470833 A7 B7 五、發明說明（1 ) 【發明之技術領域】 (請先閱讀背面之注意事項再填寫本頁) 本發明係關於氯或鹵素等鹵系腐蝕性氣體或液之製造 工廠及其等之氣體利用，於消費設備所使用之閥及其製造 方法。 【習知技術】 氯或氟等鹵系氣體係腐蝕性激烈，具有毒性之高壓氣 體，所以，在其製造設備或利用消費所設置之閥，係要求 使其等氣體不洩漏由安全性構造與防止腐蝕性氣體之腐餓 之腐蝕性。於氯（蘇打）工業設備，從長年之實績將汎用 性之塡函蓋型式，持續使用抑制其洩漏所需稍爲改良之塡 函蓋密封構造之球型閥。於第1圖表示代表性球型閥之構 造，但是，此塡函蓋密封球型閥之構造，係開閉閥體1時 所需之桿（閥桿）2爲上下移動，從貫通閥箱3之塡函蓋 (gland )部4之塡函蓋襯墊（gland packing ) 5之疲勞所 發生之間隙之氯氣之洩漏有不可避免之問題。 經濟部智慧財產局員工消費合作社印製 作爲對於此外部之氣體洩漏之防止措施，長年實施各 種改良。將其一例表示於第2圖，但是取呈長的塡函蓋部 ，將4種類之襯墊12、1 3、14、1 5重疊多層以提 升密封性，並且，在閥體突起部與塡函蓋座，當閥總開時 利用其逆座以防止洩漏之方法，或在塡函蓋部設0環1 0 (參照第1圖），加上以墊襯不能密封之氣體以二次性密 封之方法等，採取儘量避免氣體之洩漏之方法。然而，観 墊因疲勞、變形、摩粍等機能劣化變成不可避免，又，桿 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -4- 470833 A7 B7 五、發明說明（2 ) (請先閱讀背面之注意事項再填寫本頁> 因係不銹鋼製所以因氯或微量之水分之混入所發生之侵触 不銹鋼之接面氧化膜皮，使桿腐蝕’在塡函蓋襯墊之間形 成間隙、微細洩漏路徑（leak path ) ’因閥之開閉所滑動 之頻次變成愈多，此洩漏路徑就愈成長、擴大致使洩漏變 多。從塡函蓋部之腐蝕性氣體洩漏於外部時’與周圍之水 分等反應而產生鹽酸等之腐蝕性化合物’首先將塡函蓋， 接著對於◦環，再對於塡料函（stuffing box )，並且再對 於桿部，逐漸向腐蝕進行之方向前進。爲了防止洩漏變多 ，塡函蓋部之增緊及反復作業，致使手柄操作變成笨重， 終於無論增加好幾次增緊也不能停止洩漏。像這樣，塡函 蓋密封機構之閥，係本質上不能完全停止洩漏，所以，藉 進行煩雜之維修，必須更換襯墊、桿、塡函蓋、塡料函等 。又，閥座部因係金屬互相之金屬板，若嚙入金屬片、垃 圾、熔渣等異物時，就在閥體或本體片部發生傷痕，而完 全不能封閉流體，而變成內部洩漏。於此，爲了防止洩漏 反復增緊時，開閉作業就需要大的很大勞力，終於發生螺 紋斷裂或發生不良動作之原因。 經濟部智慧財產局員工消費合作社印製 由以上之理由，對於氯或氟氣體等鹵系腐蝕性氣體之 製造、消費設備所安裝、使用之閥，對於氯或氟等鹵系氣 體使用耐蝕性良好，及與外部完全遮斷，要求無外部之洩 漏。尤其蘇打工業設備殷切希望不容易發生氣體洩漏’不 容易發生腐蝕之閥。 本發明係在這種背景下所開發者，其目的係提供一種 在氯或氟等鹵系腐蝕性氣體，液體之製造工廠，其等氣體 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -5- 470833 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（3 ) 之利用或安裝於消費設備時，實現極有效之耐蝕性，防止 腐蝕之動作不良，洩漏之閥及其製造方法。 【發明之揭示】 本發明係欲達成上述目的最重要之點，對於將閥本體 使用氯或氟等鹵素等之鹵系腐蝕性氣體，液體以耐蝕性良 好之材料製作，藉其提供即使對於鹵系腐蝕性氣體，液體 基本上壽命長之閥，但是再鑑於要求各種之巧思，提供下 述者。 (1 ) 一種閥其係具有從流體入口經由閥體/閥座部 到流體出口之流體通路之閥本體（body )，與和閥本體成 一體安裝封閉流體通路之開口部之閥蓋（bonnet )，其特 徵爲：在閥本體之流體通路表面具有膜厚爲0 . 1〜5# m之金屬氟化物鈍態層。 (2 )如（1 )記載之閥，其中在本體之流體通路表 面具有鎳膜皮，將其鎳膜皮之表面強迫氧化後加以氟化以 形成上述金屬氟化物鈍態層。 (3)如（1) (2)記載之閥，其中貫通閥蓋之先 端部爲具有閥體之閥桿（stem )，閥桿貫通閥蓋所發生之 間隙爲由伸縮囊構造所密封。 (4 )如（3 ) g己載之閥，其中伸縮囊爲hastelloy製 並且爲無縫構造。 (5 )如（4 )記載之閥，其中將hastelloy製伸縮囊 焊接於has tell oy製伸縮囊環，將其伸縮囊環焊接於伸縮囊 (請先閱讀背面之注意事項再填寫本頁> 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 x 297公釐） -6- 470833 A7 ___ B7 五、發明說明（4) 凸緣及碟座（disk holder) 〇 (請先閱讀背面之注意事項再填寫本頁) (6 )如（5 )記載之閥，其中將上述凸緣在閥本體 與閥蓋間密閉地地挾持’以完成閥桿之上述密封。 (7)如（1) (2) (4) (5) (6)記載之閥 ，其中以旋轉擋止器防止閥桿之迴轉。 (8 )如（1 ) ( 2 ) ( 4 ) ( 5 ) ( 6 )記載之閥 ’其中在閥蓋內再具有閥桿之塡函蓋密封構造。 (9 )如（1 ) ( 2 ) ( 4 ) ( 5 ) ( 6 )記載之閥 ’其中將流體入口經由閥體/閥座部到流體出口之上述流 體通路成爲S字型通路。 (10)如（1) (2) (4) (5) (6)記載之 閥’其中閥開度爲閥之稱呼直徑之（1 / 3 ) X 1 . 1以 下。 (1 1 )如（1 ) ( 2 ) ( 4 ) ( 5 ) ( 6 )記載之 閥’其中至少閥本體爲低溫碳鋼製且其流體通路爲被機械 加工所形成。 (12) 如（1) (2) (4) (5) (6)記載之 經濟部智慧財產局員工消費合作社印製 閥’其中閥座部爲軟密封構造，軟密封爲聚四氟乙烯（ polytetrafluoroethylene 製。 (13) 如（1) (2) (4) ( 5 ) (6)記載之 閥’其中閥係球型閥（globe valve)。 (14) 如（1) (2) (4) (5) (6)記載之 閥，其中閥係閘閥（gate valve )或止回閥。 (15) 如（1) (2) (4) (5) (6)記載之 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 470833 A7 ____ B7 五、發明說明（5) 閥，其中閥係使用於鹵系腐蝕性氣體或液體。 (請先閱讀背面之注意事項再填寫本頁) (1 6 ) —種閥之製造方法，其特徵爲，包括：至少 閥本體之基材表面形成金屬膜皮，將其表面由氧化性物質 強迫氧化之後，將此強迫氧化膜與氟化氣體發生反應之工 程，與將閥本體與其他閥之構造零件連接之裝配工程。 (1 7 )如（1 6 )記載之製造方法，其中上述金屬 膜皮爲鎳或鎳合金之電解或無電解鍍法所形成。 (1 8 )如（1 6 ) ( 1 7 )記載之閥製造方法，其 中上述氧化性物質爲氧，低氧化氮，過氧化氮，臭氧及含 有這些混合氣體之至少一種。 (1 9 )如（1 6 ) ( 1 7 )記載之閥製造方法，其 中上述氧化性物質爲含有硝酸或過氧化氫溶液。 (2 0 )如（1 6 ) ( 1 7 )記載之閥製造方法，其 中上述氧化性物質爲由陽極氧化法在陽極所產生之氧氣。 (2 1 )如（1 6 ) ( 1 7 )記載之閥製造方法，其 中上述氟化氣體爲含有氟，三氟化氯及三氟化氮所成之群 所選擇之至少1種。 (2 2 )如（1 6 ) ( 1 7 )記載之閥製造方法，其 經濟部智慧財產局員工消費合作社印製 中包括連接閥之構造零件之裝配工程，爲將伸縮囊焊接於 伸縮囊環，將該伸縮囊焊接於伸縮囊凸緣及碟座之工程。 (2 3 )如（1 6 ) ( 1 7 )記載之閥製造方法，其 中閥本體爲低溫碳鋼製，將閥本體以機械加工形成流體通 路之後，以形成上述金屬膜皮。 【發明之詳細說明】 -8- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 470833 A7 _ B7 五、發明說明（6 ) (請先閱讀背面之注$項再填寫本頁) 本發明係較佳地使用於操作氯或氟等鹵系腐蝕性氣體 時’尤其使用於工業用氯氣製造工廠，使用蘇打電解設備 及氯氣之設備，例如使用氯氣殺菌之自來水淨化設備，紙 ’紙漿製造業設備因氯氣之漂白用製造線所設置之閥。 關於使用鹵系腐触性氣體，液體之閥，對於習知技術 之欄所記載之要求特性，本發明係基本上，（1 )提供將 閥之基材對於腐蝕性氣體，·液體具有優異耐蝕性能之閥， 更具體爲，提供一種在閥之基材流體通路表面藉形成膜厚 爲0 . 1〜5 V m之氟化鈍態膜，對於鹵系腐蝕性氣體， 液體也可較佳地使用之閥。 本發明之閥構造，並非特別加以限制，例如，可作爲 球閥、閘閥、或止回閥使用，也可使用爲球閥（ball valve )、蝶形閥（butterfly valve )、伸縮囊閥、隔膜閥等各種 構造之閥。 經濟部智慧財產局員工消費合作社印製 閥本體及構成零件，通常係由低溫用碳鋼或不銹鋼等 所構成。這些材料，係使用於氯等之腐蝕性氣體時，需要 腐蝕性對策，所以，本發明在閥之基材表面較佳爲形成金 屬膜皮，在其表面形成膜厚爲0 . 1〜5；wm，較佳爲1 〜3 更佳爲1〜2 /zm之氟化鈍態膜以提升耐触性。 形成膜厚爲0 . 1〜5 μ m之氟化鈍態膜之閥，係對於氯 系氣體等之鹵系耐系腐蝕性氣體，液體確認了可具極爲有 效之耐蝕性能。 這種氟化鈍態膜，係視其需要在閥之基材表面形成金 屬膜皮之後，將其表面由氧化性物質強迫氧化之後，將此 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -9- 470833 A7 _B7__ 五、發明說明（7 ) 強迫氧化膜與氟化氣體發生反應就可製造。 (請先閱讀背面之注意事項再填寫本頁) 於此，閥之基材表面形成金屬膜皮，將其表面由氧化 性物質強迫性地氧化之後，關於使此強迫氧化膜與氟化氣 體反應之工程，係本發明人等揭示於日本專利特開平 1 1 — 9 2 9 1 2號公報。 亦即，於本發明係首先，視其需要在閥之基材表面形 成金屬膜皮。此金屬膜皮係可一列舉含有鎳、銅、銀、銘 或至少這些以上之合金之電解鍍、無電解鍍、物理澱積（ PVD)等所成膜之膜皮。作爲電解鍍則可舉出N i — P 鍍、Ni—B 鍍、Ni— P—W鍍、Ni— P — B 鍍等。 又，作爲P VD則可舉鎳或其合金之噴鍍法。較佳爲鎳或 鎳合金之電解或無電解鍍所成膜之膜皮。欲形成膜皮之閥 之基材係如上述通常係由低溫用碳鋼或S U S 3 0 4所構 成，但是，在金屬膜皮形成前必須進行脫脂、酸洗、硏磨 、粒噴法（s h 〇 t b 1 a s t )等公知之質地處理。 經濟部智慧財產局員工消費合作社印製 接著，將金屬膜皮表面暫且強迫氧化，其後使此氧化 金屬膜皮與氟化氣體發生反應。此係於自然氧化，氧化膜 之膜厚爲數1 0〜數1 0 0埃（Angstrom )，並且，形成 牢固氧化膜之金屬係限於鋁等之特定金屬所致。發現了強 迫氧化後，進行氟化時，就發生氧之置換反應而形成氟化 層。因此.，氟化層之膜厚係比例於強迫氧化之膜厚而增大 ’依據本發明可提供金屬膜皮表面所形成之氟化層之膜厚 ，藉抑制形成於表面之氧化物膜之膜厚，得到所謂鈍態化 以上將膜厚化之氟化膜。如此地產生之氟化層係於耐蝕性 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 470833 A7 B7 五、發明說明（8 ) 或耐久性實用上具有充分耐用之基準性能。 (請先Μ讀背面之注意事項再填寫本頁) 所謂金屬氟化物層廣義爲含有氟之金屬層，但是，較 佳爲實質上完全由金屬氟化物所成之層。於此，所謂氟化 爲實質上之意義，被氧化之金屬膜皮不必1 0 0%改變成 氟化物但是氟爲被置換爲未能檢出氧基準之程度較佳。金 屬，不一定均勻地被氟化，也可以氟化層之厚度爲不均勻 ，也可混合有氟化物領域與氟擴散領域。若強迫氧化後進 行氟化處理時只有氧化層與氟置換不僅產生氟化物，對於 膜皮之金屬氟之擴散，其結果，就可形成厚氟化層。此閥 ，氟化層爲由金屬之氟化物實質上所成之第1層與下層擴 散氟之第2層所構成。 經濟部智慧財產局員工消費合作社印製 作爲強迫氧化手段，係可採用所謂氣相氧化，此時氧 或其中性或惰性氣體之混合氣體較佳，並且，低氧化氮、 過氧化氮、臭氧，或這些與中性或惰性氣體之混合氣體也 佳。此時，將這些氣體在高溫下與金屬接觸。作爲其他之 強迫氧化手段則可舉出液相氧化。此係也可在硝酸、過氧 化氫水等溶液之浸漬進行。並且，使用鹼等電解液，也可 將金屬陽極氧化在其表面形成氧化膜。如上述強迫氧化處 理之手法，可因應欲形成之氧化膜之厚度而組合。 同樣氟化處理，係氟、三氟化氯、三氟化氮等之 1 0 0%氣體，或這些氣體使用氮、氦、氬等惰性氣體稀 釋之氣體，或使用氟等之電漿氣體，使其與形成於金屬表 面上之最表層之氧化膜皮發生反應，以得到氟之擴散層或 氟化物之膜皮之方法。具體上爲如下進行即可。亦即，如 -11 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 470833 A7 B7 五、發明說明（9 ) 上述將金屬裝入於常壓氣相流通式之反應爐，流通氧化性 氣體之下，將反應爐加熱至既定之溫度，保持既定時間後 ，再在既定之溫度塡充氟化氣體使其反應既定時間，進行 表面之氟化處理即可。此時’裝入於反應爐之前，依通例 實施金屬之脫脂、脫水處理，其後提高所形成之強迫氧化 膜之純度並且成爲無缺陷者。但是，殘留於金屬表面之數 十埃以下之薄自然氧化膜係連同空白處被強迫氧化，所以 不必在強迫氧化前去除。 並且，反應爐之溫度係於鎳及銅之強迫氧化時通常到 200°C 〜6〇0°C，尤其 300 °C 〜50〇°C 較佳。反 應時間通常係1小時〜4 8小時’尤其3小時〜2 4小時 較佳。鋁係以陽極氧化處理較佳。同樣，氟化處理溫度係 在常壓下通常到1 〇〇°C〜700°C ’尤其1 50°C〜 5 0 0 °C較佳。又，反應時間通常係1小時〜4 8小時， 尤其3小時〜2 4小時較佳。這些之較佳下限溫度以下及 未滿時間時，強迫氧化層之氧未能充分被置換爲氟，又從 氟最表面之擴散也不充分，另者若超過上限溫度及時間時 氟之反應爲激烈所形成之膜皮將會發生龜裂。 本發明之閥，至少必須在閥本體之流體通路表面形成 既定膜厚之金屬氟化物層，但是’不只是閥本體也在閥蓋 等流體通路表面形成較佳。又，在閥外側雖然不需要氟化 層，但是對於閥進行表面處理時連同流體通路表面外側也 可一體地處理。 像這樣，在金屬氟化物層表面形成膜厚〇 . 1〜5 -----------:裝·-------訂· (請先閲讀背面.之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -12- 470833 A7 B7 五、發明說明（1G) (請先閱讀背面之注意事項再填寫本頁) μ m之閥，對於鹵系腐蝕性氣體，液體呈現極高之耐蝕性 ，所以，即使使用於鹵系腐蝕性氣體，液體之用途也可使 閥之壽命延長》 本發明之閥之再較佳構造說明如下。 (2 )閥構造爲伸縮囊密封構造時。 以往從球形閥之洩漏幾乎都起因於從塡函蓋部之洩漏 。一般之球形閥因係塡函蓋部密封構造，欲將構造性洩漏 變成全無係不可能之事。尤其如氯或氟氣體之毒性氣體， 因係危險所以從塡函蓋部之外部洩漏構造變成全無較佳。 從此理由，於本發明之閥，係由球形閥所代表之閥桿 先端構成閥體，閥桿貫通閥蓋構造之閥，採用形成於閥蓋 與閥桿間之間隙之密封所用之伸縮囊密封構造。又，最爲 可動構件之伸縮囊係考慮耐蝕性與壽命使用無縫之液壓一 體成形之hastelloy製，但是較佳爲使用hastelloy C-22。 經濟部智慧財產局員工消費合作社印製 又，將hastelloy製之伸縮囊使用於完全密封用途時加 以焊接安裝才可發揮其機能，但是hastelloy製伸縮囊若焊 接於不銹鋼或碳鋼時，焊接部就合金化致使耐蝕性低變成 容易劣化。於是，將hastelloy製伸縮囊一旦成hastelloy製 之構件，例如焊接於伸縮囊環，將此h a s t e丨1 〇 y製構件焊接 於凸緣與碟座等以其他方法用流體密封地安裝較佳。 hastelloy互相爲也可熔解hastelloy伸縮囊以焊接之精密焊 接。又，伸縮囊環等之hastelloy製構件，並非薄壁所以容 易牢固地安裝於不銹鋼或碳鋼，所以視其需要再以焊接或 襯墊等以流體密封地密封時就可得到耐蝕性高之構造。但 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -13- 470833 A7 B7 五、發明說明（11) (請先閱讀背面之注意事項再填寫本頁) 是，焊接伸縮囊之hastelloy製構件，因hastelloy爲昂貴， 所以將此使用於伸縮囊凸緣之大構件時畢竟不合算。於是 ，將伸縮囊焊接於小型之hastelloy製伸縮囊環，將其伸縮 囊環安裝於如不銹鋼製之伸縮囊凸緣或碟座大的構件。伸 縮囊環與伸縮囊凸緣或碟座係例如以螺絲構造牢固地固定 並且焊接密封時，焊接係只有流體密封地密封之目的所以 焊接部即使成爲hastelloy與不銹鋼之合金層也可具有充分 性能。又，伸縮囊或碟座，係使用襯墊等以流體密封地密 封爲容易之事。將閥桿以伸縮囊密封時，藉採用這種複合 構造，使用hastelloy製伸縮囊密封性就可成爲完全具耐蝕 性，構造上優於安定性，且方可提供實用價格之密封。 以往之塡函蓋部構造，爲了提高密封性需要將手柄之 增緊，而具有作業人員所嫌惡之不妥情形，但是本發明之 伸縮囊構造則與手柄之栓緊力無關因密封性完全，所以閥 (手柄）之開閉非常輕，實用上具有很大效果。 經濟部智慧財產局員工消費合作社印製 並且，於本發明，爲了防止桿之迴轉使用旋轉擋止器 (止轉），桿之運動只變成上下移動，不至於將薄伸縮囊 扭轉，可延長閥之壽命。又，桿通常係隨著上下移動而迴 轉，藉此迴轉雖然塡函蓋部發生摩粍，劣化成爲氣體洩漏 之原因，但是本發明連同伸縮囊也採用塡函蓋部並且使用 旋轉擋止器，改善閥座之碟片與閥座環之密封性，而實現 了無內部洩漏，外部洩漏之雙密封構造。 (3 )閥座部爲軟密封構造，軟密封係使用（ P T F E )。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -14 - 經濟部智慧財產局員工消費合作社印製 470833 A7 B7 五、發明說明（12) 軟密封具體爲將閥體之接觸部（碟片）替代以往之金 屬製碟片，可由具柔軟性之耐蝕性材料，例如可由 PTF E製造。藉將閥座部採用P T F E製之軟密封，藉 此就可改善關緊性能，即使嚙入些許異物也可防止洩漏。 藉此可將欲封閉之手柄扭矩變小，且成爲極容易更換之構 造。軟密封係例如可更換爲Monell製之金屬片’像這樣因 成爲Monell製金屬片也可再提高對於液化氯之耐蝕性。按 ，歯系腐蝕性流體用之閥之閥座部採用軟密封構造尙未爲 人所知曉。 (4 )氣體流路爲S字形，閥開度爲稱呼徑之（1 / 3 ) X 1 · 1 以下。 將氣體流路成爲S字形，實現了流量之確保與輕巧化 。現況之市售塡函蓋密封球形閥，入口流路係配合配管線 之中心配置成直線，出口係配置於較閥箱上部更陡峭之孔 ，所以，閥體（碟型座與碟）之開度若不採取大時，因阻 力會變大所以壓力損失爲大不能確保流量。因此，將閥體 開度設計成稱呼直徑之1 / 2或更大。本發明之伸縮囊密 封閥係爲了解決關於以往之問題，藉將氣體流路成S字形 開啓閥體時，從閥座排出之流體就可流入於出口，成爲出 口側斜孔爲直結於閥座部之構造。因藉此構造閥開度就以 稱呼直徑之1/3即可，因可將伸縮囊較以往更顯著地變 短所以也可收容於閥體內，達成了輕巧化，成本降低。閥 開度係爲了確保流量較佳地採用稱呼直徑之1 / 3，但是 實用上也可以1/3爲主在±1〇%之範圍內設計。 ------------t--------訂· (請先閲讀背面乏注項再填寫本頁> 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -15- 470833 A7 B7 五、發明說明（13) (5 )將閥座基材之流體通路以機械加工形成。 (請先閱讀背面之注意事項再填寫本頁> 閥之基材雖然多使用低溫碳鋼，但是爲了在基材之流 體通路表面施加金屬氟化處理因表面粗度必須優異，所以 ，基材之流體通路表面爲以機械加工形成較佳。又，鑄造 鋼料一般爲表面粗度爲本發明之金屬氟化處理之目的係不 充分，所以，鑄造鋼料之流體通路表面施加機械加工並非 不可能，但是將鍛造鋼進行機械加工以形成閥體較佳。 於第3圖表示本發明之一實施形態之伸縮囊球形閥之 構造。 閥本體（body ) 1 〇 1係低溫碳鋼（S F L 2 )製， 稱呼_直徑爲例如1 5mm、2 〇mm、2 5mm、40 mm、5 0mm等流體（氣體、液體）通路1 0 2係從入 口 1 0 3經由閥體/閥座部通到出口 1 0 4。閥本體 1 0 1係將通路1 0 2之上部開口部以閥蓋（bonnet ) 1 0 2所覆蓋，以形成閥箱。閥本體1 0 1 (連於第3圖 之例雖然不需要但是若需要時閥蓋）之表面，形成鎳鍍膜 皮，其表面爲強迫氧化後被氟化形成0·1〜5#m厚度 、較佳爲形成1〜2 //m厚度之金屬氟化物層。 經濟部智慧財產局員工消費合作社印製 在閥本體1 0 1途中具有構成閥座之閥座環（， SUS3 16或Monel金屬）105’與貫通閥蓋106 之閥桿（S U S 3 0 4 ) 1 0 7先端部所形成之閥體所成 之閥體/閥座部。閥桿1 0 7先端部所形成之閥體’係由 碟片座1 0 8與碟片1 0 9所成，碟片1 〇 9係以手柄 1 1 0之操作上下移動，先端閥體之PTFE製碟片 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） _ 16_ 經濟部智慧財產局員工消費合作社印製 470833 A7 _ _ B7 五、發明說明（14) 1 0 9爲對於閥座之閥座環1 0 5被推壓接觸被密封而進 行開閉。PTFE製碟片1〇9與閥座環105之密封係 軟密封。閥座環1 0 5與閥本體之間使用螺絲固定，並且 ’作爲閥座環1 0 5與閥本體間之襯墊1 〇 5 a以閥桿所 推壓較佳地使用具有不會向橫向擴大之物性之P T F E ( Gore公司製襯墊材，商品名goretex )。 閥桿1 0 7因貫通閥蓋1 〇 6所以必須以流體密封地 密封。於此例，係使用hastelloy C-22製伸縮囊1 1 2密封 。hastelloy C-22製伸縮囊1 1 2兩端係焊接於hastelloy C-27 6製伸縮囊環1 1 3、1 1 4。此焊接因係hastelloy互 相之焊接，所以可用精密焊接（熔入焊接）形成耐久性及 耐蝕性高之接合。參照第4圖時，第3圖之伸縮囊之上部 之一部放大圖，但是焊接伸縮囊1 1 2之hastelloy製伸縮 囊環1 1 3，係螺絲1 1 6 a旋入於不銹鋼製（ SUS3 1 6L)製伸縮囊凸緣1 1 5使其具有強度，所 以hastelloy製伸縮囊環1 1 3與不銹鋼製伸縮囊凸緣 1 1 5之焊接1 1 6 a只要是氣密密封之焊接即可。 hastelloy製伸縮囊環1 1 3與不銹鋼製碟片座（ SUS316L) 108之焊接也是相同。伸縮囊凸緣 1 1 5，係在閥本體1 0 1與閥蓋1 06間具有襯墊可挾 持成氣密。像這樣將hastelloy製伸縮囊環1 1 2 —旦焊接 於hastelloy製伸縮囊環1 1 3，藉將其接合於不銹鋼製之 伸縮囊凸緣1 1 5或碟片座1 0. 8，也可將高價之 hastelloy製伸縮囊強度上成爲耐蝕性也可達成具有充分接 ------------ -1--------訂_ (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -17- 470833 A7 B7 五、發明說明（15) 合及密封之經濟性構造。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 又，第3圖之閥，係流體通路1 0 2爲構成S字形。 第1圖之通路比較時，於第1圖係入口與出口之通路形成 爲約略平行，從入口之通路係經由閥座/閥體部約略成垂 直上升，較閥座相當高之位置逢到向出口之通路，成爲到 出口之形狀，所以，流體爲經由此閥座/閥體部充分順利 地流動時閥桿7爲需要具有較稱呼直徑之1/2以上大的 閥開度。與此相對，第3圖之S字型流路，係閥開度即使 爲1 / 3以下也可得到充分之流動。此小閥開度係具有顯 著使伸縮囊之尺寸變短之效果。因hastelloy製伸縮囊係金 屬製爲了實現些許上下移動也需要相當長之尺寸所致。因 此，於第3圖之閥，儘管採用伸縮囊密封構造，也可將伸 縮囊收容於以往之閥本體之尺寸中。從以往，雖然已知有 伸縮囊構造之閥，但是其時，伸縮囊之長度爲長’所以伸 縮囊係不僅是閥本體延伸到閥蓋之相當內部。於第3圖之 例，與採用閥開度小之流路形狀之相乘作用，藉將伸縮囊 之長度儘量縮短，將伸縮囊可完全收容於閥本體內部。藉 成爲這種構造，將伸縮囊1 1 5在閥本體1 0 1與閥蓋 1 〇 6間具襯墊可用挾住形式密封，提供維持強度與密封 性之簡單構造。爲了密封之焊接可變成最低限度之益處。 因焊接係強度低所以最低限度爲佳。 於第3圖之例，閥桿1 0 7係由伸縮囊密封構造上側 ，亦即在閥蓋1 0 6內部再以塡函蓋襯墊1 2 0密封’防 止異物侵入於伸縮囊，即使伸縮囊破損時’也成爲防止氣 -18- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 470833 A7 B7 五、發明說明（18) (氧化膜皮之形成/氟化處理） (.請先閱讀背面之注意事項再填寫本頁) 將形成N i -P鍍之零件裝入於常壓氣相流通式反應 爐之爐內部，在減壓下在2 0 0°C熱處理5小時釋出表面 之吸附水分等。其後，導入氧氣（9 9 . 9 % )，升溫到 4 0 0°C，將其溫度保持1 2小時將金屬表面強迫氧化。 其後，使用氮氣邊置換爲氧氣緩慢地冷卻。 當溫度到達350°C時，開始20%卩2氣（氮稀釋） 之導入，完全置換後，將氟氣使用氮氣置換，仍然保持1 小時冷卻到室溫。測定此時所得到之氟化鈍態膜厚度時， 具有約1 . 5 μ m。 (閥之裝配及測試） 在由上述方法所得到之表面形成氟化鈍態膜時之閥材 進行伸縮囊密封等之構造零件之焊接等，裝配了第3圖所 示之閥。 經濟部智慧財產局員工消費合作社印製 將此閥安裝於氯製造生產線後，實際使用。其結果， 在1個月與3個月之連續使用，初期之流量特性也沒有變 化。又’從閥座，塡函蓋部完全無洩漏，其後，一旦拆下 閥，解體確認內部之腐蝕情形，但是完全無腐鈾之痕跡。 如以上所說明，本發明之閥，係可設置於氯或氟等腐 蝕激烈，具有毒性之鹵系高壓氣體之製造設備或利用消費 之設備，不會洩漏任何氣體，也可防止因氣體之腐蝕變成 安全設備極爲有效。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -21 - 經濟部智慧財產局員工消費合作社印製 470833 A7 ___B7 五、發明說明（17) 性之高壓氣體，所以，表示要求從閥內面之釋出氣體，吸 附水分之脫離必須良好。氯氣係水解作用而變化爲氯化氫 ’鹽酸’氟氣係變化成氟酸不僅更加腐蝕性變強，因具有 浸透性所以會加速性地進行腐蝕所致。本發明之金屬氟化 物層係具有此特性。 若依據本發明就可提供上述之所有特性爲優異之閥。. 實施例 茲使用實施例再更加詳細說明如下，但是本發明並非 限定於這些實施例。 (無電解鎳-磷鍍膜皮之形成） 爲了製作如第3圖所示構造及形狀之閥，將鍛造低溫 鋼製之閥體及S U S 3 0 4製之其他構成零件以脫脂，酸 洗淨等施加質地前處理之後，升溫至9 0 °C而浸漬於調整 爲既定P Η之鍍液槽。反應既定時間，在所有表面形成 2 Ο μηι膜厚之鎳-磷鍍膜皮。於此所使用之無電解鎳-磷鍍稱爲所謂化學鎳鑛，以次磷酸鹽還原酸性化學鎳鍍之 市售藥劑已被實用化。本實施例，係將次磷酸作爲還原劑 之化學鎳鍍，亦即使用了市售之鎳—磷鍍（N i — Ρ合金 鍍）之藥劑。這些藥劑係作爲主成分爲金屬分之N i S 〇4 (硫酸鎳）25g/L，作爲還原劑使用NaHP〇2 (次 磷酸）2 0 g / L，絡化劑、安定劑、光澤劑所構成。 ----------- -t--------訂· (請先閱讀背面.之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -20- 470833 A7 _ B7 五、發明說明（16 ) 體洩漏之二重密封構造。又’閥桿1 〇 7係以旋轉擋止器 1 2 1雖然可上下移動但是防止其迴轉。若閥桿1 〇 7迴 轉時，伸縮囊容易破損所致。 氯或氟氣體等之鹵系腐蝕性氣體之製造，消費設備所 安裝使用之閥雖然要求如以下之特性，但是依據本發明就 可提供滿足這些特性之閥。 (a )對於氯或氟等之鹵系氣體其耐蝕性爲佳。 此係使用耐蝕性高之材料，或爲了增加耐蝕性能施加 表面處理，考慮價格與加工性必須選擇具有與耐蝕性能之 平衡之材料與表面處理之方法。本發明之金屬氟化物層特 別優異於此特性。又，本發明之伸縮囊密封構造係優於耐 蝕性。 (b )與外部完全遮斷，無外部洩漏。 經濟部智慧財產局員工消費合作杜印製 ---------- !裝--------訂. (請先閲讀背面之注意事項再填寫本頁) 此係消除來自外部之洩漏，儘量減少大氣之混入，外 部洩漏量係必須爲現況之測定器具有最高感度之氨（H e )洩漏探測器之檢出界限之1 Ο _ 1 2 P a · m 3/ s e c以 下。此値係表示反復動作，壓力負荷，腐蝕性環境等條件 下確實從外部所密封。若依據本發明，因閥本體基材之耐 蝕性爲高，長期維持製品初期之密封性。並且，因採用伸 縮囊密封，所以，密封性爲完全。並且，因係伸縮囊構造 ，所以具有開閉作業非常輕鬆之益處。 (c )來自閥構成零件之氣體流路表面之釋放氣體’ 吸附水分之脫離必須良好。 此係，流通內部之流體（氣體’液體）因係具有腐蝕 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） _ 19 _ 470833 A7 B7 五、發明說明（19 ) 圖式之簡單說明 第1圖係代表性塡函蓋部密封球形閥之剖面圖。 第2圖係經改良之球形閥之塡函蓋部之剖面圖。 第3圖係本發明實施形態之伸縮囊密封球形閥之剖面 圖。 第4圖係第3圖伸縮囊密封部之一部放大圖。 主要元件對照表 2 閥桿 3 閥箱 4 塡函蓋部 5 塡函蓋部襯墊 1 2，1 3，1 4，1 5 襯墊 101 閥本體 10 6 閥蓋 108 碟板座 10 9 碟板 10 7 閥桿 105 閥座環 112 hastelloy c-22 製伸縮囊環 1 1 3，1 1 4 hastelloy c-276 製伸縮囊環 115 伸縮囊凸緣 1 〇 2 流體通路 1 2 1 旋轉擋止器 ' 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） -22 - — — — —— — — I— i · I I {請先閱讀背面之注意事項再填寫本頁) -s · 經濟部智慧財產局員工消費合作社印製 470833 A7 _B7 五、發明說明（2Q ) 10 0環 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 23-470833 A7 B7 V. Description of the Invention (1) [Technical Field of the Invention] (Please read the precautions on the back before filling out this page) This invention relates to manufacturing plants of halogen-based corrosive gases or liquids such as chlorine or halogen, and the like Gas utilization, valves used in consumer equipment and manufacturing methods thereof. [Know-how] Halogen-based gas systems such as chlorine or fluorine are highly corrosive and toxic high-pressure gases. Therefore, the valves installed in their manufacturing facilities or consumption systems are required to prevent leakage of such gases by safety structures and Prevent the erosive and corrosive nature of corrosive gas. In the chlorine (soda) industrial equipment, the long-term performance will be widely used in the cover type, continued to use the slightly improved valve cover structure of the seal required to suppress its leakage. The structure of a representative ball valve is shown in Fig. 1. However, the structure of the seal-type ball valve is a rod (valve) 2 required to open and close the valve body 1. It moves up and down from the through valve box 3. There is an unavoidable problem of the leakage of chlorine gas in the gap caused by the fatigue of the gland packing 5 of the gland packing part 4. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Various measures have been implemented for many years to prevent external gas leakage. An example is shown in FIG. 2, but a long letter cover portion is taken, and four types of gaskets 12, 1, 3, 14, and 15 are stacked in multiple layers to improve the sealing performance. Letter cover seat, when the valve is always open to use its reverse seat to prevent leakage, or set the ring cover part 0 ring 1 0 (refer to Figure 1), plus the gas can not be sealed with a gasket to the secondary For the sealing method, take measures to avoid gas leakage as much as possible. However, due to fatigue, deformation, friction and other functional deterioration of the padding becomes inevitable, and the paper size of the pad is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) -4- 470833 A7 B7 V. Description of the invention (2) (Please read the precautions on the back before filling in this page >> Because it is made of stainless steel, the contact with the oxide film on the surface of the stainless steel caused by the incorporation of chlorine or a trace of water will cause the rod to corrode. A gap is formed between the gaskets, and a leak path is fine. The more the sliding frequency of the valve opens and closes, the more the leak path grows and expands, causing more leakage. Corrosive gas leakage from the cover On the outside, 'corrosive compounds such as hydrochloric acid are produced by reacting with surrounding moisture and the like', and then the cover is first covered, then the ring, then the stuffing box, and then the rod gradually progresses to corrosion. In order to prevent the leakage from increasing, the tightening and repeated operation of the letter cover portion made the handle operation cumbersome. Finally, no matter how many times the tightening is increased, the leakage cannot be stopped. Like In the same way, the valve of the seal mechanism of the seal cover cannot stop the leakage completely in essence. Therefore, for complicated repairs, the gasket, the rod, the seal cover, the seal letter, etc. must be replaced. Also, the valve seat part is made of metal. If foreign metal plates, such as metal pieces, garbage, slag, are caught, the valve body or the body part will be damaged, and the fluid cannot be sealed at all, which will cause internal leakage. Here, in order to prevent the leakage from repeatedly tightening At this time, the opening and closing operation requires a lot of labor, and finally the thread breakage or the cause of the bad action occurred. The Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the above reasons for halogen-based corrosive gases such as chlorine or fluorine gas. Valves installed and used in manufacturing and consumer equipment have good corrosion resistance for halogen-based gases such as chlorine or fluorine, and are completely blocked from the outside, requiring no external leakage. In particular, soda industrial equipment is eager to prevent gas leakage from occurring. A valve that is prone to corrosion. The present invention was developed under this background, and its purpose is to provide a halogen-based corrosive gas such as chlorine or fluorine, Liquid manufacturing factories, and other gases. The paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) -5- 470833 A7 B7. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (3) When it is used or installed in consumer equipment, it achieves extremely effective corrosion resistance, preventing corrosion from malfunctioning, leaking valve and its manufacturing method. [Disclosure of the Invention] The present invention is the most important point to achieve the above purpose. The main body uses halogen-based corrosive gas such as chlorine or fluorine, and the liquid is made of a material with good corrosion resistance. It provides a valve that basically has a long life even for halogen-based corrosive gas. (1) A valve is a valve body having a fluid passage from a fluid inlet through a valve body / valve seat portion to a fluid outlet, and an opening that closes the fluid passage is integrated with the valve body. The valve cover (bonnet) is characterized by having a film thickness of 0 on the surface of the fluid passage of the valve body. 1 ~ 5 # m passive layer of metal fluoride. (2) The valve according to (1), wherein a nickel film skin is provided on the surface of the fluid passage of the body, and the surface of the nickel film skin is forcibly oxidized and fluorinated to form the above-mentioned metal fluoride passivation layer. (3) The valve according to (1) or (2), wherein a tip end penetrating the bonnet is a stem having a valve body, and a gap occurring through the bonnet penetrating the bonnet is sealed by a bellows structure. (4) The valve according to (3) g, wherein the expansion bag is made of hastelloy and has a seamless structure. (5) The valve as described in (4), in which a bellow made of hastelloy is welded to a bellow made of has tell oy, and the bellows is welded to the bellows (please read the precautions on the back before filling this page > This paper size applies to China National Standard (CNS) A4 specification (21〇x 297mm) -6-470833 A7 ___ B7 V. Description of the invention (4) Flange and disk holder 〇 (Please read the first (Notes to fill in this page again) (6) The valve described in (5), in which the flange is tightly held between the valve body and the bonnet to complete the above-mentioned sealing of the valve stem. (7) Such as (1) (2) (4) (5) (6) The valve according to (6), wherein the rotation stop is used to prevent the valve stem from rotating. (8) The valve according to (1) (2) (4) (5) (6) 'Where there is a seal structure of the valve cover in the valve cover. (9) The valve as described in (1) (2) (4) (5) (6)' wherein the fluid inlet is passed through the valve body / seat The above-mentioned fluid passage to the fluid outlet becomes an S-shaped passage. (10) The valve described in (1), (2), (4), (5) (6), wherein the valve opening degree is equal to (1 / 3) X 1. 1 or less. (1 1) The valve according to (1), (2), (4), (5), (6), wherein at least the valve body is made of low-temperature carbon steel and its fluid path is formed by machining. (12) As described in (1) (2) (4) (5) (6), the valve printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has printed a valve, in which the valve seat is a soft seal structure, and the soft seal is polytetrafluoroethylene ( Made of polytetrafluoroethylene. (13) The valve described in (1), (2), (4), (5), (6), where the valve is a globe valve. (14) As in (1), (2) (4) (5) The valve described in (6), in which the valve is a gate valve or check valve. (15) The paper size described in (1) (2) (4) (5) (6) applies to the Chinese country Standard (CNS) A4 specification (210 X 297 mm) 470833 A7 ____ B7 V. Description of the invention (5) The valve is used for halogen-based corrosive gas or liquid. (Please read the precautions on the back before filling in this (Page 6) (16) A method for manufacturing a valve, comprising: forming a metal film on at least the surface of the base material of the valve body; forcing the surface to be oxidized with an oxidizing substance; The process of gas reaction and the assembly process of connecting the valve body with the structural parts of other valves. (17) The manufacturing method according to (16), wherein the above-mentioned metal film It is formed by electrolytic or non-electrolytic plating method of nickel or nickel alloy. (1 8) The method for manufacturing a valve according to (16) (17), wherein the oxidizing substance is oxygen, low nitrogen oxide, nitrogen peroxide, Ozone and at least one of these mixed gases. (19) The method for manufacturing a valve according to (16) or (17), wherein the oxidizing substance is a solution containing nitric acid or hydrogen peroxide. (2 0) Such as (1 6) The method for manufacturing a valve according to (17), wherein the oxidizing substance is oxygen generated at the anode by the anodizing method. (2 1) The method for manufacturing a valve according to (16) (17), wherein the above The fluorinated gas is at least one selected from the group consisting of fluorine, chlorine trifluoride, and nitrogen trifluoride. (2 2) The valve manufacturing method described in (16) (17), the wisdom of the Ministry of Economy The assembly process of the structural parts including the connecting valve included in the printing of the employee's consumer cooperative of the property bureau is to weld the expansion bag to the expansion bag ring and weld the expansion bag to the expansion bag flange and the disc seat. (2 3) Such as ( 1 6) The valve manufacturing method according to (1 7), wherein the valve body is made of low-temperature carbon steel, and the valve body [Mechanical description of the invention] -8- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 470833 A7 _ B7 V. Invention Note (6) (Please read the note on the back before filling in this page) The present invention is preferably used when operating halogen-based corrosive gases such as chlorine or fluorine ', especially used in industrial chlorine gas manufacturing plants, using soda electrolysis Equipment and chlorine gas equipment, such as chlorine water sterilization of tap water purification equipment, paper 'pulp manufacturing equipment due to chlorine gas bleaching production line of the valve. Regarding the use of halogen-based corrosive gas and liquid valves, the characteristics described in the column of conventional technology are basically the present invention. (1) The valve substrate is provided with corrosive gas and liquid with excellent corrosion resistance. The performance valve, more specifically, provides a film by forming a film thickness of 0 on the surface of the fluid path of the substrate of the valve. 1 ~ 5 V m fluorinated passive film. For halogen-based corrosive gas, liquid can also be used as a valve. The valve structure of the present invention is not particularly limited. For example, it can be used as a ball valve, a gate valve, or a check valve. It can also be used as a ball valve, a butterfly valve, a bellows valve, a diaphragm valve, etc. Valves of various constructions. The valve body and its component parts, which are printed by employees' cooperatives in the Intellectual Property Bureau of the Ministry of Economic Affairs, are usually composed of low-temperature carbon steel or stainless steel. These materials, when used in corrosive gases such as chlorine, require corrosive measures, so the present invention preferably forms a metal film on the surface of the substrate of the valve, and the film thickness on the surface is 0. 1 to 5; wm, preferably 1 to 3, more preferably 1 to 2 / zm fluorinated passive film to improve touch resistance. The resulting film thickness is 0. 1 to 5 μm fluorinated passive membrane valve is a halogen-based corrosion-resistant gas such as chlorine-based gas, and the liquid has been confirmed to have extremely effective corrosion resistance. This fluorinated passive film is formed by forming a metal film on the surface of the valve substrate as required, and after forcibly oxidizing the surface with an oxidizing substance, the paper size applies the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) -9- 470833 A7 _B7__ 5. Description of the invention (7) It can be manufactured by forcing the oxide film to react with the fluorinated gas. (Please read the precautions on the back before filling this page.) Here, a metal film is formed on the surface of the base material of the valve. The surface of the valve is forcibly oxidized with an oxidizing substance. The forced oxidation film reacts with the fluorinated gas. The project is disclosed in Japanese Patent Laid-Open No. 1 1-9 2 9 1 2 by the inventors. That is, in the present invention, first, a metal film is formed on the surface of the base material of the valve as needed. The metal film can be a film formed by electrolytic plating, electroless plating, physical deposition (PVD), etc. containing nickel, copper, silver, or at least these alloys. Examples of the electrolytic plating include Ni—P plating, Ni—B plating, Ni—P—W plating, and Ni—P—B plating. The P VD may be a spray method of nickel or an alloy thereof. Films formed by electrolytic or electroless plating of nickel or a nickel alloy are preferred. As mentioned above, the base material of the valve is usually composed of low temperature carbon steel or SUS 304. However, before the formation of the metal film skin, degreasing, pickling, honing, and grain spraying methods (sh 〇tb 1 ast) and other well-known textures. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Then, the surface of the metal film was forcibly oxidized for a while, and then the oxidized metal film was reacted with the fluorinated gas. This is due to natural oxidation. The thickness of the oxide film is in the range of 10 to 100 Angstroms. Moreover, the metal forming a strong oxide film is limited to a specific metal such as aluminum. It was found that after forced oxidation, when fluorination is performed, a substitution reaction of oxygen occurs to form a fluorinated layer. therefore. The film thickness of the fluorinated layer is increased in proportion to the film thickness of the forced oxidation. According to the present invention, the film thickness of the fluorinated layer formed on the surface of the metal film can be provided, and by suppressing the film thickness of the oxide film formed on the surface Thus, a fluorinated film having a thickness greater than the so-called passivation is obtained. The fluorinated layer produced in this way is corrosion resistant. The size of this paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 470833 A7 B7. 5. Description of the invention (8) or durability has a practically sufficient basis for durability. performance. (Please read the cautions on the reverse side before filling out this page.) The so-called metal fluoride layer is broadly defined as a metal layer containing fluorine, but it is preferably a layer made entirely of metal fluoride. Here, the so-called fluorination has a substantial meaning, and the oxidized metal film does not need to be changed to fluoride by 100%, but the degree to which fluorine is replaced to fail to detect an oxygen standard is preferable. Metals are not necessarily uniformly fluorinated, and the thickness of the fluorinated layer may be non-uniform, or they may be mixed with a fluoride field and a fluorine diffusion field. If only the oxidation layer and fluorine are replaced during the fluorination treatment after forced oxidation, not only fluorides will be produced, but also the diffusion of metal fluorine from the film skin. As a result, a thick fluorinated layer can be formed. In this valve, the fluorinated layer is composed of a first layer substantially formed by metal fluoride and a second layer which diffuses fluorine underneath. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs as a forced oxidation method, so-called gas phase oxidation can be used. At this time, oxygen or a mixed gas of neutral or inert gas is preferred, and low nitrogen oxide, nitrogen peroxide, ozone, Or a mixture of these with a neutral or inert gas is preferred. At this time, these gases are brought into contact with the metal at a high temperature. As another means of forced oxidation, liquid-phase oxidation is mentioned. This system can also be immersed in a solution such as nitric acid or hydrogen peroxide. In addition, by using an electrolytic solution such as an alkali, a metal can be anodized to form an oxide film on the surface. The methods of forced oxidation treatment described above can be combined according to the thickness of the oxide film to be formed. Similarly, the fluorination treatment is a 100% gas such as fluorine, chlorine trifluoride, nitrogen trifluoride, or a gas diluted with an inert gas such as nitrogen, helium, or argon, or a plasma gas such as fluorine. A method for reacting with an oxide film formed on the outermost surface of a metal surface to obtain a diffusion layer of fluorine or a film of fluoride. Specifically, it can be performed as follows. That is, such as -11-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 470833 A7 B7 V. Description of the invention (9) After entering the reaction furnace of atmospheric pressure gas flow type and circulating oxidizing gas, the reaction furnace is heated to a predetermined temperature and maintained for a predetermined time, and then the fluorinated gas is charged at the predetermined temperature to make the reaction react for a predetermined time to perform the surface The fluorination treatment is sufficient. At this time, before being loaded into the reaction furnace, the metal is degreased and dehydrated as usual, and then the purity of the formed forced oxide film is increased and it becomes a defect-free person. However, the thin natural oxide film remaining on the surface of the metal below a few ten angstroms is forcedly oxidized together with the blank space, so it is not necessary to remove it before the forced oxidation. In addition, the temperature of the reaction furnace is usually 200 ° C ~ 600 ° C, especially 300 ° C ~ 50 ° C, when forced oxidation of nickel and copper occurs. The reaction time is usually 1 hour to 48 hours, and particularly preferably 3 hours to 24 hours. The aluminum system is preferably anodized. Similarly, the temperature of the fluorination treatment is usually from 100 ° C to 700 ° C 'under normal pressure, especially from 150 ° C to 500 ° C. The reaction time is usually 1 hour to 48 hours, and particularly preferably 3 hours to 24 hours. Below these preferable lower limit temperatures and under full time, the oxygen of the forced oxide layer cannot be fully replaced with fluorine, and the diffusion from the outermost surface of the fluorine is insufficient, and if the upper limit temperature and time are exceeded, the reaction of fluorine is The fiercely formed membrane will crack. In the valve of the present invention, at least the metal fluoride layer of a predetermined thickness must be formed on the fluid passage surface of the valve body, but it is preferable that not only the valve body but also the fluid passage surface such as the valve cover. In addition, although a fluorinated layer is not required on the outside of the valve, it can be treated integrally with the outside of the fluid passage surface when the valve is surface-treated. In this way, a film thickness is formed on the surface of the metal fluoride layer. 1 ~ 5 -----------: Outfit ・ ------- Order (Please read the back first. Please note this page before filling in this page) This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -12- 470833 A7 B7 V. Description of invention (1G) (Please read the notes on the back before filling in This page) μm valve, for halogen-based corrosive gas, the liquid has extremely high corrosion resistance, so even if it is used for halogen-based corrosive gas, the use of liquid can extend the life of the valve. A further preferred structure is explained below. (2) When the valve structure is a bellows seal structure. In the past, almost all leaks from ball valves were caused by leaks from the cover. The general ball valve has a seal structure on the cover part, so it is impossible to make structural leakage impossible. In particular, toxic gases such as chlorine or fluorine gas are dangerous, so it is preferable that there is no leakage structure from the outside of the cover. For this reason, in the valve of the present invention, the valve body is constituted by the tip of the valve stem represented by the ball valve, and the valve structure constructed by the valve stem penetrating the valve cover adopts a bellows seal used to seal the gap formed between the valve cover and the valve stem. structure. In addition, the most flexible member of the expansion bag is a hastelloy made of seamless hydraulic pressure in consideration of corrosion resistance and longevity, but it is preferable to use hastelloy C-22. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the function of the bellows made of hastelloy can be used for welding when it is completely sealed. However, if the bellows made of hastelloy are welded to stainless steel or carbon steel, the welding department will Alloying results in low corrosion resistance and easy deterioration. Therefore, it is preferable to use a hastelloy-made expansion bladder as a component made of hastelloy, for example, welding to an expansion bladder ring, and welding this has t e 丨 10 y to a flange and a disc seat, etc., and to install it in a fluid-tight manner by other methods. Hastelloy is a precision welding that can also melt the hastelloy bellows for welding. In addition, members made of hastelloy, such as bellows, are not thin, so they can be easily and securely attached to stainless steel or carbon steel. Therefore, if necessary, a structure with high corrosion resistance can be obtained when they are sealed with a fluid seal such as welding or gaskets. . However, this paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -13- 470833 A7 B7 V. Description of the invention (11) (Please read the precautions on the back before filling this page) Yes, welding expansion Since the hastelloy components are expensive, it is not cost-effective to use this for the large components of the bellows flange. Then, the bellows is welded to a small hastelloy bellows, and the bellows ring is attached to a large member such as a bellows made of stainless steel or a large disk seat. When the deflation balloon ring and the bellows flange or the disk seat are firmly fixed with a screw structure, for example, and are welded and sealed, the welding system only has the purpose of fluid-tight sealing. Therefore, the welded portion can have sufficient performance even if it is an alloy layer of hastelloy and stainless steel. In addition, the expansion bag or the dish holder can be easily sealed in a fluid-tight manner using a gasket or the like. When the valve stem is sealed with a bellows, by adopting this composite structure, the sealability of the bellows made by Hastelloy can be completely corrosion-resistant, better in structure than stability, and only provide a practically-priced seal. In the past, the structure of the cover part required tightening of the handle in order to improve the sealing performance, and there was an inconvenience that the operator hated. However, the expansion bag structure of the present invention is completely independent of the tightening force of the handle because the sealing performance is completely Therefore, the opening and closing of the valve (handle) is very light and has a great effect in practice. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy Of life. In addition, the lever usually rotates with the up and down movement. Although the rotation of the box cover causes friction and the deterioration causes the gas leakage, the present invention also uses the box cover and the rotation stopper together with the expansion bag. Improve the sealing between the disc and seat ring of the valve seat, and realize the double seal structure without internal leakage and external leakage. (3) The valve seat has a soft seal structure, and the soft seal is used (P T F E). This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -14-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 470833 A7 B7 V. Description of the invention (12) The soft seal is specifically for the valve body. The contact portion (disc) can replace conventional metal discs, and can be made of a flexible, corrosion-resistant material, such as PTF E. By using a soft seal made of P T F E for the seat part, the closing performance can be improved, and leakage can be prevented even if some foreign matter is caught. As a result, the torque of the handle to be closed can be reduced, and the structure can be easily replaced. The soft seal system can be replaced with a metal sheet made of Monell ', for example. By forming a metal sheet made of Monell, the corrosion resistance to liquefied chlorine can be further improved. According to 歯, the valve seat of the valve for corrosive fluid uses a soft seal structure. It is not known. (4) The gas flow path is S-shaped, and the valve opening degree is (1/3) X 1 · 1 or less of the nominal diameter. The gas flow path is S-shaped, ensuring the flow rate and reducing weight. In the current state of the market, the sealed ball valve with a letter box cover, the inlet flow path is arranged in a straight line with the center of the distribution line, and the outlet is arranged in a steeper hole than the upper part of the valve box. If the degree is not adopted, the resistance will increase, so the pressure loss is large, and the flow cannot be ensured. Therefore, the valve body opening degree is designed to be 1/2 or more of the nominal diameter. In order to solve the related problems in the past, the telescoping sealed valve of the present invention, when the valve body is opened by an S-shaped gas flow path, the fluid discharged from the valve seat can flow into the outlet, and the outlet side oblique hole is directly connected to the valve seat. Department of structure. Because of this, the opening degree of the valve can be set to 1/3 of the nominal diameter, and the bellows can be significantly shorter than before, so it can be housed in the valve body. The valve opening degree is preferably 1/3 of the nominal diameter in order to ensure the flow rate, but it can also be designed within 1/3 mainly within the range of ± 10%. ------------ t -------- Order · (Please read the lack of notes on the back before filling out this page> This paper size applies to China National Standard (CNS) A4 specifications ( 210 X 297 mm) -15- 470833 A7 B7 V. Description of the invention (13) (5) The fluid path of the valve seat base material is formed by machining. (Please read the precautions on the back before filling this page > Valve Although many low-temperature carbon steels are used as the base material, in order to apply metal fluorination treatment to the surface of the fluid path of the base material, the surface roughness must be excellent. Therefore, it is preferable that the surface of the fluid path of the base material is formed by machining. Also, casting Generally, the surface roughness of the steel material is insufficient for the purpose of the metal fluorination treatment of the present invention. Therefore, it is not impossible to apply machining to the surface of the fluid path of the cast steel material, but it is better to machine the forged steel to form the valve body. Fig. 3 shows the structure of a telescoping ball valve according to an embodiment of the present invention. The valve body 1 〇1 is made of low temperature carbon steel (SFL 2), and its diameter is, for example, 15mm, 20mm, 2 5mm, 40 mm, 50mm and other fluid (gas, liquid) channels 1 0 2 series from The inlet 103 is connected to the outlet 104 through the valve body / seat section. The valve body 101 covers the upper opening of the passage 102 with a bonnet 102 to form a valve box. The surface of the valve body 1 0 1 (connected to the example in Figure 3 is not necessary but if necessary, the valve cover) is formed with a nickel coating. The surface is fluorinated to form 0 · 1 ~ 5 # m thickness after forced oxidation. It is preferable to form a metal fluoride layer with a thickness of 1 to 2 // m. The employee cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has printed a valve seat ring (SUS3 16 or Monel metal) on the way of the valve body 101. 105 'and the valve stem (SUS 3 0 4) 1 0 7 through the valve cover 106. The valve body / seat portion formed by the valve body formed by the tip portion. The valve body formed by the valve stem 1 0 7' portion It is composed of disc holder 108 and disc 10. The disc 1.09 is moved up and down by the operation of handle 1 10. The PTFE disc of the valve body at the front end of the paper is in accordance with China National Standards (CNS). A4 specifications (210 X 297 mm) _ 16_ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 470833 A7 _ _ B7 V. Description of the invention (14) 1 0 9 is for The valve seat ring 105 of the seat is pushed and contacted to be sealed and opened and closed. The sealing of the PTFE disc 10 and the valve seat ring 105 is a soft seal. The valve seat ring 105 and the valve body are fixed with screws. And as the gasket 1 0 5 between the valve seat ring 105 and the valve body, it is preferable to use a PTFE (Gore company gasket material, a product with a physical property that does not expand in the horizontal direction) by the valve rod pressing. Name goretex). The valve stem 1 07 must be fluid-tightly sealed because it penetrates the valve cover 106. In this example, a bellows made of Hastelloy C-22 1 1 2 is used for sealing. Hastelloy C-22 Expansion Cap 1 1 2 Both ends are welded to Hastelloy C-27 6 Expansion Cap Ring 1 1 3, 1 1 4. This welding is a hastelloy mutual welding, so precision welding (fusion welding) can be used to form a joint with high durability and corrosion resistance. When referring to Fig. 4, an enlarged view of the upper part of the telescoping bag in Fig. 3 is shown, but the bellow ring 1 1 3 made by Hastelloy is welded to the telescoping bag 1 1 2 and the screws 1 1 6 a are screwed into stainless steel (SUS3 1 6L) Expansion bag flange 1 1 5 to make it strong, so the welding of hastelloy expansion bag ring 1 1 3 and stainless steel expansion bag flange 1 1 5 1 1 6 a as long as it is hermetically sealed welding . The welding of hastelloy bellows 1 1 3 and stainless steel disc holder (SUS316L) 108 is also the same. The bellows flange 1 1 5 is provided with a gasket between the valve body 101 and the valve cover 106 to hold it airtight. In this way, the balloon ring 1 1 2 made by Hastelloy is welded to the balloon ring 1 1 3 made by Hastelloy, and it is joined to the stainless steel balloon flange 1 1 5 or the disc holder 10. 8. It is also possible to increase the strength of the high-priced hastelloy-made bellows into the corrosion resistance. It can also be achieved with sufficient connection ------------ -1 -------- order_ (Please read first Note on the back, please fill in this page again.) This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) -17- 470833 A7 B7 V. Description of the invention (15) Economic structure of closing and sealing. (Please read the precautions on the back before filling out this page.) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The valve in Figure 3 is a S-shaped fluid path. In the comparison of the passage in Fig. 1, the passage between the inlet and the outlet in Fig. 1 is formed approximately parallel, and the passage from the inlet rises approximately vertically through the valve seat / valve body, and is relatively higher than the valve seat. The outlet passage is shaped to the outlet. Therefore, the valve stem 7 needs to have a valve opening larger than 1/2 of the nominal diameter when the fluid flows sufficiently and smoothly through the valve seat / body. In contrast, in the S-shaped flow path in Fig. 3, a sufficient flow can be obtained even if the valve opening degree is 1/3 or less. This small valve opening has the effect of significantly shortening the size of the bellows. This is due to the fact that the metal bellows system made by hastelloy also requires a relatively long size in order to achieve a little vertical movement. Therefore, although the valve shown in FIG. 3 has a bellows sealing structure, the bellows can be accommodated in the size of a conventional valve body. Conventionally, although a valve having a bellows structure is known, at this time, the bellows has a long length, so the bellows system extends not only the valve body into a considerable portion of the valve cover. In the example in Fig. 3, by multiplying the shape of the flow path with a small valve opening, the length of the bellows can be shortened as much as possible, and the bellows can be completely contained inside the valve body. With this structure, the bellows 1 15 can be sealed with a cushion between the valve body 101 and the valve cover 106 to provide a simple structure for maintaining strength and tightness. Welding for sealing can become a minimal benefit. Since the strength of the welding system is low, it is preferably at least. In the example in Fig. 3, the valve stem 10 7 is sealed by the expansion bag on the upper side, that is, inside the valve cover 10 6 is sealed with a letter cover gasket 1 2 0 'to prevent foreign matter from invading the expansion bag, even if it is retracted. When the capsule is broken, it also becomes the prevention of gas. 18- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 470833 A7 B7 V. Description of the invention (18) (Formation of oxide film / fluorination treatment ) (. Please read the precautions on the back before filling in this page.) Put the Ni-P plated parts in the furnace of the atmospheric gas flow reactor, and heat release at 2000 ° C for 5 hours under reduced pressure. Adsorbed water on the surface. Thereafter, oxygen (9 9. 9%), the temperature was raised to 400 ° C, and the temperature was maintained for 12 hours to forcibly oxidize the metal surface. Thereafter, it was slowly cooled by replacing it with oxygen while using nitrogen. When the temperature reached 350 ° C, the introduction of 20% tritium gas (nitrogen dilution) was started. After the full replacement, the fluorine gas was replaced with nitrogen, and it was kept for 1 hour to cool to room temperature. When the thickness of the fluorinated passive film obtained at this time is measured, it has about 1. 5 μm. (Assembly and test of the valve) The valve shown in Fig. 3 was assembled by welding the structural parts such as bellows seals when the fluorinated passive film was formed on the surface obtained by the above method. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. This valve is actually used after being installed in a chlorine production line. As a result, during the continuous use of one month and three months, the initial flow characteristics did not change. From the valve seat, there was no leakage at the valve cover. After the valve was removed, it was disassembled to confirm the internal corrosion, but there was no trace of rotten uranium. As explained above, the valve of the present invention can be installed in the production equipment or consumption equipment of halogen-based high-pressure gas which is highly corrosive and toxic, such as chlorine or fluorine. It will not leak any gas and can also prevent corrosion due to gas. Turning it into a safety device is extremely effective. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -21-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 470833 A7 ___B7 V. Description of the invention (17) High-pressure gas of the nature, therefore, It is required to release gas from the inner surface of the valve, and the detachment of adsorbed moisture must be good. Chlorine-based hydrolysis changes to hydrogen chloride. Hydrochloric acid. Fluorine-based conversion to fluoric acid is not only more corrosive and strong, but also due to its permeability, it accelerates corrosion. The metal fluoride layer of the present invention has this characteristic. According to the present invention, it is possible to provide a valve having all of the above-mentioned characteristics. . EXAMPLES Examples will be described in more detail below, but the present invention is not limited to these examples. (Formation of Electroless Nickel-Phosphorus Coating) In order to produce a valve with the structure and shape shown in Figure 3, the forged low-temperature steel valve body and other components made of SUS 304 are degreased and acid-washed. After applying the texture pre-treatment, the temperature was raised to 90 ° C and immersed in a plating bath adjusted to a predetermined PΗ. A predetermined time of reaction, a nickel-phosphorus coating with a thickness of 20 μm was formed on all surfaces. The electroless nickel-phosphorus plating used here is called a so-called chemical nickel ore, and a commercially available agent for reducing acidic chemical nickel plating with hypophosphite has been put into practical use. This embodiment is a chemical nickel plating using hypophosphorous acid as a reducing agent, that is, a commercially available nickel-phosphorus plating (Ni-P alloy plating) agent is used. These agents are 25 g / L of Ni S 〇4 (nickel sulfate) as the main component, and NaHP〇2 (hypophosphite) 20 g / L is used as a reducing agent. Complexing agents, stabilizers, and gloss agents are used. Make up. ----------- -t -------- Order · (Please read the back first. Please pay attention to this page before filling in this page) This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -20- 470833 A7 _ B7 V. Description of the invention (16) The double seal structure for body leakage. The valve stem 1 07 is a rotary stopper 1 2 1 which can move up and down but prevents it from turning. If the valve stem is rotated in 107, the expansion bag is easily damaged. Although the following characteristics are required for the production of halogen-based corrosive gases such as chlorine and fluorine gas, and the consumer equipment is installed and used according to the present invention, a valve that satisfies these characteristics can be provided. (a) It has good corrosion resistance to halogen-based gases such as chlorine and fluorine. This is the use of materials with high corrosion resistance, or surface treatment in order to increase corrosion resistance, considering the price and workability must choose a material with a balance of corrosion resistance and surface treatment methods. The metal fluoride layer of the present invention is particularly excellent in this characteristic. The seal structure of the bellows of the present invention is superior to corrosion resistance. (b) Completely cut off from the outside, no external leakage. Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs on consumer cooperation ----------! (Please read the precautions on the back before filling out this page) This is to eliminate leakage from the outside and minimize the mixing of the atmosphere. The external leakage must be the ammonia leak detector with the highest sensitivity of the current detector. The detection limit is 1 〇 _ 1 2 P a · m 3 / sec or less. This system means that it is indeed sealed from the outside under repeated conditions, pressure load, and corrosive environment. According to the present invention, since the corrosion resistance of the valve body base material is high, the initial sealing properties of the product are maintained for a long period of time. In addition, since the capsular seal is used, the sealing performance is complete. In addition, because of the expansion bag structure, it has the benefit of being very easy to open and close. (c) The released gas from the surface of the gas flow path of the valve component must be well detached from the adsorbed moisture. In this system, the internal fluid (gas'liquid) in circulation is corrosive. The paper size is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) _ 19 _ 470833 A7 B7 V. Description of the invention (19) Brief description of the first figure is a cross-sectional view of a representative ball valve with a sealed cover. Fig. 2 is a cross-sectional view of the cover portion of the improved ball valve. Fig. 3 is a sectional view of a bellows sealed ball valve according to an embodiment of the present invention. FIG. 4 is an enlarged view of a portion of the bellows sealing portion of FIG. 3. Comparison table of main components 2 Valve stem 3 Valve box 4 Box cover part 5 Box cover part gasket 1 2, 1 3, 1 4, 1 5 Gasket 101 Valve body 10 6 Valve cover 108 Disc plate seat 10 9 Disc plate 10 7 Valve stem 105 Seat ring 112 Hastelloy c-22 bellows 1 1 3, 1 1 4 hastelloy c-276 bellows 115 Bellows flange 1 〇2 Fluid passage 1 2 1 Rotary stopper ' This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) -22-— — — — — — I — i · II {Please read the notes on the back before filling this page) -s · Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 470833 A7 _B7 V. Description of the Invention (2Q) 100 Rings (Please read the precautions on the back before filling this page) China National Standard (CNS) A4 Specification (210 X 297 mm) 23-