Summary of the invention
The object of the present invention is to provide a kind ofly, provide high crystalline structure dichroite-mullite matter kiln furnitures, the furnace construction refractory product of a kind of good thermal shock stability, high strength, anti-oxidant, long service life and technology is simple, cost is low, be fit to the sinter process of scale operation at the problems referred to above.
Know-why of the present invention: during refractory product is produced, composition of raw materials will determine material, wood property, and very big to the Technology problems affect that may occur in the enforcement of pilot scale, scale operation; The control matrix phase generates low-melting glassy phase, makes the matrix phase major part or is converted into the crystallite phase fully, improves the amount of crystals of trichroite, mullite in the goods, then is the key that improves goods antistrip performance, high temperature break resistant intensity and thermal shock resistance.Based on this, the present invention starts with from improving composition of raw materials, product forming technique and sinter process, in conjunction with MgO-Al
2O
3-SiO
2Be the factors such as physical and chemical performance, production cost, technology practicality and novelty of equilibrium phase diagram, raw material type and source, expection resultant, through repetition test, main way of the present invention is:
1, according to property of raw material and MgO-Al
2O
3-SiO
2Be the selected basic material of equilibrium phase diagram: trichroite (2MgO2Al
2O
35SiO
2) be MgO-Al
2O
3-SiO
2Be the low melting point phase in the equilibrium phase diagram, about 1470 ℃, its thermal expansivity low (under RT-1000 ℃ of condition, α=1.1~2.6 * 10
-6/ ℃); Mullite (3Al
2O
32SiO
2), be continuity sosoloid, load softening point height (1550 ℃~1600 ℃), thermal expansivity is moderate; Aluminium titanates (Al
2O
3TiO
2), have the lower thermal expansivity of high melt point (1860 ℃ ± 10 ℃) (under RT-1000 ℃ of condition, α<2.0 * 10
-6/ ℃), and have good heat-shock resistance: Δ Tc>1000 ℃ can be made into the fine refractory materials; Andaluzite (AL
2O
3SiO
2) have high purity, energy-conservation, need not calcine before using, easily to characteristics such as mullite conversions.Form main crystal phase material so choose, and test exploration on this basis repeatedly, seek the optimization of composition of raw materials and the improvement of production technique with trichroite, mullite, aluminium titanates, andaluzite aggregate;
2, determine raw material type and proportioning: trichroite, mullite raw material all need synthetic in the few primary high purity of occurring in nature, and raw materials used difference when synthetic has than big-difference on mineralogical character.Through comparing repeatedly, adopt sintered cordierite, the mullite synthesis material is the basic material of refractory product of the present invention, and with natural matter combination trichroite matrix phase, determined 50~80% simultaneously with trichroite, mullite, aluminium titanates, andaluzite aggregate composition main crystal phase material, be equipped with 20~50% ratio range in conjunction with the composite interstitial substance material;
3, clear and definite firing range and sintering curve: firing range and sintering curve are key problem in technology, adopt optimum seeking method to carry out repetition test, the mutual relationship of the mineral facies production rate of firing temperature, sintering curve, interpolation nucleus dosage, goods and performance index etc. is carried out a large amount of tests and comprehensive comparative analysis, seek relation and technical basis between them, finally finding the optimum temperature range that matrix phase micritization nucleation is handled is 1200 ℃~1380 ℃, found out nucleus agent kind, nucleus dosage and devitrification temperature scope, nucleus agent kind is selected ZrO for use
2Or and Quilonum Retard (Li
2CO
3), ZrO
2Generally select Zirconium dioxide powder, zircon sand, zirconium Ying Fen etc. for use;
4, improve moulding process: aspect production technique, except that considering temperature, raw material composition, grain composition, nucleus dosage, mineral facies production rate, product properties index, also work out and improve in conjunction with factors such as pressure, vacuum tightness, extrusion speeds.Quality problems such as excessive load-carrying, distortion, planeness, fine crack are improved rapidly, and form stable raw material and prescription, batch mixing, bundle material, moulding, drying, burn till, a series of technical matters systems such as finished product detection, established the Technology basis of scale operation.
Technical scheme of the present invention is:
High crystalline structure dichroite-mullite matter kiln furnitures, kiln refractory product, raw material comprise 50~80 weight parts main crystal phase material, 20~50 weight parts in conjunction with the composite interstitial substance material, selected main crystal phase material, reach 100 weight parts in conjunction with total component of composite interstitial substance material; Add again and account for above-mentioned selected main crystal phase material and in conjunction with the nucleus agent of 0.5~4.0wt% of the total amount of composite interstitial substance material; Wherein:
1), main crystal phase material is aluminium titanates, trichroite, mullite, andaluzite aggregate, wherein, the aluminium titanates aggregate accounts for main crystal phase material 0~20wt%, the trichroite aggregate accounts for 20~40wt% of main crystal phase material, mullite aggregate accounts for 20~40wt% of main crystal phase material, the andaluzite aggregate accounts for 20~35wt% of main crystal phase material, and the particle diameter of above-mentioned aggregate is less than 1mm;
2), be in conjunction with the composite interstitial substance material:
The magnesia micro mist: the MgO component content is 28~32%, fineness requirement is by 325 orders, and the magnesia fine powder accounts for 8~15wt% in conjunction with the composite interstitial substance material;
Aluminium oxide powder: Al
2O
3Component content is greater than 99%, and particle diameter is less than 1 μ m, and aluminium oxide powder accounts for 20~45wt% in conjunction with the composite interstitial substance material;
Fine silica powder: SiO
2Component content is greater than 95%, and particle diameter is less than 0.5 μ m, and fine silica powder accounts for 40~50wt% in conjunction with the composite interstitial substance material;
That adjusts that composition uses contains MgO, Al by what talcum, serpentine, attaclay, magnesia micro mist, kaolin, bauxitic clay, corundum powder obtained
2O
3, SiO
2The fire-resistant powder fineness requirement that the fire-resistant powder of composition, described adjustment composition are used is by 500 orders, and the fire-resistant powder that described adjustment composition is used accounts for 0~20wt% in conjunction with the composite interstitial substance material; In the fire-resistant powder that described adjustment composition is used, the MgO composition accounts for 8~20wt% of the total component of fire-resistant powder that described adjustment composition uses, Al
2O
3Composition accounts for 30~45wt% of the total component of fire-resistant powder that described adjustment composition uses, SiO
2Composition accounts for 40~50wt% of the total component of fire-resistant powder that described adjustment composition uses;
3), the nucleus agent is ZrO
2Or and Li
2CO
3,
Raw material is after batch mixing, bundle material, moulding, drying, and roasting is a finished product.
The present invention, the sinter process of high crystalline structure dichroite-mullite matter kiln furnitures, kiln refractory product, raw material is selected for use: comprise 50~80 weight parts main crystal phase material, 20~50 weight parts in conjunction with the composite interstitial substance material, selected main crystal phase material, reach 100 weight parts in conjunction with total component of composite interstitial substance material; Add again and account for above-mentioned selected main crystal phase material and in conjunction with the nucleus agent of 0.5~4.0wt% of the total amount of composite interstitial substance material; Wherein:
1), main crystal phase material is aluminium titanates, trichroite, mullite, andaluzite aggregate, wherein, the aluminium titanates aggregate accounts for main crystal phase material 0~20wt%, the trichroite aggregate accounts for 20~40wt% of main crystal phase material, mullite aggregate accounts for 20~40wt% of main crystal phase material, the andaluzite aggregate accounts for 20~35wt% of main crystal phase material, and the particle diameter of above-mentioned aggregate is less than 1mm;
2), be in conjunction with the composite interstitial substance material:
The magnesia micro mist: the MgO component content is 28~32%, fineness requirement is by 325 orders, and the magnesia fine powder accounts for 8~15wt% in conjunction with the composite interstitial substance material;
Aluminium oxide powder: Al
2O
3Component content is greater than 99%, and particle diameter is less than 1 μ m, and aluminium oxide powder accounts for 20~45wt% in conjunction with the composite interstitial substance material;
Fine silica powder: SiO
2Component content is greater than 95%, and particle diameter is less than 0.5 μ m, and fine silica powder accounts for 40~50wt% in conjunction with the composite interstitial substance material;
That adjusts that composition uses contains MgO, Al by what talcum, serpentine, attaclay, magnesia micro mist, kaolin, bauxitic clay, corundum powder obtained
2O
3, SiO
2The fire-resistant powder fineness requirement that the fire-resistant powder of composition, described adjustment composition are used is by 500 orders, and the fire-resistant powder that described adjustment composition is used accounts for 0~20wt% in conjunction with the composite interstitial substance material; In the fire-resistant powder that described adjustment composition is used, the MgO composition accounts for 8~20wt% of the total component of fire-resistant powder that described adjustment composition uses, Al
2O
3Composition accounts for 30~45wt% of the total component of fire-resistant powder that described adjustment composition uses, SiO
2Composition accounts for 40~50wt% of the total component of fire-resistant powder that described adjustment composition uses;
3), the nucleus agent is ZrO
2Or and Li
2CO
3,
Raw material in sintering process, divides two sections high temperature constant temperatures to carry out micritization nucleation intensive treatment after batch mixing, bundle material, moulding, drying:
1), be warming up to first section high temperature constant temperature, in the temperature of 1050~1150 ℃ of first section high temperature constant temperatures, sintering is 10~15 hours under the normal pressure;
2) be warming up to second section high temperature constant temperature, again, in the temperature of 1200~1380 ℃ of second section high temperature constant temperatures, sintering is 15~20 hours under the normal pressure.
The present invention compared with prior art, its beneficial effect and innovative point are mainly reflected in:
1, proportioning raw materials is main crystal phase material with 50~80% with aluminium titanates, trichroite, mullite, andaluzite aggregate, be equipped with 20~50% in conjunction with composite interstitial substance, add the nucleus agent simultaneously, the firing range that reaches the expansion refractory product is to carry out the purpose that High-Temperature Strengthening is handled, tradition refractory product agglomerating humidity province is about 30 ℃, and the present invention enlarges the firing range of refractory product because of adding the nucleus agent, and the agglomerating humidity province reaches about 280 ℃;
2, the key of sintering process is at 1200 ℃~1380 ℃ high temperature goods to be carried out micritization nucleation intensive treatment, generates low-melting glassy phase by the control matrix phase, and further makes the most of matrix phase or be converted into microcrystal fully; Goods are high crystalline structure after intensive treatment, antistrip performance, high temperature break resistant intensity and thermal shock resistance can be excellent;
3, technological core is that the sintering curve of micritization nucleation intensive treatment (carrying out between 1200 ℃~1380 ℃) is divided into two sections high temperature constant temperatures and carries out, goods nucleus in sintering process is formed early, the nucleus skeleton increases, shrinking percentage reduces, and after the further crystallization, the amount of crystals of trichroite, mullite increases greatly in the refractory product, reaches the purpose of the antistrip performance that improves goods, high temperature break resistant intensity, thermostability;
4, moulding process adopts special compacting, extruding and pouring forming technology to produce dichroite-mullite matter refractory product, and technology is simple, and cost is low, is fit to scale operation.
Refractory product of the present invention has the advantage of good thermal shock stability, high strength, anti-oxidant, long service life; Technology of the present invention has the advantage that technology is simple, cost is low, be fit to scale operation, is applicable to refractory slab, hollow sheeting and the preparation of kiln refractory product.
The present invention is described further in conjunction with the accompanying drawings for following embodiment.
Embodiment
Embodiment 1:
A kind of high crystalline structure dichroite-mullite matter kiln furnitures, kiln refractory product, raw material comprise 50~80 weight parts main crystal phase material, 20~50 weight parts in conjunction with the composite interstitial substance material, selected main crystal phase material, reach 100 weight parts in conjunction with total component of composite interstitial substance material; Add an amount of nucleus agent again; Wherein:
1), main crystal phase material is aluminium titanates, trichroite, mullite, andaluzite aggregate, wherein, the aluminium titanates aggregate accounts for main crystal phase material 0~20wt%, the trichroite aggregate accounts for 20~40wt% of main crystal phase material, mullite aggregate accounts for 20~40wt% of main crystal phase material, the andaluzite aggregate accounts for 20~35wt% of main crystal phase material, and the particle diameter of above-mentioned aggregate is less than 1mm;
2), be in conjunction with the composite interstitial substance material:
The magnesia micro mist: the MgO component content is 28~32%, fineness requirement is by 325 orders, and the magnesia fine powder accounts for 8~15wt% in conjunction with the composite interstitial substance material;
Aluminium oxide powder: Al
2O
3Component content is greater than 99%, and particle diameter is less than 1 μ m, and aluminium oxide powder accounts for 20~45wt% in conjunction with the composite interstitial substance material;
Fine silica powder: SiO
2Component content is greater than 95%, and particle diameter is less than 0.5 μ m, and fine silica powder accounts for 40~50wt% in conjunction with the composite interstitial substance material;
That adjusts that composition uses contains MgO, Al by what talcum, serpentine, attaclay, magnesia micro mist, kaolin, bauxitic clay, corundum powder obtained
2O
3, SiO
2The fire-resistant powder fineness requirement that the fire-resistant powder of composition, described adjustment composition are used is by 500 orders, and the fire-resistant powder that described adjustment composition is used accounts for 0~20wt% in conjunction with the composite interstitial substance material; In the fire-resistant powder that described adjustment composition is used, the MgO composition accounts for 8~20wt% of the total component of fire-resistant powder that described adjustment composition uses, Al
2O
3Composition accounts for 30~45wt% of the total component of fire-resistant powder that described adjustment composition uses, SiO
2Composition accounts for 40~50wt% of the total component of fire-resistant powder that described adjustment composition uses;
3), the nucleus agent is ZrO
2And Li
2CO
3, wherein, ZrO
2, Li
2CO
3Respectively account for above-mentioned selected main crystal phase material and in conjunction with 0.5~4.0wt% of the total amount of composite interstitial substance material;
Raw material is after batch mixing, bundle material, moulding, drying, and roasting is a finished product.
The product main technical details of present embodiment 1, features and applications:
1), main technical details
Product is divided into the trades mark such as CMA, CMB, CMC, CMD, CME by the difference of refractoriness under load.Among the CMA, C represents trichroite (cordierite); M represents mullite (mullite); A, B, C, D, E represent different refractorinesss under load.The Main physical performance index such as the following table of each product:
The trade mark |
CMA |
CMB |
CMC |
CMD |
CME |
Volume density |
≥2.00 |
≥1.95 |
≥1.90 |
≥2.00 |
≥2.05 |
Apparent porosity % |
≤26 |
≤28 |
≤30 |
≤26 |
≤28 |
The coefficient of expansion (25 ℃~1000 ℃) 10
7K
i |
≤30 |
≤24 |
≤23 |
≤26 |
≤30 |
Load softening point (T0.6) ℃ |
≥1410 |
≥1390 |
≥1380 |
≥1420 |
≥1430 |
Folding strength MPa |
Normal temperature |
≥12 |
≥8 |
≥8 |
≥9 |
≥10 |
High temperature |
≥10 |
≥7 |
≥5 |
≥8 |
≥9 |
Thermal shock resistance |
*** |
*** |
**** |
*** |
*** |
Maximum operating temperature ℃ |
In tunnel furnace |
1250 |
1220 |
1150 |
1250 |
1280 |
In shuttle kiln |
1250 |
1220 |
1150 |
1250 |
1280 |
In roller kiln |
1280 |
1280 |
1250 |
1280 |
Be not suitable for |
Remarks: * crosses many more, and the expression thermal shock resistance is good more |
2), products characteristics and purposes
Main products of the present invention comprises dichroite-mullite matter refractory slab, hollow sheeting and kiln refractory product, and its principal feature is that antistrip performance, high temperature break resistant intensity and thermal shock resistance can be excellent, and economy and practicality are unified.The purposes of product is as follows:
1., dichroite-mullite matter refractory slab: be mainly used in fine porcelain, bone china, half porcelain, fine pottery, boccaro, marmite pot, light china, colored glaze mosaic, paving tile, sanitary ware (small-sized), devitrified glass (small-sized crystallization processing), artistic decoration glass product burning till such as (surface shape processing) at tunnel furnace, roller kiln and shuttle kiln;
2., dichroite-mullite matter hollow sheeting: be mainly used in burning till of sanitary ware and goods such as crystallizing glass decoration board, domestic ceramics.Hollow sheeting is applicable to burning till fast of ceramic utensil product, has that the weight ratio solid slab alleviates half and energy-conservation, plate face supporting power increases, an advantage of flexible type, longer service life not under the high temperature;
3., dichroite-mullite matter kiln refractory product: product mainly substitutes material such as traditional Low fire ceramic utensil kiln, kiln car suspended roof brick, wall brick kiln body brick, and thoroughly change the theory of traditional kiln design and use the material method, principal feature is can prevent slag effectively, peel off the porcelain tool quality problems that cause, and energy-conservation.
Embodiment 2:
The sinter process of a kind of high crystalline structure dichroite-mullite matter kiln furnitures, kiln refractory product, raw material is selected for use: comprise 50~80 weight parts main crystal phase material, 20~50 weight parts in conjunction with the composite interstitial substance material, selected main crystal phase material, reach 100 weight parts in conjunction with total component of composite interstitial substance material; Add an amount of nucleus agent again; Wherein:
1), main crystal phase material is aluminium titanates, trichroite, mullite, andaluzite aggregate, wherein, the aluminium titanates aggregate accounts for main crystal phase material 0~20wt%, the trichroite aggregate accounts for 20~40wt% of main crystal phase material, mullite aggregate accounts for 20~40wt% of main crystal phase material, the andaluzite aggregate accounts for 20~35wt% of main crystal phase material, and the particle diameter of above-mentioned aggregate is less than 1mm;
2), be in conjunction with the composite interstitial substance material:
The magnesia micro mist: the MgO component content is 28~32%, fineness requirement is by 325 orders, and the magnesia fine powder accounts for 8~15wt% in conjunction with the composite interstitial substance material;
Aluminium oxide powder: Al
2O
3Component content is greater than 99%, and particle diameter is less than 1 μ m, and aluminium oxide powder accounts for 20~45wt% in conjunction with the composite interstitial substance material;
Fine silica powder: SiO
2Component content is greater than 95%, and particle diameter is less than 0.5 μ m, and fine silica powder accounts for 40~50wt% in conjunction with the composite interstitial substance material;
That adjusts that composition uses contains MgO, Al by what talcum, serpentine, attaclay, magnesia micro mist, kaolin, bauxitic clay, corundum powder obtained
2O
3, SiO
2The fire-resistant powder fineness requirement that the fire-resistant powder of composition, described adjustment composition are used is by 500 orders, and the fire-resistant powder that described adjustment composition is used accounts for 0~20wt% in conjunction with the composite interstitial substance material; In the fire-resistant powder that described adjustment composition is used, the MgO composition accounts for 8~20wt% of the total component of fire-resistant powder that described adjustment composition uses, Al
O 3Composition accounts for 30~45wt% of the total component of fire-resistant powder that described adjustment composition uses, SiO
2Composition accounts for 40~50wt% of the total component of fire-resistant powder that described adjustment composition uses;
3), the nucleus agent is ZrO
2And Li
2CO
3, wherein, ZrO
2, Li
2CO
3Respectively account for above-mentioned selected main crystal phase material and in conjunction with 0.5~4.0wt% of the total amount of composite interstitial substance material;
Raw material with reference to Fig. 1, in sintering process, divides two sections high temperature constant temperatures to carry out micritization nucleation intensive treatment after batch mixing, bundle material, moulding, drying:
1), be warming up to first section high temperature constant temperature, in the temperature of 1050~1150 ℃ of first section high temperature constant temperatures, sintering is 10~15 hours under the normal pressure;
2) be warming up to second section high temperature constant temperature, again, in the temperature of 1200~1380 ℃ of second section high temperature constant temperatures, sintering is 15~20 hours under the normal pressure.
The main production equipments of present embodiment 2 and technical process:
1), main production equipments: comprise that pulverizing mill, biaxial rneader, vacuum deairing machine, true powder pump, disk screen formula feeding machine, three vacuum-extruder, automatic blank cutter, high temperature shuttle kiln, strickling thicknessing machine, polishing edging line and chamfering, 5T ball mill, 2500T mouldenpress, dust removal installation, test set, distribution facility, drying cart, cold working cutting mechanics, pressure filter, ram pump, 10T deposit pulp grinder etc. at a slow speed;
2), the technological process of production: comprise compacting, extrude, the technological process of production such as cast etc.