JPH01500427A - High density chromic oxide refractory block - Google Patents
High density chromic oxide refractory blockInfo
- Publication number
- JPH01500427A JPH01500427A JP62504928A JP50492887A JPH01500427A JP H01500427 A JPH01500427 A JP H01500427A JP 62504928 A JP62504928 A JP 62504928A JP 50492887 A JP50492887 A JP 50492887A JP H01500427 A JPH01500427 A JP H01500427A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- weight
- titania
- block
- colloidal silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 title claims 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 23
- 238000010304 firing Methods 0.000 claims description 17
- 239000008119 colloidal silica Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000011819 refractory material Substances 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 description 9
- 239000006060 molten glass Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 238000007429 general method Methods 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910001120 nichrome Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/12—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on chromium oxide
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるため要約のデータは記録されません。 (57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】 高密度酸化第ニクロム耐火物ブロック 本発明は、ガラス融解炉用のライニングとして使用される高酸化第ニクロム含ｍ を有する高密度耐火物ブロックに関する。典型的には６ｘ１２ｘ３６インチのよ うな大きい寸法であるこの種の大きいブロックは、製造の間の焼成されるうちに 亀裂を生ずる傾向がある。この亀裂は、焼成の間の耐火物の不均一な緻密化に由 来する応力によって起こるものと思われる。[Detailed description of the invention] High-density Nichrome Oxide Refractory Block The present invention is directed to a highly oxidized dichromium-containing material used as a lining for a glass melting furnace. The present invention relates to a high-density refractory block having. Typically 6x12x36 inches This kind of large blocks, which are of large dimensions, are fired during manufacturing. Tends to crack. This cracking is due to uneven densification of the refractory during firing. This is thought to be caused by the stress that occurs.
かようなブロックは、各種のセラミック物品の製造の熟練者によって一般的に公 知の方法によって形成される。Such blocks are generally made publicly available by those skilled in the manufacture of various ceramic articles. Formed by the method of knowledge.
原料の調製、混合、加圧および乾燥させて均一体を形成し、次いで該物体を一般 には２６００’Ｆ（１４２７℃）より高いが、混合物の融点より低い高温度でキ ルン中で焼成してセラミック結合体にするための各種の方法は公知である。本発 明の方法の利点は、耐火物付形物の溶融注型（ｆｕｓｉｏｎ ｃａｓｔｉｎｇ） に適用されないことである。The raw materials are prepared, mixed, pressed and dried to form a homogeneous body, and then the body is is heated at a high temperature above 2600'F (1427°C) but below the melting point of the mixture. Various methods are known for firing ceramic composites in a chamber. Main departure The advantage of Akira's method is that it is suitable for fusion casting of refractory shapes. This does not apply to
大きいブロックの亀裂を防止する一方法は、焼成の間これらを実質的に気密のマ ツフル中に入れる方法である。One way to prevent cracking in large blocks is to keep them in a virtually air-tight matrix during firing. This is the method of putting it inside the tuffle.
マツフル法は、ブロック全体にわたって均一な大気並びに温度条件の確保に役立 ち、それによって緻密化および収縮が均一化され従って、損害を与える応力の形 成が防止される。マツフル化は、マツフル建造における材料費並びに労力および マツフルがキルン中で容積を占め、そのため焼成できるブロック数を減少させる ため、費用を要する方法である。The Matsuful method helps ensure uniform atmospheric and temperature conditions throughout the block. , thereby homogenizing densification and shrinkage and thus reducing damaging stress forms. development is prevented. Making Matsufuru reduces the cost of materials and labor in constructing Matsufuru. Matsufuru takes up volume in the kiln, thus reducing the number of blocks that can be fired. Therefore, it is an expensive method.
二酸化チタン、すなわち、チタニアは、高酸化第ニクロム耐火性ブロックの緻密 化助剤として以前から公知である。例えば、ｕ、ｓ、ｐ、順３．７７３．５３１ においてＨａｎｉｇａｕｌｔは、８５〜９８％の酸化第ニクロム、０．５〜５％ の二酸化チタンおよび１〜１０％のジルコンから成る耐火性物質は、非常に低い 多孔度、溶融ガラスに対する高い耐食性を有し、かつ、焼成の間の熱的亀本発明 の目的は、キルン内の還元性または酸化性雰囲気のいずれかの存在に関係なく、 亀裂を生ずることなく大きいブロックの形態で焼成できる高酸化第ニクロム含量 の耐火性物質を提供することである。Titanium dioxide, or titania, is a dense block of highly dichromic oxide refractory It has long been known as a chemical additive. For example, u, s, p, order 3.773.531 In Hanigault, 85-98% dichromium oxide, 0.5-5% A refractory material consisting of titanium dioxide and 1-10% zircon has a very low Porosity, high corrosion resistance to molten glass, and thermal resistance during firing The objective is to High dichromium oxide content that allows firing in large block form without cracking The objective is to provide fire-resistant materials.
本発明の他の目的は、溶融ガラスに対して良好な耐食性を有するａ酸化第二りＯ ム耐火性物質の大きいブロックを提供することである。Another object of the present invention is to provide a secondary oxide with good corrosion resistance to molten glass. The aim is to provide large blocks of refractory material.
一貫して亀裂のない大きい、緻密な、高酸化第ニクロム耐火物ブロックの製造方 法の提供も本発明の関連ある目的である。How to make large, dense, highly oxidized nichrome refractories blocks that are consistently crack-free Providing a method is also a related object of the present invention.
次の説明から明らかになるであろう本発明の上記および他の目的は、約８０〜約 ９８重量％の酸化第ニクロム、約１〜約４Ｆｔ！１％のチタニアおよび約９０Ｔ ｒＬ２／９またはそれ以上の表面積を有する、約１〜約３重量％のシリカ、０〜 ５重是％の酸化第二鉄、Ｏ〜約５臆１％のマグネシアを含有する混合物を配合し 、配合した固体を所望形状に加圧し、そして、雰囲気が約１．５％の過剰の可燃 物〜約１．５％の過剰の酸素を含有することができるキルン中において約２６０ ０°〜約３２００’Ｆ（１４２７〜１７６０℃）の温度で前記の加圧付形物を焼 成することによって達成される。好ましい混合物は、各々約２％のチタニアおよ びコロイド寸法のシリカを含有する。The above and other objects of the invention, which will become apparent from the following description, will be apparent from the following description. 98% by weight dichromium oxide, about 1 to about 4 Ft! 1% titania and about 90T from about 1 to about 3% by weight silica, having a surface area of rL2/9 or greater, from 0 to A mixture containing 5% ferric oxide and 1% magnesia is blended. , the blended solids are pressurized into the desired shape, and the atmosphere contains approximately 1.5% excess combustible material. in a kiln that can contain an excess of oxygen of up to about 1.5% Sinter the pressurized shape at a temperature of 0° to about 3200'F (1427-1760°C). This is achieved by doing things. A preferred mixture contains about 2% each of titania and Contains silica of colloidal size.
酸化第ニクロムは、好ましくは、１μより大きい、さらに好ましくは約２〜約１ ０μの平均粒度を有する。約９８．５％Ｃｒ２Ｏ３の純度を有する工業銘柄が適 している。顔料銘柄チタニアが好ましく、アナターゼまたはルチル型のいずれで も満足である。ＭＬ Ｉｎｄｕｓｔｒｉｅｓ、 Ｉｎｃ。The dichromic oxide preferably has a particle size greater than 1μ, more preferably from about 2 to about 1μ. It has an average particle size of 0μ. An industrial grade with a purity of about 98.5% Cr2O3 is suitable. are doing. Pigment brand Titania is preferred, either in anatase or rutile form. I am also satisfied. ML Industries, Inc.
によって商標Ｔｔｔａｎｏｘ １０７０として販売されている微細に分割された チタニアは、本発明において使用される材料の例である。finely divided sold under the trademark Tttanox 1070 by Titania is an example of a material used in the present invention.
シリカは、ＬｕＤｏｘの商標でＤｕ Ｐｏｎｔ社から販売されていることによる ゾル形態でもよく、またはＣａｂＯｔ社からＣＡＢ−０−８ｉＪフユームド シ リカとして販売されているような乾燥粉末でもよい。コロイドシリカの平均粒子 寸法は、約７〜約２４ｎｅ＋（０，００７〜０．０２４μ）でよい。Silica is sold by DuPont under the LuDox trademark. It may be in sol form or CAB-0-8iJ fumed system from CabOt. A dry powder such as that sold as Rika may also be used. Average particle of colloidal silica The dimensions may be from about 7 to about 24 ne+ (0,007 to 0.024 microns).
存在する場合の、アルミナ、酸化第二鉄、およびマグネシアは、若干の酸化第ニ クロムのような低シリカクロマイトを原料とすることができる。クロム鉄鉱であ るりロマイトは、前記の配合混合物の乾燥ｆｆ１ｌの約２８％までを構成するこ とができる。この鉱物の代表的試料は、３５．１％のＣｒ２Ｏ３，２８，８％の Ａｌ２Ｏ３，１５，４％のＦｅ２０３．１８．８％のＭＱｏ、１．８％のＳｉＯ ２および０．２％ＣａＯを含有した。この鉱物中のシリカは、上記したコロイド シリカのような機能はない；この鉱物の平均粒子寸法は、好ましくは約３．５〜 約５μであるが、１〜約１０μでもよい。ブロックの高温焼成の間、現場でシリ カを生成するジルコンおよび他の物質がコロイドシリカ源であってもよい。When present, alumina, ferric oxide, and magnesia contain some ferric oxide. Low silica chromites such as chromium can be used as raw materials. Chromite Rurilomite may constitute up to about 28% of the dry ffl of the above formulation mixture. I can do it. A representative sample of this mineral contains 35.1% Cr2O3, 28.8% Al2O3, 15.4% Fe203.18.8% MQo, 1.8% SiO 2 and 0.2% CaO. The silica in this mineral is the colloid mentioned above. There is no silica-like functionality; the average particle size of this mineral is preferably between about 3.5 and It is approximately 5μ, but may be from 1 to about 10μ. During high-temperature firing of blocks, on-site siliconization Zircon and other materials that produce moss may be the source of colloidal silica.
ブロックを前記の鉱物を添加せずに工業銘柄の酸化第ニクロムから製造する場合 には、好ましい組成は約９３〜約９８％の酸化第ニクロム、約１〜約４％のチタ ニア、および約１〜約３１１１％のコロイドシリカである。工業銘柄の酸化第ニ クロムから製造された特に好ましいブロックは、約９６％の前記の酸化物、およ び各２％のチタニアおよびコロイドシリカを含有する。If the block is manufactured from technical grade dichromium oxide without the addition of the aforementioned minerals. The preferred composition is about 93% to about 98% dichromium oxide, about 1% to about 4% titanium oxide. colloidal silica, and about 1 to about 3111% colloidal silica. Industrial grade 2nd oxide Particularly preferred blocks made from chromium contain about 96% of said oxides and and 2% each of titania and colloidal silica.
本発明の目的のために、大きい緻密な耐火物ブロックは少なくとも約０．５立方 フイート（０，０１４ｍ３）の容積および約２６０〜約３２０１ｂｓ ／ｃｕ、 ｆｔ （Ｄ密度を有するブロックと定義する。本発明の方法によって製造された 耐火物ブロックは、任意の有用な寸法または形状でよいが、本発明の利点は、例 えば）５さが６インチ、幅が１２インチ、そして、長さ２４〜３６インチである ような約２立方フイート（０，０５ｍ３）のように大きいブロックの形成におい て有利である。本発明の方法によって、直角に切断された、または半径約１イン チの内角を有するブロックも亀裂なしで製造されている。本発明のブロックの特 に有利な特徴は、それらの多孔度が０％と低いことであるが、所望ならばこれよ り高い多孔度のものも得られる。For purposes of this invention, a large dense refractory block is at least about 0.5 cu. ft (0,014 m3) and about 260 to about 3201 bs/cu, ft (defined as a block with D density. Manufactured by the method of the present invention Although the refractory blocks may be of any useful size or shape, the advantages of the present invention are that For example) 5 is 6 inches, width is 12 inches, and length is 24 to 36 inches. In the formation of blocks as large as about 2 cubic feet (0,05 m3) It is advantageous. Cut at right angles or approximately 1 inch in radius by the method of the present invention. Blocks with internal angles of 100 mm have also been produced without cracks. Features of the blocks of the invention An advantageous feature is their low porosity of 0%, but if desired High porosity can also be obtained.
本発明の生のブロックは数種の方法によって製造できる。酸化第ニクロム、チタ ニア、およびコロイドシリカを、水、有機結合剤および乳化剤でスラリー化し、 次いで、噴霧乾燥し、等圧圧縮するのが一方法である。かようなスラリーはまた 石膏型中においてスリップ注型することもできる。酸化物、混合物を約５〜１０ 重罎％の水性結合剤で給湿し、そして、水圧プレス上で８０００〜１２０００ｐ ｓｉで加圧するのが他の方法である。生のブロックの焼成は、酸化または還元雰 囲気のいずれでも行うことができる。焼成の好ましい温度は、約２７００〜約３ ２００″Ｆであり：約２７００〜約２９５０″Ｆでの還元雰囲気中における焼成 が特に好ましい。The green blocks of the present invention can be produced by several methods. Nichromium oxide, tita and colloidal silica with water, an organic binder, and an emulsifier; One method is then spray drying and isostatic pressing. Such slurry is also Slip casting in plaster molds is also possible. Oxide, mixture about 5-10 Moisturize with aqueous binder of 8000-12000p on a hydraulic press. Another method is to pressurize with si. Firing of green blocks is done in an oxidizing or reducing atmosphere. It can be done in any environment. The preferred firing temperature is about 2700 to about 3 200″F: Firing in a reducing atmosphere at about 2700 to about 2950″F is particularly preferred.
本発明を次の実施例の方法および生成物によってさらに詳細に説明する。The invention is further illustrated by the methods and products of the following examples.
実施例１ ２４８１ｂｓの水（２９，８ガロン、１１２．７都）に、５１ｂｓのＨｏｎ５ａ ｎｔｏ社のＧｅ１ｖａｔｏｌ ２０−３０ポリビニルアルコール、１．２１ｂＳ のＰｏ１ｙＧ ６００ポリエチレングリコール（Ｏｌｔｎ Ｃｈｅｍｉｃａｌ Ｃｏ、 ） 、８．ＱｌｂｓのＤａｒｖａｎ Ｃ高分子電解質（Ｖａｎｄｅｒｂ ｉｌｔ Ｃｈｅｍｉｃａｌ Ｃｏ、 ）およびシリコーン消泡剤を添加した。こ の混合物に、７６８１ｂＳの酸化第ニクロム（Ａｃｃｒｏｘ Ｃ；平均粒度−４ ，１μ、Ａ＠ｅｒｉｃａｎ Ｃｈｒｏｍｅ ａｎｄ Ｃｈｅｍｉｃａｌｓ社から 販売されている）、１６１ｂｓのチタニア（Ｔｉｔａｎｏｘ １０７０ ：ＮＬ Ｉｎｄｕｓｔｒｉｅｓ社）および１６１ｂｓのコロイドシリカ（Ｃａｂ−ｏ− ｓｉｔ Ｍ−５、表面積−２００±２５ｍ２／ｇ）を添加した。この固形物を水 性スラリーのはげしいかく拌によって混合し、スラリーの噴霧乾燥によって実質 的に均一な粒状耐火物質が得られた。Example 1 2481bs of water (29.8 gallons, 112.7m), 51bs of Hon5a nto Ge1vatol 20-30 polyvinyl alcohol, 1.21bS Po1yG 600 polyethylene glycol (Oltn Chemical Co, ), 8. Qlbs Darvan C Polyelectrolyte (Vanderb ilt Chemical Co, ) and a silicone defoamer were added. child 7681bS dichromium oxide (Accrox C; average particle size -4) , 1μ, A@erican Chrome and Chemicals sold), 161bs Titania (Titanox 1070:NL Industries) and 161bs colloidal silica (Cab-o- sit M-5, surface area -200±25 m2/g) was added. water this solid The slurry is mixed by vigorous agitation and the slurry is mixed by spray drying. A uniform granular refractory material was obtained.
６“×１２”×２４“の最終ブロック（１２，２Ｘ３０．４Ｘ６０．８ｃｍ）が 得られる寸法の型に粒状体を充填し、真空にした。２０．○０Ｏｐｓｉの等圧圧 縮によって生ブロックを形成し、その６Ｘ２４面を上にしてキルン中に置き、キ ルンが次のスケジュールによって熱された後に、２９５０下で１０時間焼成した ：周囲温度から４５０ ’Ｆまで ２０”Ｆ／時間４５０″Ｆで浸漬 ２時間 ４５０ ’Ｆから１２００’Ｆまで ２０°Ｆ／時間１２００″Ｆから１６００ 下まで ４０下／時間１６００°Ｆから２９５０ ’Ｆまで ２０°Ｆ／時間温 度が１６００下に達した後は、キルン雰囲気は、０．５〜１．５％の範囲内の過 剰可燃物質に維持した。The final block of 6" x 12" x 24" (12.2 x 30.4 x 60.8 cm) A mold of the resulting dimensions was filled with granules and evacuated. 20. ○0 Opsi equal pressure Form a green block by shrinking, place it in the kiln with its 6x24 side facing up, and place it in the kiln. After the run was heated according to the following schedule, it was fired under 2950 for 10 hours. :Ambient temperature to 450'F 20"F/hour Soak at 450"F for 2 hours 450'F to 1200'F 20°F/hour 1200'F to 1600 Down to 40°F/hour 1600°F to 2950’F 20°F/hour Temperature After the temperature reaches below 1600, the kiln atmosphere should be within the range of 0.5-1.5%. Maintained surplus combustible material.
ブロックをキルン内で周囲温度に冷却した後、これを検査し、測定した。焼成耐 火物の見掛多孔度およびかさ密度は、焼成の間ブロックの上に置いた３” Ｘ３ ’ Ｘ９’の耐火物バーの測定から決定した。After the block had cooled to ambient temperature in the kiln, it was inspected and measured. Firing resistance The apparent porosity and bulk density of the fire is 3” x 3 placed on the block during firing. Determined from measurements of 'X9' refractory bar.
ブロックの生密度は２０３１ｂｓ ／ｃｕ、ｆｔ、 （３２５０に９／７ｙＬ３ ）であり、焼成密度は約２９３ ｌｂｓ ／ｃｕ、ｆｔ、 （４６８８に９／Ｔ ｒＬ３）であった。焼成の間のブロックの収縮は長さ、幅、および厚さ寸法で、 それぞれ１０．７６％、１２．７３％および１０．５６％であったが、完成ブロ ックには亀裂はなかった。バーの３回の測定の平均で、かさ密度は２９４１ｂｓ ／ｃｕ、ｆｔ、であり、見掛多孔度は０．０％であった。The green density of the block is 2031bs/cu, ft, (9/7yL3 in 3250 ), and the firing density is approximately 293 lbs/cu, ft, (4688 to 9/T rL3). Shrinkage of the block during firing is in the length, width, and thickness dimensions; They were 10.76%, 12.73% and 10.56%, respectively, but the There were no cracks in the hook. Average of 3 measurements of bar, bulk density is 2941 bs /cu, ft, and the apparent porosity was 0.0%.
上記の結果とは対照的に、２１ＴｒＬ２７ｇの表面積を有するシリカ（Ｒｅｙｎ ｏｌｄｓ＾Ｉｕｍｉｎｕｇ＋ Ｃｏ、製）を使用したのを除いて同じ方法で製造 し、同じキルンで同時に焼成したブロックは検査によって亀裂が生じたことが判 明した。In contrast to the above results, silica (Reyn) with a surface area of 21TrL27g Manufactured using the same method except that the olds＾Iuminug+ Co. However, inspection revealed that blocks fired at the same time in the same kiln were cracked. I made it clear.
実施例１のブロックから切断した４本の艮方形試堰バーを白金るつぼ中に含まれ る溶融ガラスの３種の異なる浴の各々に縦方向につるすことによって前記のブロ ックのガラス耐食性を試験した。各場合にお番ノるＳａガラスの表面は、試験バ ーの下部端より約１．２５インチ（３１，８α）高く維持した。４本のバーの第 １組は、溶融ガラス中に２６５０″Ｆで３４８時間保持した。第２組は浴中に６ ９２．５時間保持した。第３組は溶融ガラス浴中に２７００下で６４８時間保持 した。るつぼから溶融ガラスを除去後、試験バーを冷却させ、バーの腐食の程度 をガラス線（ｇｌａｓｓ １ｉｎｅ） 、すなわち、ガラスの表面がバーと触れ た箇所およびガラス線より１７．５ｍ＋＋低い箇所で測定した。［カットＪ （ Ｃｕｔ ）と呼ばれる試験の前および後のバーの面の幅の差を記録し、次式を使 用して耐火物の使用寿命を計算した： 試験時間（時間）Ｘ２５．４縮 ガラス線で１インチのカットになる日数の平均数は、１２本の試験バーの測定に 基づいて４４０であった。ガラス線より下のバーの測定は、上式に挿入して結果 を平均ておく必要がある。Four square trial weir bars cut from the block of Example 1 were contained in a platinum crucible. The said block is suspended vertically in each of three different baths of molten glass. The corrosion resistance of the glass was tested. The surface of the Sa glass in each case was was maintained approximately 1.25 inches (31.8α) higher than the bottom edge of the base. number of four bars One set was held in molten glass at 2650"F for 348 hours. The second set was held in the bath for 6 hours. It was held for 92.5 hours. The third set was kept in the molten glass bath for 648 hours under 2700℃. did. After removing the molten glass from the crucible, let the test bar cool and measure the degree of corrosion on the bar. Glass wire (glass 1ine), that is, the surface of the glass touches the bar Measurements were taken at a location 17.5m++ lower than the glass line. [Cut J ( Record the difference in the width of the face of the bar before and after the test, called Cut, and use the following formula: The service life of refractories was calculated using: Test time (hours) x 25.4 reduction The average number of days it will take to make a 1 inch cut on glass wire is based on the measurement of 12 test bars. It was 440 based on. To measure the bar below the glass line, insert it into the above formula and get the result need to be averaged.
Ｋ豊旦ユ 酸化第ニクロムが２．３μの平均粒度を有し、スラリー水をわずか２０４１ｂｓ 使用し、かつ、閉じる前に真空にしなかったのを除いて実施例１と同じ一般的方 法で製造し、実施例１と同じキルン中において同時に焼成した耐火物ブロックを 製造した。このブロックは各寸法において収縮は比較的大きかったが、焼成、冷 却の問亀裂はなかった。K Toyotan Yu Nichromium oxide has an average particle size of 2.3μ and slurry water only 2041bs The same general procedure as in Example 1 was used, except that no vacuum was applied before closing. A refractory block manufactured by the method and fired simultaneously in the same kiln as in Example 1 was Manufactured. This block had relatively large shrinkage in each dimension, but There was no rift.
実施例３ １９６ ｌｂｓ／ｃｕ、ｆｔ、の密度を有する生ブロックおよびバーを実施例１ の一般的方法によって製造し、実施例１のスケジュールに従って焼成したが、１ ６００″Ｆの温度に達した後は、１／８〜１／４％過剰の酸素を含有する雰囲気 をキルン内に維持して焼成した。このブロックは、長さ、幅および厚が、それぞ れ１２．０４％、１４．３５％および１３．０５％収縮したにも拘らず亀裂はな かった。バーＬで測定したかぎ密度は、３００Ｉｂｓ ／ｃｕ、ｆｔ、 （４， ８ｇ／ｃｃ）であり、そして、見掛多孔度は０．０％であった。Example 3 Example 1 Green blocks and bars having a density of 196 lbs/cu, ft. was manufactured by the general method of 1 and fired according to the schedule of Example 1. After reaching a temperature of 600″F, an atmosphere containing 1/8 to 1/4% excess oxygen was kept in the kiln and fired. This block has different length, width and thickness. There were no cracks despite shrinkage of 12.04%, 14.35% and 13.05%. won. The key density measured at bar L is 300 Ibs/cu, ft, (4, 8 g/cc), and the apparent porosity was 0.0%.
実施例４ 同じ固形分含量のスラリーをＩｆ造するのにフユームドシリ力の代りにコロイド シリカゾル（Ｌｕｄｏｘ Ｈ３−４０：比表面積−２３０ｍ２７ｇ）を使用した のを除いて、実施例１の一般的方法によって６＃Ｘｉ ２’ Ｘ２４”のブロッ クおよびバーを製造した。４５０下での浸漬時間は、焼成スケジュールから省き 、そして、過剰の燃焼物雰囲気を１５００下以上に維持した。完成ブロックは、 亀裂を生ぜず、長さ寸法の収縮は１３．３％であった。バーのかさ密度は３０９ １ｂｓ ／ｃｕ、ｆｔ、（４，９５９／ｚ３）であり、見掛多孔度は０．０％で あった。Example 4 If a slurry with the same solids content is produced using colloid instead of fumed silicon, Silica sol (Ludox H3-40: specific surface area -230m27g) was used. A block of 6#Xi 2'X24'' was prepared by the general method of Example 1, except that and bars. Soaking time under 450℃ can be omitted from the firing schedule. , and the excess combustion atmosphere was maintained below 1500°C. The completed block is No cracking occurred and the shrinkage in length dimension was 13.3%. The bulk density of the bar is 309 1bs/cu, ft, (4,959/z3), and the apparent porosity is 0.0%. there were.
実施例５ 実施例１の一般的方法によって３“×３“×９“のバーを製作した。前記の方法 との相違は；工業銘柄酸化第ニクロム（約り８％純度）は、０．８μの平均粒度 を有し、かつ、これは混合物の乾燥型ａの僅か７１．１％を構成した；乾燥混合 物の２５．３％は上記の低シリカクロマイトであり、かつ、５μの平均粒度を有 した；フユームドシリ力は乾燥混合物の１．５５％を構成した：そして、スラリ ーは２８％の水、０．７４％のポリビニルアルコール、０．１３％のゲルコール および１．３％の界面活性剤を重舟基準で含有した。バーのがさ密度は２７４１ ｂｓ ／ｃｕ、ｆｔ、および見掛多孔度は０％であった。焼成による収縮は１１ ．７％であった。Example 5 A 3" x 3" x 9" bar was fabricated by the general method of Example 1. The method described above. The difference is that industrial grade dichromium oxide (approximately 8% purity) has an average particle size of 0.8μ. and this constituted only 71.1% of the dry form a of the mixture; 25.3% of the material is the above-mentioned low silica chromite and has an average particle size of 5μ. The fumed silica made up 1.55% of the dry mixture: and the slurry - 28% water, 0.74% polyvinyl alcohol, 0.13% gelcole and 1.3% surfactant on a heavy boat basis. The bulk density of the bar is 2741 bs/cu, ft, and apparent porosity were 0%. Shrinkage due to firing is 11 ．． It was 7%.
実施例６ 工業銘柄酸化第ニクロムが２μの平均粒度を有したのを除いて実施例５の一般的 方法によって、６“×１２ｎ×２４“の寸法の大きいブロックおよび３＃×３“ ×９“のバーを製造した。バーのかさ密度および見掛多孔度は、それぞれ、２７ ２ ｌｂｓ ／ｃｕ、ｆｔ、および２．４％Ｆあった。焼成収縮は長さで１１． ９％、幅で１２．３％そして厚さで１１．４％であったが、冷却したブロックに は亀裂は観察されなかった。Example 6 General of Example 5 except that the technical grade dichromium oxide had an average particle size of 2μ. By the method, large blocks with dimensions of 6" x 12n x 24" and 3# x 3" × 9” bars were manufactured. The bulk density and apparent porosity of the bars were 27”, respectively. There were 2 lbs/cu, ft, and 2.4% F. Firing shrinkage is 11. 9%, width 12.3% and thickness 11.4%, but in the cooled block No cracks were observed.
国際調査報告international search report
Claims (18)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/891,661 US4724224A (en) | 1986-08-01 | 1986-08-01 | High density chronic oxide refractory block |
| US891,661 | 1986-08-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01500427A true JPH01500427A (en) | 1989-02-16 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62504928A Pending JPH01500427A (en) | 1986-08-01 | 1987-07-23 | High density chromic oxide refractory block |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4724224A (en) |
| EP (1) | EP0277190A4 (en) |
| JP (1) | JPH01500427A (en) |
| WO (1) | WO1988000931A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5021375A (en) * | 1990-04-19 | 1991-06-04 | Norton Company | Chrome oxide refractory composition |
| GB2253844A (en) * | 1991-03-22 | 1992-09-23 | Pilkington Glass Ltd | Throat |
| US5219807A (en) * | 1991-06-27 | 1993-06-15 | Indresco Inc. | Burned high purity refractories with low soluble chromium |
| DE4140417C1 (en) * | 1991-12-07 | 1993-04-29 | Dyko Industriekeramik Gmbh, 4000 Duesseldorf, De | |
| US5454258A (en) * | 1994-05-09 | 1995-10-03 | Olin Corporation | Broad range moisture analyzer and method |
| FR2944522B1 (en) * | 2009-04-15 | 2011-09-30 | Saint Gobain Ct Recherches | FRITTE PRODUCT BASED ON CHROME OXIDE. |
| FR2971504A1 (en) | 2011-02-15 | 2012-08-17 | Saint Gobain Ct Recherches | DOPE CHROME OXIDE PRODUCT |
| TWI657067B (en) * | 2016-02-05 | 2019-04-21 | 美商聖高拜陶器塑膠公司 | Chromium oxide refractory object and methods of forming thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2498622A (en) * | 1947-11-06 | 1950-02-21 | Corning Glass Works | Refractory composition |
| US3773531A (en) * | 1972-07-13 | 1973-11-20 | Taylors Sons Co Chas | Dense chrome refractory material |
| US4028123A (en) * | 1973-06-18 | 1977-06-07 | Greenewald Jr Herbert | Compacted refractory shapes |
| US4028122A (en) * | 1973-06-18 | 1977-06-07 | Greenewald Jr Herbert | Porous refractory shapes |
| NL178586C (en) * | 1973-07-05 | 1986-04-16 | Minnesota Mining & Mfg | METHOD FOR MANUFACTURING FIRE-RESISTANT FIBERS |
| US3971665A (en) * | 1974-03-18 | 1976-07-27 | Nissan Chemical Industries, Ltd. | Refractory compositions |
| US4040847A (en) * | 1976-04-14 | 1977-08-09 | Johns-Manville Corporation | Temperature stable fibrous insulation composition and "wet" package formed thereof |
| US4047965A (en) * | 1976-05-04 | 1977-09-13 | Minnesota Mining And Manufacturing Company | Non-frangible alumina-silica fibers |
| US4119472A (en) * | 1976-09-01 | 1978-10-10 | Corning Glass Works | Rebonded fusion-cast AZS refractory grain |
| US4233079A (en) * | 1979-10-26 | 1980-11-11 | Chicago Fire Brick Company | Aluminous refractory compositions containing carbon, silicon and chrome oxide |
| US4374897A (en) * | 1980-03-04 | 1983-02-22 | Nippon Chemical Industrial Co., Ltd. | Chromium oxide-based sintered bodies and process for production thereof |
| JPS60239355A (en) * | 1984-05-14 | 1985-11-28 | 品川白煉瓦株式会社 | Chromium oxide refractories |
-
1986
- 1986-08-01 US US06/891,661 patent/US4724224A/en not_active Expired - Fee Related
-
1987
- 1987-07-23 EP EP19870905339 patent/EP0277190A4/en not_active Withdrawn
- 1987-07-23 WO PCT/US1987/001739 patent/WO1988000931A1/en not_active Application Discontinuation
- 1987-07-23 JP JP62504928A patent/JPH01500427A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| US4724224A (en) | 1988-02-09 |
| WO1988000931A1 (en) | 1988-02-11 |
| EP0277190A1 (en) | 1988-08-10 |
| EP0277190A4 (en) | 1990-06-27 |
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