KR970005890B1 - Sintering material for refractory - Google Patents
Sintering material for refractory Download PDFInfo
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- KR970005890B1 KR970005890B1 KR1019940016587A KR19940016587A KR970005890B1 KR 970005890 B1 KR970005890 B1 KR 970005890B1 KR 1019940016587 A KR1019940016587 A KR 1019940016587A KR 19940016587 A KR19940016587 A KR 19940016587A KR 970005890 B1 KR970005890 B1 KR 970005890B1
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- C—CHEMISTRY; METALLURGY
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- 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
- C04B35/14—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 silica
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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- F27D1/16—Making or repairing linings increasing the durability of linings or breaking away linings
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- 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
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
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- 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
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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- 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
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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- 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
- C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
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Abstract
Description
제1도는 본 발명에서 사용된 용사재료 분말의 입도분포를 나타내는 그래프.1 is a graph showing the particle size distribution of the thermal spraying powder used in the present invention.
본 발명은 산업로에 사용되고 있는 각종 내화물에 대한 열간 보수용 화염용사재료에 곤한 것으로서, 보다 상세하게는 코크스로 및 유리 용해로등의 내화물의 손상부위를 열간 화염용사보수시 시공체와 열간 선팽창율이 거의 동일하여 내수명성이 우수한 화염용사재료에 고나한 것이다.The present invention is to be used in hot repair flame spraying materials for various refractory materials used in industrial furnaces, more specifically, in the hot flame spraying repair the damaged parts of the refractory, such as coke oven and glass melting furnace, It is almost the same, and is excellent in flame spraying material which is excellent in durability.
일반적으로 산업로등에 사용되고 있는 각종 내화물은 계속적인 가열, 냉각의 반복적인 과정을 통해 열변화가 심하고, 이로 인하여 내화물에 균열 및 마모등이 발생하여 내화물이 손상을 입게 된다. 특히, 코크스로의 문부근에서는 다른 부분보다도 더욱 열 변동이 심하기 때문에 그 손상정도가 크다.In general, various refractory materials used in industrial furnaces undergo severe heat changes through repeated processes of continuous heating and cooling, resulting in cracking and abrasion of the refractory material, thereby causing a refractory damage. In particular, since the heat fluctuation is more severe in the vicinity of the door to the coke oven than other parts, the degree of damage is large.
이러한 내화손상부위를 열간에서 화염용사보수하는 경우 사용되는 화염용사 재료는 적당한 용융성이 있어야 할 뿐만 아니라 부착력이 높고 내마모성이 우수하여야 하며, 특히 시공체는 모재와 유사한 성질이 요구되고 있다.The flame spraying material used in the case of hot-spraying fire-resistant damaged parts should not only have proper meltability but also have high adhesion and wear resistance. In particular, the construction body is required to have properties similar to the base metal.
종래 이러한 조건을 만족하기 위해 제안된 열간보수용 화염용사재료의 대표적인 예로서, SiO2- A1203-MgO계 저팽창성 화염용사재료(일특공소 61-4790호) 및 MgO-A1203계 분말용사재료(국내공개특허공보 94-2197호)등을 들 수 있다.As a representative example of a hot repair flame spray material proposed to satisfy such a condition, SiO 2 -A1 2 0 3 -MgO-based low-expansion flame spray material (Japanese special application 61-4790) and MgO-A1 2 0 3 type powder spraying material (Domestic Patent Publication No. 94-2197) etc. are mentioned.
즉, 상기 SiO2-A12O3-MgO 계 저팽창성 화염용사재료는 SiO2: 45-70wt%, A12O3: 15-40 wt%, MgO : 10-25wt% 및 기타 불가피한 불순물이 5wt%이하로 함유되고 입도가 0.5mm이하인 분말로서, 열간 선팽창율이 적어 저팽창성면에서는 잇점이 있으나 코크스로 모재등의 손상내화물에 부착되면 온도변화에 의해 부착된 접착면이 박리되기 쉬우며, 분말이 미분으로 구성되므로 작업시 손실이 많아 비경계적이고 분진 공해를 일으키는 단점이 있다.That is, the SiO 2 -A1 2 O 3 -MgO-based low-expansion flame spray material is SiO 2 : 45-70wt%, A1 2 O 3 : 15-40 wt%, MgO: 10-25wt% and other unavoidable impurities 5wt Containing less than% and particle size less than 0.5mm, it has the advantage of low thermal expansion because of low thermal expansion rate, but when adhered to damaged refractory such as coke oven base material, the adhered surface is easily peeled off due to temperature change. Since it is composed of this derivative, there are many disadvantages in the operation, which causes non-boundary and dust pollution.
또한, 상기 공업요로의 열간보수용으로 제안된 MgO-A12O3계 분말용사재료는 입경 30um이하의 MgO 분말을 45-80wt% 함유한 MgO-A12O3계 분말용사재료로서, 이러한 용사재를 사용하면 치밀한 용사시공체를 얻을수 있으나, 각종 염기성 내화물에 적용되는 것이며 코크스로등의 모재 재질과는 큰 차이가 있어 코크스등의 내화연와의 손상부위를 보수할 때 열간선팽창율의 차이로 내수명성을 기대하기 힘든 단점이 있다.In addition, the MgO-A1 2 O 3 powder spraying material proposed for hot repair of the industrial furnace is a MgO-A1 2 O 3 powder spraying material containing 45-80wt% of MgO powder having a particle diameter of 30um or less. If you use ash, you can get dense sprayed body, but it is applied to various basic refractory materials, and it is very different from the base material such as coke oven. When repairing damaged parts with refractory smoke such as coke, It's hard to expect a reputation.
따라서, 본발명은 종래의 화염용사재료의 단점을 해결하기 위하여 제안된 것으로서, 화염용사 분체의 조성 및 그 입도를 제어하여 코크스등의 내화연와의 손상부위를 보수할 때 그 내화연와의 열간 선팽창율이 거의 같고 내수명성이 우수한 화염용사재료를 제공하고자 하는데, 그 목적이 있다.Therefore, the present invention has been proposed to solve the disadvantages of the conventional flame spray material, and the thermal linear expansion rate with the fire resistance when repairing the damaged area with the refractory smoke such as coke by controlling the composition and particle size of the flame spray powder The purpose is to provide a flame spraying material having almost the same and excellent durability.
이하, 본 발명을 설명한다.Hereinafter, the present invention will be described.
본 발명은 중량%은, SiO2: 85-95%, A12O3: 3.0-5.0%, CaO : 0.5-2.0%, Na2O+K2O : 1.0%이하 및 기타 불가피한 불순물로 조성되고, 입경이 1.0mm이하인 분말로 구성됨을 특징으로 하는 산업로 열간보수용 화염용사재료에 관한 것이다.In the present invention, the weight percent is SiO 2 : 85-95%, A1 2 O 3 : 3.0-5.0%, CaO: 0.5-2.0%, Na 2 O + K 2 O: 1.0% or less and other unavoidable impurities The present invention relates to a flame spraying material for an industrial furnace, characterized in that it is composed of a powder having a particle diameter of 1.0 mm or less.
이하 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 화염용사재료의 주성분인 SiO2의 함유량은 85-95중량%(이하, 단지 %라 한다.)로 제한함이 바람직한데, 그 이유는 SiO2의 함유량이 85%이하로 되면 SiO2양의 부족으로 내화도가 1400∼1500℃정도의 저용융점의 시공체를 만들고 비정질상으로 되며 모재인 규석 내하물과의 이질적인 상변화로 생성되며, 95%이상으로 되면 1700℃ 정도의 고용융점의 시공체가 생성될 뿐만 아니라 손상 모재와 이질적인 성분이 되며 부착량도 좋지 못하기 때문이다.The content of SiO 2 , which is the main component of the flame spray material according to the present invention, is preferably limited to 85 to 95% by weight (hereinafter, referred to simply as%), because the SiO 2 content is 85% or less. 2 Lack of quantity makes fireproof body with low melting point of about 1400 ~ 1500 ℃ and becomes amorphous phase, and is produced by heterogeneous phase change with silica material of base material, and when it is over 95%, construction of high melting point of about 1700 ℃ Not only is a sieve formed, it is a heterogeneous component with the damaged base material and the adhesion amount is not good.
상기 A12O3는 시공체를 저융점화 시키는 성분으로서, 그 함유량이 5.0%이상이 되면, 시공체의 융점 및 내화도가 낮아져서 내식성 및 내마모성이 떨어지므로 A12O3의 성분 함유량은 적을수록 바람직하나 용사재의 원료 구성 성분상 3.0%이하로 하는 것은 제조비용이 상승을 초래하므로, 상기 A12O3는 3.0-5.0%로 제한함이 바람직하다.The A1 2 O 3 is a component to the melting point-lowering a spray-applied product, when the content is more than 5.0% lowers the melting point and the fire resistance of the construction material corrosion-resistant and wear resistance because the dropped component content of A1 2 O 3 is the less preferred Since the manufacturing cost increases because the raw material constituent of the thermal spraying material is 3.0% or less, the A1 2 O 3 is preferably limited to 3.0-5.0%.
상기 CaO는 용사재중 SiO2상이 트리디마이트(tridymite)에서 크리스토발라이트(Crystobalite)로 전이하는 것을 촉진시키는 알카리류의 결정촉매제로서 역할을 하게 되는데, 그 함유량이 0.5%이하로 되거나, 2%이상이 되면 상기 SiO2상전이가 미흡하여 내마모성 및 열팽창성이 떨어지므로 상기 CaO의 함유량은 0.5-2.0%로 제한함이 바람직하다.The CaO serves as a crystal catalyst for alkalis that promotes the transition of the SiO 2 phase from tridymite to cristobalite in the thermal spray material, and when the content is less than 0.5% or more than 2% Since the SiO 2 phase transition is insufficient and wear resistance and thermal expansion property are inferior, the content of CaO is preferably limited to 0.5-2.0%.
상기 알카리 금속산화물인(Na2O+K2O)는 상기 CaO의 경우와 마찬가지로 SiO2가 크리스토발라이트로 변태하는 정도를 강하게 하는 촉진체 역할을 하며, 이때 상기 알카리 금속산화물의 함유량은 1.0%이하로 함유시키면 충분하며, 보다 바람직하게는 1.0-0.3%로 하는 것이다.The alkali metal oxide (Na 2 O + K 2 O) serves as an accelerator to strengthen the degree of transformation of SiO 2 to cristobalite, as in the case of CaO, wherein the content of the alkali metal oxide is 1.0% or less. It is enough to contain, More preferably, it is 1.0-0.3%.
통상 용사재료의 원료제조시 Fe2O3, ZrO2, MgO등과 같은 불순물이 불가피하게 함유되어 용사시공체의 열간선팽창율, 부착성 및 내마모성에 악영향을 미치므로 가급적 이들 불순물의 함유량은 억제하는데, 본 발명에서는 최대허용치를 7%까지 제한함이 바람직하다In general, when manufacturing raw materials of thermal spray materials, impurities such as Fe 2 O 3 , ZrO 2 , and MgO are inevitably contained, which adversely affects the thermal expansion coefficient, adhesion, and abrasion resistance of the thermal sprayed body. In the present invention, it is preferable to limit the maximum allowable value to 7%.
상기한 조성을 갖도록 한 본발명의 용사재 입도는 1.0mm이하로 함이 바람직한데, 그 이유는 용사재 입자크기가 1.0mm이상일 경우 산소 및 연료가스와 함께 배출되는 용사버너의 노즐을 메워 작업성이 어려우며 화염용사중 용해되지 않아 손상 내화연와와의 부착율이 저하되기 때문이다.The spray material particle size of the present invention to have the above-mentioned composition is preferably less than 1.0mm, because when the spray particle size is more than 1.0mm, filling the nozzle of the spray burner discharged with oxygen and fuel gas workability This is because it is difficult to dissolve in the flame spray and the adhesion rate with the damaged refractory smoke drops.
또한, 상기 용사재 분말은 1.0~0.005mm의 입경을 갖는 입자가 80%이상 되도록 함이 더욱 바람직한데, 그 이유는 0.005mm미만의 입자 불망이 20% 초과할 경우 연소가스에 의해 입자가 비산되어 분진공해를 일으켜 작업성이 떨어지며 용사재료 자체의 손실도 많아 비경제적이기 때문이다.In addition, the thermal spraying powder is more preferably 80% or more of the particles having a particle diameter of 1.0 ~ 0.005mm, because the particle of less than 0.005mm when the particle hope exceeds 20% particles are scattered by the combustion gas This is because it causes dust pollution and is less workable and it is uneconomical because there is also a loss of thermal spray material itself.
한편, 본발명의 용사재료는 상기한 조성 및 입자크기에 대한 제한뿐만 아니라 입자형태 자체에도 그 특징이 있다.On the other hand, the thermal spraying material of the present invention is not only limited to the composition and particle size described above, but also has characteristics of the particle shape itself.
즉, 종래의 용사재료 처럼 일반적인 구형을 갖는 분말 입자와는 달리, 본 발명의 용사재 입자는 화염에 의해 용융성이 더욱 우수하고, 열흡수 능력을 보다 크게 하도록 하기 위하여 표면을 요철로 하였다.That is, unlike the powder particles having a general spherical shape as in the conventional thermal spraying material, the thermal spraying material particles of the present invention have the surface uneven in order to have better meltability by the flame and increase the heat absorption capacity.
이러한 본 발명의 화염용사재료는 용사가스 선단의 화염중에서 용융상태로 되어 손상내화연와 부위에 부착시 로벽상에 크리스토발라이트 상의 안정한 SiO2상 형태를 갖는 피막을 형성하게 된다.The flame spray material of the present invention is melted in the flame at the tip of the sprayed gas to form a film having a stable SiO 2 phase form on cristobalite on the furnace wall when attached to the damaged refractory lead and the site.
즉, 이 크리스토발라이트상은 코크스로의 내화연화의 열간선팽창율과 거의 같으므로 가열, 냉각과정이 반복되어도 온도변화에 강하여 부착부의 내스플링성도 향상되는 것이다.That is, this cristobalite phase is almost the same as the coefficient of hot linear expansion of refractory softening to coke, and thus, even if the heating and cooling processes are repeated, it is resistant to temperature change, and the spalling resistance of the attachment portion is also improved.
이와같이, 본 발명의 용사재료는 코크스로의 내화연와와 같은 열간 성팽창율 및 내스플성을 갖는 크리스토발라이트상의 생성에 기초로하고 있기 때문에 본발명에 따른 조성범위를 벗어나게 되면 비결정질이 많이 생성되어 열변화의 저항성이 저하되어 내마모성이 떨어지게 되는 것이다.As described above, since the thermal spraying material of the present invention is based on the formation of cristobalite phase having hot expansion coefficient and spall resistance such as fire retardant to coke furnace, when it is out of the composition range according to the present invention, a large amount of amorphous is produced to cause thermal change. The resistance is lowered and wear resistance is inferior.
이하, 본 발명을 실시예를 구체적으로 설명한다.Hereinafter, an Example demonstrates this invention concretely.
실시예Example
하기 표 1과 같은 조성을 갖도록 건조한 원료를 혼합하여 제 1도와 같은 입도분포를 갖는 화염용사용 분말을 제조하고, 제조된 화염용사용 분말재료를 LPG가스 15Nm3/hr, 산소 75Nm3/hr의 조건으로 얻어진 화염을 이용하여 50kg/hr의 용사속도로 용사하여 용사시공체를 얻었다.To prepare a flame spray powder having a particle size distribution as shown in Figure 1 by mixing a dry raw material to have a composition as shown in Table 1, the prepared flame spray powder material LPG gas 15Nm 3 / hr, oxygen 75Nm 3 / hr conditions The sprayed body was sprayed at a spraying speed of 50 kg / hr to obtain a thermal sprayed body.
이때, 용사시공체는 800℃이상의 온도를 유지하여 열충격을 방지하였다.At this time, the sprayed body was maintained at a temperature of more than 800 ℃ to prevent thermal shock.
상기와 같이 제조된 용사시공체에 대하여 열간선팽창율, 상온압축강도, 내화도, 및 조직상태를 측정하고, 그 결과를 하기 표 1에 나타내었다.The thermal expansion coefficient, room temperature compressive strength, fire resistance, and texture state of the thermal sprayed body prepared as described above were measured, and the results are shown in Table 1 below.
상기 열간선팽창율은 1000℃에서 측정하였고, 상기 내화도는 KSL 3113에 의한 내화벽돌의 내화도 시험에 기준하여 측정하였다.The hot expansion coefficient was measured at 1000 ° C., and the degree of fire resistance was measured based on the fire resistance test of the fire brick by KSL 3113.
상기 표 1에 나타난 바와 같이, 본 발명의 조성범위를 만족하는 발명예(1-4)의 경우에는 열간선팽창율이 1.01-1.3%로서 코크스로의 내화연와의 팽창율인 1.0-1.3%와 같았으나, 본 발명의 조성범위를 벗어나는 비교예(1-2)의 경우에는 열간선팽창율이 0.3-0.5%로 변화가 적어 내화연와와 부착된 시공체가 가열, 냉각으로 쉽게 균열이 발생될 수 있음 알 수 있었다.As shown in Table 1, in the case of Inventive Example (1-4), which satisfies the composition range of the present invention, the hot line expansion ratio was 1.01-1.3%, which was the same as the expansion rate with refractory lead to coke furnace, 1.0-1.3%. In case of Comparative Example (1-2) outside the composition range of the present invention, the coefficient of hot expansion was less than 0.3-0.5%, so that the construction body attached with the refractory smoke can easily be cracked by heating and cooling. there was.
즉, 본 발명예(1-4)의 경우에는 그 시공체의 조직에서 알 수 있는 바와같이 결정상인 크리스토발라이트가 강하면 나타난 반면에, 비교예(1-2)의 경우에는 상대적으로 비정질상이 강하게 나타나 열간선팽창율이 적어 마모및 박리가 쉽게 일어나는 것이다.That is, in the case of Example (1-4) of the present invention, cristobalite, which is a crystalline phase, appeared to be strong as can be seen in the structure of the construction body, whereas in Comparative Example (1-2), the amorphous phase appeared to be relatively strong. Due to the low rate of trunk expansion, abrasion and peeling occur easily.
또한, 본 발명예(1-4)의 경우에는 상은 압축강도가 900~920kg/cm 정도로 800~850kg/cm 정도인 비교예(1-2)에 비하여 우수함을 알 수 있었다.In addition, in the case of the invention example (1-4), the image has a compressive strength of 900 to 920 kg / cm 800 ~ 850kg / cm It turned out that it is excellent compared with the comparative example (1-2) which is a grade.
상술한 바와같이, 본 발명에 의하면, 상온 압축강도가 우수할 뿐만 아니라, 코크스등의 내화연와의 팽창율과 거의 같은 열간 선팽창율을 갖으므로서, 열간용사보수시 내수명성이 우수한 화염용사재료를 제공하는 효과가 있는 것이다.As described above, the present invention provides a flame spraying material which is excellent in room temperature compressive strength and has a hot linear expansion rate that is almost the same as the expansion rate with refractory smoke such as coke, and thus has excellent service life during hot spraying repair. It is effective.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019940016587A KR970005890B1 (en) | 1994-07-11 | 1994-07-11 | Sintering material for refractory |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019940016587A KR970005890B1 (en) | 1994-07-11 | 1994-07-11 | Sintering material for refractory |
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| KR960004292A KR960004292A (en) | 1996-02-23 |
| KR970005890B1 true KR970005890B1 (en) | 1997-04-21 |
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| KR102332180B1 (en) * | 2020-02-17 | 2021-11-30 | 주식회사 삼성파워텍 | Motor control center unit with multi-connector structure at test connector |
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