TWI428473B - Coating material for coating platinum material, platinum material having such coating material, and glass making apparatus - Google Patents
Coating material for coating platinum material, platinum material having such coating material, and glass making apparatus Download PDFInfo
- Publication number
- TWI428473B TWI428473B TW094131413A TW94131413A TWI428473B TW I428473 B TWI428473 B TW I428473B TW 094131413 A TW094131413 A TW 094131413A TW 94131413 A TW94131413 A TW 94131413A TW I428473 B TWI428473 B TW I428473B
- Authority
- TW
- Taiwan
- Prior art keywords
- platinum
- coating
- coated
- glass
- cerium oxide
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/167—Means for preventing damage to equipment, e.g. by molten glass, hot gases, batches
- C03B5/1672—Use of materials therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Glass Compositions (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Catalysts (AREA)
- Coating By Spraying Or Casting (AREA)
Description
本發明有關為了被覆玻璃製造裝置等，在高溫環境下所使用之白金材料之被覆(coating)材料。 The present invention relates to a coating material of a platinum material used in a high-temperature environment for a coated glass manufacturing apparatus or the like.
為了製造光學玻璃、顯示器用玻璃等高品位玻璃之裝置(攪拌器、熔解槽、澄清槽等)的構成材料，一般是使用白金材料。此等塔槽類的構成材料之所以採用白金材料之原因在於，白金的熔點較高，不致於在大氣中形成氧化物層所以不會劣化，裝置在運轉時遭受變形、損傷的可能性低，同時，化學安定性方面亦優異，而污染熔融狀態玻璃之可能性低。因此作為此種白金材料者，除白金之外，尚廣泛使用白金-銠(Rhodium)合金等白金合金(有關能適用為玻璃工業之白金材料，在專利文獻1的先前技術章節中，有詳細記載。)。 In order to manufacture a material for a high-grade glass device (agitator, melting tank, clarification tank, etc.) such as optical glass or display glass, a platinum material is generally used. The reason why the constituent materials of such towers are made of platinum materials is that platinum has a high melting point and does not form an oxide layer in the atmosphere, so that it does not deteriorate, and the apparatus is less likely to be deformed or damaged during operation. At the same time, it is also excellent in chemical stability, and the possibility of contaminating molten glass is low. Therefore, as such a platinum material, in addition to platinum, a platinum alloy such as a rhodium alloy (a platinum alloy which can be applied to the glass industry) is widely used, and is described in detail in the prior art section of Patent Document 1. .).
玻璃製造過程中之裝置溫度，係因其處理內容而異，惟均在1000℃以上之1200至1600℃的高溫環境中。因上述特性之故，白金材料在如此高溫環境下仍然不致於污染裝置內部的熔融玻璃，能長時間維持充分的耐久性。 The temperature of the device during the glass manufacturing process varies depending on the processing content, but is in a high temperature environment of 1200 to 1600 ° C above 1000 ° C. Due to the above characteristics, the platinum material does not contaminate the molten glass inside the device in such a high temperature environment, and can maintain sufficient durability for a long period of time.
然而，在上述高溫環境下，在裝置外表面的相關方面存有一個問題。此問題係因白金材料中的白金會生成氣體氧化物之白金氧化物(PtO2)而發生揮發損失的情況。此種白金的揮發損失，在通常使用中會達到白金裝置重量的數個%之多，在局部性揮發量較多的部位，則會成為直接損 害白金材料的強度、安定性的要因。又，由於所揮發之白金，會附著於玻璃製造裝置周圍所設置之耐火材料、隔熱材料上，造成白金回收精製對象之構件量變得很大。再者，因高價的白金材料揮散至難於回收的空間所引起的損失亦很大。 However, in the above high temperature environment, there is a problem in the related aspect of the outer surface of the device. This problem is caused by the loss of volatilization due to the formation of platinum oxide (PtO 2 ) of gaseous oxides in the platinum in the platinum material. The volatilization loss of such platinum is as large as several % of the weight of the platinum device in normal use, and the site having a large amount of local volatilization is a factor that directly impairs the strength and stability of the platinum material. Further, since the volatilized white gold adheres to the refractory material or the heat insulating material provided around the glass manufacturing apparatus, the amount of components for the platinum recovery and purification object becomes large. Moreover, the losses caused by the high-priced platinum material being scattered to the space that is difficult to recover are also large.
又，使用白金構件之玻璃製造裝置中，在玻璃製造時，因玻璃中的水分所引起之氣泡，會有在白金構件的界面產生的問題(專利文獻2等)。此種現象，被認定為玻璃中的水進行分解，因分解所生成之氫氣即穿透白金構件並釋放至外部，結果，在白金構件的界面附近將存在氧氣濃度高的玻璃，因而產生氧氣泡所引起者。 Further, in the glass manufacturing apparatus using a platinum member, bubbles generated by moisture in the glass during the production of the glass may cause problems at the interface of the platinum member (Patent Document 2, etc.). This phenomenon is considered to be decomposition of water in the glass, and the hydrogen generated by the decomposition penetrates the platinum member and is released to the outside. As a result, there is a glass having a high oxygen concentration near the interface of the platinum member, thereby generating oxygen bubbles. Caused by.
專利文獻3中是提案為了解決上述玻璃製造時之氣泡產生的問題，於白金構件的外側表面，設置氫氣不穿透性的被璃系被覆膜。 In Patent Document 3, in order to solve the problem of the occurrence of bubbles in the production of the glass, a glass-based coating film having a hydrogen gas non-penetrability is provided on the outer surface of the platinum member.
然而，本發明人等，經研究專利文獻3中所揭示之玻璃系被覆膜之結果發現，在製造玻璃時並不能充分降低氣泡的產生。 However, as a result of investigating the glass-based coating film disclosed in Patent Document 3, the present inventors have found that the generation of bubbles cannot be sufficiently reduced in the production of glass.
專利文獻1：日本專利特開平10-280070號公報 Patent Document 1: Japanese Patent Laid-Open No. Hei 10-280070
專利文獻2：日本專利特表2001-503008號公報 Patent Document 2: Japanese Patent Laid-Open Publication No. 2001-503008
專利文獻3：日本專利特表2004-523449號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. 2004-523449
本發明之第1目的在於提供為了被覆高溫環境下所使用之白金材料的適當材料。 A first object of the present invention is to provide a suitable material for coating a platinum material used in a high temperature environment.
本發明之第2目的在於提供能降低玻璃製造時因玻璃 中的水分所引起的氣泡產生之白金材料用被覆材料。 A second object of the present invention is to provide a glass which can reduce the glass manufacturing time. A coating material for a platinum material produced by air bubbles caused by moisture in the medium.
整理高溫下使用之白金材料的被覆材料所需要之特性不外乎：第1點為，除在高溫環境下不致於熔融、變形之外，尚需要具有相當程度的柔軟性以能跟隨作為基材之白金材料的變形而變形。在裝置的運轉、停轉時，由於會發生構成材料的熱膨脹、收縮之故，如係僅為強度高而硬質的被覆材料時，則未能跟隨尺寸之變化而會裂開、以致失去其產生變形之功能。於是，第2點為，需要具有細緻的膜質且必需要難於發生針孔(pin hole)等缺陷之成分。缺陷的存在，不僅將導致使用過程中之被覆材料的損傷，且會成為基材與外氣相接觸之要因，不能充分抑制來自基材的白金之揮發損失。 The characteristics required for finishing the coating material of the platinum material used at high temperature are nothing more than the first point: in addition to being not melted or deformed in a high temperature environment, it is required to have a considerable degree of flexibility to follow the substrate. The platinum material is deformed and deformed. When the device is operated or stopped, the thermal expansion and contraction of the constituent materials may occur. If the coating material is only a high-strength and hard coating material, it may not be broken due to the change in the size, so that it may be lost. The function of deformation. Therefore, the second point is that it is necessary to have a fine film quality and it is necessary to have a component which is difficult to cause defects such as pin holes. The presence of defects not only causes damage to the coated material during use, but also causes the substrate to contact the external gas phase, and the volatilization loss of platinum from the substrate cannot be sufficiently suppressed.
因而，作為一般性耐火材料而所周知之金屬氧化物等，如從強度、高溫環境下的安定性來看，有可能作為耐火材料使用，但由於缺乏柔軟性，且因熔點高而難於藉由燒成以作成細緻的膜，故並不具備作為本發明之目的特性。 Therefore, a metal oxide or the like which is known as a general refractory material may be used as a refractory material from the viewpoint of stability in a high-strength and high-temperature environment, but it is difficult to be used due to lack of flexibility and high melting point. Since it is fired to form a fine film, it does not have the characteristics which are the objective of this invention.
本發明人等，以上述條件作為前提之下，就適宜的被覆材料的構成進行研究之結果發現，氧化鋁、二氧化矽(silica)的結晶性金屬氧化物中添加有玻璃成分之材料，可具備上述條件之事實而完成本發明。 The inventors of the present invention have studied the composition of a suitable coating material on the premise of the above-mentioned conditions, and found that a material of a glass component is added to a crystalline metal oxide of alumina or silica. The present invention has been completed in the light of the above conditions.
又發現，作為耐火材料的必須成分而含有氧化鋁及二氧化矽，並對此添加有玻璃成分之被覆材料，可有效降低玻璃製造時因玻璃中的水分所引起的氣泡產生之事實而完成本發明。 Further, it has been found that alumina and cerium oxide are contained as essential components of the refractory material, and a coating material containing a glass component is added thereto, thereby effectively reducing the fact that bubbles are generated by moisture in the glass during glass production. invention.
亦即，本發明之白金材料用的被覆材料，係為了被覆由白金或白金合金所成之白金材料表面之材料，而其特徵為：含有含氧化鋁及二氧化矽之耐火材料成分，與玻璃成分。 That is, the coating material for the platinum material of the present invention is characterized in that it contains a refractory component containing alumina and cerium oxide, and a glass material for coating a surface of a platinum material formed of platinum or a platinum alloy. ingredient.
本發明相關之被覆材料，係含有氧化鋁粒子、及玻璃成分、及二氧化矽粒子及/或膠態二氧化矽(colloidal silica)者。以下，就本發明之第1至第4實施形態所共通之技術性事項，使用「本發明」以便說明。 The coating material according to the present invention contains alumina particles, a glass component, and cerium oxide particles and/or colloidal silica. Hereinafter, the present invention will be described with reference to the technical matters common to the first to fourth embodiments of the present invention.
有關本發明較佳之第1實施形態中，二氧化矽中至少一部分是使用膠態二氧化矽。因而該被覆材料，係含有：氧化鋁粒子、玻璃成分、膠態二氧化矽、以及因應需要之二氧化矽粒子。 In a preferred embodiment of the present invention, at least a part of the cerium oxide is colloidal cerium oxide. Therefore, the coating material contains alumina particles, a glass component, colloidal cerium oxide, and cerium oxide particles as needed.
有關本發明之第1實施形態中，係氧化鋁粒子與玻璃成分、或者亦可再預先混合二氧化矽粒子。亦即，氧化鋁粒子與玻璃成分、或是再混合二氧化矽粒子，並使用經粉碎此等燒結後所得燒結物之粉碎物、與膠態二氧化矽來製成被覆材料。 In the first embodiment of the present invention, the alumina particles and the glass component may be added, or the cerium oxide particles may be further mixed. In other words, the alumina particles are mixed with the glass component or the cerium oxide particles, and the pulverized material obtained by pulverizing the sintered body or the colloidal cerium oxide is used to form a coating material.
有關本發明之第1實施形態中，較佳為將被覆材料作成料漿(slurry)形態。即，較佳為將含有氧化鋁粒子、玻璃成分、以及膠態二氧化矽或者再和二氧化矽之料漿作為被覆材料。如上述，如使用經粉碎之氧化鋁粒子與玻璃成分、或者再和二氧化矽粒子的混合物的燒結物之粉碎物時，則將含有該粉碎物與膠態二氧化矽之料漿作為被覆材料。 In the first embodiment of the present invention, it is preferable that the covering material is in the form of a slurry. That is, it is preferable to use a slurry containing alumina particles, a glass component, and colloidal ceria or cerium oxide as a coating material. As described above, when a pulverized product of a pulverized alumina particle and a glass component or a mixture of cerium oxide particles is used, a slurry containing the pulverized product and colloidal cerium oxide is used as a coating material. .
料漿中，較佳為含有作為有機黏合劑(organic binder) 之甲基纖維素等之水溶性高分子。有機黏合劑的含量，相對於料漿中的無機固體成分100重量份，較佳為在0.5至10重量份的範圍內、更佳為在1至5重量份的範圍內。 In the slurry, it is preferably contained as an organic binder A water-soluble polymer such as methyl cellulose. The content of the organic binder is preferably in the range of 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the inorganic solid content in the slurry.
將本發明之料漿形態的被覆材料被覆於白金材料之方法，可例舉：將料漿塗佈於白金材料表面後，加以燒成之方法。將料漿塗佈於白金材料表面後，較佳為例如，在40℃至95℃的溫度中使其乾燥。又，亦可在加熱白金材料之下進行料漿之塗佈。料漿較佳為採用噴霧方式進行塗佈。 The method of coating the coating material in the slurry form of the present invention on the platinum material may be a method in which the slurry is applied to the surface of the platinum material and then fired. After the slurry is applied to the surface of the platinum material, it is preferably dried, for example, at a temperature of 40 ° C to 95 ° C. Alternatively, the coating of the slurry can be carried out under heated platinum material. The slurry is preferably applied by spraying.
本發明中，將被覆材料塗佈於白金材料表面後加以燒成時的燒成溫度，較佳為在1200℃至1600℃的溫度範圍內。如利用白金材料所使用之環境溫度進行燒成時，則其使用溫度將成為燒成溫度。例如，在玻璃製造裝置中使用之白金材料之情形，由於藉由通過由白金材料所形成之構件內部的熔融玻璃而加熱白金材料之構件，於白金材料表面經塗佈之被覆材料層，即在此溫度被燒成。 In the present invention, the baking temperature at the time of baking the coating material on the surface of the platinum material is preferably in the range of 1200 ° C to 1600 ° C. When the firing is performed at the ambient temperature used for the platinum material, the use temperature will be the firing temperature. For example, in the case of a platinum material used in a glass manufacturing apparatus, since the member of the platinum material is heated by the molten glass inside the member formed of the platinum material, the coated material layer is coated on the surface of the platinum material, that is, This temperature is burned.
本發明之第1實施形態中之被覆燒成被膜，係含有氧化鋁粒子、玻璃成分與膠態二氧化矽、或再有二氧化矽粒子之被覆材塗布在白金材料之表面後，由燒成而得。二氧化矽至少有一部分因是使用膠態二氧化矽，所以顯示出膠態二氧化矽有無機黏著之功能。因此，第1實施形態之被覆燒成被膜，可形成細緻的燒成被膜。於是，可作為氫氣不穿透性優異的被膜，能有效率地降低玻璃在製造時之玻璃中的氣泡產生。需要氫氣不穿透性之用途方面，最好為形成該第1實施形態的被覆燒成被膜。又，亦可有效降低 白金的揮發損失。 In the coated fired film according to the first embodiment of the present invention, the coated material containing alumina particles, a glass component, colloidal cerium oxide or cerium oxide particles is coated on the surface of the platinum material, and then fired. And got it. At least part of the cerium oxide is due to the use of colloidal cerium oxide, so that the colloidal cerium oxide has an inorganic adhesion function. Therefore, in the coated fired film of the first embodiment, a fine fired film can be formed. Therefore, it is possible to effectively reduce the generation of bubbles in the glass at the time of production of the film which is excellent in hydrogen non-penetration. In order to use hydrogen gas non-penetration, it is preferable to form the coated fired film of the first embodiment. Also, it can be effectively reduced Volatile loss of platinum.
由於膠態二氧化矽為微小粒子，所以燒成後難於與玻璃成分區別，而成為消失於玻璃成分中的狀態。因而，在此種燒成被膜中，對由玻璃成分與膠態二氧化矽成分所成基材相(matrix phase)中，氧化鋁粒子做為分散相而成為分散之狀態。另外，如被覆材料中含有二氧化矽粒子的情形，則與氧化鋁粒子一起，二氧化矽粒子亦做為分散相而成為分散之狀態。 Since the colloidal cerium oxide is a fine particle, it is difficult to distinguish it from the glass component after firing, and it is in a state of disappearing into the glass component. Therefore, in such a baked film, in the matrix phase formed by the glass component and the colloidal cerium oxide component, the alumina particles are dispersed as a dispersed phase. Further, when the coating material contains cerium oxide particles, the cerium oxide particles are dispersed as a dispersed phase together with the alumina particles.
有關本發明之第1實施形態之被覆燒成被膜的厚度，以100至1000μm為宜、較佳為200至1000μm、更佳為500至1000μm。如被覆燒成被膜的膜厚過薄時，則氫氣遮蔽性可能會不足夠。又，被覆燒成被膜的膜厚超厚時，則不能獲得與厚度所對應的效果而成為經濟上不利者。 The thickness of the coated fired film according to the first embodiment of the present invention is preferably 100 to 1000 μm, more preferably 200 to 1000 μm, still more preferably 500 to 1000 μm. If the film thickness of the coated film is too thin, the hydrogen shielding property may be insufficient. Further, when the film thickness of the coated fired film is extremely thick, the effect corresponding to the thickness cannot be obtained, which is economically disadvantageous.
本發明中所用之氧化鋁粒子的平均粒徑，較佳為1至100μm的範圍內、更佳為在3至80μm的範圍內。又，使用二氧化矽粒子作為二氧化矽時，則其平均粒徑較佳為在1至100μm的範圍內、更佳為3至80μm的範圍內。如平均粒徑過大時，則即使含有玻璃成分，仍難於製得細緻的膜。又，如平均粒徑過小時，則有喪失對被覆膜賦與強度之填充劑作用的情形。 The average particle diameter of the alumina particles used in the present invention is preferably in the range of 1 to 100 μm, more preferably in the range of 3 to 80 μm. Further, when cerium oxide particles are used as the cerium oxide, the average particle diameter thereof is preferably in the range of 1 to 100 μm, more preferably in the range of 3 to 80 μm. If the average particle diameter is too large, it is difficult to obtain a fine film even if it contains a glass component. Further, when the average particle diameter is too small, there is a case where the filler which imparts strength to the coating film is lost.
如使用膠態二氧化矽作為二氧化矽時，則其平均粒子徑較佳為在10至100μm的範圍內，更佳為在10至50nm的範圍內，特佳為在10至30nm的範圍內。如上述，膠態二氧化矽係在被膜材料中作為無機黏合劑發揮作用者，藉 由使用膠態二氧化矽而可形成細緻的被膜。 When colloidal ceria is used as the ceria, the average particle diameter is preferably in the range of 10 to 100 μm, more preferably in the range of 10 to 50 nm, and particularly preferably in the range of 10 to 30 nm. . As described above, colloidal cerium oxide acts as an inorganic binder in the coating material, A fine film can be formed by using colloidal cerium oxide.
本發明中所用之玻璃成分，並不特別限制，惟如欲適用於無鹼玻璃(alkali free glass)的製造裝置時，需要為無鹼者。此原因乃在即使白金裝置中發生裂痕，裝置內部的玻璃(製品)中仍然不會混入鹼成分係其絕對條件之故，構成被覆材料之玻璃成分亦需要為無鹼者。同時，在本發明中，無鹼(alkali free)，係指鹼成分的含量在0.1重量%以下之意。此種玻璃成分，可例舉：硼矽酸玻璃、鋁硼矽酸玻璃。 The glass component used in the present invention is not particularly limited, and if it is to be applied to a manufacturing apparatus of an alkali free glass, it is required to be an alkali-free one. The reason for this is that even if cracks occur in the platinum device, the glass (product) inside the device does not contain the alkali component as an absolute condition, and the glass component constituting the coating material needs to be alkali-free. Meanwhile, in the present invention, "alkali free" means that the content of the alkali component is 0.1% by weight or less. Such a glass component may, for example, be a borosilicate glass or an aluminoborosilicate glass.
本發明中，玻璃成分、氧化鋁、以及二氧化矽的各構成成分的較佳含量，以固體成分為基準，玻璃成分為20至70重量%、氧化鋁為15至55重量%、二氧化矽為10至50重量%、而較佳為玻璃成分為在30至70重量%、氧化鋁為在15至45重量%、二氧化矽為在10至30重量%的範圍者。另外，採用膠態二氧化矽的情形，二氧化矽成分的合計量為與上述同樣的含量為佳。 In the present invention, a preferred content of each constituent component of the glass component, alumina, and ceria is 20 to 70% by weight based on the solid content, 15 to 55% by weight of alumina, and cerium oxide. It is in the range of 10 to 50% by weight, preferably 30 to 70% by weight of the glass component, 15 to 45% by weight of alumina, and 10 to 30% by weight of cerium oxide. Further, in the case of using colloidal cerium oxide, the total amount of the cerium oxide component is preferably the same as the above.
又，被覆材料中各成分的含量，係隨被覆材料所使用之使用溫度，而有較佳之範圍。如後述，玻璃製造設備中白金材料所使用之處所的溫度，大致可分為1000至1250℃、1250至1450℃、以及1450至1600℃等3個溫度領域。在1000至1250℃的溫度領域中，玻璃成分為35至70重量%(較佳為40至65重量%)、氧化鋁成分10至40重量%(較佳為15至35重量%)、二氧化矽成分10至50重量%(較佳為10至30重量%、更佳為15至25重量%)的含量為宜。又，在1250至1450℃的溫度領域中，玻璃成分20 至60重量%(較佳為25至45重量%)、氧化鋁成分20至60重量%(較佳為30至55重量%)、二氧化矽成分10至50重量%(較佳為10至30重量%、更佳為15至25重量%)的含量為宜。在1450至1600℃的溫度領域中，玻璃成分15至40重量%(較佳為15至35重量%)、氧化鋁成分35至70重量%(較佳為40至65重量%)、二氧化矽成分10至50重量%(較佳為10至30重量%、更佳為15至25重量%)的含量為宜。 Further, the content of each component in the coating material is preferably in accordance with the use temperature of the coating material. As will be described later, the temperature at which the platinum material is used in the glass manufacturing apparatus can be roughly classified into three temperature ranges of 1,000 to 1,250 ° C, 1,250 to 1,450 ° C, and 1,450 to 1,600 ° C. In the temperature range of 1000 to 1250 ° C, the glass component is 35 to 70% by weight (preferably 40 to 65% by weight), the alumina component is 10 to 40% by weight (preferably 15 to 35% by weight), and dioxide is used. The content of the bismuth component is preferably 10 to 50% by weight (preferably 10 to 30% by weight, more preferably 15 to 25% by weight). Also, in the temperature range of 1250 to 1450 ° C, the glass component 20 Up to 60% by weight (preferably 25 to 45% by weight), 20 to 60% by weight (preferably 30 to 55% by weight) of the alumina component, and 10 to 50% by weight (preferably 10 to 30%) of the cerium oxide component The content of % by weight, more preferably 15 to 25% by weight, is preferred. In the temperature range of 1450 to 1600 ° C, the glass component is 15 to 40% by weight (preferably 15 to 35% by weight), the alumina component is 35 to 70% by weight (preferably 40 to 65% by weight), and cerium oxide A content of 10 to 50% by weight (preferably 10 to 30% by weight, more preferably 15 to 25% by weight) of the component is preferred.
有關本發明之較佳第2實施形態的被覆材料，係使用二氧化矽粒子作為二氧化矽者。在其他玻璃成分及氧化鋁成分中，則可使用與上述的第1實施形態同樣者。 In the coating material according to the preferred embodiment of the present invention, cerium oxide particles are used as the cerium oxide. Among other glass components and alumina components, the same as in the first embodiment described above can be used.
有關本發明之較佳第2實施形態的被覆材料，亦可為料漿的形態、亦可為糊質(paste)或裸片(green sheet)的形態。如作成糊質或裸片的形態，即能形成膜厚較厚的被膜。 The coating material according to the preferred embodiment of the present invention may be in the form of a slurry or may be in the form of a paste or a green sheet. In the form of a paste or a die, a film having a thick film thickness can be formed.
有關本發明之第2實施形態中，亦可預先混合氧化鋁粒子、二氧化矽粒子、以及玻璃成分，並使其燒結。亦即，亦可使用經粉碎之氧化鋁粒子、二氧化矽粒子、以及玻璃成分的混合物的燒結物之粉碎物，來製作被覆材料。 In the second embodiment of the present invention, the alumina particles, the cerium oxide particles, and the glass component may be mixed in advance and sintered. In other words, a pulverized product of a pulverized alumina particle, cerium oxide particle, and a mixture of glass components may be used to produce a coating material.
本發明之第2實施形態中之糊質或裸片，係含有氧化鋁粒子、二氧化矽粒子、以及玻璃成分者。如上述，亦可含有經粉碎預先混合此等粒子混合物的燒結物之粉碎物。 The paste or the die in the second embodiment of the present invention contains alumina particles, cerium oxide particles, and a glass component. As described above, a pulverized product of a sinter which is pulverized and previously mixed with the particle mixture may be contained.
有關本發明之第2實施形態中之糊質或裸片中，較佳作為氧化鋁粒子者以含有纖維狀的氧化鋁粒子(氧化鋁纖維)。如此種氧化鋁纖維含於糊質或裸片中，糊質或裸片貼 附於白金材料表面並經燒成後的燒成被膜很難發生裂紋等。氧化鋁纖維的含量，於糊質或裸片的固體成分中，較佳為在0.1至30重量%的範圍內。氧化鋁纖維，Al2O3(氧化鋁)為50重量%以上、較佳為70重量%以上，而纖維長度為0.1至100mm、較佳為1mm至50mm，纖維直徑為0.1μm至50μm、較佳為1至20μm。如Al2O3在50重量%以下時，則耐熱性會降低、容易與玻璃成分反應，不能期望添加纖維之效果。如纖維長度在0.1mm以下時，則與粒子並無兩樣，纖維長度在50mm以上時，則不容易均勻混合。纖維直徑在0.1μm以下時，則不能期望有良好的耐熱性，纖維直徑在50μm以上時，則難於均勻分散。 In the paste or the dies of the second embodiment of the present invention, it is preferred that the alumina particles contain fibrous alumina particles (alumina fibers). If such an alumina fiber is contained in a paste or a die, the paste or the die is attached to the surface of the platinum material, and the fired film after firing is hard to be cracked or the like. The content of the alumina fiber is preferably in the range of from 0.1 to 30% by weight based on the solid content of the paste or the die. The alumina fiber, Al 2 O 3 (alumina) is 50% by weight or more, preferably 70% by weight or more, and the fiber length is 0.1 to 100 mm, preferably 1 mm to 50 mm, and the fiber diameter is 0.1 μm to 50 μm. Preferably it is 1 to 20 μm. When the Al 2 O 3 content is 50% by weight or less, the heat resistance is lowered and the glass component is easily reacted, and the effect of adding the fiber cannot be expected. When the fiber length is 0.1 mm or less, it is not the same as the particles, and when the fiber length is 50 mm or more, it is not easy to uniformly mix. When the fiber diameter is 0.1 μm or less, good heat resistance cannot be expected, and when the fiber diameter is 50 μm or more, it is difficult to uniformly disperse.
又，有關本發明之第2實施形態的糊質或裸片中，可以作為有機黏合劑而含有甲基纖維素等水溶性高分子。有機黏合劑的含量，對糊質或裸片中的無機固體成分100重量份，較佳為在0.5至10重量份的範圍內，更佳為在1至5重量份的範圍內。 Further, in the paste or the die of the second embodiment of the present invention, a water-soluble polymer such as methyl cellulose may be contained as an organic binder. The content of the organic binder is preferably from 0.5 to 10 parts by weight, more preferably from 1 to 5 parts by weight, per 100 parts by weight of the inorganic solid component in the paste or the die.
本發明之第2實施形態的被覆材料，可為料漿形態者。此種料漿，係混合含有氧化鋁粒子、二氧化矽粒子，以及玻璃成分之料漿。 The coating material according to the second embodiment of the present invention may be in the form of a slurry. This slurry is a slurry containing alumina particles, cerium oxide particles, and a glass component.
有關本發明第2實施形態之被覆方法的特徵為：將上述本發明之第2實施形態的被覆材料塗佈或貼附於白金材料之表面後，加以燒成。 In the coating method according to the second embodiment of the present invention, the coating material according to the second embodiment of the present invention is applied or adhered to the surface of the platinum material, and then fired.
燒成溫度等的條件，則與第1實施形態同樣。 The conditions such as the firing temperature are the same as in the first embodiment.
有關本發明第2實施形態之被覆燒成被膜之特徵為： 將上述本發明第2實施形態的被覆材料塗佈或貼附於白金材料之表面，並加以燒成而製得。 The coated fired film according to the second embodiment of the present invention is characterized by: The coating material according to the second embodiment of the present invention described above is applied or adhered to the surface of a platinum material and fired.
本發明之第2實施形態中之被覆燒成被膜，一般具有對由玻璃成分所成基材相中，氧化鋁粒子及二氧化矽粒子經分散後為分散相之形態。第1圖，係表示本發明第2實施形態中之被覆燒成被膜之模式圖。第1圖(a)，表示經1300℃程度的比較低溫所燒成之燒成被膜，在由玻璃成分所成基材相中，分散有氧化鋁粒子及二氧化矽粒子。第1圖(b)，係表示經1500℃以上之高溫領域所燒成之燒成被膜，分散相之氧化鋁粒子及二氧化矽粒子為部分熔解在基材相中，由此，基材相係成為氧化鋁及富(rich)二氧化矽的玻璃成分。由此，可提高基材相中的熱安定性，而該被覆材料則在1500℃以上的高溫下持續保持柔軟性，不致於產生變形或下垂(sagging)而可以良好狀態被覆基材。 The coated fired film of the second embodiment of the present invention generally has a form in which the alumina particles and the cerium oxide particles are dispersed in the base phase formed by the glass component to form a dispersed phase. Fig. 1 is a schematic view showing a coated fired film in a second embodiment of the present invention. Fig. 1(a) shows a fired film fired at a relatively low temperature of about 1300 °C, and alumina particles and cerium oxide particles are dispersed in a base phase formed of a glass component. Fig. 1(b) shows a fired film fired in a high temperature region of 1500 ° C or higher, in which alumina particles and cerium oxide particles in a dispersed phase are partially melted in a substrate phase, whereby the substrate phase It is a glass component of alumina and rich cerium oxide. Thereby, the thermal stability in the base material phase can be improved, and the coating material can maintain the flexibility at a high temperature of 1500 ° C or higher, and the substrate can be coated in a good state without causing deformation or sagging.
依照本發明之第2實施形態而使用糊質或裸片所形成之被覆燒成被膜的厚度，較佳為在1至10mm的範圍，更佳為在2至5mm的範圍。又，使用料漿所形成時的被覆燒成被膜的厚度，係與上述第1實施形態時同樣。 The thickness of the coated fired film formed by using a paste or a die according to the second embodiment of the present invention is preferably in the range of 1 to 10 mm, more preferably in the range of 2 to 5 mm. In addition, the thickness of the coating film to be fired when the slurry is formed is the same as that in the first embodiment.
有關本發明之較佳第3實施形態之特徵為：於白金材料表面塗佈本發明之第1實施形態中之料漿以形成料漿被覆材料層，並於該料漿被覆材料層上，貼附依照本發明之第2實施形態之糊質或裸片以形成保護被覆材料層。 According to a preferred embodiment of the present invention, the slurry according to the first embodiment of the present invention is applied to the surface of the platinum material to form a slurry coating material layer, and is applied to the slurry coating material layer. A paste or a die according to a second embodiment of the present invention is attached to form a protective covering material layer.
依照本發明第3實施形態之被覆方法之特徵為：如上述方式形式料漿被覆材料層，並於其上形成保護被覆材料 層之後加以燒成。燒成溫度等的燒成條件，係與本發明之第1實施形態同樣。 A coating method according to a third embodiment of the present invention is characterized in that a slurry coating material layer is formed as described above, and a protective coating material is formed thereon. The layer is then fired. The firing conditions such as the firing temperature are the same as in the first embodiment of the present invention.
依照本發明第3實施形態之被覆燒成被膜中之料漿被覆層部分(料漿被覆燒成層)的厚度，較佳為100至1000μm的範圍、更佳為200至1000μm的範圍，特佳為500至1000μm的範圍。又，保護被覆層部分(保護被覆燒成層)的厚度，較佳為1至10mm的範圍、更佳為2至5mm的範圍。 The thickness of the slurry coating layer portion (slurry coating firing layer) in the coated fired film according to the third embodiment of the present invention is preferably in the range of 100 to 1000 μm, more preferably in the range of 200 to 1000 μm. It is in the range of 500 to 1000 μm. Further, the thickness of the protective coating layer portion (protective coated fired layer) is preferably in the range of 1 to 10 mm, more preferably in the range of 2 to 5 mm.
本發明之第3實施形態中之燒成後的料漿被覆燒成層，例如，在由玻璃成分及膠態二氧化矽成分所成基材相中，氧化鋁粒子係作為分散相而分散之狀態。又，燒成後的保護被覆燒成層，例如，在由玻璃成分所成基材中，係氧化鋁粒子及二氧化矽粒子係作為分散相而分散之狀態。 In the third embodiment of the present invention, the slurry after the baking is coated with the fired layer. For example, in the base phase formed of the glass component and the colloidal cerium oxide component, the alumina particles are dispersed as a dispersed phase. status. In addition, in the base material formed of the glass component, the alumina particles and the ceria particle system are dispersed as a dispersed phase.
依照本發明之第3實施形態之被覆燒成被膜，與依照本發明之第1實施形態之被覆燒成被膜有同樣的料漿被覆燒成層，並於其上有經設置膜厚較厚之保護被覆燒成層者。由於直接被覆白金材料之料漿被覆燒成層係與本發明之第1實施形態的燒成被膜同樣者之故，氫氣不穿透性優異，而可有效降低玻璃製造時之玻璃中的氣泡產生。又，由於被覆其上之保護被覆燒成層係膜厚較厚的被覆燒成被膜之故，可有效保護高溫環境下之白金材料，以抑制白金之揮發損失。 According to the coated fired film of the third embodiment of the present invention, the same layer of the fired film according to the first embodiment of the present invention is coated with a fired layer, and a film having a thick film thickness is provided thereon. Protect the coated layer. Since the slurry coating layer of the direct-coated platinum material is the same as the fired coating film of the first embodiment of the present invention, the hydrogen gas non-penetration property is excellent, and the bubble generation in the glass at the time of glass production can be effectively reduced. . Further, since the protective coating coated on the fired coating layer has a thick coating film having a thick film thickness, the platinum material in a high temperature environment can be effectively protected to suppress the volatilization loss of the platinum.
燒成時的燒成溫度等的燒成條件，係與上述第1實施形態的燒成溫度等燒成條件同樣者，而較佳燒成為在料漿 被覆材料層之上形成保護被覆材料層後，同時燒成料漿被覆材料層與保護被覆材料層。 The firing conditions such as the firing temperature at the time of firing are the same as those of the firing temperature of the first embodiment, and are preferably burned in the slurry. After the protective coating material layer is formed on the coating material layer, the slurry coating material layer and the protective coating material layer are simultaneously fired.
又，於本發明之第3實施形態中，料漿被覆材料層及保護被覆材料層，可按玻璃成分、二氧化矽成分、以及氧化鋁成分的比例能實質上成為相同之方式形成各層，亦可為不相同之方式。 Further, in the third embodiment of the present invention, the slurry coating material layer and the protective coating material layer can be formed into a layer in such a manner that the ratio of the glass component, the ceria component, and the alumina component can be substantially the same. Can be different ways.
依照本發明之第4實施形態之特徵為：具有由與白金材料相接觸之第1被覆層及在第1被覆層上的第2被覆層所成之2層結構，而第1被覆層，係由氧化鋁與二氧化矽的混合物所成，第2被覆層，係由玻璃成分所成。 According to a fourth aspect of the present invention, there is provided a two-layer structure comprising a first coating layer in contact with a platinum material and a second coating layer on the first coating layer, and the first coating layer is It is made of a mixture of alumina and ceria, and the second coating layer is made of a glass component.
本發明之第4實施形態的被覆燒成膜，可由具有上述2層結構之被覆材料層經燒成而製得。燒成溫度等的燒成條件，係與上述第1實施形態同樣。第4實施形態之被覆燒成被覆膜，主要係以抑制在高溫環境下之白金揮發損失為目的而設置者。屬於第1被覆層之氧化鋁與二氧化矽的混合物將發揮作為被覆材料的基本功能，被覆即使高溫環境下仍然不會損傷之白金材料基材。並且，由玻璃成分所成之第2被覆層，係再被覆於第1被覆層上可完全遮斷基材與外氣，即使在高溫下仍然具有柔軟性能，被覆、維持第1被覆層以抑制第1被覆層之剝離。 The coated fired film of the fourth embodiment of the present invention can be obtained by firing a coating material layer having the above two-layer structure. The firing conditions such as the firing temperature are the same as those in the first embodiment. The coated fired coating film of the fourth embodiment is mainly provided for the purpose of suppressing the loss of platinum volatilization in a high temperature environment. The mixture of alumina and ceria belonging to the first coating layer serves as a basic function of the coating material, and coats the platinum material substrate which is not damaged even in a high temperature environment. Further, the second coating layer made of the glass component is completely coated on the first coating layer to completely block the substrate and the outside air, and has a soft property even at a high temperature, covering and maintaining the first coating layer to suppress Peeling of the first coating layer.
第2圖，係表示本發明之第4實施形態的被覆燒成被覆膜之模式圖。如第2圖(a)所示，在1300℃程度的燒成溫度下，仍然維持2層結構以被覆基材。然而，如第2圖(b)所示，如在1500℃以上，則第1被覆層與第2被覆層起反 應，結果變成不是2層構造而成為單層的被覆層。由此，成為由氧化鋁濃度及二氧化矽濃度增高之玻璃成分所組成之層。 Fig. 2 is a schematic view showing a coated fired coating film according to a fourth embodiment of the present invention. As shown in Fig. 2(a), at a firing temperature of about 1300 °C, a two-layer structure was maintained to coat the substrate. However, as shown in Fig. 2(b), if the temperature is above 1500 °C, the first coating layer and the second coating layer are opposite. As a result, it becomes a coating layer which is not a two-layer structure and becomes a single layer. Thereby, it is a layer which consists of a glass component which has an alumina concentration and a cerium concentration increase.
本發明之第4實施形態中，各被覆層之組成，係就氧化鋁與二氧化矽的混合層(第1被覆層)而言，較佳為作成氧化鋁15至88重量%、二氧化矽12至85重量%。因為如氧化鋁在88重量%以上時，則在1500℃以上的高溫下與玻璃相間的反應發生時容易產生缺陷，而如二氧化矽在85重量%以上時，則由於熱膨脹係數的降低而容易發生剝離之現象。另一方面，玻璃成分層(第2被覆層)可為由1種玻璃所成者，亦可適用經混合複數種玻璃者。成為第2被覆層之玻璃量，較佳為相對於氧化鋁與二氧化矽的混合層作成約為1：1。當玻璃相過多時，則在高溫環境下起反應時會產生多餘的玻璃成分，可能會產生因此種多餘的玻璃成分所引起之下垂現象。 In the fourth embodiment of the present invention, the composition of each of the coating layers is preferably 15 to 88% by weight of cerium oxide in the mixed layer (first coating layer) of alumina and cerium oxide. 12 to 85% by weight. When, for example, alumina is 88% by weight or more, defects occurring at a high temperature of 1500 ° C or higher and glass phase are likely to occur, and if the amount of cerium oxide is 85% by weight or more, the coefficient of thermal expansion is lowered. The phenomenon of peeling occurs. On the other hand, the glass component layer (second coating layer) may be one type of glass, and may be a mixture of a plurality of types of glass. The amount of glass to be the second coating layer is preferably about 1:1 with respect to the mixed layer of alumina and ceria. When the glass phase is too much, excessive glass components are generated when reacting in a high-temperature environment, and there may be a drooping phenomenon caused by such an extra glass component.
各層的膜厚，在第1被覆層中，較佳為作成50至500μm、特別是50至250μm。又，在第2被覆層中為50至500μm，尤以作成50至250μm較佳。如合併第1被覆層與第2被覆層後作成100μm以下時，則可能不會成為防止氧化所需要之細緻質的膜，如合併第1被覆層與第2被覆層後作成1000μm以上時，當發生大幅度的溫度變動時，會發生剝離‧脫落的可能性增高。 The film thickness of each layer is preferably 50 to 500 μm, particularly 50 to 250 μm in the first coating layer. Further, it is preferably 50 to 500 μm in the second coating layer, and particularly preferably 50 to 250 μm. When the first coating layer and the second coating layer are combined and formed to be 100 μm or less, it may not be a fine film required for preventing oxidation, and when the first coating layer and the second coating layer are combined and formed to have a thickness of 1000 μm or more, When a large temperature change occurs, the possibility of peeling and falling off increases.
如上述，本發明之被覆材料，係以氧化鋁、二氧化矽、玻璃成分作為必需成分者，惟需要時，除此等成分以外， 尚可含有氧化鋯(ZrO)、二氧化鈦(TiO2)、富鋁紅柱石(mullite)等其他陶瓷成分。 As described above, the coating material of the present invention contains alumina, cerium oxide, and a glass component as essential components, and may contain zirconium oxide (ZrO) or titanium oxide (TiO 2 ) in addition to these components. Other ceramic components such as mullite.
本發明中，作為基材之白金材料而言，並不特別限定，除純白金之外，亦能適用於白金合金。以白金合金而言，可例舉：白金-銠合金、白金-金合金、白金-鈀(Palladium)合金、白金-銥(Iridium)合金、白金-釕(Ruthenium)合金。又，不僅固溶體(solid solation)合金，對一般稱為強化合金之粒子分散強化型的白金合金，亦能適用本發明之被覆材料。 In the present invention, the platinum material as the substrate is not particularly limited, and can be applied to a platinum alloy in addition to pure platinum. The platinum alloy may, for example, be a platinum-niobium alloy, a platinum-gold alloy, a platinum-palladium alloy, a platinum-iridium alloy, or a platinum-ruthenium alloy. Further, not only a solid solation alloy but also a white gold alloy which is generally referred to as a particle dispersion-strengthening type of a strengthened alloy, the coating material of the present invention can be applied.
本發明之白金材料，係由白金或白金合金所成之白金材料，其特徵為：被覆有依照上述本發明之第1實施形態、第2實施形態、第3實施形態、或第4實施形態之被覆材料，或者，表面形成有被覆燒成被膜。被覆有被覆材料之白金材料，係指將被覆材料塗佈或貼附以被覆後，進行燒成之前的狀態的白金材料之意。表面形成有被覆燒成被膜之白金材料，係指將經被覆之被覆材料進行燒成之後的白金材料之意。 The platinum material of the present invention is a platinum material formed of platinum or a platinum alloy, and is characterized by being coated with the first embodiment, the second embodiment, the third embodiment, or the fourth embodiment of the present invention. The coating material or the surface of the coating is formed with a coating film. The platinum material coated with the coating material means a platinum material in a state before the coating material is coated or attached to be coated and then baked. A platinum material having a coated fired film formed on the surface means a platinum material after the coated material is fired.
本發明之玻璃製造裝置，係一種玻璃製造裝置，其特徵為：將被覆有依照上述本發明之第1實施形態、第2實施形態、第3實施形態或第4實施形態之被覆材料，或者，形成有被覆燒成被膜之白金材料作為構成材料。與上述者同樣，將被覆有被覆材料之白金材料作為構成材料之玻璃製造裝置，係指將被覆材料進行燒成之前的狀態者之意，而將形成有被覆燒成被膜之白金材料作為構成材料之玻璃 製造裝置，係指經燒成被覆材料之後的狀態者之意。 The glass manufacturing apparatus of the present invention is characterized in that the coating material according to the first embodiment, the second embodiment, the third embodiment, or the fourth embodiment of the present invention is coated, or A platinum material having a coated fired film is formed as a constituent material. In the same manner as the above, the glass manufacturing apparatus in which the platinum material coated with the coating material is used as the constituent material means the state before the coating material is fired, and the platinum material on which the coating film is formed is used as the constituent material. Glass The manufacturing apparatus means the state after the baking of the coating material.
如採用本發明，即使在1000℃以上的高溫環境下仍然不致於發生白金的揮發損失，可維持其優異的高溫特性。 According to the present invention, excellent volatilization characteristics can be maintained even if the volatilization loss of platinum does not occur in a high-temperature environment of 1000 ° C or higher.
又，如採用本發明，則可減少玻璃製造時之氣泡的發生。 Further, according to the present invention, the occurrence of bubbles at the time of glass production can be reduced.
以下，將依照本發明之實施例，與比較例一起加以說明。 Hereinafter, the embodiment will be described together with the comparative example in accordance with an embodiment of the present invention.
本實施例，係採用依照本發明之第1實施形態的料漿形態被覆材料之實施例。 In the present embodiment, an embodiment of a slurry form coating material according to the first embodiment of the present invention is employed.
在此，在白金合金基材上製造經以玻璃成分作為基材相，而將氧化鋁、二氧化矽作為分散相分散之被覆材(燒成被膜)，並檢討來自基材的白金揮發損失之情形。本實施形態中，係製造各成分的含量有不相同的4種類被覆材料。首先，製造按照所製造之被覆材料的組成之原料溶膠(Sol)(料漿)。 Here, a coating material (a baking film) in which a glass component is used as a substrate phase and alumina and cerium oxide are dispersed as a dispersed phase is produced on a platinum alloy substrate, and the platinum volatilization loss from the substrate is reviewed. situation. In the present embodiment, four types of coating materials having different contents of the respective components are produced. First, a raw material sol (slurry) in accordance with the composition of the coated material to be produced is produced.
原料溶膠(料漿)所用之氧化鋁、二氧化矽，係採用脫離子型膠質溶液(無鹼)的狀態者(膠態二氧化矽)。將成為分散相之氧化鋁、二氧化矽，較佳為如本實施形態般，氧化鋁、二氧化矽中之任一係源自膠質溶液者。另一方面，作為玻璃成分係使用日本電氣硝子(股)社製無鹼鋁硼矽酸玻璃(材質名OA-10、組成(重量%)：SiO2 60%、B2O3 10%、Al2O3 15%、CaO 5%、SrO 5%、BaO 2%)及日本電氣硝子(股) 社製無鹼鋁硼矽酸玻璃(材質名EF、組成(重量%)：SiO2 55%、B2O3 6%、Al2O3 14%、CaO+MgO 24%)。然後，原料溶膠(料漿)的製造時，將玻璃、與氧化鋁、二氧化矽的膠質溶液懸浮於固體重量2倍之水中，再添加相當於固體重量3重量%的甲基纖維素，攪拌後作成原料溶膠。 The alumina and cerium oxide used in the raw material sol (slurry) are in the state of a deionized glial solution (alkali-free) (colloidal cerium oxide). The alumina or cerium oxide to be a dispersed phase is preferably one of alumina and cerium oxide derived from a colloidal solution as in the present embodiment. On the other hand, as the glass component, an alkali-free aluminum boron borosilicate glass manufactured by Nippon Electric Glass Co., Ltd. (material name OA-10, composition (% by weight): SiO 2 60%, B 2 O 3 10%, Al) was used. 2 O 3 15%, CaO 5%, SrO 5%, BaO 2%) and Nippon Electric Glass Co., Ltd. Non-alkali Aluminoborosilicate Glass (Material name EF, Composition (% by weight): SiO 2 55%, B 2 O 3 6%, Al 2 O 3 14%, CaO+MgO 24%). Then, in the production of the raw material sol (slurry), glass, a colloidal solution of alumina and cerium oxide is suspended in water twice the weight of the solid, and then methyl cellulose corresponding to 3% by weight of the solid is added and stirred. It is then made into a raw material sol.
基材則作為試片而採用Pt(白金)-10wk%Rh(銠)合金的平板(尺寸：75mm□×1.0mm)。然後，從背面使用熱噴***(hot air gun)在加熱之下使用攪拌器攪拌原料溶膠之下供給於噴霧嘴，對試片重複噴霧溶膠，以塗佈至200μm之厚度。在兩面塗佈溶膠後，在電氣爐中1300℃下燒成，製造被覆材料(燒成被膜)。 As the test piece, a flat plate (size: 75 mm□×1.0 mm) of Pt (Platinum)-10wk% Rh (铑) alloy was used as the test piece. Then, a hot air gun was used from the back side to supply a spray nozzle under stirring using a stirrer under heating, and the spray sol was repeatedly applied to the test piece to be applied to a thickness of 200 μm. After coating the sol on both surfaces, it was fired in an electric furnace at 1300 ° C to produce a coating material (a fired film).
就形成有被覆材料(燒成被膜)之試片，檢討白金的揮發損失之情形。此種檢討，係將試片在外氣中，1300℃、1500℃下加熱100小時，進行測定加熱後的重量變化。其結果如表1表示。表1中一併表示未形成有被覆材料(燒成被膜)之Pt-10wt% Rh合金的試驗結果。 A test piece in which a coating material (baking film) was formed was examined, and the volatilization loss of platinum was examined. In this review, the test piece was heated in an external air at 1300 ° C and 1500 ° C for 100 hours, and the weight change after heating was measured. The results are shown in Table 1. Table 1 shows the test results of the Pt-10wt% Rh alloy in which the coating material (fired film) was not formed.
從表1可確認由各實施例中所形成之被覆材料(燒成被膜)所被覆之白金合金並未發生白金損失，確認具有優異的保護作用。此事實，在1500℃以上的高溫中，亦屬同樣。另一方面，未被覆有被覆材料(燒成被膜)之白金合金，則經確認在1300℃、1500℃均發生0.1g以上的白金損失，確認其損失量係隨著溫度上升而增多。 From Table 1, it was confirmed that the platinum alloy coated with the coating material (baking film) formed in each of the examples did not cause platinum loss, and it was confirmed that it had an excellent protective effect. This fact is also the same in the high temperature of 1500 ° C or higher. On the other hand, it was confirmed that the platinum alloy which was not coated with the coating material (the fired film) had a loss of platinum of 0.1 g or more at 1300 ° C and 1500 ° C, and it was confirmed that the amount of loss increased as the temperature increased.
本實施例，係依照本發明之第4實施形態之實施例。 This embodiment is an embodiment according to the fourth embodiment of the present invention.
在本實施例中，製造2層構造之被覆材料(燒成被膜)。首先，作為第1被覆層，於基板上塗佈含有氧化鋁與二氧化矽之原料溶膠(料漿)(氧化鋁53.1重量%、二氧化矽46.9重量%)。在本實施例中的原料溶膠的溶媒、調整方法，係與實施例1至4同樣，而僅調整調配量。又，其塗佈方法，與實施例1至4同樣，依噴霧塗佈所實施者。並且，在溶膠的塗佈後進行乾燥、燒成，以形成第1被覆層(厚度150μm)。 In the present embodiment, a coating material (a fired film) having a two-layer structure was produced. First, as a first coating layer, a raw material sol (slurry) containing alumina and ceria (53.1 wt% of alumina and 46.9 wt% of cerium oxide) was applied onto a substrate. The solvent and the adjustment method of the raw material sol in the present example were the same as in the first to fourth embodiments, and only the blending amount was adjusted. Further, the coating method was carried out by spray coating in the same manner as in Examples 1 to 4. Then, after the application of the sol, drying and baking were carried out to form a first coating layer (thickness: 150 μm).
在形成第1被覆層之後，再於其上形成第2被覆層。該第2被覆層，係玻璃成分含OA-10、EF(均為日本電氣硝子(股)社製)各50重量%之玻璃成分層。第2被覆層的形成過程，係與上述同樣，依溶膠的噴霧塗佈來實施，其膜厚則作成150μm。 After the first coating layer is formed, a second coating layer is formed thereon. In the second coating layer, the glass component contained 50% by weight of a glass component layer each of OA-10 and EF (all manufactured by Nippon Electric Glass Co., Ltd.). The formation process of the second coating layer was carried out by spray coating of a sol in the same manner as described above, and the film thickness was 150 μm.
就上述形成有被覆材料(燒成被膜)之試片，依與實施例1至4同樣方法檢討白金的揮發損失。其結果如表2所示。 The test piece in which the coating material (baking film) was formed was examined for the volatilization loss of platinum in the same manner as in Examples 1 to 4. The results are shown in Table 2.
從表2可確認，與實施例1至4同樣，由被覆材料(燒成被膜)所被覆之白金合金並未發生白金損失之事實。另外，確認該被覆材料(燒成被膜)在1300℃下時雖維持有2層構造，但在1500℃時就變化成單層。但，經確認在1500℃下仍未喪失其保護作用。 As is clear from Table 2, in the same manner as in Examples 1 to 4, the platinum alloy coated with the coating material (baking film) did not suffer from platinum loss. In addition, it was confirmed that the coating material (baking film) maintained a two-layer structure at 1300 ° C, but changed to a single layer at 1500 ° C. However, it was confirmed that the protective effect was not lost at 1500 °C.
本實施例，係依照本發明之第1實施形態之實施例。 This embodiment is an embodiment according to the first embodiment of the present invention.
按表3所示玻璃成分，調製Al2O3、SiO2以及ZrO2(二氧化鋯)的組成料漿。玻璃成分係使用OA-10(平均粒徑7μm)，Al2O3係使用氧化鋁粒子(平均粒徑50μm)，SiO2 係使用膠態二氧化矽(二氧化矽的膠質溶液：平均粒徑20nm)、ZrO2(二氧化鋯)係使用氧化鋯粒子(平均粒徑6μm)。將此等懸浮於固體重量2倍之水中，以相對於固體重量3重量%之方式添加甲基纖維素，調製成料漿。 According to the glass component shown in Table 3, a composition slurry of Al 2 O 3 , SiO 2 and ZrO 2 (zirconium dioxide) was prepared. OA-10 (average particle diameter: 7 μm) is used for the glass component, alumina particles (average particle diameter: 50 μm) are used for the Al 2 O 3 system, and colloidal cerium oxide (the colloidal solution of cerium oxide: average particle diameter) is used for the SiO 2 system. As the 20 nm) and ZrO 2 (zirconia), zirconium oxide particles (average particle diameter: 6 μm) were used. These were suspended in water twice the weight of the solid, and methyl cellulose was added in an amount of 3% by weight based on the weight of the solid to prepare a slurry.
將經噴砂(Sand blast)處理過之白金坩堝(直徑46mm、高度40mm)的內面，在使用熱噴***加熱之狀態下，對白金坩堝的外側底面及外側側面依噴霧塗裝方式塗佈料漿。側面，係從底面塗佈至25mm高度的位置。在80℃下乾燥後，在1500℃下燒成白金坩堝5小時，藉以燒成被覆材料層。被覆燒成被膜的厚度為500μm。 The inner surface of the white gold crucible (46 mm in diameter and 40 mm in height) treated by sand blasting is sprayed on the outer bottom surface and the outer side surface of the platinum crucible by heating with a hot air gun. Pulp. The side is applied from the bottom surface to a height of 25 mm. After drying at 80 ° C, the platinum crucible was fired at 1500 ° C for 5 hours to thereby fire the coating material layer. The thickness of the coated fired film was 500 μm.
上述被覆材料的燒成後，在降低溫度到1300℃之狀態下，將鋁硼矽酸玻璃(OA-10)填充於白金坩堝內，依10℃/分鐘的升溫速度升溫至1500℃，並在1500℃下保持1小時。 After the coating material is fired, the aluminum borosilicate glass (OA-10) is filled in the platinum crucible at a temperature lowering to 1300 ° C, and the temperature is raised to 1500 ° C at a temperature increase rate of 10 ° C / min. Hold at 1500 ° C for 1 hour.
白金坩堝內，幾乎不能認出氣泡者作為○、經認出多量發泡者作為×，以評估界面發泡狀態，並將評估結果表示於表3。 In the platinum crucible, the bubble was hardly recognized as ○, and the amount of foaming was recognized as × to evaluate the state of the interface foaming, and the evaluation results are shown in Table 3.
另外，將白金坩堝內之玻璃發泡狀態的照片，表示於第4圖至第7圖。第4圖為實施例6，第5圖為比較例2、第6圖為比較例3、第7圖為比較例4。 In addition, a photograph of the glass foaming state in the platinum crucible is shown in Figs. 4 to 7 . Fig. 4 is a sixth embodiment, and Fig. 5 is a comparative example 2, a sixth drawing is a comparative example 3, and a seventh drawing is a comparative example 4.
從表3所示結果及第4圖至第7圖明確可知，依照本發明而於玻璃成分中作為必需成分而含有Al2O3及SiO2之實施例6係較玻璃中僅含有Al2O3之比較例2、玻璃中僅含有SiO2之比較例3、以及玻璃中含有SiO2及ZrO2之比較例4，更能顯著減少發泡之事實。由此可知，如欲減少玻璃製造時之發泡，則依照本發明，需要將氧化鋁及二氧化矽作為必需成分而含有。 As is clear from the results shown in Table 3 and Figs. 4 to 7, the example 6 containing Al 2 O 3 and SiO 2 as an essential component in the glass component according to the present invention contains only Al 2 O in the glass. In Comparative Example 2 of 3, Comparative Example 3 containing only SiO 2 in the glass, and Comparative Example 4 containing SiO 2 and ZrO 2 in the glass, the fact of foaming was remarkably reduced. From this, it is understood that, in order to reduce foaming during glass production, according to the present invention, it is necessary to contain alumina and ceria as essential components.
又，本實施例的被覆材料，係與實施例1至5同樣，能減少白金的揮發損失者。 Further, in the covering material of the present embodiment, as in the first to fifth embodiments, the volatilization loss of platinum can be reduced.
本實施例，係依照本發明之第1實施形態之實施例。 This embodiment is an embodiment according to the first embodiment of the present invention.
調製表4中所示實施例7至9的組成的料漿溶液。玻璃成分以Al2O3以及SiO2而言，採用與實施例6所使用者同樣者。 The slurry solutions of the compositions of Examples 7 to 9 shown in Table 4 were prepared. The glass component was the same as that of the user of Example 6 in the case of Al 2 O 3 and SiO 2 .
將經噴砂處理過之白金坩堝(直徑46mm，高度40mm)的內面，在使用熱噴***加熱之狀態下，對白金坩堝的外 側底面及外側側面，按與實施例6同樣方式，進行上述料漿之噴霧塗裝。按燒成後的膜厚能成為500μm之方式塗裝後，在80℃下乾燥，以形成料漿被覆材料層。 The inner surface of the blasted white gold crucible (diameter 46 mm, height 40 mm) is heated to the outside of the platinum crucible with a hot air gun. The slurry coating of the slurry was carried out in the same manner as in Example 6 on the side bottom surface and the outer side surface. After the film thickness after firing was 500 μm, it was dried at 80 ° C to form a slurry coating material layer.
將依上述方式形成有料漿被覆材料層之白金坩堝，在試驗溫度下燒成5小時後，降低較試驗溫度為低200℃之溫度後，將鋁硼矽酸玻璃(OA-10)填充於白金坩堝內，就實施例7至9而言，依10℃/分鐘的升溫速度升溫至表4所示試驗溫度，然後，在各試驗溫度下保持1小時。將此時的界面發泡狀態，表示於表4中。 The platinum crucible having the slurry coating material layer formed in the above manner is baked at a test temperature for 5 hours, and then lowered to a temperature lower than the test temperature by 200 ° C, and the aluminoborosilicate glass (OA-10) is filled in platinum. In the examples, in the examples 7 to 9, the temperature was raised to the test temperature shown in Table 4 at a temperature increase rate of 10 ° C /min, and then maintained at each test temperature for 1 hour. The state of the interface foaming at this time is shown in Table 4.
從表4所示結果明瞭，如依照本發明於經塗佈作為必需成分而在玻璃成分中含有Al2O3及SiO2之被覆材料之實施例7至9中，能減少在玻璃製造時之發泡。又，如表4所示，如隨著使用溫度領域之升高而減少玻璃成分並增加氧化鋁成分，則可對被覆材料中賦與能耐高使用溫度領域之耐熱性。 As is apparent from the results shown in Table 4, in Examples 7 to 9 in which the coating material containing Al 2 O 3 and SiO 2 in the glass component was coated as an essential component according to the present invention, it was possible to reduce the glass production time. Foaming. Further, as shown in Table 4, if the glass component is decreased and the alumina component is increased as the temperature of use increases, the heat resistance in the field of high temperature can be imparted to the coating material.
本實施例之被覆材料，係與實施例1至5同樣，能減 少白金的揮發損失者。 The covering material of the present embodiment can be reduced as in the first to fifth embodiments. Less platinum loss of volatiles.
本實施例，係使用依照本發明之第2實施形態之糊質形態之被覆材料之實施例。 In the present embodiment, an embodiment of a coating material in a paste form according to the second embodiment of the present invention is used.
如表5所示，使用玻璃成分(OA-10)37.5重量%、氧化鋁(Al2O3)粒子39.0重量%、以及二氧化矽(SiO2)粒子23.5重量%，首先製作此等的混合物的燒結物。二氧化矽粒子係使用平均粒徑20μm者、氧化鋁粒子係使用在實施例6所使用者。燒結條件，係作成1500℃，24小時，將所得燒結物加以粉碎以作成平均粒徑20μm程度的粉碎物。 As shown in Table 5, using a glass component (OA-10) of 37.5 wt%, alumina (Al 2 O 3 ) particles of 39.0 wt%, and cerium oxide (SiO 2 ) particles of 23.5% by weight, the mixture was first prepared. Sinter. As the cerium oxide particles, those having an average particle diameter of 20 μm and alumina particles were used in the user of Example 6. The sintering conditions were 1500 ° C for 24 hours, and the obtained sintered product was pulverized to obtain a pulverized product having an average particle diameter of about 20 μm.
所得粉碎物當100重量份，將氧化鋁纖維(Al2O3 97重量%-SiO23重量%、平均纖維長度100mm、平均纖維直徑3μm)按能成為5重量份之方式，添加成以9重量%之方式溶解有甲基纖維素樹脂之水溶液中，以製作混合糊質。甲基纖維素樹脂水溶液的比例，係對粉碎物和氧化鋁纖維合計100重量份，作成40重量份。 100 parts by weight of the obtained pulverized product, the alumina fiber (Al 2 O 3 97% by weight - SiO 2 3 % by weight, average fiber length 100 mm, average fiber diameter 3 μm) was added in an amount of 5 parts by weight. The aqueous solution of the methylcellulose resin was dissolved in a weight % manner to prepare a mixed paste. The ratio of the methylcellulose resin aqueous solution was 40 parts by weight based on 100 parts by weight of the total of the pulverized product and the alumina fiber.
於經噴砂處理過之白金坩堝(直徑46mm、高度40mm)的外側底面及外側側面，貼附上述糊質。欲貼附糊質之位置，係作成與實施例6同樣的位置。經貼附糊質後，在1500℃下燒成5小時，燒成後降低溫度到1300℃，並在此溫度下於白金坩堝內填充鋁硼矽酸(OA-10)，然後依10℃/分鐘的升溫速度升溫至1500℃，並在1500℃下保持1小時。將此時的界面發泡狀態加以評估，並表示於表5中。 The paste was attached to the outer bottom surface and the outer side surface of the blasted white gold crucible (diameter 46 mm, height 40 mm). The position to which the paste was to be attached was set to the same position as in Example 6. After the paste is attached, it is fired at 1500 ° C for 5 hours, and after firing, the temperature is lowered to 1300 ° C, and at this temperature, the platinum lanthanum is filled with aluminum borohydride (OA-10), and then at 10 ° C / The temperature increase rate in minutes was raised to 1500 ° C and maintained at 1500 ° C for 1 hour. The state of the interface foaming at this time was evaluated and shown in Table 5.
如表5所示，可知使用依照本發明之第2實施形態之膠質形態的被覆材料之實施例10中，能減少玻璃製造時之發泡現象。又，本實施例的糊質係在燒成後仍不會發生龜裂等者。又，與實施例1至5同樣，係能減少白金的揮發損失者。 As shown in Table 5, in Example 10 in which the coating material of the colloidal form according to the second embodiment of the present invention was used, it was found that the foaming phenomenon at the time of glass production can be reduced. Further, the paste of the present embodiment is such that cracks do not occur even after firing. Further, in the same manner as in the first to fifth embodiments, it is possible to reduce the loss of volatilization of platinum.
本實施例，係依照本發明之第3實施形態之實施例者。 This embodiment is an embodiment according to the third embodiment of the present invention.
如表6所示，作為玻璃成分者係使用OA-10、Al2O3係使用氧化鋁粒子，SiO2係使用膠態二氧化矽以調製料漿形態的被覆材料。在此，氧化鋁粒子及膠態二氧化矽，係使用與實施例6同樣者。表6中的膠態二氧化矽之欄所示( )內的數值，係作為膠態二氧化矽的溶液的調配比例。作為有機黏合劑，而依表6所示調配比例使用甲基纖維素樹脂的1.5重量%水溶液，調製3種類之料漿a1、b1及c1 As shown in Table 6, as the glass component, OA-10 and Al 2 O 3 were used as the alumina particles, and SiO 2 was a colloidal ceria to prepare a coating material in the form of a slurry. Here, the alumina particles and the colloidal cerium oxide were used in the same manner as in Example 6. The values in ( ) shown in the column of colloidal cerium oxide in Table 6 are the ratio of the solution as a solution of colloidal cerium oxide. As an organic binder, a 1.5% by weight aqueous solution of methyl cellulose resin was used in the proportion shown in Table 6, and three types of slurry a1, b1, and c1 were prepared.
依表7所示比例混合玻璃成分(OA-10)、Al2O3以及SiO2，在1500℃下燒結混合物24小時，並粉碎所得燒結物，以調製燒結物粉碎物a2、b2以及c2。 The glass component (OA-10), Al 2 O 3 and SiO 2 were mixed at a ratio shown in Table 7, and the mixture was sintered at 1500 ° C for 24 hours, and the obtained sintered body was pulverized to prepare pulverized materials a2, b2 and c2.
接著，對所得燒結物粉碎物，如表8所示，混合有機黏合劑及氧化鋁纖維，以調製3種糊質：a3、b3以及c3。 Next, as shown in Table 8, the obtained pulverized product of the sintered product was mixed with an organic binder and alumina fibers to prepare three types of pastes: a3, b3, and c3.
在使用熱噴***加熱經噴砂處理過之白金坩堝(直徑46mm、高度40mm)內面之狀態下，於白金坩堝的外側底面及外側側面，分別噴霧塗裝表6所示料漿形態的被覆材料a1、b1、以及c1之後，在80℃下乾燥，形成料漿被覆材料層。 In the state in which the inner surface of the blasted white gold crucible (diameter 46 mm, height 40 mm) is heated by a hot air gun, the coating material in the form of slurry shown in Table 6 is spray-coated on the outer bottom surface and the outer side surface of the platinum crucible, respectively. After a1, b1, and c1, it was dried at 80 ° C to form a slurry coating material layer.
接著，將表8中所示a3、b3以及c3糊質貼附於如上述方式所形成之料漿被覆材料層上後，使其乾燥，以形成保護被覆材料層。 Next, the a3, b3, and c3 pastes shown in Table 8 were attached to the slurry coating material layer formed as described above, and then dried to form a protective coating material layer.
接著，將如上述方式形成有料漿被覆材料層及保護被覆材料層之白金坩堝，依10℃/分鐘的升溫速度升溫至試驗溫度並保持該試驗溫度5小時，以燒成料漿被覆材料層及保護被覆材料層。在此，各實施例中所得燒成被膜的料漿被覆燒成層的厚度為500μm，而保護被覆燒成層的厚度為500μm、保護被覆燒成層的厚度為5mm。 Next, the platinum coating material having the slurry coating material layer and the protective coating material layer formed as described above is heated to a test temperature at a temperature increase rate of 10 ° C /min, and the test temperature is maintained for 5 hours to fire the slurry coating material layer and Protect the coating material layer. Here, the thickness of the slurry-coated fired layer of the fired film obtained in each of the examples was 500 μm, the thickness of the protective coated fired layer was 500 μm, and the thickness of the protective coated fired layer was 5 mm.
在將如上述方式形成有被覆燒成被膜之實施例11至 13的白金坩堝，在降低較試驗溫度低200℃之狀態下，填充鋁硼矽酸玻璃(OA-10)，然後，依10℃/分鐘的升溫速度升溫至試驗溫度，並保持各試驗溫度1小時。此時的界面發泡狀態在表9中表示。 In the embodiment 11 in which the coated fired film is formed as described above, Platinum crucible of 13 is filled with aluminoborosilicate glass (OA-10) at a temperature lower than the test temperature by 200 ° C, and then heated to the test temperature at a temperature increase rate of 10 ° C / min, and the test temperature is maintained. hour. The interface foaming state at this time is shown in Table 9.
從表9所示結果明確可知，依照本發明之第3實施形態之實施例11至13中，能減少玻璃製造時之發泡情形。 As is clear from the results shown in Table 9, in Examples 11 to 13 according to the third embodiment of the present invention, the foaming state at the time of glass production can be reduced.
又，本實施例的被覆材料，係與實施例1至5同樣，能減少白金的揮發損失。 Further, in the covering material of the present embodiment, as in the first to fifth embodiments, the volatilization loss of platinum can be reduced.
其次，就經適用本發明之玻璃製造設備，以及有關使用該裝置之顯示器用玻璃的製造方法所實施之實施例，加以說明。首先，說明玻璃製造設備的構成。第3圖，係表示玻璃製造設備的構成之說明圖。 Next, an embodiment of a glass manufacturing apparatus to which the present invention is applied, and a method of manufacturing a glass for a display using the apparatus will be described. First, the configuration of the glass manufacturing equipment will be described. Fig. 3 is an explanatory view showing the configuration of a glass manufacturing apparatus.
玻璃製造設備1具有：成為熔融玻璃的供給源之略為成矩形的熔解槽2、經設置於該熔解槽2的下游側之澄清槽3、經設置於澄清槽3的下游側之攪拌槽4、以及經設置於攪拌槽4的下游側之成型裝置5，而溶解槽2、澄清槽3、 攪拌槽4、以及成型裝置5，係分別藉由連通流路6、7、8所連接。 The glass manufacturing equipment 1 has a slightly rectangular melting tank 2 serving as a supply source of molten glass, a clarification tank 3 provided on the downstream side of the melting tank 2, and a stirring tank 4 provided on the downstream side of the clarification tank 3. And a molding device 5 disposed on the downstream side of the agitation vessel 4, and the dissolution tank 2, the clarification tank 3, The stirring tank 4 and the molding apparatus 5 are connected by the communication flow paths 6, 7, and 8, respectively.
熔解槽2，具有底牆、側牆以及天花牆，而此等各牆，係以耐火物所形成者。熔解槽2中設置有燃燒器、電極等，係能熔融玻璃原料者。於熔解槽2的下游側之側牆上形成有流出口，隔著在上游端具有該流出口之寬度狹窄的連通流路6，使熔解槽2與澄清槽互相連通。 The melting tank 2 has a bottom wall, a side wall, and a ceiling wall, and the walls are formed by refractory materials. The melting tank 2 is provided with a burner, an electrode, or the like, and is capable of melting a glass raw material. An outlet port is formed on the side wall on the downstream side of the melting tank 2, and the melting channel 2 and the clarification tank are communicated with each other via a communication passage 6 having a narrow width at the upstream end.
澄清槽3，具有底牆、側牆以及天花牆。底牆及側牆的內牆面(至少與熔融玻璃相接觸之內牆面部位)，係由白金或白金合金所形成，而在其外側，設置有保護耐火物。澄清槽3，係在上游側的側牆上有連通流路6之下游端開口。該澄清槽3，主要是進行玻璃澄清之部位，而玻璃中所含之微細氣泡，即被澄清劑所釋放之澄清氣體所擴大而浮出上面，並從玻璃中去除。於澄清槽3下游側的側牆上，形成有流出口，隔著在上游端具有流出口之寬度狹窄的連通流路7而於澄清槽3下游側連通攪拌槽4。 The clarification tank 3 has a bottom wall, a side wall and a ceiling wall. The inner wall surface of the bottom wall and the side wall (at least the inner wall portion in contact with the molten glass) is formed of platinum or a platinum alloy, and on the outer side thereof, a protective refractory is provided. The clarification tank 3 has a downstream end opening of the communication flow path 6 on the side wall on the upstream side. The clarification tank 3 is mainly a portion where the glass is clarified, and the fine bubbles contained in the glass, that is, the clarified gas released by the clarifying agent, are enlarged and floated upward, and are removed from the glass. An outlet port is formed on the side wall on the downstream side of the clarification tank 3, and the agitation tank 4 is connected to the downstream side of the clarification tank 3 via a communication passage 7 having a narrow outlet port at the upstream end.
攪拌槽4，具有底牆、側牆以及天花牆。底牆及側牆的內牆面(至少與熔融玻璃相接觸之內牆面部位)，係由白金或白金合金所形成，而在其外側，設置有保護耐火物。攪拌槽4，主要係使用攪拌器等攪拌熔融玻璃，為均質化之部位。 The agitation tank 4 has a bottom wall, a side wall and a ceiling wall. The inner wall surface of the bottom wall and the side wall (at least the inner wall portion in contact with the molten glass) is formed of platinum or a platinum alloy, and on the outer side thereof, a protective refractory is provided. In the agitation vessel 4, the molten glass is mainly stirred by a stirrer or the like to be a homogenized portion.
在攪拌槽4下游側的側牆上形成有流出口，隔著在上游端具有流出口之寬度狹窄的連通流路8而於攪拌槽4的下游側連通成型裝置5。 An outlet port is formed on the side wall on the downstream side of the agitation vessel 4, and the molding device 5 is connected to the downstream side of the agitation vessel 4 via a communication passage 8 having a narrow outlet port at the upstream end.
成型裝置5，例如，在顯示用玻璃的成型的情形，可使用下抽(down-draw)成型裝置、上抽(up-draw)成型裝置、浮流法(float)成型裝置等板玻璃成型裝置。在液晶用板玻璃的情形，溢流式下抽(overflow down-draw)成型法特別合適。 For example, in the case of molding the glass for display, the molding apparatus 5 can use a sheet glass molding apparatus such as a down-draw molding apparatus, an up-draw molding apparatus, and a float molding apparatus. In the case of sheet glass for liquid crystal, an overflow down-draw molding method is particularly suitable.
又，連接熔解槽2與澄清槽3之連通流路6，係由耐火物所形成者，而另一方面，其他連通流路，亦即，連接澄清槽3與攪拌槽4之連通流路7、以及連接攪拌槽4與成型裝置5之連通流路8，係由白金或白金合金所形成，並在其外側設置有保護耐火物。 Further, the communication flow path 6 connecting the melting tank 2 and the clarification tank 3 is formed of a refractory material, and on the other hand, the other communication flow path, that is, the communication flow path 7 connecting the clarification tank 3 and the stirring tank 4 And the communication passage 8 connecting the stirring tank 4 and the molding device 5 is formed of platinum or a platinum alloy, and a protective refractory is provided on the outer side thereof.
本實施例中，係在上述製造設備中，於由白金或白金合金所成玻璃製造設備(在此即為澄清槽2至連通流路8)的外表面，形成依照本發明之第3實施形態之被覆燒成被膜，亦即，於料漿被覆燒成層之上形成有保護被覆燒成層之被覆燒成被膜。此種被覆燒成被膜，例如在實施例11至13的被覆材料上很適合使用。 In the present embodiment, in the above-described manufacturing apparatus, in the outer surface of the glass manufacturing apparatus (here, the clarification tank 2 to the communication flow path 8) made of platinum or platinum alloy, the third embodiment according to the present invention is formed. The coating film is fired, that is, a coated fired film having a protective coating fired layer is formed on the slurry-coated fired layer. Such a coated fired film is suitably used, for example, on the covering materials of Examples 11 to 13.
於是，使用具有如上述構成之玻璃製造設備來製造顯示器用玻璃之方法，係如下所述。 Thus, a method of manufacturing a glass for a display using a glass manufacturing apparatus having the above configuration is as follows.
首先，調配玻璃原料。例如，按能具有SiO2-Al2O3-B2O3-RO(RO係MgO、CaO、BaO、SrO以及ZnO中的1種以上)系的組成之玻璃方式，具體而言，以質量百分率計，按能成為含有SiO2 50至70%、Al2O3 10至25%、B2O3 5至20%、MgO 0至10%、CaO 3至15%、BaO 0至10%、SrO 0至10%、ZnO 0至10%、TiO2 0至5%、P2O5 0 至5%之無鹼方式調配玻璃原料。又，上述成分以外，尚可添加澄清劑等各種成分。 First, mix the glass raw materials. For example, in the case of a glass having a composition of SiO 2 -Al 2 O 3 -B 2 O 3 -RO (one or more of RO-based MgO, CaO, BaO, SrO, and ZnO), specifically, mass In terms of percentage, it can be 50 to 70% containing SiO 2 , 10 to 25% of Al 2 O 3 , 5 to 20% of B 2 O 3 , 0 to 10% of MgO, CaO 3 to 15%, and BaO 0 to 10%. The glass raw material is formulated in an alkali-free manner of SrO 0 to 10%, ZnO 0 to 10%, TiO 2 0 to 5%, and P 2 O 5 0 to 5%. Further, various components such as a clarifying agent may be added in addition to the above components.
接著，將所調配之玻璃原料投入熔解槽2中，進行熔融、玻璃化。在熔解槽2內，使用燃燒器的燃燒火焰而從上方加熱玻璃。在上述SiO2-Al2O3-B2O3-RO系玻璃的情形，係以1500至1650℃左右熔融玻璃。 Next, the prepared glass raw material is put into the melting tank 2, and is melted and vitrified. In the melting tank 2, the glass is heated from above using the combustion flame of the burner. In the case of the above SiO 2 -Al 2 O 3 -B 2 O 3 -RO-based glass, the glass is melted at a temperature of about 1,500 to 1,650 °C.
在熔解槽2內被玻璃化之熔融玻璃，則通過連通流路6而導引至澄清槽3。熔融玻璃中雖然含有玻璃化反應時所發生之初期氣泡，惟在澄清槽3中，藉由從澄清劑成分所釋放之澄清氣體而使該初期泡擴大浮上以去除。 The molten glass which is vitrified in the melting tank 2 is guided to the clarification tank 3 through the communication flow path 6. Although the molten glass contains the initial bubbles which occur at the time of the vitrification reaction, in the clarification tank 3, the initial bubble is expanded and removed by the clarified gas released from the clarifier component.
在澄清槽3內所澄清之熔融玻璃，則通過連通流路7而被導引至攪拌槽。在攪拌槽4內，玻璃即被旋轉之攪拌器所攪拌而均質化。 The molten glass clarified in the clarification tank 3 is guided to the stirring tank through the communication flow path 7. In the stirring tank 4, the glass is stirred and homogenized by a rotating agitator.
經於攪拌槽4均質化之熔融玻璃，則通過連通流路8而被導引至成型裝置5，並被成型為板狀。如此，即可製得顯示器用玻璃。 The molten glass homogenized in the agitation tank 4 is guided to the molding apparatus 5 through the communication flow path 8, and is formed into a plate shape. In this way, the glass for the display can be obtained.
一般，從熔解槽2至澄清槽3的連通流路6，係相當於1450℃至1600℃的使用溫度領域，澄清槽3、從澄清槽3至攪拌槽4的連通流路7、以及攪拌槽4，係相當於1250℃至1450℃的使用溫度領域，而從攪拌槽4至成型裝置5的連通流路8，係相當於1000℃至1250℃的使用溫度領域。 In general, the communication flow path 6 from the melting tank 2 to the clarification tank 3 corresponds to a use temperature range of 1450 ° C to 1600 ° C, the clarification tank 3, the communication flow path 7 from the clarification tank 3 to the stirring tank 4, and the stirring tank. 4 is a use temperature range of 1250 ° C to 1450 ° C, and the communication flow path 8 from the stirring tank 4 to the molding apparatus 5 corresponds to a use temperature range of 1000 ° C to 1250 ° C.
本實施例之玻璃製造裝置中，在上述玻璃之製造方法的實施時，即使長期間的裝置運轉後，仍能抑制來自製造裝置的白金之揮發損失。其結果均能長期間維持製造裝置 的強度及安定性。又，均能減少玻璃製造時的氣泡發生。因而，有關本實施例之裝置，在顯示器用玻璃以外的玻璃製造上，當然亦能適用。 In the glass manufacturing apparatus of the present embodiment, in the implementation of the glass manufacturing method described above, even if the apparatus is operated for a long period of time, the volatilization loss of platinum from the manufacturing apparatus can be suppressed. The result is that the manufacturing device can be maintained for a long period of time. Strength and stability. Moreover, the occurrence of bubbles at the time of glass production can be reduced. Therefore, the apparatus according to the present embodiment can of course be applied to the manufacture of glass other than glass for display.
1‧‧‧玻璃製造設備 1‧‧‧Glass manufacturing equipment
2‧‧‧熔解槽 2‧‧‧melting tank
3‧‧‧澄清槽 3‧‧‧Clarification tank
4‧‧‧攪拌槽 4‧‧‧Stirring tank
5‧‧‧成型裝置 5‧‧‧Molding device
6,7,8‧‧‧連通流路 6,7,8‧‧‧Connected flow path
第1圖，係依模式表示依照本發明之第2實施形態之一實施例的被覆燒成被膜之圖。 Fig. 1 is a view showing a coated fired film according to an embodiment of the second embodiment of the present invention in a mode.
第2圖，係依模式表示依照本發明之第4實施形態之一實施例的被覆燒成被膜之圖。 Fig. 2 is a view showing a coated fired film according to an embodiment of the fourth embodiment of the present invention in a mode.
第3圖，係表示玻璃製造裝置的裝置構成的一例之圖。 Fig. 3 is a view showing an example of a device configuration of a glass manufacturing apparatus.
第4圖，係表示實施例6的界面發泡狀態之圖。 Fig. 4 is a view showing the state of the interface foaming of Example 6.
第5圖，係表示比較例2的界面發泡狀態之圖。 Fig. 5 is a view showing the state of the interface foaming of Comparative Example 2.
第6圖，係表示比較例3的界面發泡狀態之圖。 Fig. 6 is a view showing the state of the interface foaming of Comparative Example 3.
第7圖，係表示比較例4的界面發泡狀態之圖。 Fig. 7 is a view showing the state of the interface foaming of Comparative Example 4.
1‧‧‧玻璃製造設備 1‧‧‧Glass manufacturing equipment
2‧‧‧熔解槽 2‧‧‧melting tank
3‧‧‧澄清槽 3‧‧‧Clarification tank
4‧‧‧攪拌槽 4‧‧‧Stirring tank
5‧‧‧成型裝置 5‧‧‧Molding device
6,7,8‧‧‧連通流路 6,7,8‧‧‧Connected flow path
Claims (32)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004265720 | 2004-09-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW200615399A TW200615399A (en) | 2006-05-16 |
| TWI428473B true TWI428473B (en) | 2014-03-01 |
Family
ID=36059991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW094131413A TWI428473B (en) | 2004-09-13 | 2005-09-13 | Coating material for coating platinum material, platinum material having such coating material, and glass making apparatus |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20080090087A1 (en) |
| JP (2) | JP4316615B2 (en) |
| KR (1) | KR101314889B1 (en) |
| CN (1) | CN101044265B (en) |
| TW (1) | TWI428473B (en) |
| WO (1) | WO2006030738A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI782040B (en) * | 2017-06-19 | 2022-11-01 | 美商康寧公司 | Refractory article, coating composition for preventing redox reaction, and method of manufacturing a refractory article |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4720777B2 (en) * | 2007-04-24 | 2011-07-13 | 旭硝子株式会社 | Glass manufacturing apparatus and manufacturing method |
| US20100218855A1 (en) * | 2007-10-05 | 2010-09-02 | Duncan Roy Coupland | Metal protection |
| US20090176430A1 (en) * | 2008-01-07 | 2009-07-09 | Wang Wadelee | Method of making white light source by violet-LED |
| JP4978564B2 (en) * | 2008-05-30 | 2012-07-18 | Ｔｄｋ株式会社 | Method for forming glass film |
| FR2938554B1 (en) * | 2008-11-19 | 2011-05-06 | Areva Nc | METHOD FOR COATING A METAL CUP ELEMENT BY A GLASS AND CERAMIC MIXTURE |
| JP5458571B2 (en) * | 2008-12-26 | 2014-04-02 | 日本電気硝子株式会社 | Dry coating of platinum material container and method for forming the same |
| JP5776548B2 (en) * | 2010-03-25 | 2015-09-09 | 日本電気硝子株式会社 | Manufacturing method of glass manufacturing apparatus and glass manufacturing apparatus |
| JP5692223B2 (en) * | 2010-04-28 | 2015-04-01 | 旭硝子株式会社 | Molten glass processing apparatus, manufacturing method thereof, and use thereof |
| DE102010047898B4 (en) * | 2010-10-11 | 2013-06-06 | Heraeus Materials Technology Gmbh & Co. Kg | Platinum or platinum alloy component and process for reducing the evaporation of platinum or platinum alloy components |
| DE102010047896B4 (en) * | 2010-10-11 | 2016-03-03 | Heraeus Deutschland GmbH & Co. KG | Reduction of the evaporation rate from platinum and Pt alloys: component and process |
| JP2012121740A (en) * | 2010-12-06 | 2012-06-28 | Nippon Electric Glass Co Ltd | Glass production apparatus and glass production method using the same |
| JP5557333B2 (en) * | 2010-12-27 | 2014-07-23 | コバレントマテリアル株式会社 | Silica glass crucible for silicon single crystal pulling |
| WO2012133107A1 (en) * | 2011-03-28 | 2012-10-04 | 旭硝子株式会社 | Molten glass holding refractory, glass manufacturing apparatus using molten glass holding refractory and method for manufacturing glass using glass manufacturing apparatus |
| CN103030359A (en) * | 2012-12-03 | 2013-04-10 | 彩虹显示器件股份有限公司 | Coating material for platinum material in high-temperature environment and preparation method thereof |
| CN104150771B (en) * | 2013-08-27 | 2018-02-23 | 东旭集团有限公司 | A kind of coating material for platinum channel |
| CN107531537A (en) | 2015-05-06 | 2018-01-02 | 康宁股份有限公司 | For handling the apparatus and method of melted material |
| KR20180125117A (en) * | 2017-05-12 | 2018-11-22 | 코닝 인코포레이티드 | Refractory article, composition for coating refractory article and method of manufacturing the refractory article |
| JP7228357B2 (en) * | 2018-10-04 | 2023-02-24 | 株式会社フルヤ金属 | Volatilization suppression part and its manufacturing method |
| JP7304178B2 (en) * | 2019-03-18 | 2023-07-06 | イビデン株式会社 | Three-dimensional molding and method for producing metal substrate with coating layer |
| JP7266866B2 (en) * | 2019-07-31 | 2023-05-01 | アーテック株式会社 | Glass coating layer forming method and glass coating layer obtained thereby |
| KR20210081554A (en) * | 2019-12-24 | 2021-07-02 | 코닝 인코포레이티드 | Glass manufacturing apparatus and methods for processing a molten material |
| DE102020205046A1 (en) * | 2020-04-21 | 2021-10-21 | Schott Ag | Apparatus for melting and refining glass and a method for producing such a device |
| CN115490413B (en) * | 2022-07-28 | 2024-01-05 | 湖南兆湘光电高端装备研究院有限公司 | Method for protecting platinum channel |
| CN115558892A (en) * | 2022-10-14 | 2023-01-03 | 上海奥莱雅康医疗科技有限公司 | Coating containing platinum |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3397076A (en) * | 1964-11-20 | 1968-08-13 | Ritter Pfaudler Corp | Semicrystallized ground coats and enameled articles manufactured therefrom |
| JPS62212228A (en) * | 1986-03-13 | 1987-09-18 | Tanaka Kikinzoku Kogyo Kk | Platinum container for high temperature |
| JPS632816A (en) * | 1986-06-20 | 1988-01-07 | Tanaka Kikinzoku Kogyo Kk | Platinum vessel for high temperature use |
| JPH01201033A (en) * | 1988-02-04 | 1989-08-14 | Canon Inc | Melting device and melting vessel using same |
| DE4136115C1 (en) * | 1991-11-02 | 1993-01-28 | Schott Glaswerke, 6500 Mainz, De | |
| US5629067A (en) * | 1992-01-30 | 1997-05-13 | Ngk Insulators, Ltd. | Ceramic honeycomb structure with grooves and outer coating, process of producing the same, and coating material used in the honeycomb structure |
| EP1722008B1 (en) * | 2000-11-30 | 2015-03-11 | Schott AG | Use of H2 or H2 and O2 resistant barrier layer for coating in glass manufacturing |
| US7032412B2 (en) * | 2003-03-13 | 2006-04-25 | Corning Incorporated | Methods of manufacturing glass sheets with reduced blisters |
-
2005
- 2005-09-12 JP JP2006535874A patent/JP4316615B2/en not_active Expired - Fee Related
- 2005-09-12 CN CN2005800355188A patent/CN101044265B/en not_active Expired - Fee Related
- 2005-09-12 WO PCT/JP2005/016757 patent/WO2006030738A1/en active Application Filing
- 2005-09-12 KR KR1020077005786A patent/KR101314889B1/en not_active IP Right Cessation
- 2005-09-12 US US11/662,503 patent/US20080090087A1/en not_active Abandoned
- 2005-09-13 TW TW094131413A patent/TWI428473B/en not_active IP Right Cessation
-
2008
- 2008-11-14 JP JP2008291802A patent/JP4769854B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI782040B (en) * | 2017-06-19 | 2022-11-01 | 美商康寧公司 | Refractory article, coating composition for preventing redox reaction, and method of manufacturing a refractory article |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101314889B1 (en) | 2013-10-04 |
| CN101044265B (en) | 2010-05-05 |
| JP2009084697A (en) | 2009-04-23 |
| KR20070053749A (en) | 2007-05-25 |
| JPWO2006030738A1 (en) | 2008-05-15 |
| JP4769854B2 (en) | 2011-09-07 |
| CN101044265A (en) | 2007-09-26 |
| WO2006030738A1 (en) | 2006-03-23 |
| TW200615399A (en) | 2006-05-16 |
| US20080090087A1 (en) | 2008-04-17 |
| JP4316615B2 (en) | 2009-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI428473B (en) | Coating material for coating platinum material, platinum material having such coating material, and glass making apparatus | |
| US7032412B2 (en) | Methods of manufacturing glass sheets with reduced blisters | |
| JP4393766B2 (en) | Coated precious metal parts for glass manufacturing | |
| CN102869621B (en) | Molten glass treatment apparatus, process for production thereof, and use thereof | |
| JP2006137637A (en) | Low melting glass, sealing composition and sealing paste | |
| TWI400216B (en) | High zirconia cast refractory | |
| JP2023065446A (en) | Refractory article, coating composition for preventing oxidation-reduction reaction, and method for manufacturing refractory article | |
| JP2006076871A (en) | Production apparatus for borosilicate sheet glass article, production process therefor and borosilicate sheet glass article | |
| CN102352143B (en) | Glass coating and film technology for reducing platinum rhodium alloy bushing plate loss | |
| CN104150771B (en) | A kind of coating material for platinum channel | |
| CN104163571B (en) | A kind of platinum channel coating material | |
| SE461662B (en) | COATED TO APPLY ENAMEL COATING CONTAINING POWDERED METAL ON A METAL SUBSTRATE | |
| JP2010228942A (en) | Method for manufacturing apparatus for producing glass, and apparatus for producing glass | |
| TWI496753B (en) | Glass powder material and porous glassy film manufacturing method | |
| JP2020520875A (en) | Refractory articles, compositions for coating refractory articles, and methods of making refractory articles | |
| KR20060117316A (en) | Production apparatus for borosilicate sheet glass article, production process therefor and borosilicate sheet glass article | |
| JP2006077318A (en) | Method for modifying surface of apparatus for producing glass | |
| JP2010188299A (en) | Method of forming dry coating film and fired coating film of platinum material container | |
| EP1230183B1 (en) | Water-resistant porcelain enamel coatings and method of manufacturing same | |
| JP7490382B2 (en) | Slurry composition for glass lining and method for producing glass lining product | |
| WO2023032531A1 (en) | Ceramic product and composition for decoration | |
| JP2024052937A (en) | Glass-lined product and its manufacturing method | |
| TW201202479A (en) | Filler for glass making vessel, filler layer for glass making vessel, glass making device and method for making a glass making device | |
| JP5458571B2 (en) | Dry coating of platinum material container and method for forming the same | |
| JPH02188444A (en) | Material for thermally spraying glass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |