/1 95 6 A7 B7 經濟部智慧財產局貝工消費合作社印製 五、發明說明（/ ) 【發明所需之技術領域】 本發明係關於一種以MoSh基材或以含有MoSh主成分 70%以上之基材所構成(以下皆稱爲”以MoSh爲主體，，)之發 熱材料；特別是關於一種使在發熱材料之表面上所形成之 玻璃質表面氧化被膜爲具有低氧擴散性之發熱材料。 【習知之技術】 由於MoSh群發熱材料於1〇〇〇〜1800°C之氧化性周圍 氣氛下會形成抗氧化性優異的玻璃質表面氧化被膜（下稱 玻璃質被膜），因此其係一種可使用於氧化性周圍氣氛之 超高溫領域之少數發熱材料。 MoSh群發熱材料之成分，爲了調整電阻値、成形助劑 或玻璃質被膜之生成助劑等，因此於MoSh中添加有數％〜 數10%之多成分系玻璃成分等。 MoSh基材通常係藉以表面氧化或塗佈等適宜方法以形 成玻璃質之保護被膜後，而得作爲加熱器使用。 又，MoSu群發熱材料係例如加工成爲如第1圖之形狀 後，裝設於爐體內，以作爲加熱器使用。 圖中之⑷稱爲電極部，與MoSh基材完全電氣接續， 因此在去除玻璃質被膜之母材上通常噴鍍有A1等之金屬。 電極部在電阻加熱MoSh群發熱體時，係擔任端子的任務 。又，圖之⑻稱爲夾持(grip)部，藉使其直徑較⑻發熱部爲 粗，用以降低電阻，以迎合電阻發熱。夾持部係使發熱部 與電極部間生成熱梯度，以防止電極部曝露於高溫下而被 氧化。圖之(c)稱爲發熱部，其正是擔任將爐體溫度昇高時 3 本紙張尺度適用ΐ國國家標準（CNS)A4規格（210 X 297公爱） (請先閱讀背面之注意事項ΜΓί/寫本頁) -V,裝 訂 β --線_ B7 4 6 7 956 五、發明說明（>) 之加熱器之任務。 【發明欲解決之課題】 --------I------v—--- (請先閱讀背面之注意事項再r.窝本頁) 在使用習知MoSh群發熱料料作爲氣爐之發熱體（加 熱器）之情形，大致上可列舉兩個問題點。 第一個問題係：於300〜600°C之氧化性周圍氣氛下被 長期保持之M〇Sh群發熱材料，其在1〇〇〇〜ig〇〇°c領域會 產生不同的氧化舉動，因擴散於玻璃質被膜中之氧氣會使 得Mo和Si同時發生氧化而生成氧化物粉末，會引起被稱 作害蟲(pest)之粉化現象。該現象通常見於電阻發熱體之夾 持部，再生的產隹通電不良而造成發熱體斷裂的原因。 • - ·........ 另一個問題係：若將電阻發熱體重複昇降溫使用時， 發熱部之直徑會減少，且發熱體性能會劣化。在此所謂性 能劣化係指發熱部之直徑變爲比初期狀態細小而使電阻値 產生變化，或發熱部之表面積變小而對爐的昇溫速度帶來 障礙等。 本發明之課題係改良上述問題點，而提供一以具有優 異的耐粉化性且長斯間性能不會劣化之MoSh爲主體之發 ... ..... 經濟部智慧財產局員工消費合作社印製 熱材料。 【解決課題之手段】 本發明者們爲了解決上述課題，經潛心硏究之結果獲 得以下之認知。 在習知MoSh群發熱材料中產生粉化g象或減少直徑 之原因係在M〇Sh群發熱材料之表面所生成的玻^質被膜 之耐氧化特性不一定充分之緣故。 :....... <' 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 4 五、發明說明（^) 因此，爲了解決以上課題’有必要針對能生成耐氧化 性十分優異的玻璃質被膜之發熱材料加以改善。 換言之’一般藉由玻璃質被膜的形成之耐氧化特性的 提高，係利用玻璃質被膜之低氧擴散性來達成之β玻璃質 被膜中之氧擴散係如第2(a)圖所示，藉由氧分子在玻璃質 被膜之三次元構造之間隙移動而進行之。 又，在玻璃中存有某種不適宜成分，例如Α1之情形， 如第2(b)圖所示，三次元網眼構造被切斷，網眼之間隙變 擴大。其結果，致使氧分子於三次元網眼構造之間隙易於 移動及擴散，因此抗氧化性會劣化而且在習知MoSh群 發熱材料之情形’並沒有對於彼等不適宜成分之含量施行 特別的控管，因而得知此點乃爲導致抗氧化性降低之原因 。至於不適宜成分，可確認係爲A卜Ca、Mg、K、P、Pb 、Μη。因此了解到，至於MoSh群原料以及爲了調節電阻 値等所添加之原料，使用彼等不適宜成分含量低的高純度 原料，藉此形成爲會生成網眼細小的玻璃質被膜之發熱材 料，由此即可解決上述問題。 基於此認知，本發明係提供下列發熱材料： 1 ·—種發熱材料，係由MoSh基材或以含有70%以 上之MoSh爲主成分之基材所構成者，其特徵爲該基材中 所包含之Al、Ca、Mg、Na之含量分別在300ppm以下。 2 · —種發熱材料，係由MoSh基材或以含有70%以 上之MoSh爲主成分之基材所構成者，其特徵爲該基材中 所包含之Al、Ca、Mg、Na之含量分別在l〇〇Ppm以下β 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） (請先閱讀背面之注意事項再填k本頁) .. .線 經濟部智慧財產局員工消費合作杜印製 A7 B7 經濟部智慧財產局員工消費合作社印製 4 6 7 9 5 6 五、發明說明（+) 3 · —種發熱材料，係由MoSh基材或以含有70%以 上之MoSh爲主成分之基材所構成者，其特徵爲該基材中 所包含之A卜Ca、Mg、Na、K、P、Pb、Μη之含量分別在 300ppm 以下。 4 ·—種發熱材料，係由MoSh基材或以含有70%以 上之MoSh爲主成分之基材所構成者，其特徵爲該基材中 所包含之Al、Ca、Mg、Na、K、P、Pb、Μη之含量分別在 lOOppm 以下。 5 · —種發熱材料，係由MoSh基材或以含有70%以 上之M〇Sh爲主成分之基材所構成者，其特徵爲該基材中 所包含之 Al ' Ca、Mg、Na、K、Li、Ba、B、P、Pb、Μη、 Zni含量分別在lOOppm以下。 6 _ ~種發熱材料，係由M〇Si2基材或以含有70%以 上之MoSh爲主成分之基材所構成者，其特徵爲該基材中 所包含之 Al、Ca、Mg、Na、K、Li、Ba、B、P、Pb、Μη、 Zii之含量分別在l〇〇ppm以下。 是以，藉由減低MoSh基材中所含之不適宜成分，即 可抑制玻璃質被膜之三次元網眼構造之間隙擴大。因此， 在玻璃質被膜之三次元網眼構造中氧分子之移動亦會受到 限制。此結果，致使抗氧化性大幅度地提高。 〔發明之實施形態】 本發明係以MoSh基材或以含有MoSh主成分70%以上 之基材爲對象。本發明的目的，係藉選擇適當的氧化物或 矽化物作爲成分以減低MoSh含量至約70%爲止，因此在 6 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） - - .Ί (請先閱讀背面之注意事項再^窝本頁)/ 1 95 6 A7 B7 Printed by Shelley Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs, 5. Description of Invention (/) [Technical Field Required for Invention] The present invention relates to a MoSh base material or containing more than 70% of the main component of MoSh A heat-generating material made of a base material (hereinafter referred to as "MoSh as the main body,"); in particular, a glassy surface oxide film formed on the surface of the heat-generating material is a heat-generating material with low oxygen diffusion [Known Technology] Since MoSh group heating materials form a glassy surface oxide film (hereinafter referred to as a glassy film) with excellent oxidation resistance in an oxidizing ambient atmosphere at 1000 ~ 1800 ° C, it is a kind of A few heating materials that can be used in the ultra-high temperature field of the oxidizing surrounding atmosphere. The components of the MoSh group heating materials are added to MoSh in order to adjust the resistance 値, forming aids, or glass-forming coatings. 10% of multi-component glass components, etc. MoSh substrates are usually formed by a suitable method such as surface oxidation or coating to form a glassy protective film. In addition, the MoSu group heat-generating material is processed into a shape as shown in FIG. 1 and is installed in a furnace to be used as a heater. The ⑷ in the figure is called an electrode part and is completely electrically connected to the MoSh substrate. The base material from which the glassy coating is removed is usually spray-coated with metal such as A1. The electrode part is responsible for the terminal when the MoSh group heating element is heated by resistance. Also, the figure is called the grip part. Its diameter is thicker than the heat-generating part, which is used to reduce the resistance to meet the resistance heating. The clamping part generates a thermal gradient between the heat-generating part and the electrode part to prevent the electrode part from being exposed to high temperature and oxidized. ) Is called the heating part, which is responsible for raising the temperature of the furnace body. 3 paper sizes are applicable to the national standard (CNS) A4 (210 X 297 public love) (Please read the precautions on the back first. Page) -V, binding β --line_ B7 4 6 7 956 V. The task of the heater of the invention (>). [Questions to be solved by the invention] -------- I ---- --v —--- (Please read the precautions on the back before r. nest this page) Use the conventional MoSh group heating material as The situation of the heating element (heater) of the gas furnace can be roughly listed as two problems. The first problem is the Mosh group heating material which is maintained for a long time in the oxidizing ambient atmosphere at 300 ~ 600 ° C. It will produce different oxidation behaviors in the field of 1000 ~ ig00 ° c. The oxygen diffused in the glassy coating will cause Mo and Si to oxidize at the same time to produce oxide powder, which will cause the so-called pests ( The phenomenon of pulverization of pests. This phenomenon is usually found in the clamping part of the resistance heating element, and the cause of the heating element breakage due to poor current generation of the regenerative dysprosium. •-· ........ Another problem is: if When the resistance heating body is repeatedly used for temperature rise and fall, the diameter of the heating part will be reduced, and the performance of the heating body will be deteriorated. Here, the term "performance degradation" means that the diameter of the heating portion becomes smaller than the initial state and changes the resistance 値, or the surface area of the heating portion becomes smaller, which hinders the heating rate of the furnace. The problem of the present invention is to improve the above problems, and to provide a main product based on MoSh, which has excellent powder resistance and does not deteriorate the performance between long-term ... Cooperatives print thermal materials. [Means for solving problems] In order to solve the above problems, the present inventors obtained the following knowledge as a result of diligent research. The reason for the occurrence of chalking or reduction in diameter in the conventional MoSh group heating material is that the oxidation resistance of the glassy coating formed on the surface of the MoSh group heating material may not be sufficient. : ....... < '4 This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 4 5. Description of the invention (^) Therefore, in order to solve the above problems, it is necessary to The heat-generating material that produces a glassy film with excellent oxidation resistance is improved. In other words, 'the oxidation resistance of the glassy coating is generally improved by the formation of the glassy coating. The oxygen diffusion in the β glassy coating is achieved by using the low oxygen diffusion of the glassy coating, as shown in Figure 2 (a). It is carried out by oxygen molecules moving through the gap of the three-dimensional structure of the vitreous coating. In addition, in the case where there is some unsuitable component in the glass, such as A1, as shown in FIG. 2 (b), the three-dimensional mesh structure is cut off, and the gap between the meshes is enlarged. As a result, it is easy to move and diffuse the oxygen molecules in the gap of the three-dimensional mesh structure, so the oxidation resistance will be deteriorated. In the case of the known MoSh group heating material, there is no special control on the content of their unsuitable ingredients. Tube, and thus learned that this is the cause of the decrease in oxidation resistance. As for the unsuitable component, it was confirmed that it was Abu Ca, Mg, K, P, Pb, Mη. Therefore, it was learned that, as for the raw materials of the MoSh group and the raw materials added for the purpose of adjusting the resistance 値, high-purity raw materials with low content of unsuitable components were used to form a heat generating material that would generate a fine-grained glassy film. This will resolve the issue. Based on this knowledge, the present invention provides the following heat-generating materials: 1. A heat-generating material, which is composed of a MoSh substrate or a substrate containing more than 70% of MoSh as a main component, which is characterized in that The content of Al, Ca, Mg, and Na included is 300 ppm or less, respectively. 2. A kind of heat-generating material, which is composed of a MoSh base material or a base material containing more than 70% of MoSh as a main component, and is characterized in that the contents of Al, Ca, Mg, and Na contained in the base material are respectively Below 5 〇Ppm β 5 This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 public love) (Please read the precautions on the back before filling in this page) .. Printed by employee Du A7 B7 Printed by employee consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 6 7 9 5 6 V. Invention Description (+) 3 · A kind of heating material, which is made of MoSh base material or contains 70% or more MoSh is composed of a base material having a main component, which is characterized in that the contents of Ca, Mg, Na, K, P, Pb, and Mn contained in the base material are each 300 ppm or less. 4—A kind of heat-generating material, which is composed of a MoSh base material or a base material containing 70% or more of MoSh as a main component, and is characterized by Al, Ca, Mg, Na, K, The contents of P, Pb, and Mn are each 100 ppm or less. 5 · A kind of heat-generating material, which is composed of MoSh base material or a base material containing 70% or more of MoSh as a main component, and is characterized by Al 'Ca, Mg, Na, The contents of K, Li, Ba, B, P, Pb, Mn, and Zni are 100 ppm or less, respectively. 6 _ ~ kinds of heat-generating materials, which are composed of MoSi2 substrate or a substrate containing more than 70% MoSh as the main component, and are characterized by Al, Ca, Mg, Na, The contents of K, Li, Ba, B, P, Pb, Mn, and Zii are each 100 ppm or less. Therefore, by reducing the inappropriate components contained in the MoSh substrate, it is possible to suppress the expansion of the gap of the three-dimensional mesh structure of the glassy film. Therefore, the movement of oxygen molecules in the three-dimensional mesh structure of the vitreous coating is also restricted. As a result, the oxidation resistance is greatly improved. [Embodiments of the Invention] The present invention is directed to a MoSh substrate or a substrate containing 70% or more of the main component of MoSh. The purpose of the present invention is to reduce the MoSh content to about 70% by selecting an appropriate oxide or silicide as a component, so the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied at 6 paper sizes- -.Ί (Please read the notes on the back before ^ nesting this page)
A7 B7 7 95 6 五、發明說明（f) 此處亦包含含有MoSh主成分70%以上之基材。基材的製 --------------裝ij - - C請先閱讀背面之注意事項再'ν'ίί本頁) 法不拘。基材之形態亦任意。又，亦可使用與該基材同種 類者作爲被覆材。 在使用作爲電阻發熱體之情形，藉適當的方法以模製 成棒狀，再進行焙燒。視需要雖可添加添加成分(玻璃成分 等），但重要者爲，MoSh以及視需要而使用之添加成分皆 使用高純度原料，該原料係儘可能減低不適宜成分（亦即 A卜Ca、Mg、Na)之含量。在MoSh基材燒結體中所含A1 、Ca、Mg、Na之含量應分別爲300ppm以下，較佳爲 lOOppm 以下。 又，關於 K、P、Pb、Mn、Li、Ba、B、Zn，彼等成分 之含量亦應分別爲300ppm以下，較佳爲lOOppm以下。 另，較佳者爲，該等不適合成分之合計量應爲 lOOOppm以下，較佳爲lOOppm以下。 --線· 又，對MoSh基材利用適當的方法實施彤成表面氧化 被膜之處理，通常係於1000〜1800°C之氧化周圍氣氛下， 經濟部智慧財產局員工消費合作社印製- _藉表面之氧化以形成玻璃質被膜。如第2(b)圖所示，若基 材中存有許多上述芣素W，則所形成玻璃質被膜之 三次元網眼構造被切斷，且網眼之間隙變擴大，其結果將 導致氧分子在三次元網眼構造之間隙易於移動擴散，因此 玻璃質被膜之耐氧化性會劣化，但藉由將基材中不適宜成 分之含量分別規定於300ppm以下，即可使所生成玻璃質被 膜形成低氧擴散性。 【實施例】 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 4 ;7956 A7 B7 五、發明說明（石） 基於實施例說明如下，但本發明不受實施例之限制。 a .夾持部之耐粉化性試驗 (請先閱讀背面之注急事項再堉貧本頁) (實施例1 ) ^ 使用高純度原料粉末，製作由MoSh — 15%K^k燒結 體所構成之直徑爲9mm之MoSh群發熱體。該M〇Si2群發 熱體之化學分析値如表1所示（實施例1)。不適宜成分 分別在20ppm以下。又，爲了比較，製備習知的MoSh群 發熱體（比較例1 )。 〔表1〕 化學分析値 單位：ppm A1 Ca Mg Na K Ρ Pb Μη 實施例1 <10 <1 2 <1 <1 <10 <1 13 比較例1 3300 560 740 85 9 <10 <10 8 -線 經濟部智慧財產局員工消費合作社印製 對於前述發熱體進行耐粉化試驗，各發熱體切斷成爲 lOOmm長度，未形成玻璃質被膜兩端之切斷面塗佈抗氧化 劑。各發熱材料置放於如圖3所示之可重複溫度周期 (200〜480°C)之大氣爐內，針對被玻璃質被膜覆蓋之母材粉 化成粉狀之程度加以比較。 其結果，在實施例1中，即使80周期終了後亦仍完善 。另一方面，在比較例1中，於25周期後，藉透過玻璃質 被膜之氧氣在母材產生Mo和Si之同時氧化，表面附近粉 狀化，而玻璃質被膜會剝離。 (實施例2 ) 使用含有異於高純度MoSh的不適宜成份之SiCb，製 本紙張尺度適用令國國家標準<CNS)A4規格（210 X 297公釐〉 A7 4 6 7956 B7_ 五、發明說明（j ) ----1---1------'m--- (請先閱讀背面之注意事項再r^·本頁) 作3種類的MoSh— 10%SiCb燒結體所構成之直徑9mm、長 度100mm之MoSh群發熱體(實施例2及比較例2、3 )。 該MoSh群發熱體之化學分析値如表2所示。 〔表2〕 化學分析値 _單位：ppm A1 Ca Mg Na K Ρ Pb Μη 實施例2 22 95 35 86 5 <10 <1 25 比較例2 330 380 68 <1 12 <10 <1 22 比較例3 1200 210 260 45 7 <10 <1 34 --線- 對於該等發熱體利用與實施例1相同的方法進行耐粉 化試驗。其結果，依據實施例2，80周期終了後，在表面 產生略微的粉狀氧化物。另一方面，在比較例2中係於70 周期後、比較例3係於35周期後，表面附近劇烈的粉狀化 ，而玻璃質被膜會剝離。 b·玻璃質被膜之成長速度試驗 (實施例3、4) 經濟部智慧財產局員工消費合作社印製 製作不適合成分不同之2種MoSh- 5%Si〇2燒結體所 構成之直徑4mm之MoSh—群發熱體（實施例3、4)。該 MoSi2群發熱體之化學分析値如表3所示。 〔表 3〕 ' 化學分析値 _ 單位：ppm A1 Ca Mg Na K Li Ba B P Pa Mn Zn 實施例3 <10 <1 4 <1 <1 <1 <1 <1 <10 <1 16 <1 實施例4 200 <1 <1 <1 <1 <1 <1 1000 <10 <1 20 <1 比較例4 2600 530 130 130 17 <1 <1 <1 <10 <1 8 <1 9 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） A7 4 6 7 9 5 6 ______B7_ 五、發明說明) 又，爲了比較，製備習知以心^群發熱體（比較例4 )。在本試驗中，藉由測定玻璃質被膜之成長速度以比較 高溫下玻璃質被膜之抗氧化性。試驗順序爲：首先將發熱 體利用電阻加熱昇溫至1650°C，且於大氣中保持10、30、 90、120小時之後降溫至室溫。又，爲了求出發熱體之玻 璃質被膜之膜厚度，浸漬於氫氟酸以溶解表面之玻璃質被 膜。玻璃質被膜之膜厚係測定溶解前後之發熱體之直徑， 並由此差値計算出之。相對於1650°C的保持時間之玻璃質 被膜的膜厚變化如第4圖所示。 在比較例4中，由於氧分子於玻璃質被膜中易於擴散 而抗氧化性不充分，因此在120小時後之膜厚爲42mm。另 一方面，在本發明品之實施例3、實施例4中，由於具有 低氧擴散性之玻璃質被膜，因此既可抑制代表著氧化進行 之玻璃質被膜成長，膜厚亦爲16#m以下。又，純度較實 施例4爲高的實施例3，其抗氧化性更優異。 一般而言，一旦玻璃質被膜成長至某厚度以上，因受 到在昇降溫發熱體時所產生之熱變形等之影響，會從母材 表面剝離之。在剝離後之新生面會重新生成玻璃質被膜， 且該玻璃質被膜會重覆的成長，但在某厚度以上又會剝離 。藉由該周期致使發熱體之直徑逐漸減少，而會使發熱部 之性能劣化。 由於本發明品係低氧擴散性玻璃被膜，因此會抑制被 膜之成長速度。亦即，本發明品爲了成長至玻璃質被膜會 剝離之膜厚需要長時間，能將減少發熱部直徑之周期顯著 ________10_ 紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱) (請先閱讀背面之注意事項#..r寫本頁) •裝 .線 經濟部智慧財產局員工消费合作社印製 A7 B7 46 7 95 6 五、發明說明) 地低速化，因而得以製成長時間使用性能亦不致劣化之發 熱體。 C .最高使用溫度試驗 (實施例5 ) 使用高純度原料粉末，製作由MoSh- 5%Si〇2燒結體 所構成之直徑4mm、長度200mm之MoSia群發熱體(實施例 5)。該MoSh群發熱體之化學分析値如表4所示。 〔表4〕 化學分析値 _單位：ppm A1 Ca Mg Na K Ρ Pb Μη 實施例5 <10 <1 6 <1 <1 <10 <1 38 比較例5 3300 560 740 85 9 <10 <10 8 又，爲了比較，製備習知“(^“群發熱體（比較例5) 。對於該等發熱體，進行最高使用溫度附近之高溫抗氧化 性試驗。試驗的程序，係利用電阻加熱在60秒內昇溫至 1650°C，之後以0.5°C/sec之速率加熱至1825°C。但在昇溫 中斷或製成的玻璃質被膜被破壞之情形，以此時點作爲試 驗終了。溫度管理係利用放射溫度計施行之。本發明品係 即使溫度達到1825°C之後保持300秒，玻璃質被膜表面亦 未見變化。另一方面，習知材料係在1750°C附近會產生因 內部氧化所發生氣體成分之吹出，而使玻璃質被膜被破壞 〇 d.化學反應性試驗 使用與上述實施例5及比較例5相同的樣品，使其與 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） --------------裝--- (請先閱讀背面之注意事項再本頁) 訂.. --線· 經濟部智慧財產局員工消費合作社印製 6 6 A7 B7 經濟部智慧財產局員X.消費合作社印製 4 5 7 95 6 五、發明說明（/β) 耐火磚等所用之氧化鉻及矽線石在165(TC大氣中予以接觸 ，以進行調查化學反應性之試驗。其結果，本發明品係在 與耐火物之接觸部不會產生反應，但在玻璃質被膜中含有 不適宜成分之習知材料係與其等耐火物發生反應並熔接。 使用作爲電氣爐之發熱體時，由於與耐火碍等之熔接乃爲 破損之原因，因此由此點也能明顯地得知本發明製品之性 質優異。 〔發明效果〕 本發明之以具有減低不適宜成分含量之低氧擴散性玻 璃質被膜的MoSh爲主體之發熱材料，其耐粉化性優異， 且可抑制代表著氧化進行之玻璃質被膜之成長，在最高使 用溫度附近之高溫抗氧化性及化學反應性亦優異，在長期 間性能亦鮮少劣化。 〔圖式之簡單說明〕 第1圖係由MoSi2群構成的電氣爐用發熱體（加熱器 )之模式圖。 第2圖之(a)係顯示玻璃質被膜之三次元網眼構造之說 明圖，又(b)係顯示三次元網眼構造被切斷而網眼之間隙擴 大狀態之說明圖。 第3圖係顯示耐粉化試驗所使用的反覆加熱試驗之溫 度周期(200 ~480°C)之圖。 第4圖係顯示相對於大氣中1650°C的保持時間之玻璃 質被膜之膜厚變化之圖。 -- 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐 言 (請先閱讀背面之注意事項再r寫本頁)A7 B7 7 95 6 V. Description of the invention (f) This also includes substrates containing more than 70% of MoSh as the main component. Manufacture of base material -------------- install ij--C, please read the precautions on the back before 'ν'ί this page) The shape of the substrate is also arbitrary. In addition, the same type as the substrate may be used as the covering material. When it is used as a resistance heating element, it is molded into a rod shape by an appropriate method and then fired. Additives (glass components, etc.) can be added as needed, but it is important that high-purity raw materials are used for MoSh and the added ingredients that are used as needed. This raw material is to reduce unsuitable ingredients (ie, Ca, Mg) , Na) content. The content of A1, Ca, Mg, and Na contained in the MoSh substrate sintered body should be 300 ppm or less, preferably 100 ppm or less. In addition, with regard to K, P, Pb, Mn, Li, Ba, B, and Zn, the contents of these components should also be 300 ppm or less, preferably 100 ppm or less. In addition, it is preferable that the total amount of these unsuitable ingredients should be 100 ppm or less, and preferably 100 ppm or less. --Line · Also, the MoSh substrate is treated with a suitable surface oxide film by an appropriate method, usually in an ambient atmosphere of oxidation at 1000 ~ 1800 ° C. It is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The surface is oxidized to form a glassy coating. As shown in Fig. 2 (b), if there is a lot of the above-mentioned halogens W in the substrate, the three-dimensional mesh structure of the glassy coating formed is cut off, and the gap between the meshes is enlarged. As a result, Oxygen molecules are easy to move and diffuse in the gap of the three-dimensional mesh structure, so the oxidation resistance of the glassy coating will be deteriorated. However, by setting the content of unsuitable components in the substrate to 300 ppm or less, the resulting glassy can be made. The film forms a low oxygen diffusivity. [Examples] This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 4; 7956 A7 B7 V. Description of the invention (Stones) The description based on the examples is as follows, but the present invention is not limited by the examples . a. Powdering resistance test of the clamping part (please read the urgent notes on the back side before depleting this page) (Example 1) ^ Using high-purity raw material powder, made of MoSh — 15% K ^ k sintered body The MoSh group heating element is 9mm in diameter. The chemical analysis of this MoSi2 group heating body is shown in Table 1 (Example 1). Unsuitable components are 20 ppm or less. For comparison, a conventional MoSh group heating element was prepared (Comparative Example 1). [Table 1] Unit of chemical analysis: ppm A1 Ca Mg Na K P Pb Mη Example 1 < 10 < 1 2 < 1 < 1 < 10 < 1 13 Comparative example 1 3300 560 740 85 9 < 10 < 10 8-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The powder heating resistance test was performed on the aforementioned heating elements. Each heating element was cut to a length of 100 mm, and the cut surface coating at both ends of the glassy film was not formed. Antioxidants. Each heat-generating material was placed in an atmospheric furnace with a repeatable temperature cycle (200 to 480 ° C) as shown in Figure 3, and the degree to which the base material covered with the glassy film was powdered was compared. As a result, in Example 1, it was perfect even after the 80 cycle was completed. On the other hand, in Comparative Example 1, after the 25 cycles, the base material was oxidized by the simultaneous generation of Mo and Si by oxygen passing through the glassy coating, and the surface was powdered, and the glassy coating was peeled off. (Example 2) Using SiCb containing unsuitable ingredients other than high-purity MoSh, the paper size of the paper is adapted to the national standard < CNS) A4 specification (210 X 297 mm> A7 4 6 7956 B7_ V. Description of the invention ( j) ---- 1 --- 1 ------ 'm --- (Please read the precautions on the back before r ^ · this page) Made of 3 types of MoSh-10% SiCb sintered body A MoSh group heating element with a diameter of 9mm and a length of 100mm (Example 2 and Comparative Examples 2 and 3). The chemical analysis of the MoSh group heating element is shown in Table 2. [Table 2] Chemical analysis 値 Unit: ppm A1 Ca Mg Na K Ρ Pb Mn Example 2 22 95 35 86 5 < 10 < 1 25 Comparative Example 2 330 380 68 < 1 12 < 10 < 1 22 Comparative Example 3 1200 210 260 45 7 < 10 < 1 34 --Line- A powdering resistance test was performed on these heating elements by the same method as in Example 1. As a result, according to Example 2, a slight powdery oxide was generated on the surface after the end of the 80 cycle. On the other hand, in Comparative Example 2, after 70 cycles, and Comparative Example 3 after 35 cycles, the vicinities of the surface were drastically powdered, and the vitreous coating was peeled off. B. Formation of vitreous coating Speed test (Examples 3 and 4) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed on two types of MoSh- 5% SiO 2 sintered bodies with different compositions and 4 mm diameter MoSh-group heating elements (Example 3 4). The chemical analysis of the MoSi2 group heating element is shown in Table 3. [Table 3] 'Chemical analysis'_ Unit: ppm A1 Ca Mg Na K Li Ba BP Pa Mn Zn Example 3 < 10 < 1 4 < 1 < 1 < 1 < 1 < 1 < 10 < 1 16 < 1 Example 4 200 < 1 < 1 < 1 < 1 < 1 < 1 1000 < 10 < 1 20 < 1 Comparative Example 4 2600 530 130 130 17 < 1 < 1 < 1 < 10 < 1 8 < 1 9 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) A7 4 6 7 9 5 6 ______B7_ V. Description of the invention) Also, for comparison, a conventional heat-receiving body was prepared (Comparative Example 4). In this test, the growth rate of glassy coatings was measured to compare the oxidation resistance of glassy coatings at high temperatures. The test sequence is: first, the heating body is heated to 1650 ° C by resistance heating, and is maintained in the atmosphere for 10, 30, 90, 120 hours, and then cooled to room temperature. In addition, in order to obtain the thickness of the glassy film of the heating body, the glassy film was immersed in hydrofluoric acid to dissolve the surface. The film thickness of the vitreous coating is measured by calculating the diameter of the heating element before and after dissolution. The change in film thickness of the vitreous film with respect to the holding time at 1650 ° C is shown in Fig. 4. In Comparative Example 4, since the oxygen molecules easily diffused in the vitreous film and the oxidation resistance was insufficient, the film thickness after 120 hours was 42 mm. On the other hand, in Examples 3 and 4 of the product of the present invention, since the glassy film has low oxygen diffusion, it can suppress the growth of the glassy film representing the progress of oxidation, and the film thickness is 16 # m the following. In addition, Example 3, which is higher in purity than Example 4, has better oxidation resistance. Generally, once the glassy film grows to a certain thickness or more, it is peeled off from the surface of the base material due to the influence of thermal deformation and the like that occur when the heating element is heated and lowered. After peeling, the new surface will regenerate a glassy film, and the glassy film will grow repeatedly, but it will peel off at a certain thickness or more. Due to this period, the diameter of the heating element is gradually reduced, and the performance of the heating portion is deteriorated. Since the product of the present invention is a low oxygen diffusive glass film, the growth rate of the film is suppressed. That is, it takes a long time for the product of the present invention to grow to a film thickness where the glassy film will peel off. It can significantly reduce the period of reducing the diameter of the heating part. ________10_ Paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 public love) (Please read the note on the back # .. r first to write this page) • Install. Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 46 7 95 6 V. Description of the invention) Low speed, so it can be made for a long time A heating element that does not deteriorate in performance. C. Maximum use temperature test (Example 5) Using a high-purity raw material powder, a MoSia group heating element composed of a MoSh-5% SiO 2 sintered body with a diameter of 4 mm and a length of 200 mm was produced (Example 5). The chemical analysis of the MoSh group heating element is shown in Table 4. [Table 4] Chemical analysis 値 _ Unit: ppm A1 Ca Mg Na K P Pb Mn Example 5 < 10 < 1 6 < 1 < 1 < 10 < 1 38 Comparative example 5 3300 560 740 85 9 < 10 < 10 8 For comparison, a conventional "(^" group heating element (Comparative Example 5) was prepared. For these heating elements, a high-temperature oxidation resistance test near the maximum operating temperature was performed. The procedure of the test, It is heated to 1650 ° C in 60 seconds by resistance heating, and then heated to 1825 ° C at a rate of 0.5 ° C / sec. However, if the temperature rise is interrupted or the finished glassy coating is damaged, this point is used as a test Finally, the temperature management is implemented by using a radiation thermometer. Even if the temperature of the product of the present invention is 300 seconds after the temperature reaches 1825 ° C, the surface of the glassy coating does not change. On the other hand, the conventional material will produce near 1750 ° C. The glassy coating was destroyed due to the gas component blown out due to internal oxidation. The chemical reactivity test uses the same samples as those in Example 5 and Comparative Example 5 above, and applies the Chinese National Standard (CNS) to this paper scale. ) A4 size (210 X 297 mm) ---- ---------- Equipment --- (Please read the precautions on the back first, then this page) Order: --line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6 6 A7 B7 Wisdom of the Ministry of Economic Affairs Printed by member of the property bureau X. Consumer cooperatives 4 5 7 95 6 5. Description of the invention (/ β) The chromium oxide and sillimanite used in refractory bricks and so on are exposed in the atmosphere of 165 (TC) to conduct tests to investigate chemical reactivity. As a result, the product of the present invention does not react at the contact portion with the refractory, but the conventional material containing an unsuitable component in the glassy film reacts with the refractory and the like and is fused. Used as a heating element of an electric furnace At this time, since the welding with the fire resistance is the cause of damage, it can be clearly seen from this point that the product of the present invention is excellent in properties. [Inventive effect] The present invention has a low oxygen diffusion to reduce the content of unsuitable components. MoSh, which is a glassy film, is a main heating material, which has excellent powder resistance, and can inhibit the growth of glassy film, which represents the progress of oxidation. It is also excellent in high temperature oxidation resistance and chemical reactivity near the highest operating temperature. In long During the period, the performance rarely degrades. [Simplified description of the diagram] Figure 1 is a schematic diagram of a heating element (heater) for an electric furnace composed of a MoSi2 group. Figure 2 (a) shows the glass coating film three times. The elementary mesh structure is an explanatory diagram, and (b) is an explanatory diagram showing a state in which the tertiary elementary network structure is cut and the mesh gap is enlarged. Fig. 3 is a graph showing the temperature of the repeated heating test used in the powder resistance test Graph of period (200 ~ 480 ° C). Fig. 4 is a graph showing a change in film thickness of a glassy film with respect to a holding time of 1650 ° C in the atmosphere. -12 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before writing this page)