200846495 九、發明說明 【發明所屬之技術領域】 本發明係有關以金屬被膜被覆電鑄成形磚表面之附金 屬被膜之電鑄成形磚及其製造方法，特別有關於玻璃製造 _ 設備中，構成爲與熔融玻璃接觸之部份等耐熱性及耐久性 '所需之構造部份之構件，適用之附金屬被膜之電鑄成形磚 及其製造方法。 【先前技術】 — 以金屬被膜被覆基材的方法例如電漿熔射、氫氧焰熔 射等之熔射法（例如··下述專利文獻1 )。此係使熔融金 屬呈粒子狀噴射，噴塗於基材之薄膜形成法，可任意適用 於導電性材料及絕緣性材料。 以金屬熔射被膜被覆金屬基材時，一般爲了提昇金屬 基材與熔射被膜之固定性，而於金屬基材表面施予噴塗處 φ 理等之前處理。詳細者係噴出硬質陶瓷粒子，撞擊於金屬 基材表面後，於金屬基材表面形成適當的粗度之凹凸。藉 由形成此凹凸，所熔射之金屬粒子侵入凹部，於凹部所固 化之金屬發揮錨效果後，實現金屬基材與熔射金屬被膜之 接合。 上述之方法係利用金屬基材之柔軟度及塑性變形性之 高度，而非成形磚等之金屬製基材時，由其基材之硬度、 脆度、塑性變形性之低度，並不適用於噴塗處理。 因此，以熔射被膜被覆成形磚時，藉由熔膠、凝膠法 -4- 200846495 等於成形磚表面設置陶瓷之中間層，介由此，意圖提昇成 形磚基材及金屬熔射被膜之接合。該中間層係經由陶瓷與 成形磚中玻璃（二氧化矽）相之化學鍵結形成強固的接合 ，於陶瓷中間層中吸入熔射金屬粒子，使熔射被膜固定之 〇 又，利用基材之多孔性，於存在於耐火物基材表面之 氣孔中塡充鉑微粒子與無機質材料之混合物，進行加熱燒 Φ 成後，磨蝕表面後，露出部份鉑微粒子，形成熔射被膜之 方法等被揭示之（下述專利文獻2 )。 * 〔專利文獻1〕英國專利1 242996號公報 〔專利文獻2〕特開平1 0- 1 95623號公報 惟，使用上述之陶瓷中間層之方法，相對於不含玻璃 相之基材而言，藉由化學鍵結後無法期待固定，故爲無效 者。因此，不適於以熔射被膜被覆玻璃相少之電鑄成形磚 〇 • 又，該專利文獻2之方法僅適用於多孔性之材料，因 此，一般不易適用於氣孔率較低之電鑄成形磚。 由此情況，對於玻璃相少、精密性高之電鑄成形磚而 言，欲經由熔射形成金屬被膜者有其困難，熔射後之金屬 於熔射中或熔射後之冷卻中，容易由電鑄成形磚剝離。 【發明內容】 本發明之課題係提供一種於玻璃相少、精密性高之陶 瓷基材中可形成緊密固定不易剝離之金屬被膜的金屬被覆 -5- 200846495 技術之開發，作成耐久性高之耐熱構造材料，有用之附金 屬被膜之電鑄成形碍。 另外，本發明之課題係提供一種所被覆之金屬被膜經 由應力不會剝離，可簡易且穩定的提供可作爲耐熱構造材 料使用之附金屬被膜之電鑄成形磚之附金屬被膜之電鑄成 形磚的製造方法。 爲解決該課題，本發明者進行精密硏討後結果發現， φ 刻意於電鑄成形磚表面形成凹凸後，藉由金屬與成形磚之 熱收縮量之差適當分散熱應力，可使適當發揮錨效果之金 屬被膜設置於電鑄成形磚表面，進而完成本發明。 本發明之一形態其主旨係附金屬被膜之電鑄成形磚具 備表面上形成有規則性錨用凹部之電鑄成形磚與被覆於該 電鑄成形磚之表面且被設置成塡滿該錨用凹部之金屬被膜 ，其中該金屬被膜含有鉑族金屬，該電鑄成形磚之氣孔率 在5容積％以下，玻璃相之比例在1 5質量％以下。 • 本發明另一形態其主旨係，附金屬被膜之電鑄成形磚 之製造方法係在氣孔率爲5容積％以下，玻璃相比例爲1 5 質量％以下之電鑄成形磚的表面上，形成規則的錨用凹部 ，將含鉑金屬之金屬熔射於該電鑄成形磚上，形成充滿該 錨用凹部且被覆該電鑄成形磚的表面之金屬被膜。 藉由本發明，於電鑄成形磚表面所形成之規則的凹凸 中，金屬被膜與電鑄成形磚間產生應力適度分散作用後， 不會產生凸部之斷裂，金屬被膜之變形，適度發揮錨效果 。因此，提供一種耐熱性及耐久性高，抑制經由溫度變化 -6 - 200846495 之金屬被膜剝離之附金屬被膜之電鑄成形磚 熱構造材料之使用。 【實施方式】 〔發明實施之最佳形態〕 高溫加熱之玻璃蜜用之耐熱構造材料中 磚’其中所需耐久性之臨界截面部中，又使 金之熔射被膜進行被覆之耐火成形磚。近年 昇確立了製造強度高之電鑄成形磚，針對玻 ’以電鑄成形磚取代耐火成形磚之使用固定； 電鑄成形磚係使耐火原料以艾魯式電i 1 900〜2500 °c，使完全熔融之耐火原料於所 下進行鑄造及漸冷固化後，取得耐火物，高 般燒成成形磚之強度及耐久性高。惟，電鑄 玻璃相之比例少，因此，作成提高與金屬被 方法，使用前述之陶瓷中間層爲無效者。又 氣孔率多半約爲5%以下，故仍不易利用於 獻2之含有金屬焊料之氣孔的塡充。另外， 材之製造方法，則並非週期性存在於爐材中 而已。因此，對於氣孔塡充含有金屬焊料時 即使作成具有錨效果，該錨效果當然亦僅偶 其結果，有錨效果之部份與無錨效果之部份 膜與爐材之黏著性出現不同部份，導致不易 成穩定的黏著金屬被膜。因此，提昇與金屬 ，有效作爲耐 使用耐火成形 用以鉛或鉛合 來藉由技術提 璃富用耐火物 丨瓜爐算加熱至 定形狀之鑄塑 密度下，比一 成形磚大致上 膜之黏著性之 ，氣孔亦少， 如前述專利文 氣孔若考量爐 ，僅偶而存在 ，其塡充焊料 而存在而已。 中，其金屬被 於整體被膜形 被膜之黏著性 200846495 時，被考量進行與金屬基板相同之噴塗處理，而實際上’ 於噴塗處理之電鑄成形磚上施予鉛熔射後，出現熔射中或 隨後鉑被膜之剝離，不易使鋁被膜固定。鉑被膜之剝離使 其噴塗處理所形成之成形磚表面凸部經由應力造成斷裂狀 態，原因係藉由熔射時之金屬與電鑄成形磚之溫度差產生 極大之熱收縮量之差，而產生極大之應力，以及噴塗處理 時，無法形成有效發揮錨效果之凹凸。 由此，爲抑制電鑄成形磚表面凸部之斷裂，使由金屬 被膜所加入之拉伸應力儘可能均勻分散，且於電鑄成形磚 表面施予使錨效果有效作用於電鑄成形磚表面之凹凸加工 步驟爲其重點。本發明中，於電鑄成形磚表面設置作成錨 用凹部之規則的凹凸，將金屬熔射於塡滿此凹部使表面被 覆之成形磚表面上。以下，針對本發明進行詳細說明。 金屬熔射係不僅導電性基材，即使對於絕緣性基材仍 可形成金屬被膜之被覆方法，可射出各種金屬之熔融粒子 ，一般使用鋅、鋁、錫、銅、黃銅、鋼等之金屬，而構成 作爲玻璃製造爐之構造材料可使用之耐熱、耐久性金屬熔 射成形磚時，使用熔點高之Pt、Ir、Ru、Rh等鉑族金屬 ，或含有1種以上鉑族金屬之合金。作爲合金例者如：1^_ 5%Au、Pt-10%Ir、Pt-l〇%Rh等之鉑合金等例。此等鉑族 金屬及其合金之熱膨脹係數大約爲8 X 1 (Γ6〜1 5 X 1 (Γ 6 ( 2 0 °C )。經由熔射法所射出之金屬粒子係塡充電鑄成形磚之凹 部’堆積於表面上形成被膜。金屬熔射被膜之厚度可藉由 熔射量適度調整。當被膜太厚時，恐不耐拉伸應力之變形 -8- 200846495 ，因此，理想之被膜厚度（去除凹部之被覆成形磚表面之 厚度）爲100〜400 μιη，更佳者爲200〜350 μπι。 成形磚係以氧化鋁、矽酸氧化鋁、鉻-模來石、二氧 化矽或二氧化鈦等爲構成成份之陶瓷、固化黏土等原料後 ，經由燒成取得者爲燒成成形磚，未經熱處理，經由化學 鍵結之結合及成形者爲耐火成形磚，而電鑄成形磚係以電 爐使原料完全熔解所鑄造之成形磚。作爲電鑄成形磚者有 :AZS ( Al203-Si02-Z:r02 )成形磚、α氧化鋁質成形磚、 /3氧化鋁質成形磚、α ^氧化鋁質成形磚、氧化鋁、鉻成 形磚等。電鑄成形磚中，更存在因應其用途進行改良之成 形磚，如：提高氧化锆含量之高氧化銷質成形磚、降低氣 孔率之無間隙（VF )成形磚等，各自提昇耐鈾性、精密性 等。 本發明中，電鑄成形磚，由其作爲璃製造爐之構造材 料使用時之成形磚之強度，所生產玻璃之品質等面觀之， 氣孔率爲5容積％以下，特別爲3容積％以下，玻璃相之 比例爲15容積％以下，特別爲1〇容積％以下者宜。當玻 璃相之比例高時，作爲玻璃製造爐之構造材料使用時，其 電鑄成形磚中之玻璃相成份於熔融玻璃熔出後，恐造成所 生產玻璃組成之不良影響，亦可能降低電鑄成形磚本身之 強度。另外，電鑄成形磚之氧化砂成份之比例亦依組成而 異’ 一般爲8質量％以下者宜。電鑄成形磚之密度爲 3·5〜5.5g/cm2者宜。又，AZS成形磚大部份其玻璃相之比 例若超出1 5容積％，將不適用於本發明。 -9- 200846495 如上述之電鑄成形磚，不易進行介由陶瓷中間層之熔 射，使用含有金屬焊料之錨接合，而本發明則可適用於此 高密度、低玻璃相之硬質電鑄成形磚。 電鑄成形磚其熱膨脹係數約爲6xl0_6〜8χ1(Γ6(20 = 8 0 °C之平均熱膨脹率），彎曲強度約爲80〜120kg/cm2，壓縮 強度爲超出200kg/cm2，高氧化鍩質電鑄成形磚中顯示超 出2500kg/cm2之高壓縮強度。惟，爲使由金屬被膜所受 的應力未出現斷裂，固定金屬被膜，因此，務必作成電鑄 成形磚表面形成錨用凹部之形態。 由金屬被膜於電鑄成形磚所負荷之拉伸應力進行均勻 分散時，錨用凹部務必使凹部於電鑄成形磚表面形成規則 的微細分散配置者。作爲錨用凹部之規則的配列形態者， 如：呈平行配列複數的溝之形態，更考量各向同性之配列 形態者’有複數之溝（線狀凹陷）爲交叉格子形狀、複數 之圓柱形或多角柱形之凹部爲均勻分散之斑狀。凸部（凹 部間隔部份）之強度面視之，爲圓形凹部之斑狀形態者宜 ，另外’加工之容易度以格子形狀之溝者宜，實用上易採 用格子形狀。格子形狀有交叉格子、菱形格子、方平格子 、三角格子等，對於應力之凸部強度面，如圖i ( a )之正 方形交叉格子（碁盤孔）者宜。 接著，針對錨用凹部之截面（於成形磚表面上垂直之 截面）形狀進行考量’圖1代表於電鑄成形磚1設置其錨 用凹邰3之截面形狀爲長方形之複數直線溝g所成之格子 狀溝的實施形態，該形態中，各溝g之側面垂直於成形碍 -10- 200846495 表面，溝幅W爲一定者。當與該實施形態不同 之深部其溝幅縮小之側面爲傾斜時，經由金屬 拉伸應力對於側面作成剪切應力作用後容易引 之，往凹部之深部其溝幅擴大之側面爲傾斜時 該應力集中於深部（凸部之基底）後容易切斷 ，由對於側面之應力作用之觀點視之，如圖1 方形之溝g構成錨用凹部3之形態者宜，應力 表面適度往垂直之溝的側面進行作用，側面之 份爲錨效果之作用。 以下，參考圖2，針對截面形狀爲長方形 與金屬被膜之關係，進行詳細說明。又，圖2 1之電鑄成形磚1熔射金屬後，形成金屬被膜： 有效取得錨效果中，務必於構成錨用凹部 有某種程度的深度，若太深的溝則降低電鑄成 表面之強度，加工亦不易。因此，此等面求取 ，其溝的深度爲5〇〜3 5 0 μπι者宜，更佳者爲 。此係相當於前述理想之金屬被膜5之厚度5 金屬被膜之厚度爲m、溝的深度爲d，求出比 想之d/m爲1/2〜1，更佳者爲1/2〜3/4。 另外，於金屬被膜5與電鑄成形磚1之間 力分散度係藉由溝間距（溝間間隔）P而改變 後於單處縮小該應力時，務必務小溝間距p。 行討論金屬被膜5之應力耐久性及電鑄成形磚 ，溝間距p爲2.5mm以下者宜，更佳者爲1. 時，往凹部 被膜收縮之 起剝離。反 ，於側面之 凸部。因此 之截面以長 係於成形磚 垂直應力成 之格子狀溝 係代表於圖 5之一例。 3之溝中具 形碍1整體 適當範圍者 15 0〜250 μπι :1/2〜5/4 ， 率 d/m，理 所產生之應 ，分散應力 針對此點進 1之強度後 5mm 以下 〇 -11 - 200846495 相同的理由，溝幅W亦爲狹窄者宜，又，維持電鑄成形磚 1之表面部份之強度面亦以其溝幅w爲狹窄者宜。惟，相 較於熔射金屬粒子之粒徑，其溝幅w較狹窄時，於熔射粒 子無法塡充溝，因此，溝幅w受限於熔射粒子之尺寸。通 常，熔射粒子的粒徑爲1 00 μπι以上，因此，溝幅w亦爲 100 μηι以上者宜，較佳者爲150 μιη以上（藉由熔射法可 減少至40 μπι)。又，凸部爲對抗應力，爲保有不切斷之 強度，務必確保因應應力之凸部寬度X (=溝間間隔、溝 間距Ρ與溝幅w之差）。由金屬被膜5所加入之拉伸應力 係伴隨電鑄成形磚1所形成之金屬被膜5之厚度m而增加 。因此，金屬被膜厚度愈厚所需凸部之寬度愈增加。此點 ，凸部寬度X爲金屬被膜厚度m之4倍以上者宜，更考量 縮小溝間距P之面，理想之凸部寬度X爲膜厚度m之 2· 5〜5倍。亦即，x/m比爲4〜5。以前述理想之金屬被膜厚 度m爲基準，決定所需之凸部寬度X，凸部寬度X爲700 μπι〜2.2mm者宜，更理想者爲750 μπι〜1.3mm。此結果，理 想之溝間距P爲800 μπι〜2.5mm，更佳者爲1〜1.5mm。因 此，考量該凸部寬度X及溝間距ρ後，溝幅w爲3 0 0 μπι 以下者宜，更佳者爲250 μπι以下。 於溝側面之該應力，其溝愈深（側面大），愈分散應 力於整體側面，凸部愈不易切斷。因此，相對於溝之深度 d，其溝間距ρ之比例：p/d愈小，應力分散性愈高，愈容 易抑制被覆之剝離。以前述之理想的溝間距ρ及溝深度d 爲基準，求出適度分散應力之p/d値，爲3〜8者宜。 12- 200846495 上述之實施形態係分別將構成錨用凹部3之溝g兩側 面規定於1個平面，使截面呈長方形所構成者，而實際加 工上，如圖3 ( a )〜（d )，其溝之各側面亦可變更規定於 複數的平面或彎曲面。此等鋪用凹部3a〜d中，其溝ga〜gd 之側面僅經凹部稍微突出或凹陷，於2個平面1 1、1 3、2 1 、23(圖3(a)及（c)或彎曲面15、25(圖3(b)及（ d))所構成者，溝ga〜gd係由電鑄成形磚la〜Id之表面 往深部由溝幅w’往溝幅w縮窄。圖3 ( a)及（b )中，於 成形磚表面附近擴大溝ga、gb之錐度，平面1 3及深部之 彎曲面15與成形磚表面垂直。圖3(c)及（d)中，深部 之溝gb、gd之錐度大，平面21及成形磚表面附近之彎曲 面25與成形磚表面垂直。圖3(a)及（b)之形態提高凸 部之耐久性而爲理想者。惟，圖3之實施形態中，爲防止 剪切應力之剝離，實質上以可近似長方形程度之變形者宜 ，因此，溝ga〜gd之狹窄率（成形磚表面中對於溝幅w’之 溝幅減少（w’-w)之百分率）爲90%以下者宜。狹窄度超 出其之溝比例爲未達構成錨用凹部之整體溝之40% (比例 係以溝之長度爲基準算出）者宜。圖1之截面爲長方形之 溝與如圖3之狹窄溝經組合後，溝成錨用凹部亦可。此時 ，構成錨用凹部之整體溝之60%以上其截面爲長方形之溝 g或狹窄率爲90%以下之溝ga〜gd者宜。 作爲錨用凹部者，設置斑狀凹部時，考量加工則以圓 柱形凹部爲實用者，此時凹部之尺寸及配置之理想範圍亦 與上述同法決定之。亦即，凹部之深度爲前述之溝的深度 -13- 200846495 ，凹部之直徑爲前述之溝幅，凹部間之間隔爲前述之溝間 間隔，凹部之間距只要配置於前述之溝間距即可。 使上述之錨用凹部藉由形成於電鑄成形磚表面，取得 可穩定固定金屬熔射被膜之電鑄成形磚。溝的形成可使用 以砥石、金剛石混合器等所構成之磨削刃所裝置之磨削機 ，機械性進行之。或亦可使用雷射等高能量波束、高壓水 流進行之。形成斑狀凹部作爲錨用凹部時，使用軸頭、等 之形態的磨削器即可。形成錨用凹部之前，預先經由磨削 機切取等使電鑄成形磚之表面調整成精密度高之平面後， 可回避源於未預測之凹凸導致金屬熔射被膜之剝離之面極 爲理想。 電鑄成形磚具有其他成形磚所沒有之玻璃相少之特徵 ，極爲堅固，不易於表面進行凹凸加工，因此，通常不進 行凹凸加工。惟，經過幾個表面加工技術之試算誤差，出 現漸具錨效果之凹凸加工法與不至損毀凸部之凹凸形狀， 而呈可實現化。具體而言，被膜之突起部表面剝離問題與 經由被膜應力之突起部搶毀問題藉由§式算誤差被解決。 又，本發明爲適用於玻璃熔解等所使用之電鑄成形磚 ，該基材多半爲立方體等之單純形狀，因此，實施熔射之 表面幾乎呈平面。惟，電鑄成形磚之適用範圍廣，因此， 藉由用途，被要求使成形磚於彎曲面形狀等進行加工後， 使用較複雜之形狀亦不少。此時，經由熔射被覆金屬之表 面亦必然呈具有彎曲面之三維形狀。通常，硬質、精密之 電鑄成形磚係典型的不易加工材料，本發明所揭示之形狀 -14- 200846495 及尺寸爲使精密控制之溝加工成如上述之三維形狀，務必 高度的加工技術，此所需成本亦不能忽視。 要求對於如前述之三維形狀之表面的被覆時，可選擇 間歇性之孔加工作爲溝的代替，極利於加工之難度及成本 面。本發明效果所取得之孔以形成於交叉格子（碁盤孔） 之交叉位置者宜，或配置於與孔間距距離相同之交叉狀位 置者宜。孔間距之距離以〇·7〜2.5mm者宜，更佳者爲 1〜1.6mm。該孔直徑以 0·2〜0.5mm 者宜，更佳者爲 0.3〜0.4mm。孔的深度爲 〇 · 〇 5〜0 · 3 5 mm者宜，更佳者爲 0 · 1 5 〜0 · 2 5 m m 〇 如上述所形成錨用凹部之電鑄成形磚係藉由熔射法， 使熔融金屬粒子射出噴塗後，金屬經由冷卻固化後形成金 屬熔射被膜。熔射法中有雷射熔射、火焰線熔射法、雷漿 熔射法、電弧熔射法、氫氧火焰熔射法等，任意方法均可 。射出之金屬粒子爲微細者宜，依熔射方法之種類可減少 至40 μιη，——般以熔射法所射出之金屬粒子爲50〜150 μπι 。熔射金屬粒子之溫度約爲700〜1 5 00°C，因此，進行熔射 時，電鑄成形磚經加熱後，熔射金屬與電鑄成形碍之溫度 差減少，成形磚與熔射金屬被膜之密合性提昇，爲理想者 ，電鑄成形磚經加熱之狀態下，於熔射後漸漸冷卻至常溫 。電鑄成形磚之加熱溫度爲熔射金屬之溫度以下’具體而 言，爲200〜5 00 °C者宜，更佳者爲300〜400 °C。漸冷時的 降溫速度儘可能放慢者宜，以1〇 °C /分鐘以下者宜。金屬 熔射被膜係藉由粒子堆積所形成之被膜，因此不同於熔融 -15- 200846495 金屬之塗佈等的固化膜等，截面中藉由粒狀堆積構造之出 現而區別。該構造中，相對的密度比較低，藉由膨脹、收 縮，其應力比一般金屬膜較爲緩和。 如上述，一度以金屬熔射被膜被覆電鑄成形磚，則金 屬熔射被膜緊密固定於成形磚表面，實用時之溫度變化在 不太劇烈範圍下，避免藉由金屬之塑流變形，屈服能力之 剝離。取得附金屬被膜之電鑄成形磚高溫下具有良好的耐 久性，不僅適於玻璃製造設備用之耐火、耐熱構造材料， 亦適用於氣體用反應觸媒壁等。 以下，參考實施例，針對本發明進行具體的說明。 〔實施例〕 依以下操作，於電鑄成形磚施予溝加工後，進行金屬 熔射，作成附金屬被膜之電鑄成形碍，其間進行觀察金屬 熔射被膜之狀態。表1記載實施例1〜3中試料之形態及熔 射結果。 〔實施例1〕 (試料Z1) 將高氧化鉻電鑄成形磚（旭硝子公司製·· X9 5 0、密度 5.45g/cm2、氧化矽4.5%、Zr02含量95質量％以上、壓縮 強度 400kg/cm2、彎曲強度 90kg/cm2、張力強度 66.67kg/cm2、熱膨脹係數〇·68、氣孔率0.6容積％、玻璃 相比例7容積％ )切成縱50mmx橫50mmx高度1 〇mm之成 -16- 200846495 形磚片，將此成形磚片之 50mmx50mm之一面利用裝置 #1〇〇砥石之橫軸磨削機進行磨削。於此磨削面利用裝置摻 混金剛石之加工機，形成溝幅w: 0.2mm、溝之深度d : 0.1 m m、溝間距p ·· 1 m m、凸部寬度X ·· 0 · 8 m m之父叉格子 形狀之溝。 使該電鑄成形磚片於大氣氛圍中，加熱至300 °C，於 形成溝之面上利用火焰線熔射法開始進行鉑熔射（飛行熔 射粒徑：100 μιη、溫度約100°C )，持續進行熔射至鈾被 膜之膜厚爲3 00 μηι，將成形磚片漸漸冷卻至常溫爲止。 熔射中，觀察膜厚於200 μιη時熔射被膜之剝離。另外， 熔射被膜之剝離係指即使僅一部份被膜由爐材料剝離，仍 記載爲剝離。 (試料Ζ2) 除將溝的交叉格子形狀作成溝幅w : 0.2mm、溝深度 d: 0.2mm、溝間距 p: 0.4mm、凸部寬度 X: 0.2mm之外 ，與試料Z1同法操作，於電鑄成形磚片之磨削面上形成 溝，進行鈾之熔射。該結果顯示，熔射被膜之膜厚爲100 μιη時，熔射被膜出現剝離。 (試料Ζ3) 除將溝的交叉格子形狀作成溝幅w: 〇.2mm、溝深度 d : 0.2mm、溝間距p : 0.6mm、凸部寬度X : 0.4mm之外 ，與試料Z 1同法操作，於電鑄成形磚片之磨削面上形成 -17- 200846495 溝，進行鉑之熔射。該結果顯示，熔射被膜之膜厚爲100 μιη時，出現熔射被膜之剝離。 (試料Ζ4) 除將溝的交叉格子形狀作成溝幅w :0.2mm、溝深度 d : 0.2mm、溝間距p : 1mm、凸部寬度X : 0.8mm之外， 與試料Z 1同法操作，於電鑄成形磚片之磨削面上形成溝 ，進行鉑之熔射。熔射中未出現熔射被膜之剝離，冷卻後 熔射被膜仍密合於電鑄成形磚。熔射被膜之膜厚爲3 00 μηι。又，被膜之耐久性亦高，亦適用於耐熱構造體。 (試料Ζ5 ) 除將溝的交叉格子形狀作成溝幅w : 0.2mm、溝深度 d: 0.2mm、溝間距 p: 1.4mm、凸部寬度 X: 1.2mm之外 ，與試料Z1同法操作，於電鑄成形磚片之磨削面上形成 溝，進行鉑之熔射。熔射中未出現熔射被膜之剝離，冷卻 後熔射被膜仍密合於電鑄成形磚片。熔射被膜之膜厚爲 3 00 μιη。且被膜之耐久性亦高，亦適用於耐熱構造體。 (試料Ζ6) 除將溝的交叉格子形狀作成溝幅w: 0.3mm、溝深度 d: 0.3mm、溝間距p: 0.6mm、凸部寬度 X: 0.3mm之外 ，與試料Z1同法操作，於電鑄成形磚片之磨削面上形成 溝，進行鉑之熔射。該結果，於熔射中未出現熔射被膜之 -18- 200846495 剝離，惟漸漸冷卻時卻出現被膜之剝離。熔射被膜之膜厚 爲 3 0 0 μιη 〇 (試料Ζ7) 除將溝的交叉格子形狀作成溝幅w :0.3mm、溝深度 d : 0.3 m m、溝間距p : 1.2 m m、凸部寬度X : 0.9 m m之外 ，與試料Z 1同法操作，於電鑄成形磚片之磨削面上形成 溝，進行鉑之熔射。熔射中未出現熔射被膜之剝離，冷卻 後，熔射被膜仍密合於電鑄成形磚片上。熔射被膜之膜厚 爲300 μιη。且被膜之耐久性亦局，亦適用於耐熱構造體 〔實施例2〕 (試料A 1 ) 將氧化鋁電鑄成形磚（旭硝子公司製_· MB-A、密度 3.9g/cm2、氧化矽1%、Al2〇3含量95質量％以上，壓縮強 度 250kg/cm2、彎曲強度 83kg/cm2、拉伸強度 41.67kg/cm2 、熱膨脹係數〇·7、氣孔率2·0容積％、玻璃相比例1容積 %以下）切成縱50mmx橫50mmx高度l〇mm之成形磚片， 此成形磚片之50 mmx50 mm之一面利用裝置#1〇〇之砥石之 橫軸磨削機進行磨削。於此磨削面利用裝置摻混金剛石之 加工機，形成溝幅w : 0.2mm、溝深度d : 0.2mm、溝間距 p : 0,4mm、凸部寬度X : 0.2mm之交叉格子形狀之溝。 使該電鑄成形磚片於大氣氛圍中加熱至3 0 0 °C，於形 -19- 200846495 成溝之面上，利用火焰線熔射法，開始進行鉑之熔射（飛 行熔射粒徑：100 μηι、溫度約1 000°c )、特續進行熔射 至鉑被膜之膜厚至3 00 μπι爲止，再使成形磚片漸漸冷卻 至常溫。熔射中膜厚爲100 μηι時出現熔射被膜之剝離。 (試料Α2 ) 除將溝之交叉格子形狀作成溝幅w : 0.2mm、溝深度 d : 0 · 2 m m、溝間距p ·· 1.4 m m、凸部寬度X : 1 · 2 m m之外 ，與試料A 1同法操作，於電鑄成形磚片之磨削面上形成 溝，進行鉑之熔射。熔射中未出現熔射被膜之剝離，冷卻 後熔射被膜仍密合於電鑄成形磚片上。熔射被膜之膜厚爲 3 00 μπι。且被膜之耐久性亦高，亦適用於耐熱構造體。 (試料A3 ) 除將溝之交叉格子形狀作成溝幅w :0.2mm、溝深度 d: 0.2mm、溝間距 p: 5mm、凸部寬度 X: 4.8mm，之外 ，與試料A1同法操作，於電鑄成形磚片之磨削面上形成 溝，進行鉑之熔射。此結果，於熔射中未出現熔射被膜之 剝離，惟漸漸冷卻時，出現被膜的剝離。熔射被膜之膜厚 爲 3 00 μπι 〇 〔實施例3〕 (試料Ζ8) 除將熔射之金屬由鉑變更爲Pt-10%Rh合金之外，與 -20- 200846495 試料Z4同法操作，於磨削面形成溝之電鑄成形磚片上進 行熔射。熔射中未出現熔射被膜之剝離，冷卻後，熔射被 膜仍密合於電鑄成形磚片上。熔射被膜之膜厚爲3 00 μπι 。且被膜耐久性亦高，亦適用於耐熱構造體。 (試料Α4 ) 除將熔射之金屬由鉑變更爲Pt-10%Rh合金之外，與 試料A2同法操作，於磨削面形成溝之電鑄成形磚片上進 行熔射。熔射中未出現溶射被膜之剝離，冷卻後熔射被膜 仍密合於電鑄成形磚片上。熔射被膜之膜厚爲3 00 μπι。 且被膜耐久性亦高，亦適用於耐熱構造體。200846495 IX. Description of the Invention [Technical Field] The present invention relates to an electroformed brick with a metal film coated on a surface of an electroformed brick by a metal film, and a method for producing the same, and more particularly to a glass manufacturing apparatus An electroformed brick with a metal film and a method for producing the same, which are required for the heat resistance and durability of the portion in contact with the molten glass. [Prior Art] A method of coating a substrate with a metal film, for example, a spray method such as plasma spray or oxyhydrogen flame spray (for example, Patent Document 1 below). This is a film forming method in which molten metal is sprayed in a particulate form and sprayed on a substrate, and can be suitably applied to a conductive material and an insulating material. When the metal substrate is coated with a metal spray coating, in general, in order to improve the fixing property between the metal substrate and the spray coating, the surface of the metal substrate is treated before the spraying. Specifically, the hard ceramic particles are ejected, and after impinging on the surface of the metal substrate, irregularities of appropriate thickness are formed on the surface of the metal substrate. By forming the irregularities, the molten metal particles intrude into the concave portion, and the metal solidified in the concave portion exhibits an anchoring effect, and then the metal substrate and the molten metal coating are joined. The above method utilizes the height of softness and plastic deformability of the metal substrate, and is not applicable to the low hardness, brittleness, and plastic deformability of the substrate when the metal substrate is not formed of a brick or the like. Spray treatment. Therefore, when the formed film is coated with the spray film, the intermediate layer of the ceramic is set by the melt glue and the gel method -4-200846495, which is intended to enhance the joining of the formed brick substrate and the metal spray film. . The intermediate layer is formed by strong bonding between the ceramic and the glass (ceria oxide) phase in the shaped brick, and the molten metal particles are sucked into the ceramic intermediate layer to fix the molten film, and the porous substrate is used. A method in which a mixture of platinum fine particles and an inorganic material is added to pores existing on the surface of a refractory substrate, and after heating and firing, the surface is abraded, and a portion of the platinum fine particles are exposed to form a sprayed film is disclosed. (Patent Document 2 below). [Patent Document 1] British Patent No. 1 242 996 (Patent Document 2) Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. It cannot be expected to be fixed after chemical bonding, so it is invalid. Therefore, it is not suitable for electroforming a brick which is coated with a glass film by a spray coating. Further, the method of Patent Document 2 is only applicable to a porous material, and therefore, it is generally not easily applicable to an electroformed brick having a low porosity. . In this case, it is difficult for the electroformed brick having a small glass phase and high precision to form a metal film by spraying, and the molten metal is easily melted or cooled after the melt. Stripped by electroformed bricks. SUMMARY OF THE INVENTION An object of the present invention is to provide a metal coating which is capable of forming a metal film which is tightly fixed and which is not easily peeled off in a ceramic substrate having a small glass phase and high precision, and is developed to have high durability. The construction material is useful for the electroforming of the metal film. Further, an object of the present invention is to provide an electroformed brick which is provided with a metal film of an electroformed brick which can be used as a heat-resistant structural material and can be easily and stably provided without being peeled off by a metal film to be coated. Manufacturing method. In order to solve this problem, the inventors of the present invention have found that after φ is intentionally formed on the surface of the electroformed brick, the thermal stress is appropriately dispersed by the difference in heat shrinkage between the metal and the formed brick, so that the anchor can be appropriately exerted. The metal film of the effect is provided on the surface of the electroformed brick to complete the present invention. According to one aspect of the present invention, an electroformed brick to which a metal film is attached is provided with an electroformed brick having a regular anchor recess formed on a surface thereof and coated on a surface of the electroformed brick and disposed to fill the anchor. The metal film of the concave portion, wherein the metal film contains a platinum group metal, and the electroporation brick has a porosity of 5 vol% or less and a glass phase ratio of 15% by mass or less. In another aspect of the present invention, the method for producing an electroformed brick with a metal film is formed on the surface of an electroformed brick having a porosity of 5 vol% or less and a glass ratio of 15% by mass or less. The regular anchor recess is formed by spraying a metal containing platinum metal on the electroformed brick to form a metal film that fills the anchor recess and covers the surface of the electroformed brick. According to the present invention, in the regular irregularities formed on the surface of the electroformed brick, after the stress is moderately dispersed between the metal film and the electroformed brick, no cracking of the convex portion occurs, the metal film is deformed, and the anchor effect is moderately exerted. . Therefore, the use of an electroformable brick thermal structural material having a high heat resistance and durability and suppressing the metal film peeled off by the metal film of the temperature change -6 - 200846495 is provided. [Embodiment] [Best Mode for Carrying Out the Invention] In a heat-resistant structural material for glass honey for high-temperature heating, a refractory brick in which a gold spray coating is coated in a critical cross-section portion of a required durability is used. In recent years, it has established an electroformed brick with high manufacturing strength, which is used to replace the use of electroformed bricks to replace the refractory bricks. The electroformed bricks make the refractory materials use the Eru-type electric i 1 900~2500 °c. After the completely fused refractory raw material is cast and cooled and solidified, a refractory material is obtained, and the high-fired formed brick has high strength and durability. However, since the proportion of the electroformed glass phase is small, it is not effective to use the ceramic intermediate layer described above for the method of improving the metal coating. Further, since the porosity is about 5% or less, it is still difficult to utilize the charge of the metal-containing solder pores. In addition, the method of manufacturing the material is not periodically present in the furnace material. Therefore, even if the pores are filled with the metal solder, even if it has an anchor effect, the anchor effect is of course only a result, and the part of the anchor effect and the part of the film having no anchor effect and the furnace material are different. , resulting in a difficult to form a stable adhesive metal film. Therefore, the lifting and the metal are effectively used as a resistance to the use of refractory forming for lead or lead to be heated by the refractory of the technical refractory, and the casting density is higher than that of a shaped brick. Adhesive, there are few pores, such as the aforementioned patent vents, if only the occasional existence, it is only filled with solder. In the case where the metal is adhered to the entire film-formed film at 200846495, it is considered to be sprayed in the same manner as the metal substrate, and in fact, after the lead is sprayed on the electroformed brick of the spray treatment, the spray is formed. The middle or subsequent peeling of the platinum film makes it difficult to fix the aluminum film. The peeling of the platinum film causes the surface convex portion of the shaped brick formed by the spraying treatment to cause a fracture state due to stress, because the temperature difference between the metal and the electroformed brick at the time of spraying causes a great difference in heat shrinkage amount, resulting in a difference When the stress is extremely great and the spraying process is performed, the unevenness of the anchor effect can not be effectively formed. Therefore, in order to suppress the breakage of the convex portion on the surface of the electroformed brick, the tensile stress added by the metal film is dispersed as uniformly as possible, and the surface of the electroformed brick is applied to make the anchor effect effective on the surface of the electroformed brick. The embossing process is the focus. In the present invention, regular irregularities which are formed as anchor recesses are formed on the surface of the electroformed brick, and the metal is sprayed on the surface of the shaped brick which is covered with the recess to cover the surface. Hereinafter, the present invention will be described in detail. The metal melting system is not only a conductive substrate but also a coating method for a metal film even for an insulating substrate, and can emit molten particles of various metals, and generally uses a metal such as zinc, aluminum, tin, copper, brass, or steel. When a heat-resistant and durable metal-molded brick that can be used as a structural material for a glass-making furnace is used, a platinum group metal such as Pt, Ir, Ru, or Rh having a high melting point or an alloy containing one or more platinum group metals is used. . Examples of the alloy include platinum alloys such as 1^_5% 5%, Pt-10% Ir, and Pt-l%% Rh. The platinum group metals and their alloys have a thermal expansion coefficient of about 8 X 1 (Γ6~1 5 X 1 (Γ 6 (20 ° C). The metal particles emitted by the spray method are recessed in the cast-cast brick) 'Stacked on the surface to form a film. The thickness of the metal spray film can be adjusted by the amount of spray. When the film is too thick, it is not resistant to the deformation of tensile stress -8- 200846495, therefore, the ideal film thickness (removal The thickness of the surface of the coated brick of the concave portion is 100 to 400 μm, and more preferably 200 to 350 μπ. The shaped brick is composed of alumina, alumina citrate, chromium-molecule, cerium oxide or titanium dioxide. After the raw materials such as ceramics and solidified clay are obtained, the fired and formed bricks are obtained by firing, and the joints and the molds are formed into refractory bricks without chemical treatment, and the electroformed bricks are completely melted by electric furnace. The formed bricks are cast as AZS (Al203-Si02-Z:r02) shaped bricks, α-alumina shaped bricks, /3 alumina shaped bricks, α-alumina shaped bricks, Alumina, chrome forming bricks, etc. In the forming bricks, there are more shaped bricks that are modified according to their use, such as high-oxidation pin-shaped bricks that increase the zirconia content, and gap-free (VF) bricks that reduce the porosity, and each enhances uranium resistance and precision. In the present invention, the electroformed brick is used as the structural material of the glass manufacturing furnace, and the quality of the produced glass is such that the porosity is 5 vol% or less, particularly 3 volumes. % or less, the ratio of the glass phase is 15% by volume or less, and particularly preferably 1% by volume or less. When the ratio of the glass phase is high, when used as a structural material of a glass manufacturing furnace, the glass phase in the electroformed brick is used. After the components are melted out of the molten glass, it may cause adverse effects on the composition of the produced glass, and may also reduce the strength of the electroformed brick itself. In addition, the proportion of the oxidized sand component of the electroformed brick varies depending on the composition 'generally 8 The mass% or less is suitable. The density of the electroformed brick is preferably 3·5~5.5g/cm2. Also, if the ratio of the glass phase of the AZS brick is more than 15% by volume, it will not be applicable to the hair. -9- 200846495 The electroformed brick as described above is not easy to be sprayed through the ceramic intermediate layer, and the anchor joint containing the metal solder is used, and the present invention can be applied to the hard electroforming of the high density and low glass phase. Shaped bricks. Electroformed bricks have a thermal expansion coefficient of about 6x10_6~8χ1 (Γ6 (20 = 80 °C average thermal expansion rate), bending strength of about 80~120kg/cm2, compressive strength of over 200kg/cm2, high oxidation. The tantalum electroformed brick exhibits a high compressive strength exceeding 2,500 kg/cm2. However, in order to prevent the stress on the metal film from being broken, the metal film is fixed. Therefore, it is necessary to form an anchor recess on the surface of the electroformed brick. form. When the metal film is uniformly dispersed by the tensile stress applied to the electroformed brick, the anchor recess must have a concave portion formed on the surface of the electroformed brick to form a regular fine dispersion. As a regular arrangement form of the anchor recess, for example, a groove in which a plurality of grooves are arranged in parallel, and an isotropic arrangement form is considered as a groove having a complex number (linear depression) having a cross lattice shape and a plural cylindrical shape. Or the polygonal cylindrical recess is a uniformly dispersed patch. The strength of the convex portion (the concave portion of the concave portion) is preferably a patchy shape of the circular concave portion, and the ease of processing is preferably a lattice shape groove, and the lattice shape is practically easy to adopt. The lattice shape has a cross lattice, a diamond lattice, a square lattice, a triangular lattice, etc., and for the stress strength surface of the convex portion, as shown in Fig. i (a), the square cross lattice (the disk hole) is suitable. Next, the shape of the cross section of the anchor recess (the cross section perpendicular to the surface of the forming brick) is considered. FIG. 1 represents that the electroformed brick 1 is formed by a plurality of straight grooves g whose cross-sectional shape of the anchor recess 3 is rectangular. In the embodiment of the lattice groove, in this embodiment, the side surface of each groove g is perpendicular to the surface of the forming barrier-10-200846495, and the groove width W is constant. When the side surface of the deep portion which is different from the embodiment is inclined, the metal tensile stress is easily induced by the shear stress on the side surface, and the stress is increased when the side of the groove is enlarged in the deep portion of the concave portion. It is easy to cut after focusing on the deep part (the base of the convex part). From the viewpoint of the stress on the side surface, as shown in Fig. 1, the square groove g constitutes the shape of the anchor recess 3, and the stress surface is moderately oriented to the vertical groove. The side works, and the side parts are the anchor effect. Hereinafter, the relationship between the rectangular shape and the metal film in the cross-sectional shape will be described in detail with reference to Fig. 2 . Further, after the electroformed brick 1 of Fig. 2 is sprayed with metal, a metal film is formed: in order to effectively obtain the anchor effect, it is necessary to have a certain depth in the anchor recess, and if it is too deep, the electroformed surface is lowered. The strength and processing are not easy. Therefore, the depth of the groove is 5〇~3 5 0 μπι, and the better is. This corresponds to the thickness of the ideal metal coating 5. The thickness of the metal coating is m, the depth of the groove is d, and the ratio d/m is 1/2 to 1, and more preferably 1/2 to 3. /4. Further, when the force dispersion degree between the metal film 5 and the electroformed brick 1 is changed by the groove pitch (inter-groove interval) P, and the stress is reduced at a single place, the small groove pitch p is always required. The stress durability of the metal film 5 and the electroformed brick are discussed. The groove pitch p is preferably 2.5 mm or less, and more preferably 1. When the film is contracted, the film is peeled off. On the opposite side of the convex part. Therefore, the cross section of the cross section which is long in the vertical stress of the formed brick is represented by an example in Fig. 5. In the groove of 3, the overall range of the obstacle 1 is 15 0~250 μπι : 1/2~5/4 , the rate d/m, the result of the treatment, the dispersion stress is 5 mm or less after the intensity of 1 point. -11 - 200846495 For the same reason, the groove width W is also suitable for the narrow one. Moreover, it is preferable to maintain the strength surface of the surface portion of the electroformed brick 1 with the groove width w being narrow. However, compared with the particle size of the molten metal particles, when the groove width w is narrow, the molten particles cannot be filled into the grooves, and therefore, the groove width w is limited by the size of the spray particles. Usually, the particle size of the sprayed particles is 100 μm or more. Therefore, the groove width w is preferably 100 μηι or more, preferably 150 μηη or more (by the spray method, it can be reduced to 40 μπι). Further, the convex portion is resistant to stress, and in order to maintain the strength without cutting, it is necessary to ensure the width X of the convex portion (the difference between the groove interval, the groove pitch Ρ and the groove width w) in response to the stress. The tensile stress added by the metal film 5 increases with the thickness m of the metal film 5 formed by the electroformed brick 1. Therefore, the thicker the thickness of the metal film, the more the width of the convex portion is increased. In this case, the width X of the convex portion is preferably four times or more the thickness m of the metal film, and the surface of the groove pitch P is reduced. The width X of the convex portion is preferably 2.5 to 5 times the thickness m of the film. That is, the x/m ratio is 4 to 5. The desired width X of the convex portion is determined based on the desired metal film thickness m, and the width X of the convex portion is preferably 700 μπι to 2.2 mm, more preferably 750 μπι to 1.3 mm. As a result, the ideal groove pitch P is 800 μπι to 2.5 mm, and more preferably 1 to 1.5 mm. Therefore, after considering the width X of the convex portion and the groove pitch ρ, the groove width w is preferably 3 0 0 μπι or less, and more preferably 250 μπι or less. The stress on the side of the groove is deeper (larger side), and the more dispersed it is to the overall side, the more difficult the convex part is cut. Therefore, the ratio of the groove pitch ρ with respect to the depth d of the groove: the smaller the p/d, the higher the stress dispersion property, and the more easily the peeling of the coating is suppressed. Based on the above-described ideal groove pitch ρ and groove depth d, the p/d 适 of the moderately dispersed stress is determined to be 3 to 8. 12-200846495 In the above-described embodiment, the two side faces of the groove g constituting the anchor recess 3 are defined in one plane, and the cross section is formed in a rectangular shape. Actually, as shown in FIGS. 3(a) to (d), The sides of the groove may also be changed to a plurality of planes or curved faces. In these paving recesses 3a to 3d, the sides of the grooves ga to gd are slightly protruded or recessed only by the recesses, in two planes 1 1 , 1 3 , 2 1 , 23 (Fig. 3(a) and (c) or In the case where the curved faces 15 and 25 (Figs. 3(b) and (d)) are formed, the grooves ga to gd are narrowed from the surface of the electroformed bricks la1 to Id to the groove width w by the groove width w'. In 3 (a) and (b), the taper of the grooves ga and gb is enlarged near the surface of the shaped brick, and the curved surface 15 of the plane 13 and the deep portion is perpendicular to the surface of the shaped brick. In Figs. 3(c) and (d), deep The grooves gb and gd have a large taper, and the flat surface 21 and the curved surface 25 near the surface of the forming brick are perpendicular to the surface of the forming brick. The shapes of Figs. 3(a) and (b) are ideal for improving the durability of the convex portion. In the embodiment of Fig. 3, in order to prevent the peeling of the shear stress, it is preferable to substantially deform the shape of the rectangle. Therefore, the stenosis rate of the grooves ga to gd (the groove width of the groove width w' in the surface of the formed brick is reduced. The percentage of (w'-w) is preferably 90% or less. The ratio of the narrowness beyond the groove is preferably 40% of the total groove which constitutes the recess for the anchor (the ratio is calculated based on the length of the groove). figure 1 The groove having a rectangular cross section is combined with the narrow groove of Fig. 3, and the groove may be a recess for the anchor. At this time, 60% or more of the entire groove constituting the recess for the anchor has a rectangular groove g or a stenosis ratio of 90. The groove below ga to gd is preferably used as the groove for the anchor. When the grooved recess is provided, the cylindrical recess is considered as a practical one. The ideal range of the size and arrangement of the recess is also determined by the same method. That is, the depth of the concave portion is the depth of the aforementioned groove -13 - 200846495, the diameter of the concave portion is the aforementioned groove width, and the interval between the concave portions is the interval between the grooves, and the distance between the concave portions may be disposed at the aforementioned groove spacing. The anchor recessed portion is formed on the surface of the electroformed brick to obtain an electroformed brick which can stably fix the metal spray coating. The groove can be formed by using a grinding blade composed of a vermiculite, a diamond mixer or the like. The grinding machine of the device can be mechanically carried out, or it can be carried out by using a high-energy beam such as a laser or a high-pressure water stream. When forming a concave portion as an anchor recess, a grinding head of a shaft head or the like can be used. Before the anchor recess is formed, the surface of the electroformed brick is adjusted to a plane having high precision by cutting through a grinder, etc., and it is possible to avoid the surface of the metal spray coating which is caused by unpredicted irregularities. Casting bricks have the characteristics of few glass phases that are not found in other shaped bricks. They are extremely strong and are not easy to be surface-concave-concave. Therefore, the concave-convex processing is usually not performed. However, after several trials of surface processing techniques, the anchoring occurs. The effect of the concave-convex processing method and the concave-convex shape of the convex portion are not damaged, and the problem of the surface peeling of the protrusion portion of the film and the problem of looting through the protrusion of the film stress are solved by the § calculation error. . Further, the present invention is applied to an electroformed brick used for glass melting or the like, and the substrate is mostly in a simple shape such as a cube. Therefore, the surface on which the melt is applied is almost flat. However, since the electroformed brick has a wide application range, it is required to use a more complicated shape after processing the shaped brick in a curved surface shape or the like by use. At this time, the surface of the metal to be coated by the spray also necessarily has a three-dimensional shape having a curved surface. In general, hard and precise electroformed bricks are typically difficult to machine materials, and the shape disclosed in the present invention is -14,046,495 and the size is such that the precisely controlled groove is processed into a three-dimensional shape as described above, and a high degree of processing technology is required. The cost required cannot be ignored. When it is required to cover the surface of the three-dimensional shape as described above, intermittent hole processing can be selected as a substitute for the groove, which is advantageous for processing difficulty and cost. It is preferable that the holes obtained by the effects of the present invention are formed at the intersections of the intersecting lattices (the disk holes) or at the intersections of the same distance from the holes. The distance between the holes is preferably 〇·7 to 2.5 mm, and more preferably 1 to 1.6 mm. The diameter of the hole is preferably from 0.2 to 0.5 mm, more preferably from 0.3 to 0.4 mm. The depth of the hole is preferably 〇· 〇5~0 · 3 5 mm, and more preferably 0 · 1 5 〜 0 · 2 5 mm 〇 The electroformed brick of the anchor recess formed as described above is by the spray method After the molten metal particles are sprayed and sprayed, the metal is solidified by cooling to form a metal sprayed film. In the spray method, there are laser spray, flame line spray method, slurry spray method, arc spray method, and hydrogen-oxygen flame spray method, and any method can be used. The metal particles to be injected are preferably fine, and the type of the spray method can be reduced to 40 μm, and the metal particles emitted by the spray method are generally 50 to 150 μπι. The temperature of the molten metal particles is about 700 to 1 500 ° C. Therefore, when the electroformed brick is heated after heating, the temperature difference between the molten metal and the electroforming is reduced, and the formed brick and the molten metal are formed. The adhesion of the film is improved, and it is desirable that the electroformed tile is gradually cooled to a normal temperature after being melted. The heating temperature of the electroformed brick is below the temperature of the molten metal 'specifically, it is preferably 200 to 500 ° C, more preferably 300 to 400 ° C. When the temperature is gradually cold, the cooling rate should be as slow as possible, and it should be 1 〇 ° C / min or less. Since the metal spray coating is formed by the deposition of particles, it is different from the cured film of the coating of the metal such as the melt -15-200846495, and the cross section is distinguished by the appearance of the granular deposition structure. In this configuration, the relative density is relatively low, and the stress is more moderate than that of the general metal film by expansion and contraction. As described above, once the electroformed brick is coated with a metal spray film, the metal spray film is tightly fixed on the surface of the formed brick, and the temperature change in practical use is less severe, avoiding plastic flow deformation by metal, yielding ability Stripping. The electroformed brick with metal film has good durability at high temperatures, and is suitable not only for fire-resistant and heat-resistant structural materials used in glass manufacturing equipment, but also for reaction catalyst walls for gas. Hereinafter, the present invention will be specifically described with reference to the embodiments. [Examples] After the electroforming brick was subjected to the groove processing, the metal was sprayed, and the metal film was formed by electroforming, and the state of the metal spray film was observed. Table 1 shows the morphology and the results of the melting of the samples in Examples 1 to 3. [Example 1] (Sample Z1) High chromium oxide electroformed brick (X950, manufactured by Asahi Glass Co., Ltd., density 5.45 g/cm2, cerium oxide 4.5%, Zr02 content 95% by mass or more, compressive strength 400 kg/cm2) , bending strength 90kg/cm2, tensile strength 66.67kg/cm2, thermal expansion coefficient 〇·68, porosity 0.6% by volume, glass compared with case 7 volume %) cut into vertical 50mmx horizontal 50mmx height 1 〇mm into -16- 200846495 A brick piece was used, and one of the 50 mm x 50 mm faces of the formed tile was ground using a #1 vermiculite horizontal axis grinding machine. In this grinding surface, a diamond processing machine is used to form a groove w: 0.2 mm, a groove depth d: 0.1 mm, a groove pitch p··1 mm, and a convex width X ·· 0 · 8 mm The groove of the fork lattice shape. The electroformed brick was heated to 300 ° C in an atmosphere, and platinum spraying was started on the surface of the groove by flame line spraying (flying particle size: 100 μm, temperature: about 100 ° C) ), the film thickness of the uranium film is continuously sprayed to 300 μm, and the formed tile is gradually cooled to room temperature. In the spraying, the peeling of the film was observed when the film thickness was 200 μm. Further, the peeling of the sprayed film means that even if only a part of the film is peeled off from the furnace material, it is described as peeling. (Sample Ζ 2) The same operation as the sample Z1 was carried out except that the groove lattice shape of the groove was made into a groove width w: 0.2 mm, a groove depth d: 0.2 mm, a groove pitch p: 0.4 mm, and a convex portion width X: 0.2 mm. A groove is formed on the grinding surface of the electroformed brick to perform uranium spraying. As a result, when the film thickness of the sprayed film was 100 μm, the sprayed film was peeled off. (Sample Ζ3) The same method as the sample Z 1 except that the groove lattice shape of the groove was made into a groove width w: 〇. 2 mm, groove depth d: 0.2 mm, groove pitch p: 0.6 mm, and convex portion width X: 0.4 mm. In operation, a groove of -17-200846495 is formed on the grinding surface of the electroformed tile to perform platinum spraying. As a result, when the film thickness of the sprayed film was 100 μm, peeling of the sprayed film occurred. (Sample Ζ4) The same operation as the sample Z 1 was carried out except that the groove grid shape of the groove was groove width w: 0.2 mm, groove depth d: 0.2 mm, groove pitch p: 1 mm, and convex portion width X: 0.8 mm. A groove is formed on the ground surface of the electroformed tile to perform platinum spraying. No peeling of the sprayed film occurred during the spraying, and after cooling, the molten film was still adhered to the electroformed brick. The film thickness of the sprayed film is 300 μηι. Moreover, the durability of the film is also high, and it is also suitable for a heat-resistant structure. (Sample Ζ5) The same operation as the sample Z1 was carried out except that the groove lattice shape of the groove was made into a groove width w: 0.2 mm, a groove depth d: 0.2 mm, a groove pitch p: 1.4 mm, and a convex portion width X: 1.2 mm. A groove is formed on the ground surface of the electroformed tile to perform platinum spraying. No peeling of the sprayed film occurred in the spray, and after cooling, the sprayed film was still adhered to the electroformed tile. The film thickness of the sprayed film was 300 μm. Moreover, the durability of the film is also high, and it is also suitable for a heat-resistant structure. (Sample Ζ6) The same operation as the sample Z1 was carried out except that the groove lattice shape of the groove was made into a groove width w: 0.3 mm, a groove depth d: 0.3 mm, a groove pitch p: 0.6 mm, and a convex portion width X: 0.3 mm. A groove is formed on the ground surface of the electroformed tile to perform platinum spraying. As a result, -18-200846495 peeling of the sprayed film did not occur in the spray, but peeling of the film occurred at the time of gradually cooling. The film thickness of the sprayed film was 300 μm 〇 (sample Ζ 7) except that the groove lattice shape of the groove was groove width w: 0.3 mm, groove depth d: 0.3 mm, groove pitch p: 1.2 mm, and convex width X: In addition to 0.9 mm, the sample was operated in the same manner as the sample Z 1 to form a groove on the ground surface of the electroformed tile, and platinum was sprayed. No peeling of the sprayed film occurred during the spraying, and after cooling, the molten film was still adhered to the electroformed tile. The film thickness of the sprayed film was 300 μm. And the durability of the film is also applicable to the heat-resistant structure [Example 2] (Sample A 1 ) Alumina electroformed brick (made by Asahi Glass Co., Ltd. _· MB-A, density 3.9 g/cm 2 , yttrium oxide 1) %, Al2〇3 content 95% by mass or more, compressive strength 250kg/cm2, bending strength 83kg/cm2, tensile strength 41.67kg/cm2, thermal expansion coefficient 〇·7, porosity 2·0% by volume, glass comparison example 1 The volume is less than or equal to) a 50 mm x 50 mm x height l 〇 mm shaped tile, and one of the 50 mm x 50 mm faces of the formed tile is ground using a cross-axis grinder of the device #1 砥 砥. In this grinding surface, a diamond processing machine is used to form a groove having a groove width w: 0.2 mm, a groove depth d: 0.2 mm, a groove pitch p: 0, 4 mm, and a convex portion width X: 0.2 mm. . The electroformed tile is heated to 300 ° C in an atmospheric atmosphere, and on the surface of the groove -19-200846495, the spraying of platinum is started by the flame line melting method (flying spray particle size) : 100 μηι, temperature: about 1 000 ° C), continuous spraying until the film thickness of the platinum film is up to 300 μπι, and then the formed tile is gradually cooled to room temperature. The peeling of the sprayed film occurred when the film thickness in the spray was 100 μm. (Sample Α2) In addition to the groove shape of the groove, the groove width w: 0.2 mm, the groove depth d: 0 · 2 mm, the groove pitch p · · 1.4 mm, the width of the convex portion X: 1 · 2 mm, and the sample A 1 is operated in the same manner, and a groove is formed on the grinding surface of the electroformed brick to perform platinum spraying. No peeling of the sprayed film occurred in the spray, and after cooling, the sprayed film was still adhered to the electroformed tile. The film thickness of the sprayed film was 300 μm. Moreover, the durability of the film is also high, and it is also suitable for a heat-resistant structure. (Sample A3) The same operation as the sample A1 was carried out except that the groove grid shape of the groove was made into a groove width w: 0.2 mm, a groove depth d: 0.2 mm, a groove pitch p: 5 mm, and a convex portion width X: 4.8 mm. A groove is formed on the ground surface of the electroformed tile to perform platinum spraying. As a result, no peeling of the sprayed film occurred during the spraying, but peeling of the film occurred when it was gradually cooled. The film thickness of the sprayed film was 300 μπι 〇 [Example 3] (Sample Ζ 8) Except that the molten metal was changed from platinum to Pt-10% Rh alloy, it was operated in the same manner as -20-200846495 sample Z4. The electroforming is performed on the electroformed tile formed on the grinding surface to form a groove. No peeling of the sprayed film occurred during the spraying, and after cooling, the sprayed film was still adhered to the electroformed tile. The film thickness of the spray film is 300 μπι. Moreover, the film is also durable, and is also suitable for heat-resistant structures. (Sample Α4) Except that the molten metal was changed from platinum to Pt-10%Rh alloy, it was operated in the same manner as the sample A2, and was sprayed on the electroformed tile formed on the grinding surface to form a groove. No peeling of the sprayed film occurred in the spray, and after cooling, the sprayed film was still adhered to the electroformed tile. The film thickness of the sprayed film is 300 μm. Moreover, the film is also durable, and is also suitable for heat-resistant structures.
(表1 ) 溝之形態與金屬被膜之剝離 試料 熔射金屬 溝（n Lm) 被膜剝離 溝幅w 深d 間距P 凸部寬x Ζ1 Pt 0.2 0.1 1.0 0.8 於200 μ m剝離 Ζ2 Pt 0.2 0.2 0.4 0.2 於100 μπι剝離 Ζ3 Pt 0.2 0.2 0.6 0.4 於200 μπι剝離 Ζ4 Pt 0.2 0.2 1.0 0.8 未剝離 Ζ5 Pt 0.2 0.2 1.4 1.2 未剝離 Ζ6 Pt 0.3 0.3 0.6 0.3 於漸冷中剝離 Ζ7 Pt 0.3 0.3 1.2 0.9 未剝離 Ζ8 Pt-Rh 0.2 0.2 1.0 0.8 未剝離 Α1 Pt 0.2 0.2 0.4 0.2 於100 μ m剝離 Α2 Pt 0.2 0.2 1.4 1.2 未剝離 A3 Pt 0.2 0.2 5.0 4.8 實際剝離 Α4 Pt-Rh 0.2 0.2 1.4 1.2 未剝離 -21 - 200846495 〔實施例4〕 除採用間距：1.4mm之交叉格子的交叉位置上配置直 徑：0.4mm、深度：〇.2mm之圓柱形凹部之斑狀凹部取代 交叉格子形狀之溝，作爲錨用凹部之外，與試料Z1同法 操作’於電鑄成形磚片之磨削面上形成錨用凹部進行鉑之 熔射。熔射中未出現熔射被膜之剝離，冷卻後熔射被膜仍 密合於電鑄成形磚片。 【圖式簡單說明】 〔圖i〕代表本發明電鑄成形磚之一實施形態的平面 圖（a)、及（a)之電鑄成形磚之A — A線箭頭所見之截面 圖。 〔圖2〕代表本發明附金屬被膜之電鑄成形磚之一實 施形態的截面圖。 〔圖3〕代表本發明電鑄成形磚之其他實施形態之截 面圖（a )〜（d )。 【主要元件符號說明】 1，la〜Id :電鑄成形磚 3，3a〜3d :錨用凹部 5 :金屬被膜 g，ga〜gd ··溝 11，13’ 21 ^ 23 ：平面 15，2 5 ’·彎曲面 -22- 200846495(Table 1) The shape of the groove and the peeling of the metal film. The molten metal groove (n Lm) is peeled from the groove w. The depth d is the pitch P. The width of the convex portion is x Ζ1 Pt 0.2 0.1 1.0 0.8 at 200 μm. Ζ2 Pt 0.2 0.2 0.4 0.2 at 100 μπι stripped Ζ3 Pt 0.2 0.2 0.6 0.4 at 200 μπι stripped Ζ4 Pt 0.2 0.2 1.0 0.8 unpeeled Ζ5 Pt 0.2 0.2 1.4 1.2 unpeeled Ζ6 Pt 0.3 0.3 0.6 0.3 stripped in gradual cooling Ζ7 Pt 0.3 0.3 1.2 0.9 not stripped Ζ8 Pt-Rh 0.2 0.2 1.0 0.8 Unpeeled Α1 Pt 0.2 0.2 0.4 0.2 Peeled at 100 μm Α2 Pt 0.2 0.2 1.4 1.2 Not peeled off A3 Pt 0.2 0.2 5.0 4.8 Actual peeling Α4 Pt-Rh 0.2 0.2 1.4 1.2 Not peeled-21 - 200846495 [Embodiment 4] A groove-like recess having a cylindrical recess having a diameter of 0.4 mm and a depth of 〇.2 mm is disposed at an intersection of a cross-grid having a pitch of 1.4 mm instead of a groove of a cross-grid shape as an anchor recess. In addition, in the same manner as the sample Z1, an anchor recess is formed on the grinding surface of the electroformed tile to perform platinum deposition. No peeling of the sprayed film occurred in the spray, and after cooling, the sprayed film was still adhered to the electroformed tile. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. i] is a cross-sectional view showing the plane A (A) of the embodiment of the electroformed brick of the present invention and the arrow A-A of the electroformed brick of (a). Fig. 2 is a cross-sectional view showing an embodiment of an electroformed brick to which a metal film of the present invention is attached. Fig. 3 is a cross-sectional view (a) to (d) showing another embodiment of the electroformed brick of the present invention. [Description of main component symbols] 1, la~Id: electroformed bricks 3, 3a to 3d: anchor recess 5: metal film g, ga~gd · groove 1, 13' 21 ^ 23: plane 15, 2 5 '·弯面-22- 200846495
d :溝深度 p :溝間距 X :凸部寬度 W :溝幅 -23-d : groove depth p: groove pitch X: convex width W: groove width -23-