CN101113100A - High-purity corundum pouring material containing nano calcium carbonate and preparation method thereof - Google Patents
High-purity corundum pouring material containing nano calcium carbonate and preparation method thereof Download PDFInfo
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- CN101113100A CN101113100A CNA2007100547085A CN200710054708A CN101113100A CN 101113100 A CN101113100 A CN 101113100A CN A2007100547085 A CNA2007100547085 A CN A2007100547085A CN 200710054708 A CN200710054708 A CN 200710054708A CN 101113100 A CN101113100 A CN 101113100A
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Abstract
The invention relates to a high pure corundum castable material containing nanometer calcium carbonate and a preparation method thereof. Based on the present commonly used corundum castable material, by adding nanometer calcium carbonate powder as well as adopting efficient dispersant and suitable mixing technology, the invention prepares corundum castable material that contains nanometer calcium carbonate. The invention solves the disadvantage of low strength of the present high pure corundum castable material in low and middle temperature, more particularly, the strength in about 800 DEG C. Furthermore, the variation of the burnt cool strength of the corundum castable material containing nanometer calcium carbonate from 800 DEG C to 1600 DEG C is comparatively small, and the cool strength and hot strength are both higher than those of the corundum castable material containing cement with the same content of CaO. The corundum castable material that contains nanometer calcium carbonate and is prepared by the utility model can be widely applied to such industries fields as iron and steel, nonferrous metals, ceramics and petrochemical etc. The invention can also be applied to fireproof materials products cast, molded and burnt by a porous brick etc., which can greatly reduce the burnt temperature and save energy.
Description
Technical field
The invention belongs to technical field of inorganic nonmetallic materials.Be specifically related to a kind of high-purity corundum pouring material that contains nano-calcium carbonate and preparation method thereof.
Background technology
Compare with shaping refractory product, unshape refractory is as a big class of refractory materials, because of its advantage at production, labour productivity, operating efficiency, materials consumption, aspect such as energy-conservation, all obtained development rapidly in countries in the world.In recent years, because the appearance of high-quality, high-performance raw material, the introducing of super-fine powder and efficient dispersion technology, the employing of novel construction method and the reinforcement of fundamental research etc., make one of the principal item mould material of unshape refractory obtain developing rapidly at aspects such as material, kind, performance, construction and application, increasing refractory castable substitutes the setting goods and is used for high temperature position, thereby also more and more higher to the mould material performance demands.The particularly application of fine silica powder and alumina powder, make mould material be developed to low cement, ultra-low cement and non-cement direction by traditional cement combination, corresponding combination is developed by hydration combination → Chemical bond → (hydration combination+cohesion combination) → cohesion combination.The tradition mould material utilize cement at normal temperatures aquation form hydrate and produce combination, thereby have higher normal temperature strength.But with the rising of temperature, middle thermophase hydrate is sloughed a large amount of combination water (its hydrated product CaOAl
2O
310H
2O, 2CaOAl
2O
38H
2O, 3CaOAl
2O
36H
2O and Al
2O
33H
2The water content of O is respectively 53.3%, 40.2%, and 28.6% and 34.6%), produce a large amount of pores, and pottery combination this moment forms not as yet, cause intensity to reduce.After high temperature burnt, though formed ceramic combination, because pore and defect influence that the hydrate dehydration produces, intensity was still lower, and these shortcomings have greatly limited the application of traditional mould material at high temperature position.The main path that overcomes above shortcoming is to reduce the content of cement in the mould material, and people or/and fine silica powder partly replaces aluminous cement, obtain low cement and ultra-low cement deposit material with alumina powder for this reason.Compare with traditional mould material, low cement and ultra-low cement deposit material are owing to reduced the cement add-on and the construction amount of water, and every performance all is improved, and especially at middle warm area (900～1200 ℃), its mechanical property is improved.For further reducing the influence of cement, people have developed the non-cement mould material, owing to do not introduce CaO, adopt the cohesion combination fully, by adding and the cohesion of micro mist that the main material chemical ingredients is similar or gel and producing combines, thereby have advantages such as high-temperature behavior is good.
High-purity corundum pouring material has the excellent high-temperature performance, has obtained widespread use in industries such as metallurgy, building materials, petrochemical compleies.Present high-purity corundum pouring material can be divided three classes by used wedding agent: a class is the mould material that does not contain cement, and its wedding agent mainly is fine silica powder, amorphous alumina, aluminium silicon sol and magnalium colloidal sol etc.; Second class is aluminous cement, alumina powder and fine silica powder bonded corundum pouring material; The 3rd class is aluminous cement and alumina powder bonded corundum pouring material.
Adopt in the first kind corundum pouring material (non-cement in conjunction with) fine silica powder in conjunction with the time, though can under lower temperature, generate mullite its medium temperature intensity is improved, but baked strength is lower, and because the introducing of silicon-dioxide, material is reacted when contacting with slag generate the low melting point ore deposit mutually, reduced high-temperature behavior, and then its application is restricted, especially under strongly reducing atmosphere, silicon-dioxide is reduced and the destruction that causes material structure, therefore should reduce as far as possible even avoids using silicon-dioxide fully.Dry performance preferably though hydrated aluminum oxide bonded corundum pouring material has, middle Wen Shiqi hydrate decomposes, and this fashion does not have new ore deposit and generates mutually, so medium temperature intensity is very low, the hydrated aluminum oxide unstable properties has also limited its application simultaneously.
The second class corundum base mould material (low cement and ultra-low cement combination) belongs to Al
2O
3-CaO-SiO
2Three-part system is formed point when matrix and is in sub-trilateral △ A-A
3S
2-CAS
2When middle, the temperature that liquid phase occurs is 1512 ℃; Form point when matrix and be in sub-trilateral △ A-CA
6-CAS
2When middle, the temperature that liquid phase occurs is 1495 ℃; Therefore, when aluminous cement and fine silica powder used simultaneously, the temperature that liquid phase appears in mould material was lower, greatly reduces the high-temperature behavior of material.
The 3rd class corundum pouring material is the most common at present, and it consists of Al
2O
3-CaO two component system is a principal crystalline phase with the corundum, and its temperature that liquid phase occurs is up to 1900 ℃.Along with the rising of temperature, the CaO in 1350 ℃ of cement begins and the aluminum oxide reaction, generates the tabular calcium hexaluminate crystal of six sides, and this six side's shape crystal cross-distribution have improved the high-temperature behavior of material in the corundum skeleton.Owing to do not introduce silicon-dioxide in the mould material, thereby mould material has good slag resistance and anti-reducing atmosphere performance.The adding of alumina powder slightly improves medium temperature intensity, but because its wedding agent mainly is a cement, thereby with compare after normal temperature and high temperature burn, medium temperature intensity is still lower, and aluminous cement is higher with the aluminum oxide reaction new ore deposit of generation temperature mutually, not easy-sintering.Thereby be necessary when reducing sintering temperature, further to improve wherein warm nature energy, and then improve its result of use and life-span.
Summary of the invention
A kind of high-purity corundum pouring material that contains nano-calcium carbonate that purpose of the present invention is developed at existing problem in the above-mentioned prior art just and preparation method thereof.
The object of the invention is to utilize tiny, the easy decomposition of nano-calcium carbonate powder granularity, decomposition back to generate advantages such as highly active calcium oxide, improve present corundum castable medium temperature intensity low, be difficult for the agglomerating shortcoming, prepare a kind of in warm nature can be excellent the high-purity corundum pouring material that contains nano-calcium carbonate.
The objective of the invention is to realize by following technology incidence of criminal offenses: the high-purity corundum pouring material that contains nano-calcium carbonate of the present invention comprises that the aggregate of fused white corundum and/or sintering plate corundum and fine powder, nano-calcium carbonate calcium powder, activated alumina micro mist, alumina hydrate powder and/or pure calcium aluminate cement, water reducer form, and each raw material weight per-cent is as follows:
The aggregate of fused white corundum and/or sintering plate corundum and fine powder 80～90%
Nano-calcium carbonate calcium powder 0.5～4%
Activated alumina micro mist 5～14%
Alumina hydrate powder and/or pure calcium aluminate cement 1～8%
Water reducer 0.05～0.3%.
In the present invention, the mass ratio of aggregate and fine powder is (58%～72%)/(42%～28%) in the mould material.The chemical ingredients of fused white corundum requires to be Al
2O
3〉=98.5%, the chemical ingredients of sintering plate corundum requires to be Al
2O
3〉=99.0%.
Described nano-calcium carbonate calcium powder refers to such an extent that be the wetting ability calcium carbonate powder of granularity less than 100nm, and Chemical Composition requires CaCO
3〉=95.0%.The chemical ingredients of described activated alumina micro mist requires Al
2O
3〉=98.5%, median size requires≤5 μ m.
The wedding agent that the present invention adopts is alumina hydrate powder or pure calcium aluminate cement, described alumina hydrate powder is a kind of unbodied aluminum oxide, can aquation produce bonding strength under the normal temperature, when only using alumina hydrate powder, its addition is 1～6% of a whole raw material.Described pure calcium aluminate cement refers to Al
2O
3Content is 65～82% aluminous cement, and when only using pure calcium aluminate cement, its addition is 1～8% of a whole raw material.Also but both add together for alumina hydrate powder, pure calcium aluminate cement, and adding total amount is 1～8% of whole raw material.
Described water reducer refers to the polyethylene glycols water reducer.
The preparation method who contains the high-purity corundum pouring material of nano-calcium carbonate is: with nano-calcium carbonate calcium powder, activated alumina micro mist, alumina hydrate powder and/or pure calcium aluminate cement and water reducer thorough mixing evenly after, the aggregate and the fine powder that add fused white corundum and/or sintering plate corundum, further thorough mixing promptly makes product of the present invention.
The present invention has the following advantages:
1, because the nano-calcium carbonate granularity is little, under lower temperature (about 690 ℃), begin to decompose, decompose fully substantially in the time of 800 ℃.Decompose to generate nano level calcium oxide particulate, have very high specific surface area and reactive behavior, generating calcium aluminate with aluminum oxide reaction in the mould material is mineral, produces the reaction in combination, makes mould material just have very high cold conditions and hot strength in the time of 800 ℃.From 800 ℃ to 1400 ℃, its strength maintenance high level and remaining unchanged substantially.Thereby compare with the mould material that does not contain nano-calcium carbonate, the intensity between its 800 ℃～1400 ℃ is greatly improved, and with the variation of temperature and nano-calcium carbonate add-on, the intensity increase rate reaches 100%～500%.
2, after high temperature burnt, the corundum pouring material that contains nano-calcium carbonate had identical mineral facies with pure calcium aluminate cement bonded corundum pouring material.Compare with cement bonded corundum castable, contain the corundum pouring material of nano-calcium carbonate because nano-calcium carbonate has the advantages that granularity is tiny, be more evenly distributed, its high temperature reacts the also well-proportioned distribution of calcium hexaluminate that generates with aluminum oxide down, make mould material have more uniform tissue structure, thereby have higher intensity and better thermal shock resistance.
3, raise with temperature, contain that to generate calcium aluminate in the corundum castable of nano-calcium carbonate be mineral, and the combination of generation reaction in, follow volumetric expansion in the reaction process, filled pore, generated equally distributed calcium hexaluminate, thereby compared with cement bonded corundum castable and to have better slag resistance.
4, it is simple to contain the corundum castable production technique of nano-calcium carbonate, and whole technological process does not need cost and complex equipment, has kept the production technique of existing mould material, is suitable for large-scale industrial production.
5, the used nano-calcium carbonate calcium source of the present invention is easy, and other oxide nonmetallic powder price is lower relatively, can be applied to industrial production.
Embodiment
Characteristics of the present invention are by introducing nano-calcium carbonate, and especially medium temperature intensity, heat-shock resistance and slag resistance etc. are improved greatly to make the intensity of corundum castable.The production technique that contains the nano-calcium carbonate corundum castable is identical with the technology of present mould material.Main raw material (comprising aggregate and fine powder) is used for sintering plate corundum or fused white corundum and both.Be that example illustrates enforcement of the present invention and characteristics below with the fused white corundum, but the present invention is not limited to following embodiment.For proving absolutely characteristics of the present invention, each embodiment has been provided corresponding contrast sample, introduce CaO by adding cement in the contrast sample, its CaO content is suitable with embodiment, and the two compares.
Embodiment 1: the each component proportioning is (mass percent) fused white corundum 88.5%, activated alumina micro mist 8%, pure calcium aluminate cement 2%, nano-calcium carbonate powder 1.5%, water reducer 0.2% (adding).
Comparative Examples 1: the each component proportioning is (mass percent) fused white corundum 87.2%, activated alumina micro mist 8%, pure calcium aluminate cement 4.8%, water reducer 0.2% (adding).
Embodiment 2: the each component proportioning is (mass percent) sintering plate corundum 84%, activated alumina micro mist 11%, alumina hydrate powder 2%, nano-calcium carbonate powder 3%, water reducer 0.1% (adding).
Comparative Examples 2: the each component proportioning is (mass percent) sintering plate corundum 81.4%, activated alumina micro mist 11%, alumina hydrate powder 2%, pure calcium aluminate cement 5.6%, water reducer 0.1% (adding).
Embodiment 3: the each component proportioning is (mass percent) sintering plate corundum 44%, fused white corundum 40%, activated alumina micro mist 14%, alumina hydrate powder 1%, nano-calcium carbonate powder 1%, water reducer 0.3% (adding).
Comparative Examples 3: the each component proportioning is (mass percent) sintering plate corundum 43.1%, fused white corundum 40%, activated alumina micro mist 14%, alumina hydrate powder 1%, pure calcium aluminate cement 1.9%, water reducer 0.3% (adding).
With activated alumina micro mist, alumina hydrate powder, pure calcium aluminate cement, nano-calcium carbonate calcium powder and the water reducer thorough mixing of aforementioned proportion evenly after, adding corundum aggregate and fine powder secondary in proportion mixes, the water that adds 4.2% (mass percent) again, after mixing it is poured into band sample, place the demoulding after 24 hours, its performance of test the results are shown in down subordinate list after 110 ℃ of bakings 24 hours and treatment of different temperature.
Subordinate list:
| Performance | Embodiment 1 | Comparative Examples 1 | Embodiment 2 | Comparative Examples 2 | Embodiment 3 | Comparative Examples 3 | |
| Folding strength/MPa | 110℃，3h | 12.0 | 22.0 | 10.2 | 25.1 | 6.5 | 11.1 |
| 800℃，3h | 24.4 | 5.6 | 25.7 | 6.2 | 21.0 | 3.6 | |
| 1100℃，3h | 21.7 | 15.6 | 24.7 | 17.0 | 17.3 | 10.6 | |
| 1400℃，3h | 22.2 | 15.2 | 24.8 | 16.3 | 19.4 | 11.2 | |
| 1600℃，3h | 22.4 | 21.6 | 23.4 | 22.6 | 22.4 | 18.0 | |
| Hot modulus of rupture/MPa | 800 ℃ (800 ℃ of 3h pre-burnings) | 23.2 | 6.2 | 24.5 | 6.9 | 17.1 | 3.6 |
| 1100 ℃ (1100 ℃ of 3h pre-burnings) | 28.2 | 17.4 | 32.8 | 19.5 | 19.2 | 9.9 | |
| 1400 ℃ (1400 ℃ of 3h pre-burnings) | 14.4 | 8.5 | 17.2 | 9.7 | 9.7 | 3.9 | |
| 1400 ℃ (1400 ℃ of 3h pre-burnings) | 14.3 | 13.6 | 16.2 | 15.4 | 9.4 | 7.1 | |
| Remaining folding strength (1100 ℃ water-cooled 1 time)/MPa | 8.3 | 7.1 | 8.7 | 7.4 | 8.1 | 5.9 | |
Annotate: sintering plate corundum and fused white corundum can be replaced between mutually wholly or in part in the above-described embodiments, and every index performance of its products obtained therefrom is basic identical.
Claims (8)
1. high-purity corundum pouring material that contains nano-calcium carbonate, it is characterized in that: it comprises the aggregate of fused white corundum and/or sintering plate corundum and fine powder, nano-calcium carbonate calcium powder, activated alumina micro mist, alumina hydrate powder and/or pure calcium aluminate cement, water reducer, and each raw material weight per-cent is as follows:
The aggregate of fused white corundum and/or sintering plate corundum and fine powder 80～90%
Nano-calcium carbonate calcium powder 0.5～4%
Activated alumina micro mist 5～14%
Alumina hydrate powder and/or pure calcium aluminate cement 1～8%
Water reducer 0.05～0.3%.
2. the high-purity corundum pouring material that contains nano-calcium carbonate according to claim 1 is characterized in that: the mass ratio of aggregate and fine powder is (58%～72%)/(42%～28%) in the mould material.
3. the high-purity corundum pouring material that contains nano-calcium carbonate according to claim 1 is characterized in that: the chemical ingredients of fused white corundum requires to be Al
2O
3〉=98.5%, the chemical ingredients of sintering plate corundum requires to be Al
2O
3〉=99.0%.
4. the high-purity corundum pouring material that contains nano-calcium carbonate according to claim 1 is characterized in that: the nano-calcium carbonate calcium powder refers to such an extent that be the wetting ability calcium carbonate powder of granularity less than 100nm, and Chemical Composition requires CaCO
3〉=95.0%.
The high-purity corundum pouring material that contains nano-calcium carbonate according to claim 1 is characterized in that: activated alumina micro mist chemical ingredients requires Al
2O
3〉=98.5%, median size requires≤5 μ m.
5. the high-purity corundum pouring material that contains nano-calcium carbonate according to claim 1 is characterized in that: alumina hydrate powder is a kind of unbodied aluminum oxide, can aquation produce bonding strength under the normal temperature.
6. the high-purity corundum pouring material that contains nano-calcium carbonate according to claim 1, it is characterized in that: pure calcium aluminate cement refers to Al
2O
3Content is 65%～82% aluminous cement.
7. the high-purity corundum pouring material that contains nano-calcium carbonate according to claim 1 is characterized in that: water reducer refers to the polyethylene glycols water reducer.
8. one kind according to the described preparation method who contains the high-purity corundum pouring material of nano-calcium carbonate of claim 1, it is characterized in that: with nano-calcium carbonate calcium powder, activated alumina micro mist, alumina hydrate powder and/or pure calcium aluminate cement and water reducer thorough mixing evenly after, the aggregate and the fine powder that add fused white corundum and/or sintering plate corundum, further thorough mixing promptly makes the high-purity corundum pouring material that contains nano-calcium carbonate of the present invention.
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