、呔瞍丁基芊基蜡 Mt/t/7 Ser?2T7 Phthalate，BBP)、苽i 二铒（p〇iy ethyl glyc〇1，PEG) 0 分散則(7^Spersant)可以使用魚油〇i7;，脂肪睃、或笨磺睃 。其他小量添加則則包括除泡則及勒度調整則~7.sc〇s7." adjusting agent) 〇 而分散陶变粉末使漿料均勻的方法可用球磨（包括以77 m7.n， attrition min ...等），超音波粟盪（ultras〇nicann)寄。 將此等漿料形成兩種以上厚度均勻之生胚薄$，並切成遑當尺寸。 生胚薄另製作方法有刮刀成形法（iape casi7»,塗佈法…治叩） ’或擠出成獅（e_s㈣。彻成或塗佈法係個彻 或塗賴—W職料在朗、金上佩-厚度 么勻之蛛膜’待漿料乾燥後即形成生胚薄片〇生崎度依使用之需要約 J卿’將生胚切成適於加工之大小，例如直徑2"〜s"之圓形 請先閲讀背面之注意事項再填寫本頁) .裝· •訂· •線· 甲 4(210X297 公潑） —9 — 219354 Ιί濟部中央榡芈局印製 A6 B6 五、發明説明（> 或正方形薄片。 上將多片此等生胚薄片疊於一起，燒結後具有較小熱膨脹係數者至少各一 片分置於上下表層，燒結後具有较大熱膨脹係數者至少一月夹於上下表 層之中間，並加溫加餍疊成一體。如果強化層之生胚種類多於—種時， 則按照其熱膨脹係數之大小順序，依序將熱膨脹係數較小者置於较外層 Ο 依產品厚度之需求，將逋當層數疊於一起，再加壓加溫疊壓 Ha/ni/jaie)成一體之試片。綦壓溫度範团為仂〜以，綦壓蜃力範固 為J000〜5000PS1.，疊壓時間約爲J〜扣分鐘，堆積fstadthgj試爿時 ，需將熱膨脹係數較大者央置於中間，熱膨脹係數較小者置於表層。表 層厚度以約為0.05〜0.5細爲佳，其厚度视產品之總厚度調整。 如欲褽作電子構裝用多層陶瓷基板，可於生胚上用沖頭或雷射打出 許多通孔(Tia h〇7e)，再於通孔内充填金屬膏>eia7 pa犲句，再以網 印法Screen pn.nti⑻在生胚上網印導線圊形（conductor panerW , 再將此等印有線路之生胚片疊恩成一體。金屬音之金屬可以是金、銀、 銀/鈀合金、鎳或銅。 將眷恩後之生跖置於燒結坺中燒結並強化之。 將綦壓後之多層生胚置於空氣域中或吁控制氟氛如^^或、之坺 1-乂 j〜6c/m.n之速率升溫至4⑽〜印〇<>c ;停留〜4小時，將 生肱內之有機物完全燒除；再以2〜之速率升溫至6卯〜忉〇〇 ^，停留〇.5〜4小時，燒結以得到紙密化之基板；再以2〜J5〇c/;nin 之遑年降至室溫，即得到強化基板，強化作用在降溫過程中自然形成， 不需另外熱處理。 本發明之製程流程如附阁所示。 (請先閲讀背面之注意事項再填寫本頁) •裝. •痒 甲 4(210X297H) 10 - 219354 A6 B6 五、發叼說明（，i 本發明之製程流程圖 經濟部中央標準局印裂Printed by the Central Bureau of Economics of the Ministry of Economic Affairs 219354 A6 ___ B6 V. Description of the Invention () Background of the Invention The ceramic composite substrate with broken glass is made of broken glass and dispersed with ceramic particles in it. The broken glass is the main component of the substrate. The basic properties of the substrate are affected by the type and composition of the glass; and the ceramic filler is used to change or strengthen the physical or chemical characteristics of the substrate, so the glass composition and the type of ceramic filler can be adjusted And ratio to change the characteristics of ceramic / glass to meet different needs. For example, the multi-layer ceramic substrate used in the electronically built multi-chip chess set m〇du7asj ~ w7t7'7ayer ceramic substrate), which can be made of low dielectric constant and low thermal expansion glass when it is made of ceramic / glass composite substrate , Such as borosilicate glass, with ceramic fillers such as amorphous silicon dioxide (fiysec / s / 77.ca), cordierite (corc / 7.eri.ie), forsterier (forsierKe) , Vaporized aluminum, etc., and by adjusting the ratio of broken glass to ceramic filler, the substrate can be sintered in S such as ~ J⑽ (TC dense, so you can use low melting point and low resistance metals such as gold, silver, copper It is a line conductor, which is made into a multi-layer ceramic substrate with a low dielectric constant and a thermal expansion coefficient close to that of a silicon wafer, achieving a high-density structure, high wiring density, density, and T reliability, and reducing the signal The transmission delay of the substrate and the generated noise can meet the design requirements of the big computer system and supercomputer. In the case of hard disk drive for recording media, when making a magnetic disk X substrate with a ceramic / glass broken composite substrate, the flattening characteristics of glass at high temperature softening can be used to obtain a high flatness substrate, and then in the glass broken substrate Adding olive fine ceramic granules, after polishing, they naturally form tiny undulations of tens to hundreds of angstroms on the surface. Therefore, this process can obtain a hard disk substrate with high hardness, high flatness, and excellent surface texture itexturd, and can simplify the process of the hard disk month, increase the hard disk density, which is in line with the high-capacity disk; i demand. Can also use low thermal expansion coefficient and good thermal shock resistance and other characteristics of broken glass such as 堋 silica glass, aluminum silicon glass, and with high mechanical strength and high thermal conductivity of ceramic fillers such as vaporized aluminum, destructive or H The chemical material is made into a heating plate with a heating circuit, a heated far-infrared ray emitter, etc .. The ceramic / Borui composite substrate has the above advantages, so it has a wide range of bearing capacity; however, this system has inherent mechanical strength. Weakness, so its scope of application is limited. A4 (210X 297 issue) Please read the precautions on the back before writing this page) it A6 B6 219354 Fifth, the description of the invention (, 丨 ceramic or glass materials due to their brittleness, when the surface has cracks or When surface defects such as scratches are in a tensWe stress condition, surface defects can easily grow inwards and lead to the breaking of ceramic variants. The method of glass or ceramic strengthening is to generate a compressive stress on the surface. ) To suppress the growth of surface cracks. At this time, in order to grow surface cracks, additional tensile stress is required to exceed this surface compressive stress, so the strength of the ceramic body is improved. Before the present invention, it was formed on the broken glass surface There are five kinds of compressive stress techniques: J ion exchange method, 2. thermal tempering method ft / jenna? Ie / ^ er7 · / ^); 3. Surface crystallization control method; pressing method na / nfnaiej; 5. Surface coating Complex method. Here are brief descriptions as follows: J. Ion exchange method This method is to immerse the to-be-reinforced article in the melting class, so that the ions on the surface of the article exchange ions with the ions in the class. Due to the difference between strengthening institutions and temperature gardens, this law is divided into one category. The first type of treatment temperature is below the strain point (stra / n p0 / n ~), and the larger ions in the melted ions half ## are used to replace the ions in the half of the ions in the month to be strengthened. This is a general flat broken glass Strengthening method. For example, the ions in the glass are replaced by _ ions. Due to the large accumulation of adulterous ions, a frictional stress is generated on the surface of the broken glass after entering the broken glass. The heat treatment is set below the change point to avoid glass The material produces rheological Hew), which causes the Enqi stress to decay. The first type of treatment temperature is above the strain point temperature, and ions with a smaller ion radius replace ions with a larger radius. For example, the lithium ions replace the ions in the glass. Lithium broken glass has a smaller thermal expansion coefficient than cobalt glass, so during the cooling process, the surface layer containing lithium ions generates a compressive stress, and the glass sheet is strengthened. The ion exchange method is widely used because it is developed early and the technology is mature. It is not limited to glass and crystals. However, its shortcomings are that the thin skeleton is deformed. After heat treatment, argon attaches to the surface, which is easy to cause pollution, and it cannot strengthen the items containing components and circuits, such as ceramics. In the US patent J, after the glass is broken, the sodium | ions on the surface are replaced with lithium ions by ion exchange method. In the subsequent heat treatment, crystallization of quartz solid solution I occurs on the surface of the broken glass, resulting in a small surface thermal expansion coefficient. After cooling, compressive stress is generated and the surface is strengthened by f W. A 4 (210X2972 splash) Please read the precautions on the back before filling in this page) • Installed · 1 4-219354 A6 B6 Ind. V. Central Standards Bureau, Ministry of Economic Affairs, India 5. Description of the invention () Hot tempering method This method is based on broken glass After forming, when the broken glass is still at a high temperature, it is blown and cooled to the stress relief (TlmieaHng Temperaiurej). At this time, the surface cools faster and the volume shrinkage is larger, forcing the inner layer still staying at a higher temperature to produce rheology, so the outer layer does not have any Tensile stress is formed and then cooled at a lower cooling rate. Because the surface temperature is lower, the amount of shrinkage after cooling to room temperature is smaller, and the amount of shrinkage of the inner layer is larger. Therefore, compressive stress is generated on the surface, and the surface temperature It is lower than the stress relief point, and the compression stress is not easy to attenuate, so it is called to achieve the strengthening effect. This is also the commonly used method for strengthening glass. Basically, this method is only used for glass or glass-rich simple-shaped objects. The intrusion point is The method is simple and the cost is low; the disadvantages are: only used for glass or glass-rich items; can only handle simple and thick items; control is not easy and easy to deform; when used at high temperatures, the effect is strengthened It disappears automatically and the working temperature range is small. ≫ 3. Surface crystallization control method This method is used for crystallizable glass or glass ceramics, using physical or chemical methods, or using only the ingredients to control the brake, so that the article is shaped after The state of surface crystallization during heat treatment is different from the inside, resulting in a surface with a low thermal expansion coefficient, which is strengthened by compressive stress after cooling. The US patent uses SO? Gas to react with glass objects to dissolve lithium ions on the surface, causing the surface composition to be different from the inside. In the subsequent heat treatment, the surface is completely crystallized, and the internal part is crystallized. Due to the different thermal expansion coefficients, the shrinkage stress is generated on the surface during cooling and strengthened. US Patent 4,2_ZS, 5J2 utilizes the subsequent crystallization heat treatment at a high temperature, and the glass surface is broken Volatile substances such as ZnO, b〇, S0205, L7 · / », and f volatilize the surface and the internal damage, the crystallization behavior is different, the private skin expansion coefficient of the surface is small, and the health check after cooling It is strengthened by compressive stress. The biggest disadvantage of the surface crystallization control method is that it is not easy to control, the variability of the article is large, the reliability is poor, and the processing steps There are many, many variables, and high cost. In addition, the material composition range that can be used in this method is narrow ^ The application range is small. 4. The pressing method is to first make glass thin moons with different thermal expansion coefficients, and then combine different thermal expansion coefficients. 210X297 Gongfa) -5-Please read the precautions on the back before filling in this page) _Installed • Line • 219354 A6 B6 Printed by the Central Bureau of Central Bureau of Ministries 5. Description of invention (, 1 thin; ί, plus When the temperature is above the softening point of the glass, it is pressed into a body by pressure, resulting in a surface layer with a small thermal expansion coefficient. The surface layer after cooling generates compressive stress to strengthen it. US Patent 3,549,440 is an example. The advantage of this method is that it is easy to break the glass and thin the moon. The composition and thickness control the thickness of the strengthening layer and the magnitude of compressive stress. Therefore, the patent department first makes the glass plate and then presses it, and the processing temperature is as high as J35 (TC, so it cannot be used to make electronic components or screen printing (Screen PrhiingJ circuits. If the glass sheet is too thin, the thickness uniformity is poor, so it cannot be hesitated. It is made of thin strengthened glass plate. 5. The surface is covered by this method. This method is applied to the surface of the sintered object, and the material with low thermal expansion coefficient is plated by CM (chemical vapor phase j or sputtering). After cooling, it is formed on the surface of Wuya and strengthened by #shrinkage stress. U.S. Patent 4,7SJ, 970 is an example. The reinforced article is mainly vaporized aluminum or glass ceramic substrate. The coating is divaporized silicon or metal nitrogen The thickness of the plating layer of the compound 0 is from 200 angstroms to 2 olives. Its advantage is that it can strengthen the article with a very thin reinforcement layer, and can strengthen the ceramic substrate containing components and circuits. The disadvantage is that the thickness of the reinforcement layer cannot be too thick f cannot exceed Several micrometers), can not bear the scratches on the surface, the application of Fanyuan is very limited. In summary, several previous technologies are first heating the raw material above the melting point to melt it into a fluid, and then cooling the melt and doing Flat glass Or articles, and then surface treatment to form surface compressive stress to strengthen it. Or use broken glass with different thermal expansion coefficient at high temperature and repeated it to achieve the purpose of forming surface shrinkage stress. Cooling after melting In addition to forming glass broken products, glass powder or mixed powder of glass and ceramics can also be used to make green embryos of the desired shape using powder forming techniques such as blade forming, dry pressing, extrusion, injection molding, etc.) Body, and then sinter the green body at a temperature far lower than the melting temperature to make a dense ceramic / glass composite material or article. For example, glass is used as the base material, and the ceramic structure is added to the electronic structure. Multi-layer ceramic substrate. Generally, it can not achieve high strength, usually the strength is only about J50 ~ Ja⑽Pa. The strength is not enough to be an important shortcoming of ceramic / glass lining made by sintering. Please read the precautions on the back before writing this page} • Ordered. Line. A 4 (2l〇X297i'sea) -6-The Ministry of Economic Affairs Central Quarantine Bureau printed 219354 A6 ___B6 V. Description of the invention () The purpose of the invention is due to the current ceramic change / glass The shortcomings of the reinforcement method of composite materials or articles are an improved method after a long period of experimental research. The reason is that the main purpose of the present invention is to provide a reinforcement method that can greatly increase the strength of the original material substrate, and the process is simple and easy to control The cost is low. Another object of the present invention is to provide a strengthening method that can greatly increase the thickness of the enhanced layer, and the thickness of the strengthening layer is easy to control. The second object of the present invention is to provide a strengthening method that can be made to strengthen the internal circuit and electronics The multilayer ceramic circuit board of the component. Another object of the present invention is to provide a strengthening method, which has a wide range of types and ratios of applicable glass and ceramics, and a wide range of applications. The detailed description of the present invention enables the review committee to be more To understand the physical content, features and functions of the present invention, the detailed description is as follows: The term "quote / ceramic / glass" used in the present invention refers to the use of glass as the base material, plus the addition of other ceramic or glass fine powder filler (fiHer ) The said composite material. Fillers are used to strengthen glass substrates or change their physical or chemical properties. The weight ratio of the filler can be ~, when it is 0, it is a broken glass material. The process of the present invention first forms glass and ceramic powder into a green embryo, and then sinters it to densify it. During powder preparation and embryo formation, several powder formulas need to be prepared. After these powders with different formulations are made into embryos and sintered, they have different thermal expansion coefficients. These thermal expansion coefficients can be calculated from the physical and chemical characteristics of each composition. It can also be obtained by actually measuring the thermal expansion connection number of the sintered item. The strengthening principle of the present invention is that green embryos with different cooked expansion coefficients will be stacked together during forming, and the forming steps will be properly arranged so that the smaller the thermal expansion coefficient is in the outer layer and the larger the thermal expansion coefficient is in the middle To form a multilayer structure. When heat-treating this broken glass structure at high temperature, because A 4 (210X297 public issue) knows the precautions on the back first and then fills in this page) • Installation · • Line · A6 B6 219354 V. Description of invention () {Please read the back side first Please pay attention to this page and then fill in this page} The softening and rheology of the glass, try; j is tightly integrated as a result of dense sintering. At the ground junction temperature, the glass can rheologically relieve stress. After the sintering is completed, the temperature starts to cool down. When the temperature is lower than the softening point of the glass, the stress caused by the different thermal expansion coefficients of the material is not easy to eliminate. Due to the cooked expansion of the outer layer; the coefficient is small, so the collection volume is small, and the middle layer has a large thermal expansion coefficient and a large amount of shrinkage. The outer layer is subject to constriction stress due to the pulling force of the shrinkage of the middle layer, which can prevent the crack from advancing. To produce a strengthening effect. The strengthening principle of the present invention can be applied to any process and product that is formed from powder into green embryos and then sintered into products. The basic principle is to form a material with a small coefficient of thermal expansion on the outer layer 0 during the forming of the green embryo. The strength of the product depends on the strength of the material before strengthening, the thickness of the surface compressive stress layer, and the thermal expansion of the surface layer and the intermediate layer material. The difference in coefficients depends on the size and number of defects contained in the material. However, regardless of any changes in these factors, as long as there is a shrinkage stress layer on the surface, the strength of the finished product can be increased. The invention is particularly suitable for strengthening flat plates, especially multi-layer ceramic substrates (T / t77t7 * -7ayer Ceramic substrate) and this multi-layer ceramic variable substrate can be used for multi-layer ceramic variable structure (Xian / Xuan 7, 7ayer Ceramic Pac / rage) Or a hard disc substrate with electromagnetic shielding f £ 7eciT〇-mag / 7eiic sMe7c / 7.ng). The strengthening method of the present invention includes the following steps: J. After two or more types are sintered, they are different The thermal expansion coefficient of broken glass powder or mixed powder of glass and ceramic, dissolution, adhesion, dispersion, plasticization and other additions are mixed into two or more uniform materials or s7 / pJ〇.The main components of the glass powder are Di-vaporized silicon, boron oxide, alkali metal vapors, such as: A / a /, "20, Li20, etc., alkaline earth gold repeated vapors containing 0, Ca0, and SaO, and other metal vapors such as P60, / Vi2〇3, and Xian 2〇5 Ministry of Economic Affairs Central Standards Bureau-etc. Ceramic powders include: vaporized aluminum (W), olivine (Yorsier / trej, quartz, dioxide #iZrOp, aluminum nitride (/ I7 / V), boron krypton, cordierite (cordieritrej, titanium dioxide Π · %), Broken silicon (S / Cj, silicon nitride (5 / / V4>), magnesium oxide ("gCM, or A4 (210X297 meals)-8-219354 A6 B6 Ministry of Economic Affairs Central Standard M India 5. Description of the invention () Amorphous fused silicon dioxide (fused siHca). The average particle size of glass or ceramic powder is in the heart "~ 忉 .0" 7 ", and 0.5 ~ 4 / χ m is better 0 The solvent can be water, methylbenzine fto7uene), n-butyryl M-iJiviancW), G alcohol (et / ianoU, methanol Onethano ^, methyl ketone ethy7 fcetonej, methyl isobutyl ketone 7.so/jutW Jteionej, three The gas G embankment (frycWoro ei / janeJ, acetone, isopropanol f / so-propa / 7〇7J 〇Liejie can be polyhexamethylene butyral Hη_κ7 Suiyra7, / Ψβ), poly-G-enol h / 7y7 / 17co / 7〇7, ZΨ / U, carboxyl cellulose (Wet 7 ceHtWoseJ, G-based iron weisu (^ ί7 »/ 7 ceNWosehJl cycylpyrrolidine S purpose fp〇7ymei / 7_K7 methacry7ate, PWW / 1J, loyal Cj Kibing Chanba s purpose (/? 〇7y et / jy7 mei / 7acry7ateJ, methyl / acrylic acid met / jacrj ^ 7_c acid), or other acrylic resins (acrylic polymers) 〇Plasticization is called dioxin (Zh-ociyi / j /? I / ia7aie, flOPj, 呔 政 二 丁 S purpose P / jt / 7a7ate,, 垔 瞍 butylfluorenyl wax Mt / t / 7 Ser? 2T7 Phthalate, BBP), 苽 i Er Er (P〇iy ethyl glyc〇1, PEG) 0 Dispersion (7 ^ Spersant) can use fish oil 〇i7 ;, fat or sulfonate. Other small additions include defoaming and degree adjustment rules ~ 7.sc〇s7. &Quot; adjusting agent) 〇The method of dispersing the ceramic powder to make the slurry uniform can be used ball milling (including 77 m7.n, attrition min ... etc.), ultrasonic milling (ultras〇nicann) Send. Use this slurry to form two or more thick green embryos with even thickness, and cut them to an appropriate size. The thin green embryos are also made by scraper forming method (iape casi7 », coating method… 治 叩) or Extruded into a lion (e_s㈣. Finishing or coating method is a thorough or coating method-W materials are in Lang, Jinshangpei-the thickness of the uniform arachnid 'will be formed into a thin slice of green embryo after the slurry is dried. Qing 'cut the green embryo into a size suitable for processing, such as a circle with a diameter of 2 " ~ s ", please read the precautions on the back before filling in this page). Install · • Order · • Line · A 4 (210X297 public splash ) —9 — 219354 ΙίMinistry of Economy Central Bureau of Public Affairs printed A6 B6 V. Description of the invention (> or square flakes. A number of these green embryo flakes are stacked together, after sintering, at least each with a smaller coefficient of thermal expansion One piece is placed on the upper and lower layers, and the one with a larger thermal expansion coefficient after sintering is sandwiched between the upper and lower layers for at least one month, and is heated and stacked to form a whole. If there are more types of green embryos in the strengthening layer, then follow the In order of thermal expansion coefficient, place the one with the smaller thermal expansion coefficient in the outer layer in order. According to the product thickness, stack the layers together, then pressurize, heat and stack (Ha / ni / jaie) into one. Audition. The pressure temperature range is around ~, the pressure pressure range is J000 ~ 5000PS1. The stacking time is about J ~ minutes, when the stacking fstadthgj is tested, the center with the larger thermal expansion coefficient needs to be placed in the middle. The one with the smaller coefficient of thermal expansion is placed on the surface. The thickness of the surface layer is preferably about 0.05 ~ 0.5. The thickness is adjusted according to the total thickness of the product. If you want to use as a multilayer ceramic substrate for electronic construction, you can punch a lot of through holes (Tia h〇7e) on the green embryo, and then fill the through holes with metal paste > eia7 pa 犲 句, then Use the screen printing method Screen pn.nti⑻ to print the conductor panerW on the green embryo screen, and then stack the green embryos printed with lines into one. The metal of the metal sound can be gold, silver, silver / palladium alloy , Nickel or Copper. Put the raw plantlets after the favor in the sintered sinter and strengthen it. Put the multi-layered green embryos after pressing in the air domain or control the fluorine atmosphere such as ^^ or, Zhi 1- 乺The temperature of j ~ 6c / mn is raised to 4⑽ ~ 印 〇 < >c; staying for ~ 4 hours, the organic matter in the raw brachial is completely burned out; then the temperature is raised to 690 ~ 忉 〇 ^ at a rate of 2 ~ Stay for 0.5 ~ 4 hours and sinter to obtain a paper-densified substrate; then reduce the temperature to room temperature by 2 ~ J5〇c /; nin, that is to obtain a strengthened substrate, the strengthening effect will naturally form during the cooling process Additional heat treatment is required. The process flow of the present invention is shown in the attached cabinet. (Please read the precautions on the back before filling this page) • Install. • Itch 4 (210X 297H) 10-219354 A6 B6 V. Release notes (, i Process flow chart of the present invention is printed by the Central Bureau of Standards of the Ministry of Economic Affairs
請先閎讀背面之注意事項再填寫本百) •線. 甲 4(210X297 公发） 219354 A6 B6 五、發叼説明（； 實旄例J-3 f玻璃平板之強化^ 將平均粒度約爲3 um，燒結後熱膨脹係數不同之兩種破璃粉末（玻 璃‘g7ass /1，·玻璃S-g7ass β)，分別與饜克力樹腊，酞晈二辛碏，三氯 C·烷均勻混合，球磨24小時，得兩種均勻漿料，成份比例如表一所示。 以刮刀將此兩種聚料分別成形於高分子薄膜上，乾垛後即成為厚約心』腳 之兩種生胚薄爿。 實施例J及實施例2旨在顯示兩種不同破璃材料/1及Wass ~ 之強化性質，其玻璃成份如表二所示。g7ass /1為低膨脹係數材料，gkss β為高膨脹係數材料0實旄例3為含有此兩種破璃之三明治結構。上下兩 層為g7ass 4 ;內一層為g7ass β 〇上下兩層厚度均約爲200 u m ;内央 場厚良b 2.8_。 表一、g7ass /1及β兩種漿料成份比例 請先閲讀.背面之注意事項再瑱寫本頁一 .装· glass A ： 50g ---OOP ·· 5g 三氣G烷：S5cc 展克力樹腊：抑 glass B ·· 50g •訂· 經濟部中央標準局印- 表二、g7ass /1及g7ass β之成份 glass A glass B Si〇2 54.8 56.1 % 23.2 16.1 ΑΨ3 6.1 10.5 10 17.4 RO 5.9 4.9 f代表鹼金屬 /?代表鹼土金屬 •線· 12 - 甲 4(210X2971'髮) 219354 A6 B6Please read the precautions on the back before filling in the hundred) • Line. A 4 (210X297 public issue) 219354 A6 B6 V. Release notes (; Example of strengthening J-3 f glass plate ^ The average particle size will be approximately 3 um, two kinds of broken glass powders (glass' g7ass / 1, · glass S-g7ass β) with different thermal expansion coefficients after sintering, and they are evenly mixed with cresyl wax, phthaloxane, trichloro C · alkane After 24 hours of ball milling, two uniform slurries were obtained, the composition ratio of which is shown in Table 1. The two aggregates were formed on the polymer film with a doctor blade, and after dry stacking, they became two thick and thick feet. The embryo is thin. Example J and Example 2 are designed to show the strengthening properties of two different broken glass materials / 1 and Wass ~, and their glass compositions are shown in Table 2. g7ass / 1 is a low expansion coefficient material and gkss β is High expansion coefficient material 0. Example 3 is a sandwich structure containing these two broken glass. The upper and lower layers are g7ass 4; the inner layer is g7ass β 〇The thickness of the upper and lower layers are about 200 um; the inner central field is good and good b 2.8 _. Table 1, the ratio of g7ass / 1 and β two slurry ingredients, please read first. The precautions on the back before writing this page 1. Pack · glass A: 50g --- OOP · · 5g tri-gas G-Alkane: S5cc Zhanli tree wax: glass B · · 50g • order · printed by the Central Bureau of Standards of the Ministry of Economic Affairs-Table 2, g7ass / 1 and Composition of g7ass β glass A glass B Si〇2 54.8 56.1% 23.2 16.1 ΑΨ3 6.1 10.5 10 17.4 RO 5.9 4.9 f represents alkali metal /? represents alkaline earth metal • wire 12-A 4 (210X2971 'hair) 219354 A6 B6
生胚X在7iTC及20⑽ρ5ϊ.壓力下鲞壓分鋟。綦壓後之生胚以 nv_之速牟在破中幵溫至冒c，保持2小時，將有機物燒除，再升 溫至65(TC燒結J小時，燒結後之基板強度如表三所示。由表中資料顛示 ，具有三明治結構的實施例3之材料较實施例j及2的早—坡璃材料，強 度増加了一倍，頭示以熱膨脹係數不同之玻璃生胚疊壓並燒結成基板，吁 有效提高破璃基板之機械強度。 表三 實 施 例 1 2 3 外 層 glass A glass B glass a 内 層 glass A glass B glass B 軟化點Ts f 565 588 熱膨脹係教〜5iWTC ( X扣力 71 106 Bending strength (MPa) 74.8 74.2 144.4 實施例(陶瓷/玻璃之強化） 不同熱膨脹係數之陶瓷/玻璃材料是將如表四所示一定比例的陶变與 玻璃粉末，和即黏結則，卯p及塑化刻及異丙醇及甲G酮的溶則混 合，球磨小時以成均勻漿料，以到刀將此漿料成形於高分子薄膜上， 乾燥後生胚薄片厚度為生胚薄片切成5anX5c/w大小，取加至 <32片生胚薄月，在70。〇：及200£?PS7·壓力下疊壓J0分鐘，綦層生胚以3 «C/znin速率升溫至600。(：，保持2小時，以消除有機物；再升溫至9〇〇 。〇燒結J小時，表四顒示實施例4至S各單一材料之性質。 請先閑續背面、ί/;;·χ意事項再填寫本頁) -裝. •缘. 經濟部中央標準局印裝 甲4(210X 297父髮） -13 - 219354 A6 B6 五、發明説明（! 表四 實 施 例 4 5 6 7 8 GAS GC GA GAF GfiQ Borosilicate glass 50 50 50 50 50 Alumina 25 — 50 25 25 Fused Si〇2 25 — — — — Cordierite — 50 — —* — Forsterite — 一 — 25 — Quartz — — — — 25 TCE(X10~7) 4Ch^600°〇 50.9 52.1 76.3 70.2 101.7 Bending Strength (MPa) 147.8 77.8 154.2 177.5 150.7 請先閱讀背面之注意事項再填寫本页) 表五 實 施 例 9 10 11 12 外 層 GC GAS G/IS GAS 内 層 GA GA GAF GfiQ TCE 之盖值（Xl(f7) 24.2 25.4 19.3 50.8 bending strength (MPa) 228.3 248.5 216.9 222.6 強度增加比例 48 61 22 48 •訂· .線. 經濟部中央標準局印裝 表四及表五中G代表玻璃相，其成份爲The raw embryo X is pressed under 7iTC and 20⑽ρ5ϊ. Pressure. The green embryo after the pressing is heated at the speed of nv_ and heated to the temperature of c, kept for 2 hours, the organic matter is burned out, and then heated to 65 (TC sintering J hours, the strength of the substrate after sintering is shown in Table 3 As indicated by the data in the table, the material of Example 3 with a sandwich structure is doubled in strength compared to the earlier-slope glass material of Examples j and 2, and the head shows that glass green embryos with different thermal expansion coefficients are stacked and burnt. Formed into a substrate, it can effectively improve the mechanical strength of the broken glass substrate. Table 3 Example 1 2 3 Outer layer glass A glass B glass a Inner layer glass A glass B glass B Softening point Ts f 565 588 Thermal expansion system ~ 5iWTC (X buckle 71 106 Bending strength (MPa) 74.8 74.2 144.4 Examples (strengthening of ceramics / glasses) Ceramic / glass materials with different thermal expansion coefficients are a certain proportion of ceramics and glass powders as shown in Table 4 The plasticized engraving and the dissolution of isopropyl alcohol and methyl G ketone are mixed, and the ball is milled to form a uniform slurry, so that the knife forms the slurry on the polymer film, and the thickness of the green embryo sheet after drying is cut into 5anX5c / w size, add to & l t; 32 pieces of green embryo thin month, at 70.〇: and 200 £? PS7 · pressure stacked for J0 minutes, Qi layer of green embryo at a rate of 3 «C / znin to 600. (:, hold for 2 hours, Eliminate organic matter; then heat up to 900. 0 sintering for J hours, Table 4 shows the properties of each single material of Examples 4 to S. Please rest on the back first, ί /; • Fate. Central Armament Bureau of the Ministry of Economic Affairs printed armor 4 (210X 297 father) -13-219354 A6 B6 5. Description of the invention (! Table 4 Example 4 5 6 7 8 GAS GC GA GAF GfiQ Borosilicate glass 50 50 50 50 50 Alumina 25 — 50 25 25 Fused Si〇2 25 — — — — Cordierite — 50 — — * — Forsterite — One — 25 — Quartz — — — — 25 TCE (X10 ~ 7) 4Ch ^ 600 ° 〇50.9 52.1 76.3 70.2 101.7 Bending Strength (MPa) 147.8 77.8 154.2 177.5 150.7 Please read the precautions on the back before filling this page) Table 5 Example 9 10 11 12 Outer layer GC GAS G / IS GAS Inner layer GA GA GAF GfiQ TCE Cover value (Xl (f7) 24.2 25.4 19.3 50.8 bending strength (MPa) 228.3 248.5 216.9 222.6 strength increase Example 48 61 22 48 • · Order Line. Ministry of Economic Affairs Bureau of Standards Table 4 and Table printing apparatus Fifth G represents a glass phase, which is a component
Si〇2 57.1% A12°3 10.2% B2°3 22.7% e2〇 4.5% RO 5.5% 14 一 甲 4(210X 297 乂发) 219354 A6 B6 五、發明説明（ ）f代表鹼金屬；/?代表鹼土金屬 其他符號之意義為：Z :氣化弈（a/iymkaj C :堇音石（corc/7'eriiej F :媒橄视石（forsterite) Q ··石矣（quartz)5 :非晶贫二氣化石夕fftysed sW icaj 漿料成份比例 陶究粉末 PVB DOP DBP 異丙碎 甲G酮 l〇〇g 6g 2g 2g 40 c.c. 40 c.c. 請先閱讀背面之注意事項再填寫本頁) 部 榡 準 局 印 實施例 利用上述不同熱膨脹係數的材料製備的三明治結構材料，用與實施例 4-β相同之簦壓及燒結條件將實施例9_J2之材料綦靨及燒結f各實施例 材料上下兩層厚度皆為，内層厚度為，燒結後之材料性質 如表五所示。表五示實施例9_j〇顒示相同内層材料加不同外層材料，皆 有強化效果，強化效果與内層材料相比可提高5σ〜5〇%;實施例頭 不，不同内層材料加相同外層強化材料，亦皆有強化效果。強化效果與内 層材料相比可提高Μ〜5似，由以上各實例吁知，此種利用熱膨脹係數的 差異，不論差異大小，皆有強化效果。故τ證明，利用熱膨脹係數之不同 ’以生胚H魏結方式狀之絲，確可有賴高陶究/玻璃基板之 強度。 _崎上所述，本發明多層陶瓷/玻璃平板之強化方法利用熱膨賬係數不 同〈内外層生胚，予^織再燒結方式不需其他處理程序即能大幅提高 甲4(210X297 公沒） 15 — •訂· 219354 A6 B6Si〇2 57.1% A12 ° 3 10.2% B2 ° 3 22.7% e2〇4.5% RO 5.5% 14 Yijia 4 (210X 297 异 发) 219354 A6 B6 V. Description of the invention () f stands for alkali metal; /? Stands for alkaline earth The meanings of other symbols of metal are: Z: gasification game (a / iymkaj C: coriander stone (corc / 7'eriiej F: forsterite) Q ·· stone carry (quartz) 5: amorphous poor two Gasification stone fftysed sW icaj slurry composition ratio ceramic powder PVB DOP DBP isopropyl methyl ketone l〇〇g 6g 2g 2g 40 cc 40 cc Please read the precautions on the back and then fill out this page) Example The sandwich structure material prepared by using the above materials with different thermal expansion coefficients, using the same pressure and sintering conditions as in Example 4-β, the thickness of the material of Example 9_J2 and the sintering of the two layers of each example are the same , The thickness of the inner layer is, the properties of the material after sintering are shown in Table 5. Table 5 shows Example 9_j〇 颙 shows the same inner layer material plus different outer layer materials, all have a strengthening effect, the strengthening effect can be increased by 5σ ~ 5 compared with the inner layer material 〇%; Example head, different inner layer material plus the same outer layer strength The materials also have a strengthening effect. The strengthening effect can be improved by Μ ~ 5 compared to the inner layer material. From the above examples, it is known that this difference in the use of thermal expansion coefficients, regardless of the size of the difference, has a strengthening effect. Therefore, τ proves that Utilizing the difference in thermal expansion coefficients, the filaments in the form of green embryo H Wei knots can indeed depend on the strength of high ceramics / glass substrates. _As mentioned above, the strengthening method of the multilayer ceramic / glass plate of the present invention uses thermal expansion coefficient Different "Inner and outer layer embryos, pre-woven re-sintering method can greatly improve A4 (210X297 male) without other processing procedures 15-• Order · 219354 A6 B6
五、發明説明（J 表四 實 施 例 4 5 6 7 8 GAS GC GA GAF GAQ Borosilicate glass 50 50 50 50 50 Alumina 25 一 50 25 25' Fused Si〇2 25 — — — — Cordierite — 50 — — — Forsterite — — 一 25 — Quartz — — _ — 25 TCE(X10~7) 40—600〇C 50.9 52.1 76.3 70.2 101.7 Bending Strength (MPa) 147.8 77.8 154.2 177.5 150.7 ί請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局印裂 表五 實 施 例 9 10 11 12 外 ，層 GC GAS G^is GAS 内 層 GA GA GAF GAQ TCE 之差值（Xl(f7) 24.2 25.4 19.3 50.8 bending strength (MPa) 228.3 248.5 216.9 222.6 強度増加比例 48 61 22 48 表四及表五中G代表玻璃相，其成份為V. Description of the invention (J Table 4 Example 4 5 6 7 8 GAS GC GA GAF GAQ Borosilicate glass 50 50 50 50 50 Alumina 25-50 25 25 'Fused Si〇2 25 — — — — Cordierite — 50 — — — Forsterite — — 25 — Quartz — — _ — 25 TCE (X10 ~ 7) 40—600〇C 50.9 52.1 76.3 70.2 101.7 Bending Strength (MPa) 147.8 77.8 154.2 177.5 150.7 ί Please read the notes on the back before filling this page) The fifth example of the printed table of the Central Bureau of Standards of the Ministry of Economic Affairs 9 10 11 12 The difference between the outer layer GC GAS G ^ is GAS inner layer GA GA GAF GAQ TCE (Xl (f7) 24.2 25.4 19.3 50.8 bending strength (MPa) 228.3 248.5 216.9 222.6 Strength increase ratio 48 61 22 48 In Tables 4 and 5, G represents the glass phase, and its composition is
Si〇2 57.1% A12°3 10.2% B2°3 22.7% E2° 4.5% RO 5.5% 14 - 甲 4(210X 297 公发） 219354 A6 B6Si〇2 57.1% A12 ° 3 10.2% B2 ° 3 22.7% E2 ° 4.5% RO 5.5% 14-A 4 (210X 297 public) 219354 A6 B6
五、發明説明（ '! f代表鹼金屬；代表鹼土金屬 其他符號之意義爲： >1 :氣化銘 fa7u/n/naj C:蓋音石（cordferftej f : ί美橄欖石（forsterUeJ Q :石英 S:非晶質二氧化·5夕（fused s/7/caJ 聚料成佾比例 陶变粉末 PVB DOP DBP 異丙轉 甲G酮 100g 6g 2g 29 40 c.c· 40 c.c. 請先聞請，背面之注意事項再填莴本頁) .裝· 經濟部中央標準局印装 實施例9-J2 利用上述不同熱膨脹係數的材料製僙的三明治結構材料，用與實施例 ‘8相同之疊餍及燒結條件將實施例之材料綦壓及絶結^各實施例 材料上下兩層厚度皆爲·?OOjU/n，内廣厚度爲2.8/mnJ，燒結後之材料性質 如表五所示。表五示實施例9-J0顼示相同内層材料加不同外層材料，皆 有強化效果，強化效果與内層材料相比可提高50〜6〇%;實施例jj-jp顯 示，不同内層材料加相同外層強化材料，亦皆有強化效果。強化效果與内 層材料相比可提高〜5似，由W上各實例可知，此種利用熱膨脹係數的 差異，不論差異大小，皆有強化效果。故可證明，利用熱膨脹係數之不同 ，以生胚、綦壓及燒結方式製成之基板，確可有效提高陶究/玻璃基板之 強度。 综上所述，本發明多層陶瓷/玻璃平板之強化方法利用熱膨脹係數不 同之内外層生胚，予以疊蜃後再燒結方式不需其他處理程序即能大幅提高 .訂. •線. 甲4(210X297 公沒） 15 - 219354 A6 B6 五、發明説明（） 陶变/破璃基板之強度f與原材質基板比較，強度可有效提高卯〜忉， 且製程簡單，控制容易，成本低廉。本發明亦吁大幅増加強化層厚度ΓΤ 達5卯以上），而離子交換法、熱回火法、及表面被復法強化層厚度 最多僅十幾橄米，相差甚多，故鋰本發明方法強化後之平板有較佳抗麽損 能力，且強化層厚度可由生胚之厚度及層數調整，控制容易。又本發明方 法可以強化内藏線路及電子元件之多層陶瓷線路板。具有經濟償值，利於 工業生產，應合於申請發明專利之條件。又有待言者，凡依本發明申請範 面之特微及精神所做之各種變化及修飾，皆應仍屬本發明涵蓋之範面。 請先聞讀背面之注意事項再填寫本頁) .裝. •線 經濟部中央標準局印裂 甲 4(210X 297W 发) 16 —V. Description of the invention ('! F stands for alkali metal; the meaning of other symbols for alkaline earth metal is: > 1: gasification Mingfa7u / n / naj C: cover sound stone (cordferftej f: ί 美 peridot (forsterUeJ Q: Quartz S: Amorphous dioxide · 5 eve (fused s / 7 / caJ Aggregate into stoichiometric ratio ceramic powder PVB DOP DBP Isopropyl methyl ketone 100g 6g 2g 29 40 cc · 40 cc Please listen first, back (Notes and refill this page). Installation · Printed by the Central Bureau of Standards of the Ministry of Economic Affairs Example 9-J2 Using the above materials with different thermal expansion coefficients to make a sandwich structure material, using the same stacking and sintering as in Example '8 The conditions of the materials of the examples are compressive and absolute. ^ The thickness of the upper and lower layers of the materials of each example is · OOjU / n, and the inner wide thickness is 2.8 / mnJ. The properties of the materials after sintering are shown in Table 5. Table 5 shows Example 9-J0 shows that the same inner layer material plus different outer layer materials all have a strengthening effect, and the strengthening effect can be increased by 50 ~ 60% compared with the inner layer material; Example jj-jp shows that different inner layer materials plus the same outer layer strengthening material , Also have a strengthening effect. The strengthening effect can be improved compared to the inner layer material ~ 5, as can be seen from the examples above, this difference in the use of thermal expansion coefficient, regardless of the size of the difference, has a strengthening effect. It can be proved that the use of the difference in thermal expansion coefficient is made by green embryo, pressing and sintering. The substrate can indeed effectively improve the strength of the ceramic / glass substrate. In summary, the strengthening method of the multilayer ceramic / glass plate of the present invention uses the inner and outer layers of different thermal expansion coefficients to generate embryos, which are superimposed and then sintered without additional treatment. The procedure can be greatly improved. Order. • Line. A 4 (210X297 public) 15-219354 A6 B6 5. Description of the invention () The strength f of the ceramic / broken glass substrate is compared with the original material substrate, and the strength can be effectively improved. In addition, the process is simple, the control is easy, and the cost is low. The invention also calls for a substantial increase in the thickness of the chemical layer ΓΤ (more than 590), while the thickness of the ion exchange method, thermal tempering method, and the surface reinforced layer is only a dozen at most There are many differences between olives, so the flat plate strengthened by the method of the present invention has better resistance to damage, and the thickness of the strengthened layer can be adjusted by the thickness of the green embryo and the number of layers, which is easy to control. The method can strengthen the multi-layer ceramic circuit board with built-in circuits and electronic components. It has economic compensation value, is conducive to industrial production, and should meet the conditions for applying for patents for inventions. All the changes and modifications made should still fall within the scope of the present invention. Please read the precautions on the back and then fill out this page). Packing. • The Central Bureau of Standards of the Ministry of Economic Affairs prints Split Armor 4 (210X 297W issued ) 16 —