KR100307064B1 - gas input type porosity refractory composile - Google Patents
gas input type porosity refractory composile Download PDFInfo
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- KR100307064B1 KR100307064B1 KR1019990012815A KR19990012815A KR100307064B1 KR 100307064 B1 KR100307064 B1 KR 100307064B1 KR 1019990012815 A KR1019990012815 A KR 1019990012815A KR 19990012815 A KR19990012815 A KR 19990012815A KR 100307064 B1 KR100307064 B1 KR 100307064B1
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- porous refractory
- mullite
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 19
- 239000011819 refractory material Substances 0.000 claims abstract description 18
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 10
- 239000011707 mineral Substances 0.000 claims abstract description 10
- 239000004927 clay Substances 0.000 claims abstract description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000007664 blowing Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 33
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 239000012798 spherical particle Substances 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000010459 dolomite Substances 0.000 claims description 2
- 229910000514 dolomite Inorganic materials 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 8
- 230000035939 shock Effects 0.000 abstract description 10
- 230000008595 infiltration Effects 0.000 abstract description 7
- 238000001764 infiltration Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 6
- 238000004901 spalling Methods 0.000 description 6
- 238000005245 sintering Methods 0.000 description 5
- 230000005587 bubbling Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- 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
- 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
- C04B35/10—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 aluminium oxide
- C04B35/101—Refractories from grain sized mixtures
- C04B35/106—Refractories from grain sized mixtures containing zirconium oxide or zircon (ZrSiO4)
-
- 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
- C04B35/16—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 silicates other than clay
- C04B35/18—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 silicates other than clay rich in aluminium oxide
- C04B35/185—Mullite 3Al2O3-2SiO2
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- 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
- C04B38/08—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding porous substances
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- 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
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
- C04B2235/3248—Zirconates or hafnates, e.g. zircon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
본 발명은 금속 용융물에 가스를 취입하여 정련시키는데 필요한 다공성 내화재 조성물에 대하여 내용손 및 내침윤성을 증대시키고, 강도 등 내열 충격을 향상시키는 것에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to increasing the solvent resistance and infiltration resistance of a porous refractory material composition necessary for blowing gas into a metal melt and refining it, and to improving heat shock such as strength.
이에 따른 구성은 소결 또는 전융 알루미나 또는 멀라이트 30-160 중량부, 산화크롬(Cr2O3) 1-8 중량부, 점토와 프릿트 2-6 중량부, CaO, MgO 함유 광물 1-10 중량부로 하거나 여기에 가소 알루미나를 5-30 중량부 첨가 하거나 또는 여기에 알루미나, 지르코니아-멀라이트 혼합물을 10-50 중량부 첨가시키서된 가스 취입형 다공성 내화재 조성물로 이루어진다The composition is sintered or molten alumina or mullite 30-160 parts by weight, chromium oxide (Cr 2 O 3 ) 1-8 parts by weight, clay and frit 2-6 parts by weight, CaO, MgO containing minerals 1-10 parts by weight Or a gas blown porous refractory composition prepared by adding 5-30 parts by weight of calcined alumina thereto or by adding 10-50 parts by weight of alumina and zirconia-mullite mixture thereto.
Description
본 발명은 용탕(熔湯)에 가스 취입을 위한 다공성 내화재 조성물에 관한 것으로, 특히 다공성 내화재가 예열이나 주조시 열 충격에 의한 균열이 없고, 물리적 및 화학적 반응에 대한 내용손 및 내침윤성을 갖게 하는데 적합한 다공성을 갖는 내화재 조성물에 관한 것이다.The present invention relates to a porous refractory material composition for blowing gas into a molten metal, and in particular, the porous refractory material does not have cracks due to thermal shock during preheating or casting, and has a resistance to damage and infiltration against physical and chemical reactions. A fire retardant composition having a suitable porosity.
철강 및 비철금속 제조시 래들(Ladle)이나 턴디쉬(Tundish)등 각종 정련로에서는 용융물에 아르곤(Ar)이나 질소(N2) 등의 가스를 포러스(porous) 내화재를 통하여 취입하여 버블링시킴으로서 불순물 등의 비금속 개재물을 부상시켜 제거된 청정하고 균일한 용융물을 얻는다.In the manufacture of steel and nonferrous metals, various refinery furnaces such as ladle and tundish blow bubbles of argon (Ar) and nitrogen (N 2 ) into the melt through a porous refractory material and bubbling them to form impurities. The non-metallic inclusions of flotation are floated to obtain a clean, uniform melt that has been removed.
이러한 가스투입용 다공성(porous) 내화재가 갖추어야 할 기본 특성은 통기량 및 기포 발생능의 버블링 기능 이외에 사용중 용강류가 비금속 개재물에 의한 화학적, 물리적 침식에 견디어야 하고 사용전 예열이나 주조시 열 충격에 의한 균열이 없어야 하며 용강부착, 침윤이 이루어지지 않아야 한다.In addition to the bubbling function of air flow rate and bubble generation capability, the basic characteristics of the porous refractory material for gas injection are that the molten steel must withstand chemical and physical erosion by non-metallic inclusions during use, and the thermal shock during preheating or casting. There should be no cracking and no molten steel adhesion or infiltration.
상기 요구 조건 중 가장 중요한 버블링 기능 향상은 다공성 내화재의 미세 구조제어 등 기공 크기에 의존한다.The most important improvement of the bubbling function among the above requirements depends on the pore size such as microstructure control of the porous refractory material.
내화재 기공을 통과한 가스에 따른 버블은 그 크기가 클수록 개재물의 포집능은 저하되나 부상 분리능은 높아지므로 이에 대한 최적 크기의 내화재의 미세 구조, 즉 적정한 기공 크기와 기공율이 요망된다.The larger the size of the bubble that passes through the pores of the refractory material, the lower the trapping ability of the inclusions, but the higher the separation resolution. Therefore, the fine structure of the refractory material of the optimal size, that is, the appropriate pore size and porosity is required.
기공 크기는 제조되는 Porous 내화재의 입자 크기에 의해 결정되고, 소결제, 소성온도, 가압력 등에 따라서도 변화된다.The pore size is determined by the particle size of the porous refractory material to be produced and also changes depending on the sintering agent, the firing temperature, the pressing force, and the like.
균일한 기공경의 분포는 형성되는 버블 크기가 균일하게 되어 부상시 합체되는 문제를 최소화 할 수 있다.Uniform pore diameter distribution can minimize the problem of coalescing when the bubble size is formed uniform.
사용 수명의 향상은 용강과 비금속 개재물과의 내용성을 높여야 하고 이의 개선을 위해서는 낮은 기공율과 적당한 기공경 크기가 바람직하다.In order to improve the service life, it is necessary to increase the resistance between molten steel and non-metallic inclusions, and low porosity and proper pore size are desirable for the improvement.
한편 물리적인 요소 이외에 용강과 비금속 개재물에 대한 화학적 반응에 의한 용손을 개선하기 위해서는 화학 조성의 제어가 필요하다.On the other hand, in order to improve the melt damage caused by chemical reactions to molten steel and non-metallic inclusions in addition to physical factors, control of chemical composition is required.
특히 용강의 침윤과 산화에 의한 Fe산화물과 개재물에 의한 침윤은 내화재와의 구성 성분과 저융물의 형성 및 침윤에 따른 통기성의 저하를 초래하므로 이에 대한 성분 제어의 배려가 필요하다.In particular, infiltration of Fe oxides and inclusions by infiltration and oxidation of molten steel causes deterioration of air permeability due to formation and infiltration of constituents and low melts with refractory materials, and consideration of component control is therefore required.
한편 다회 사용시 또는 주조중 산소에 의한 개공이나 부착된 잔탕의 제거시 온도가 급격히 상승되고 내화재의 용손이 급속히 이루어지므로 산소세척(이하 산세)에 대한 높은 용융점을 갖는 성분이 필요하다.On the other hand, since the temperature is rapidly increased and the melting of the refractory material is rapidly increased during the use of multiple times or during the removal of pores by the oxygen during casting, the components having a high melting point for oxygen washing (hereinafter pickling) are necessary.
마지막으로 열 스폴링에 의한 균열은 주입되는 가스의 누기와 용강의 침윤 및 유출의 문제가 발생되므로 입자 형상의 개선과 미세 조직의 개선, 저팽창성 광물에 의한 열충격 문제의 개선이 이루어져야 한다.Finally, cracks due to thermal spalling cause problems of leakage of injected gas, infiltration and leakage of molten steel, and improvement of particle shape, microstructure, and thermal shock due to low-expansion minerals.
이와 관련한 종래의 내화재는 소결 또는 전융 알루미나(Al2O3) 또는 멀라이트(Mullite)를 입경별로 하여 75∼100 중량부, 가소 알루미나 5-10 중량부, 점토(clay)와 프리트(frit) 2-6 중량부로 조성되고 있다.Conventional refractory materials in this regard are sintered or molten alumina (Al 2 O 3 ) or mullite (Mullite) by particle size of 75 to 100 parts by weight, plastic alumina 5-10 parts by weight, clay (clay) and frit (frit) 2 It is comprised at -6 weight part.
그러나 상기와 같은 종래의 내화재는 내열 충격성을 비롯한 강도 및 내용성(耐熔性), 내스폴링성이 불충분하고, 기공경 분포의 불균일로 버블 형성능이 충분치 않는 등의 문제점이 있다.However, such a conventional fireproof material has problems such as insufficient strength, solvent resistance, spalling resistance including thermal shock resistance, and insufficient bubble formation ability due to uneven distribution of pore diameter.
본 발명은 상기한 종래의 문제점을 개선하기 위한 것으로, 원료의 조성 및 입경 분포를 적절히 조절하여 미세 구조의 제어로 적절한 기공률 및 기공 크기를 갖게 함으로서 버블링 효과를 향상시킴과 함께 내용성, 내스폴링성 및 내열 충격성등 강도가 증대된 다공성 내화재를 얻고자 하는데 그 목적이 있다.The present invention is to improve the above-mentioned problems, and by appropriately adjusting the composition and particle size distribution of the raw material to have a proper porosity and pore size by controlling the microstructure to improve the bubbling effect, as well as resistance, spalling The purpose is to obtain a porous refractory material with increased strength, such as resistance and thermal shock resistance.
상기한 목적을 달성하기 위한 본 발명의 제 1 발명은 소결 또는 전융 알루미나(Al2O3) 또는 멀라이트가 30-160 중량부, 산화크롬(Cr2O3)이 1-8 중량부, 점토와 프릿트(frit)가 2-6 중량부, CaO와 MgO 함유 광물이 1-10 중량부로 조성됨을 특징으로 하는 가스 취입형 다공성 내화재 조성물로 이루어진다.The first invention of the present invention for achieving the above object is 30-160 parts by weight of sintered or molten alumina (Al 2 O 3 ) or mullite, 1-8 parts by weight of chromium oxide (Cr 2 O 3 ), clay And frit is composed of a gas blown porous refractory material, characterized in that 2-6 parts by weight, and CaO and MgO-containing minerals are composed of 1-10 parts by weight.
상기한 조성에서 소결 또는 전융 알루미나 또는 멀라이트(Mullite) 30∼160중량부는 입경 분포를 적절히 배합하여 사용함이 바람직하다.In the above composition, 30 to 160 parts by weight of sintered or molten alumina or mullite is preferably used in combination with the particle size distribution.
즉, 3-1㎜ 입경은 10 중량부 이하로 하고, 1-0.2㎜ 입경의 경우는 20∼80 중량부로 하며, 0.2㎜ 이하 입경의 경우는 70 중량부 이하로 한다.That is, 3-1 mm particle diameter shall be 10 weight part or less, 20-80 weight part in the case of 1-0.2 mm particle diameter, and 70 weight part or less in the case of 0.2 mm or less particle diameter.
상기한 입경을 갖는 입자 형태는 구형 또는 각형으로 하거나 그 형태를 혼합시켜 사용할 수 있다.The particle form having the above-mentioned particle diameter may be used in the form of a sphere or a square or a mixture of the forms.
그리고 산화크롬(Cr2O3)의 경우는 50㎛ 이하 입경으로 함이 바람직하다.In the case of chromium oxide (Cr 2 O 3 ), the particle size is preferably 50 μm or less.
상기 CaO, MgO를 함유한 광물로서는 활석(Talc), 백운석(Dolomite), 세피얼라이트(Sepiolite)를 들수 있으며, 바람직하게 이들 광물의 입경이 0.3㎜ 이하가 좋다.Examples of the CaO and MgO-containing minerals include talc, dolomite, and sepiolite, and the particle diameter of these minerals is preferably 0.3 mm or less.
그리고 본 발명의 제 2 발명은 상기한 제 1 발명의 조성에 추가하여 50㎛ 이하의 입경을 갖는 가소 알루미나를 5-30 중량부 조성시킬 수 있다.In addition, in the second invention of the present invention, 5-30 parts by weight of calcined alumina having a particle size of 50 µm or less can be added in addition to the composition of the first invention.
또한 본 발명의 제 3 발명은 상기한 제 2 발명에 추가하여 소결 또는 전융 알루미나, 지르코니아 - 멀라이트를 10-50 중량부 조성시킨다.In addition, the third invention of the present invention comprises 10-50 parts by weight of sintered or molten alumina and zirconia-mullite in addition to the second invention described above.
상기한 소결 또는 전융 알루미나, 지르코니아 - 멀라이트 중에는 2-1㎜ 입경의 것을 5-25 중량부로 하고, 1-0.2㎜ 입경을 5-25 중량부로 함이 바람직하다.In the above-mentioned sintered or molten alumina and zirconia-mullite, it is preferable to make the thing of 2-1 mm particle diameter into 5-25 weight part, and to make 1-0.2 mm particle diameter into 5-25 weight part.
상기한 지르코니아 - 멀라이트 중에는 ZrO2가 27-39wt%, Al2O3가 40-46wt%, SiO2가 15-20wt% 함유된 품위를 갖게하여 사용함이 바람직하다.Among the zirconia-mullites described above, ZrO 2 is preferably 27-39 wt %, Al 2 O 3 is 40-46 wt %, and SiO 2 is 15-20 wt %.
본 발명이 종래와 상이한 점은 제 1 발명과 같이 Cr2O3를 1-8 중량부로 함과함께 소결조제로서 CaO, MgO 함유 광물을 1-10 중량부로 조성시키고 있으며, 또한 0.2㎜ 입경 분포를 갖는 소결 또는 전융 알루미나 또는 멀라이트 사용량을 증대시키는데 있다.The present invention differs from the prior art in that 1-8 parts by weight of Cr 2 O 3 is contained as well as 1-10 parts by weight of CaO and MgO-containing minerals as a sintering aid, and a 0.2 mm particle size distribution. To increase the amount of sintered or molten alumina or mullite having.
여기서 Cr2O3는 내용선 개선을 위하여 첨가되는 것으로 이는 Fe산화물과 비금속 개재물과의 반응에 의해 저융물 형성을 억제하여 고융점, 고점도의 화합물을 형성하고, 산세시 고온에 의한 국부 용손을 억제시킨다.Here, Cr 2 O 3 is added to improve the content line, which suppresses low melt formation by the reaction of Fe oxide and non-metallic inclusions to form a high melting point and high viscosity compound, and suppresses local loss due to high temperature during pickling. Let's do it.
그러나 그 첨가량이 8 중량부를 초과하면 내열 스폴링성 문제의 야기로 내열 충격성이 저하되므로 8 중량부 이하로 함이 바람직 하다.However, if the added amount exceeds 8 parts by weight, the thermal shock resistance is lowered due to the problem of heat spalling resistance, so it is preferable to set it to 8 parts by weight or less.
소결조제로서 첨가되는 CaO, MgO 함유 광물은 주 구성 성분인 알루미나 (Al2O3)와 비교적 저온에서 소결이 이루어지므로 제품의 강도 발현은 물론이고 용강류 마모에 의한 내용성이 현저히 개선될 수 있다.CaO and MgO-containing minerals added as a sintering aid are sintered at a relatively low temperature with alumina (Al 2 O 3 ), which is a main component, and thus the strength of the product and the durability of molten steel wear can be significantly improved. .
또한 입자 형태가 구형의 것으로 제조된 제품은 기공경 분포는 균일하나 소성후에 강도 발현이 곤란하므로 점토와 Frit의 첨가와 CaO, MgO 함유 광물 첨가시 강도 발현 효과가 높아 구형의 입자 제품에서 발생되는 문제점의 보완이 가능하다.In addition, products made of spherical particles have a uniform pore diameter distribution, but it is difficult to develop strength after firing. Therefore, the effect of high strength expression upon the addition of clay and frit and the addition of CaO and MgO-containing minerals results in spherical particle products. It is possible to supplement.
또한 본 발명은 상기한 특성을 갖는 제 1 발명에 50㎛ 이하 입경을 갖는 가소 알루미나를 5-30 중량부 첨가시켜 사용하는데 특징이 있다(제 2 발명).In addition, the present invention is characterized in that 5-30 parts by weight of calcined alumina having a particle size of 50 µm or less is added to and used in the first invention having the above-described characteristics (second invention).
초미분 가소 알루미나는 입간 결합력을 개선하므로(소결성 향상) 강도가 증가된다.Ultra-fine calcined alumina improves interdental bonding (improving sintering) and thus increases strength.
그러나 너무 과량(30 중량부 이상) 첨가시는 통기량이 저하되므로 30 중량부이하로 한다.However, when the excess amount (more than 30 parts by weight) is added, the amount of air flow is reduced to 30 parts by weight or less.
또한 본 발명은 제 2 발명에 소결 또는 전융 알루미나, 지르코니아 - 멀라이트를 첨가함으로서 내열 충격성 개선이 가능하다(제 3 발명).In addition, the present invention can improve the thermal shock resistance by adding sintered or molten alumina and zirconia-mullite to the second invention (third invention).
즉, 내열 스폴링성은 저팽창이고 열간에서 결정전이에 따른 팽창, 수축에 따른 열충격 흡수가 가능한 지르코니아 - 멀라이트계 원료를 적용시 내열 스폴링성이 개선될 수 있으며, 바람직하게는 Al2O340-46wt%, ZrO227-39wt%, SiO215-20wt% 함유한 품위를 갖는 지르코니아 - 멀라이트를 15-50 중량부 사용한다.That is, the thermal spalling property can be improved when applying a zirconia-mullite-based raw material that is low expansion and thermal shock absorption due to expansion and contraction due to crystal transition in the hot heat, preferably Al 2 O 3 15-50 parts by weight of zirconia-mullite having a content containing 40-46 wt %, ZrO 2 27-39 wt %, and SiO 2 15-20 wt % is used.
상기한 본 발명에서 증대되는 압축강도 발현을 위한 바람직한 경우는 소결 또는 전융 알루미나 또는 멀라이트 30-160 중량부 내에는 3-1㎜ 입경으로서 각형의 입자가 10 중량부 이하이고, 1-0.2㎜ 입경으로서 구형의 입자가 20-80 중량부이고, 0.2㎜ 이하 입경으로서 각형의 입자가 10-70 중량부이다.The preferred case for increasing the compressive strength in the present invention described above is 30-1160 parts by weight of sintered or molten alumina or mullite, with a particle diameter of 3-1 mm, 10 parts by weight or less, and 1-0.2 mm particle size. 20 to 80 parts by weight of spherical particles, and 10 to 70 parts by weight of square particles with a particle diameter of 0.2 mm or less.
(표 1) 및 (표 2)는 본 발명에 따른 실시예를 나타낸 것이다.Table 1 and Table 2 show examples according to the present invention.
본 실시예에 (1-5)에 나타난 바와같이 본 발명은 종래에 비해 물성을 비롯한 내열 스폴링성, 버블 형성능, 내용성 등이 우수함을 알 수 있다.As shown in the present embodiment (1-5), it can be seen that the present invention has superior heat spalling resistance, bubble forming ability, and solvent resistance, including physical properties, as compared with the prior art.
* 1600℃ 버너 가열에 의한 균열 발생기간 및 균열크기, 개수 비교* Comparison of crack initiation period, crack size and number by 1600 ℃ burner heating
** 기포제를 바른 다음 0.1Bar에서 형성되는 버블 형성능 비교** Comparison of bubble forming ability at 0.1Bar after applying foaming agent
*** 고주파 유도로 1600℃에서 2시간 용강과 Slag를 반응시킨 후 내침식성 비교(기존을 100으로 하고 값이 낮을수록 우수)*** Comparison of erosion resistance after reacting molten steel and slag at 1600 ° C for 2 hours at high frequency induction furnace.
이상에서와 같이 본 발명은 주성분을 알루미나(Al2O3)로 한 원료에 미세 입경을 갖는 산화크롬과 가소 알루미나 또는 지르코니아 - 멀라이트와 소결조제 등을적절히 배합시킴과 함께 알루미나 입경을 조절하므로서 내용성 및 강도가 증대되고 내열 충격성이 향상된 효과를 갖는 다공성 내화재를 얻게 된다.As described above, the present invention provides a raw material containing alumina (Al 2 O 3 ) as the main component, by appropriately mixing chromium oxide and plasticized alumina or zirconia-mullite with a sintering aid, etc. It is possible to obtain a porous refractory material having an effect of increased resistance and strength and improved thermal shock resistance.
Claims (9)
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