CN101500964B - 焙烧的耐火制品 - Google Patents
焙烧的耐火制品 Download PDFInfo
- Publication number
- CN101500964B CN101500964B CN2007800299257A CN200780029925A CN101500964B CN 101500964 B CN101500964 B CN 101500964B CN 2007800299257 A CN2007800299257 A CN 2007800299257A CN 200780029925 A CN200780029925 A CN 200780029925A CN 101500964 B CN101500964 B CN 101500964B
- Authority
- CN
- China
- Prior art keywords
- mgo
- spinel
- goods
- goods according
- phase
- 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.)
- Active
Links
- 239000011029 spinel Substances 0.000 claims description 29
- 229910052596 spinel Inorganic materials 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 24
- 239000011362 coarse particle Substances 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 18
- 230000006835 compression Effects 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 4
- 239000011449 brick Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 239000011214 refractory ceramic Substances 0.000 abstract description 5
- 230000000712 assembly Effects 0.000 abstract 1
- 238000000429 assembly Methods 0.000 abstract 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 64
- 239000000395 magnesium oxide Substances 0.000 description 33
- 238000005266 casting Methods 0.000 description 22
- 239000011347 resin Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 239000010419 fine particle Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 239000004568 cement Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 208000002173 dizziness Diseases 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical class COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 1
- 244000287680 Garcinia dulcis Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
-
- 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
- C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
- C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
-
- 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
- C04B35/44—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 aluminates
- C04B35/443—Magnesium aluminate spinel
-
- 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
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- 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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0038—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by superficial sintering or bonding of particulate matter
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H5/00—Armour; Armour plates
- F41H5/02—Plate construction
- F41H5/04—Plate construction composed of more than one layer
- F41H5/0414—Layered armour containing ceramic material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H5/00—Armour; Armour plates
- F41H5/02—Plate construction
- F41H5/04—Plate construction composed of more than one layer
- F41H5/0492—Layered armour containing hard elements, e.g. plates, spheres, rods, separated from each other, the elements being connected to a further flexible layer or being embedded in a plastics or an elastomer matrix
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00431—Refractory materials
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5463—Particle size distributions
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/80—Phases present in the sintered or melt-cast ceramic products other than the main phase
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Furnace Housings, Linings, Walls, And Ceilings (AREA)
Abstract
本发明涉及焙烧的耐火陶瓷制品。根据本发明,这一类概念既涵盖成形的制品,又涵盖非成形的制品。成形的制品为那些具有特定形状、便于由制造商大量生产的制品。成形的制品包括:砖、喷嘴、管、止动件、板等。概念非成形的制品包括那些大部分由用户使用适当的泥料而制造的制品。它们包括由泥料铸造而成的炉子总成的底部,而且还包括修理用泥料等。
Description
描述
本发明涉及焙烧的耐火陶瓷制品。根据本发明,这一类概念既涵盖成形的制品,又涵盖非成形的制品。成形的制品为那些具有特定形状、从而可由制造商大量生产的制品。成形的制品包括:砖、喷嘴、管、止动件、板等。非成形的制品这一概念包括那些大部分由用户使用适当的泥料(Masse)而制造的制品。在此包括由泥料铸成的炉子总成的底部,但也同样包括修理用泥料等。
成形的制品可以焙烧或未焙烧的形式供应给用户。与非成形的制品相同,成形的制品也最迟在其使用的过程中,通过这样方式,即,将它们至少加热到充填料成分(Versatzkomponenten)烧结的温度,而被焙烧。
在这一点上,耐火的充填料材料(Versatz-Material)的概念既包括已经具有耐火特性的材料,也包括直到在热处理(焙烧)的过程中或热处理(焙烧)之后才变得耐火的材料。
这种类型的耐火陶瓷制品长时间以来在无数的实施例中为人知晓。对这种制品的要求取决于相应的应用场合。基本的是,要求耐受高温。耐受高达1300℃高温的制品通常足够用于作水泥回转窑的衬里(Auskleidung)。用于冶金应用场合(熔融容器、喷嘴、止动件、气体冲洗塞、滑板等的衬里)的耐火陶瓷制品通常具有耐受至少1400℃至1700℃的热稳定性。用于作垃圾焚烧设备的衬里的制品的耐火性通常在1300℃至1500℃之间。以下应用场合(例如)要求超过1700℃的热稳定性:玻璃熔炼罐、用于金属熔体的生产及处理的单元。
其它主要的特性为:热冲击稳定性、腐蚀特性、结构弹性、压软化(Druckerweichen)、气体渗透性、低温抗压强度(如必要时,还包括在温度交变之后的),高温抗弯强度。
同样在这一点上,特定的制品要求取决于特定的应用场合。例如,以下原则适用于给玻璃熔炼罐作衬里的制品:玻璃熔炼罐大多数利用大尺寸(例如1.0×0.5×0.5m)的耐火砖来加衬里。因此,对于这种应用场合,除降低对腐蚀的敏感性之外,需争取改善(降低)脆性。
DE 100 54 125A1描述了一种用于生产耐火陶瓷制品的充填料。充填料包含熔化相形成物(Schmelzphasenbildner)作为主要成分,该熔化相形成物在700℃至1300℃的运行温度下形成熔液/玻璃相。该熔化相应当尽可能地将制品中开放孔隙度(offene Porositaet)填满,以便在焙烧之后获得尽可能致密的制品。
本发明目标在于提供耐火的陶瓷制品,该陶瓷制品同样适合于高温的应用场合(>1500℃,甚至>1700℃),并且除了高的温度稳定性之外,还累加地具有尽可能多的以下特性:良好的热冲击稳定性、较高的温度变化后的低温抗压强度、较低的气体渗透性。该制品可优选地使用于还原气氛和/或氧化气氛中。
为了实现这些目标进行了大量的实验。其中还获得了以下信息:
-除了化学组成之外,焙烧制品的结构(Gefuege)起着关键的作用。
-针对开放孔隙度(offene Porositaet)的绝对数值并不关键。然而,孔的类型(Art)和构造(Ausbildung)对制品的特性具有较大的影响。通过选择特定的充填料成分及颗粒尺寸(Korngroessen)同样可适当地(gezielt)影响孔隙度。
-同样的也适用于结构弹性。
-所需的特性通过这样的结构来实现,即,该结构除了粗的由MgO形成的粒子(Teilchen)之外还具有由细粒子状的(feinteiligen)(<100μm)充填料成分形成的基于MA-(MgO·Al2O3)尖晶石的基体。
-基体应相当大部分地,最好完全地,由MA尖晶石组成。在任何情况下根据本发明允许极微的(minimale)游离MgO粒子的含量(Anteile)。其含量(相对于整个基体)应当<1.0M.-%(%质量),最好<0.5M.-%或<0.1M.-%。
-基体的MA尖晶石可以是预合成的(vorsynthetisiert)充填料的组成成分(Bestandteil)。有利的是,尖晶石成比例地(anteilig)在制品的焙烧中在原位置形成。在此,充填料中的氧化铝(AL2O3)与MgO细颗粒含量发生反应,并且/或者在MgO粗粒子的表面区域发生反应。相再形成(Phasenneubildung)(MA尖晶石的在原位置的形成)与容积增加相关联。
-MgO与MA尖晶石的不同的热膨胀和收缩用来在两种结构相之间形成裂缝状的空腔(spaltartige Hohlraeume)。
-在细粒子状的基体内,并且通过围绕着粗粒子的裂缝状的(spaltartigen)孔,来确定开放孔隙度。孔终止于粗颗粒状的(最致密的)MgO粒子。
-MgO粗颗粒(MgO-Grobkorn)的含量应为超过50M.-%,例如52M.-%至60M.-%。其余部分主要地由由MA尖晶石形成的基体所形成。
-可通过MgO粗颗粒与充填料的细颗粒组成成分(Bestandteilen)之间的颗粒间隙(Kornluecke)来影响制品特性。MgO粗颗粒可以颗粒尺寸>0.5mm的形式,或者甚至以>1mm的形式而在充填料中被使用。形成基体的组成成分以绝大部分(d90)<100μm的形式被使用,经常甚至<50μm。颗粒尺寸在焙烧时几乎不发生变化。然而,却会发生烧结并由此发生较小的单独颗粒的结合或充填料粒子之间的架桥(Bruecken)的形成。通过在颗粒表面处的尖晶石形成,颗粒会一定程度地“长大”。
本发明在其最普遍的实施例中涉及焙烧的耐火制品,耐火制品的结构包括MA尖晶石基体(第一结构相),在其中,MgO粗颗粒以粒子尺寸d90>300μm的形式(第二结构相)而存在,其中,在该两种结构相之间形成有三维的裂缝状的孔。
根据一个实施例,孔(粗颗粒与周围的尖晶石基体之间的间距)应在相应的粗颗粒表面的超过50%上延伸。该数值可增加到60%,70%,75%,80%,90%。具体而言,这意味着,具有表面面积X的MgO粗颗粒可最多以0.5X的表面面积与周围的基体材料接触。基于一个实施例,沿着MgO粗颗粒的表面延伸的裂缝状的孔最多占MgO粗颗粒的体积含量的1/20。该数值可降低到1/30,1/50,1/70或1/100,其中,最小值可为1/100,1/80,1/60,1/40或1/25。
除了由于技术上的原因导致的“杂质”之外,制品应在至少98M.-%,最好>99M.-%的程度上由MgO粗颗粒加上MA尖晶石基体组成。SiO2含量(Gehalt)最好<1.5M.-%或<0.5M.-%。由此,锰-铝硅酸盐(Magnesium-Aluminium-Silikaten)的形成尽可能地被抑制。
一种这种制品可由这样的充填料制成,除了带有d90>300μm的颗粒尺寸的MgO粗颗粒之外,该充填料还包括至少一种来自Al2O3组(或Al2O3+MgO)和/或预合成的MA尖晶石的带有d90<100μm的颗粒尺寸的细粒子状的成分。
被证明是有利的是,次级尖晶石(即,直到制品的第一次焙烧时才形成的尖晶石)的含量为至少10M.-%(相对于整个制品(bozogen aufdas Gesamtprodukt))。也就是说,相应的充填料除了预合成的MA尖晶石(作为细粒子状成分的组成成分)之外还包括可与MgO(例如MgO粗颗粒的MgO)反应的Al2O3,或者被使用以用于MA尖晶石的直接在原位置处的形成的细粒子状的Al2O3与MgO(成比例的)的混合物。
充填料中的游离的、细粒子状的Al2O3的含量此外还具有以下优点,即,游离的MgO的可能的所不希望的含量(尤其是细颗粒成分中的)在焙烧的中转变成MA尖晶石。
在这一点上,本发明力争获得这样的焙烧制品,即,该焙烧制品——除了MgO粗颗粒之外——从技术上的角度来看,不含有游离的MgO。在任何情况下,细粒子状的基体中的相应的含量应被如下地限制,即,其相对于整个制品而言,<1.0M.-%。
同样,焙烧制品的结构中的游离的氧化铝也应尽可能地被避免。
就制品——该制品的低温抗压强度可>50MPa(基于EN993-5)——改善的延展性而言,所述焙烧制品以MgO粗颗粒为主要的成分。这一点与常规的MA尖晶石砖相反,在常规的MA尖晶石砖中,尖晶石颗粒引起了结构的本来的柔性。MgO粗颗粒对充填料的处理也起到积极的作用。例如,与带有硬的MA尖晶石粗颗粒的充填料相比,在根据本发明的充填料的使用中,压模(Pressformen)的磨损(Verschleiss)明显地较低。
与DE 100 54 125A1的教导内容相反,根据本发明,孔不经由熔化相的升高的含量被填充,相反:两种结构相之间的裂缝状的孔对于制品的特性是相当重要的。在1500℃时,根据本发明的制品应形成<5%的熔化相。
存在于尖晶石基体中的MgO颗粒使得该结构如此地柔韧,以使得相应的制品,例如砖,甚至可用于回转窑(例如用于水泥生产的回转窑)中。
其它的应用可能性包括:
-用于玻璃熔炼罐的衬里的砖。
-用于玻璃罐的回热炉(Regenerator)中的砖(例如格子砖,(Topfsteine)),尤其是在这种回热炉的硫酸盐凝结区中,特别是在还原条件下。
焙烧制品的总的开放孔隙度通常地<20Vol.-%(%体积),经常<17Vol.-%,但是也可以为15Vol.-%(根据EN 993第1部分而确定)。
对于根据本发明的制品的结构而言很重要的裂缝状的孔(Poren)限定了——虽然不是完全地,但却在相应的粗颗粒表面的相当大的部分上——围绕着粗MgO颗粒的孔空间/孔晕(Porenraum/Porenhof)。
作为MgO-原材料,可例如使用合成的烧结氧化镁,但是熔融氧化镁(Schmelzmagnesia)或由天然菱镁矿(Naturmagnesit)焙烧成的MgO也是可以的。MgO粗颗粒(第二结构相的粒子)通常具有这样的颗粒尺寸,即,<8mm,大多数<6mm的,经常地甚至具有<4mm的颗粒尺寸。
焙烧制品应基本上由该两种结构相及位于其间的孔来表征。相应地,充填料应当包含尽可能少的除此之外的成分,通常<3%质量(<3Masse.-%)。
通常地(例如)利用临时粘结剂(例如木质素磺酸盐溶液Ligninsulfonatloesung)来进行充填料的处理。混合物然后被压成砖,被干燥并例如地在1500℃-1600℃下被焙烧。
图1显示了根据本发明的制品典型的结构图像,包括标注的部分放大图(图1a)。
结构相1,即,MA尖晶石基体,标注为1(或m),粗MgO颗粒(=第二结构相)标注为2(或k)。尖晶石基体由细粒子状的充填料成分在焙烧时形成。该结构包含大约10M.-%的次级尖晶石,该次级尖晶石直到焙烧时才形成。
粗MgO颗粒在其表面的较大范围(grosse Bereiche)上通过三维的裂缝状的孔(p)而与周围的基体分隔。这些孔在制品焙烧的过程期间通过结构相的不同的热膨胀特性及在原位置的尖晶石形成而形成。图1还显示了所采用的借助于反射光显微镜以确定结构相含量的方法的原理。在Radex-Rundschau 1988,第4卷,172-182页中所描述的方法允许通过直线交叉方法(Linienschnittmethode)来确定不同结构相的体积含量。在图1中标出了一条这种直线且其显示,在MgO粗颗粒的几乎所有表面上都存在有这种孔(p)。具体的评价按如下方式进行:切片(Anschliff)上被叠加有任意选择的测量线。沿着这些线测量切割的相,即,颗粒(k),孔/孔晕(p),以及基体(m),的弦长(Sehnenlaenge)。相的体积含量相应于相内的测量线在总的测量线上的份额,还可以参见等式[1]:
Vx=(∑Lx)/Lges |
[1]
Vx...相x的体积含量,单位[Vol.-%]
x...相:颗粒k、孔晕p、基体m
Lx...相x内的弦长
Lges...测量线的总长度
为得到有代表性且可再现的评价,每切片应有50至100条线被评价,其中,线沿不同的方向延伸。另外,应在坐标系的三个不同的方向上取至少三个切片作为基础。结构相及孔的体积含量从由此获得的单独数据的平均值计算中获得。
Claims (8)
1.一种焙烧的耐火制品,所述耐火制品在达1500℃的使用温度下形成少于5%质量的熔化相,所述耐火制品的结构包括MA尖晶石基体即第一结构相,在其中存在粒子尺寸d90>300μm的MgO粗颗粒即第二结构相,其中,该制品在>98%质量的程度上由MgO粗颗粒加上MA尖晶石基体组成且其中,在所述两种结构相之间形成三维的裂缝状的孔。
2.根据权利要求1所述的制品,其特征在于,所述裂缝状的孔在所述MgO粗颗粒的表面的多于50%上延伸。
3.根据权利要求1所述的制品,其特征在于,所述裂缝状的孔最多包括所述MgO粗颗粒的体积含量的1/20。
4.根据权利要求1所述的制品,其特征在于,带有达20Vol-%的开放孔隙度。
5.根据权利要求1所述的制品,其特征在于,带有≥50MPa的低温抗压强度。
6.根据权利要求1所述的制品,其特征在于,所述MgO粗颗粒的含量超过50%质量。
7.根据权利要求1所述的制品,其特征在于,所述MgO粗颗粒的含量在60%质量和80%质量之间。
8.根据权利要求1所述的制品,其特征在于,所述MgO粗颗粒的粒子尺寸d90>500μm。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102006040270A DE102006040270B4 (de) | 2006-08-28 | 2006-08-28 | Gebranntes feuerfestes Produkt |
DE102006040270.7 | 2006-08-28 | ||
PCT/EP2007/006998 WO2008025440A1 (de) | 2006-08-28 | 2007-08-08 | Gebranntes feuerfestes produkt |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101500964A CN101500964A (zh) | 2009-08-05 |
CN101500964B true CN101500964B (zh) | 2012-08-15 |
Family
ID=38890249
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2007800299257A Active CN101500964B (zh) | 2006-08-28 | 2007-08-08 | 焙烧的耐火制品 |
Country Status (14)
Country | Link |
---|---|
US (1) | US7939459B2 (zh) |
EP (1) | EP2057106B1 (zh) |
JP (1) | JP5149294B2 (zh) |
CN (1) | CN101500964B (zh) |
AU (1) | AU2007291592B2 (zh) |
BR (1) | BRPI0716400B1 (zh) |
CA (1) | CA2661071C (zh) |
DE (1) | DE102006040270B4 (zh) |
EA (1) | EA016194B1 (zh) |
ES (1) | ES2387415T3 (zh) |
MX (1) | MX2009000957A (zh) |
PL (1) | PL2057106T3 (zh) |
WO (1) | WO2008025440A1 (zh) |
ZA (1) | ZA200900695B (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI405742B (zh) | 2009-02-19 | 2013-08-21 | Corning Inc | 用於燒結大型耐火性物體的方法 |
US20100212359A1 (en) * | 2009-02-23 | 2010-08-26 | Hilary Tony Godard | Spinel isopipe for fusion forming alkali containing glass sheets |
FR3018804B1 (fr) | 2014-03-18 | 2016-03-25 | Saint Gobain Ct Recherches | Grains fondus d'aluminate de magnesium riche en magnesium. |
FR3040993A1 (fr) * | 2015-09-14 | 2017-03-17 | Saint-Gobain Centre De Rech Et D'Etudes Europeen | Grain fondu d'aluminate de magnesium riche en magnesium |
US10424012B2 (en) | 2016-10-11 | 2019-09-24 | The Toronto-Dominion Bank | Computing device and method for the temporal arrangement of data |
CN112811929A (zh) * | 2021-01-08 | 2021-05-18 | 武汉科技大学 | 一种SiC晶须增强的镁铝尖晶石透气耐火材料及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10054125A1 (de) * | 2000-10-31 | 2002-05-23 | Refratechnik Holding Gmbh | Feuerfester Förmkörper sowie Versatz und Verfahren zu seiner Herstellung |
WO2004048290A1 (de) * | 2002-11-22 | 2004-06-10 | Refractory Intellectual Property Gmbh & Co. Kg | Feuerfester keramischer formkörper |
WO2004065323A1 (de) * | 2003-01-17 | 2004-08-05 | Refractory Intellectual Property Gmbh & Co. Kg | Versatz zur herstellung eines feuerfesten keramischen formkörpers, daraus gebildeter formkörper und eine verwendung |
DE102004007062A1 (de) * | 2004-02-13 | 2005-09-01 | Refractory Intellectual Property Gmbh & Co. Kg | Gebranntes feuerfestes Erzeugnis und Versatz zu seiner Herstellung |
WO2007006350A1 (de) * | 2005-07-11 | 2007-01-18 | Refractory Intellectual Property Gmbh & Co. Kg | Gebranntes, keramisches, feuerfestes produkt |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DD279375A3 (de) * | 1982-07-15 | 1990-06-06 | Lutz Zachmann | Verfahren zur herstellung eines mikroporenhaltigen, mikrospinellhaltigen, hochverschleissfesten basischen feuerfestmaterials |
CA1219883A (en) * | 1982-12-20 | 1987-03-31 | Ronald R. Smyth | Ceramic composites with improved thermal shock resistance |
JPS6051659A (ja) * | 1983-08-30 | 1985-03-23 | ハリマセラミック株式会社 | ポ−ラスノズル |
DE3527789C3 (de) | 1985-08-02 | 1994-02-24 | Refratechnik Gmbh | Grobkeramischer Formkörper sowie dessen Verwendung |
JP3276061B2 (ja) * | 1996-11-19 | 2002-04-22 | 東京窯業株式会社 | 誘導炉 |
DE19803327C2 (de) * | 1998-01-29 | 1999-12-09 | Schott Glas | Verfahren zur Herstellung von keramischen hochtemperaturbeständigen Werkstoffen mit einem einstellbaren thermischen Ausdehnungskoeffizienten und deren Verwendung |
JP2000191363A (ja) * | 1998-12-25 | 2000-07-11 | Yotai Refractories Co Ltd | 耐スポ―リング性スピネル質れんが |
JP2001247380A (ja) * | 2000-03-01 | 2001-09-11 | Tokyo Seitetsu Kk | マグネシア・アルミナ質不定形耐火物 |
JP4234330B2 (ja) * | 2001-02-09 | 2009-03-04 | 品川白煉瓦株式会社 | 不定形耐火組成物 |
JP2004149396A (ja) * | 2002-10-30 | 2004-05-27 | Yotai Refractories Co Ltd | 塩基性耐火物 |
-
2006
- 2006-08-28 DE DE102006040270A patent/DE102006040270B4/de active Active
-
2007
- 2007-08-08 EP EP07786616A patent/EP2057106B1/de active Active
- 2007-08-08 WO PCT/EP2007/006998 patent/WO2008025440A1/de active Application Filing
- 2007-08-08 CA CA2661071A patent/CA2661071C/en not_active Expired - Fee Related
- 2007-08-08 US US12/375,292 patent/US7939459B2/en active Active
- 2007-08-08 BR BRPI0716400-9A patent/BRPI0716400B1/pt active IP Right Grant
- 2007-08-08 ES ES07786616T patent/ES2387415T3/es active Active
- 2007-08-08 MX MX2009000957A patent/MX2009000957A/es active IP Right Grant
- 2007-08-08 JP JP2009525941A patent/JP5149294B2/ja active Active
- 2007-08-08 AU AU2007291592A patent/AU2007291592B2/en not_active Ceased
- 2007-08-08 PL PL07786616T patent/PL2057106T3/pl unknown
- 2007-08-08 EA EA200900075A patent/EA016194B1/ru not_active IP Right Cessation
- 2007-08-08 CN CN2007800299257A patent/CN101500964B/zh active Active
-
2009
- 2009-01-29 ZA ZA200900695A patent/ZA200900695B/xx unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10054125A1 (de) * | 2000-10-31 | 2002-05-23 | Refratechnik Holding Gmbh | Feuerfester Förmkörper sowie Versatz und Verfahren zu seiner Herstellung |
WO2004048290A1 (de) * | 2002-11-22 | 2004-06-10 | Refractory Intellectual Property Gmbh & Co. Kg | Feuerfester keramischer formkörper |
WO2004065323A1 (de) * | 2003-01-17 | 2004-08-05 | Refractory Intellectual Property Gmbh & Co. Kg | Versatz zur herstellung eines feuerfesten keramischen formkörpers, daraus gebildeter formkörper und eine verwendung |
DE102004007062A1 (de) * | 2004-02-13 | 2005-09-01 | Refractory Intellectual Property Gmbh & Co. Kg | Gebranntes feuerfestes Erzeugnis und Versatz zu seiner Herstellung |
WO2007006350A1 (de) * | 2005-07-11 | 2007-01-18 | Refractory Intellectual Property Gmbh & Co. Kg | Gebranntes, keramisches, feuerfestes produkt |
Also Published As
Publication number | Publication date |
---|---|
JP2010501462A (ja) | 2010-01-21 |
DE102006040270B4 (de) | 2009-06-10 |
ES2387415T3 (es) | 2012-09-21 |
DE102006040270A1 (de) | 2008-03-20 |
CA2661071C (en) | 2012-11-13 |
EP2057106B1 (de) | 2012-06-27 |
AU2007291592A1 (en) | 2008-03-06 |
JP5149294B2 (ja) | 2013-02-20 |
WO2008025440A1 (de) | 2008-03-06 |
ZA200900695B (en) | 2010-03-31 |
AU2007291592B2 (en) | 2012-01-19 |
CN101500964A (zh) | 2009-08-05 |
BRPI0716400A2 (pt) | 2013-09-17 |
EA016194B1 (ru) | 2012-03-30 |
PL2057106T3 (pl) | 2012-10-31 |
CA2661071A1 (en) | 2008-03-06 |
US20100016146A1 (en) | 2010-01-21 |
US7939459B2 (en) | 2011-05-10 |
MX2009000957A (es) | 2009-02-06 |
BRPI0716400B1 (pt) | 2018-04-10 |
EP2057106A1 (de) | 2009-05-13 |
EA200900075A1 (ru) | 2009-08-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101500964B (zh) | 焙烧的耐火制品 | |
RU2496745C2 (ru) | Спеченный огнеупорный материал на основе карбида кремния с нитридом кремния в качестве связующего вещества | |
US5559064A (en) | Chrome-free brick | |
US4585485A (en) | Refractory sliding nozzle plate | |
EP0877719B1 (en) | Formation of a refractory repair mass | |
US2949704A (en) | Refractory materials | |
US5851941A (en) | Si/SiC-based sintered material having excellent corrosion resistance and kiln furniture | |
JP3667403B2 (ja) | βアルミナ質電鋳耐火物 | |
CA2706152C (en) | Fireproof ceramic mix, fireproof ceramic molded body formed of said mix and use thereof | |
EP2640878B1 (en) | Inorganic fiber | |
GB2280429A (en) | Silica refractory mix | |
JP3343297B2 (ja) | 内張り用焼成耐火れんが | |
EP3307695B1 (en) | Refractories for applications in combustion chambers intended for producing energy and/or waste disposal | |
CN1319905C (zh) | 氧化镁-氧化锆砖的应用 | |
JPH10218676A (ja) | βアルミナ質電鋳耐火物 | |
Kerber et al. | Insulating refractories based on rice husk ashes functionalized by flame-sprayed alumina coatings for steel ingot casting | |
Chaudhary et al. | Failure analysis of bullnose refractory in reheating furnace of Hot Strip Mill | |
Mandal | Investigation of Zinc Aluminate as a Refractory Material | |
Koenig et al. | Ceramics | |
JP2017523122A (ja) | ガラス溶融槽の上部構造内に投入するための耐火材料の製造方法並びに耐火成形体の分光放射強度の向上方法 | |
Kumari | MULTIDIMENSIONAL PERSPECTIVES OF INDUSTRIAL CERAMICS AND ALLIED ASPECTS | |
JPS62241869A (ja) | ジルコニア質耐火物の製造方法 | |
Prigent | Study of impregnation-corrosion of Al 2 O 3-MgO refractory castables by secondary metallurgy steel ladle slags. | |
Vynatheya et al. | Quantitative estimation of mullite in alumina based porcelain insulators samples | |
Houseman et al. | Electric Arc Furnaces-2 Roof and Electrodes |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |