CN105130411B - Zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material and preparation method thereof - Google Patents
Zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material and preparation method thereof, belong to technical field of refractory materials.Zircon fine powder accounts for 70 97wt% in the described zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material, coated by titanium dioxide zirconium dioxide fine powder accounts for 3 30wt%, it can effectively improve composite diphase material sintering character, the titanium dioxide of temporary transient higher concentration can be provided around zirconium dioxide particle, promote the sintering and the compatibility with zirconium dioxide interface of zircon, reduce the porosity of composite diphase material；Its preparation method includes ball milling, drying, four steps of shaping and sintering, and operating method is simple and feasible, with good economic benefit.
Description
Technical field
The present invention relates to a kind of zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material and its
Preparation method, belongs to technical field of refractory materials.
Background technology
Compact zircon brick is its excellent high-temperature physical property, such as low-thermal-expansion system as the advantage of refractory material
Number, lower thermal conductivity and good corrosion resistance, can resist the erosion of glass, slag and liquid metal alloy.Compact zircon brick
As the crucial inner lining material of alkali-free glass fibre tank furnace, pool wall backing brick, bottom paving block as melting tank and depositing reservoir
With subgrade brick, the nogging of primary path and operation access, bottom brick, chute brick and wire drawing brick etc..
The main mechanism that alkali-free glass liquid is corroded it washes away for glass metal to brick body surface, is caused by open pore
Glass metal makes short texture to brick body diffusion inside and infiltration, and brick body surface is weakened with internal bond strength, adds rushing for glass metal
Brush is acted on, outer layer brick body slow mechanism dissolved.Thus, reduce the raising that the porosity is conducive to material corrosion resistance.
Compact zircon brick the disadvantage is that, with the raising of temperature in use, under the erosion-resisting characteristics of compact zircon brick
Drop, therefore its temperature in use is preferably below 1370 DEG C.Additionally, in order that zircon brick densified sintering product, usually used higher
Temperature is sintered or adds a small amount of sintering aid, but both approaches easily cause the decomposition of zircon, cause short texture, and can produce
A part of christobalite phase of life, can reduce its anti-glass attack.
Zirconia refractory has the aggressivity of good high temperature resistance melt, is allowed in alkali-free glass melting furnaces as contact
The inner lining material of glass metal is widely adopted.Zirconia content is more preferable for the high zirconia electrocast refractories of 85-95% has
Corrosion resistance, it is low to glass feed liquid contaminative, be particularly suited for low alkali and alkali-free glass melting furnaces.
Sintering oxidation Zr refractory material generally carries out all or part of stabilization treatment, adds Y2O3, the stabilizer such as MgO, CaO
To prevent it from being burst apart because of volume excessive variation.However, this high zirconia sintered refractory containing stabilizer is used
When on glass furnace, stabilizer can be dissolved in glass metal, and stabilizing zirconia is changed into unstable zirconium oxide again, cause tissue crisp
Weak, Simultaneous Stabilization agent is combined with glass metal, may be triggered in glass and the defects such as gravel, calculus is occurred.In addition, zirconia material valency
Lattice are high, and production high-purity zirconia material will significantly increase cost.
With reference to zircon and the characteristic of zirconium oxide, zircon/zirconium oxide composite diphase material research and application attract attention, according to
Its chemical composition, corrosion resistance is better than zircon material.But, after introducing zirconium oxide, zirconium oxide is alternate with zircon two
Agglutinating property it is poor, cause the porosity of composite diphase material higher, have impact on the raising of the anti-glass attack performance of composite diphase material.
The content of the invention
It is an object of the invention to provide a kind of zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide complex phase
Material, solves the problems, such as that zircon present in existing process/zirconium oxide composite diphase material sintering densification is difficult, improves zirconium English
The sintering character of stone/zirconium oxide composite diphase material, reduces the porosity of composite diphase material；Present invention simultaneously provides its preparation method.
Zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material of the present invention, by zirconium
Diamond stone fine powder and coated by titanium dioxide zirconium dioxide fine powder are made.
Wherein：
Described zircon fine powder accounts for 70-97wt%, and coated by titanium dioxide zirconium dioxide fine powder accounts for 3-30wt%.
Between 1-10 μm, zircon coats the average grain of zirconium dioxide fine powder to the average grain diameter of described zircon fine powder
Footpath is between 0.1-3 μm.
Content of titanium dioxide in described coated by titanium dioxide zirconium dioxide fine powder is the 1-10wt% of coated powder.
The preparation method of described coated by titanium dioxide zirconium dioxide fine powder is comprised the following steps：
(1) zirconium dioxide suspension is prepared：
Dispersant is dissolved in the water, its pH value is adjusted between 4-5, zirconium dioxide powder is added, obtains steady after ball milling
The fixed zirconium dioxide suspension for suspending；
(2) coated by titanium dioxide zirconium dioxide fine powder is prepared：
Stirring zirconium dioxide suspension, to TiO 2 sol is added dropwise in zirconium dioxide suspension, continues after completion of dropping
Stirring, makes sol particles adsorb on zirconium dioxide particle surface, then suspension is heated and is kept stirring for, and makes moisture evaporation；So
First it is dried afterwards, then is heat-treated, titanium dioxide is closely coated on zirconium dioxide particle surface, most afterwards through grinding
Mill, sieving, obtain coated by titanium dioxide zirconium dioxide fine powder.
Dispersant is modified polycarboxylic acid salt AN-2000 in step (1), with newborn acid for adjusting pH value between 4-5, step (1)
The consumption of middle dispersant is the 0.2-0.4wt% of zirconium dioxide powder, and zirconium dioxide powder is 25-50 with the volume ratio of water:50-
75, Ball-milling Time is 24-48h.
It is added dropwise in step (2) after TiO 2 sol is finished and continues to stir 4-8h；Be heated to for suspension in (2) by step
80-90 DEG C and it is kept stirring for；Drying temperature is 200-250 DEG C, and drying time is 4-8h；Heat treatment temperature is 600-1000 DEG C,
Heat treatment time is 4-10h；Powder in step (2) after grinding heat treatment crosses 200 mesh sieves, obtains coated by titanium dioxide titanium dioxide
Zirconium powder body.
The preparation of the zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material of the present invention
Method, comprises the following steps：
(1) ball milling has been weighed by metering zircon fine powder and the mixing fine powders of coated by titanium dioxide powdered zirconium oxide, obtain
To well mixed slurry；
(2) dry slurry obtain for be molded mixed powder；
(3) powder is shaped to green compact；
(4) sintering green compact obtain composite diphase material.
Wherein：
When preparing slurry in step (1), dispersant and binding agent that this area is common can be added；
Drying process is using drying or mist projection granulating, preferably mist projection granulating in step (2)；
Moulding process uses isostatic pressing or dry-pressing formed, preferably isostatic pressing in step (3)；
Green compact sinter 20-30h at 1550-1650 DEG C in step (4).
Beneficial effects of the present invention are as follows：
The present invention solves asking for zircon present in existing process/zirconium oxide composite diphase material sintering densification difficulty
Topic, can provide the titanium dioxide of temporary transient higher concentration around zirconium dioxide particle, promote the sintering of zircon and with two
The compatibility at zirconium oxide interface, improves the sintering character of zircon/zirconium oxide composite diphase material, reduces the porosity of composite diphase material；
Its preparation process is simple, it is easy to industrialized production.
Specific embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
The preparation process of the zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material is as follows：
About 1 μm of zircon fine powder average grain diameter, about 3 μm of coated by titanium dioxide powdered zirconium oxide average grain diameter.Wherein, dioxy
The content of titanium dioxide changed in titanium cladding zirconium dioxide fine powder is the 1wt% of coated powder.Above two fine powder in mass ratio 70:
30 weigh.Above-mentioned fine powder is added water and carry out ball milling after mixing, obtain mixed slurry.
Mixed slurry mist projection granulating, about 80 μm of the average grain diameter of granulation material.
By granulation material isostatic pressing, briquetting pressure 200MPa.
Shaping green compact are dried, and are sintered 20 hours at 1550 DEG C.The porosity of sintered specimen is about 5%.
Wherein, the preparation process of coated by titanium dioxide zirconium dioxide fine powder is as follows：
3 μm of zirconium dioxide average grain diameter, dispersant modified polycarboxylic acid salt AN-2000 consumptions are zirconium dioxide quality
0.2%, zirconium dioxide powder is 50 with the volume ratio of water:50, by above-mentioned metering ratio, dispersant is dissolved in the water, use lactic acid
The pH value for adjusting solution is 4, adds zirconium dioxide powder, and ball milling disperses 24 hours, obtains zirconium dioxide suspension.
Above-mentioned suspension is stirred, TiO 2 sol is slowly added dropwise.In terms of titanium dioxide, zirconium dioxide and two in suspension
The mass ratio of titanium oxide is 99:1.Completion of dropping, continues to stir 8 hours, and suspension then is heated into 90 DEG C, stirs drying,
Drying box was placed in again in 250 DEG C of dryings 4 hours.Above-mentioned powder is heat-treated 4 hours at 1000 DEG C, room temperature is down to.At grinding heat
Powder after reason, crosses 200 mesh sieves, obtains coated by titanium dioxide zirconium dioxide powder.
Embodiment 2
The preparation process of the zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material is as follows：
About 5 μm of zircon fine powder average grain diameter, about 1 μm of coated by titanium dioxide powdered zirconium oxide average grain diameter.Wherein, dioxy
The content of titanium dioxide changed in titanium cladding zirconium dioxide fine powder is the 5wt% of coated powder.Above two fine powder in mass ratio 80:
20 are weighed, and ball milling is carried out after the mixing that adds water, and obtain mixed slurry.
Mixed slurry mist projection granulating, about 100 μm of the average grain diameter of granulation material.
By granulation material isostatic pressing, briquetting pressure 250MPa.
Shaping green compact are dried, and are sintered 25 hours at 1580 DEG C.The porosity of sintered specimen is about 1%.
Wherein, the preparation process of coated by titanium dioxide zirconium dioxide fine powder is as follows：
1 μm of zirconium dioxide average grain diameter, dispersant modified polycarboxylic acid salt AN-2000 consumptions are zirconium dioxide quality
0.3%, zirconium dioxide powder is 40 with the volume ratio of water:60, by above-mentioned metering ratio, dispersant is dissolved in the water, use lactic acid
The pH value for adjusting solution is 4.5, adds zirconium dioxide powder, and ball milling disperses 30 hours, obtains zirconium dioxide suspension.
Above-mentioned suspension is stirred, TiO 2 sol is slowly added dropwise.In terms of titanium dioxide, zirconium dioxide and two in suspension
The mass ratio of titanium oxide is 95:5.Completion of dropping, continues to stir 4 hours, and suspension then is heated into 85 DEG C, stirs drying,
Drying box was placed in again in 220 DEG C of dryings 6 hours.Powder will be dried to be heat-treated 8 hours at 800 DEG C, room temperature will be down to.Grinding heat treatment
Powder afterwards, crosses 200 mesh sieves, obtains coated by titanium dioxide zirconium dioxide powder.
Embodiment 3
The preparation process of the zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material is as follows：
Compare weighing by following quality：10 μm of zircon fine powders 50% of average grain diameter, about 5 μm of zircon fine powders of average grain diameter
10%, about 1 μm of zircon fine powder 37% of average grain diameter, the coated by titanium dioxide zirconium dioxide fine powder of about 0.1 μm of average grain diameter
3%.Wherein, the content of titanium dioxide in coated by titanium dioxide zirconium dioxide fine powder is the 10wt% of coated powder.Will be above-mentioned thin
Powder adds water after mixing and carries out ball milling, obtains mixed slurry.
Mixed slurry mist projection granulating, about 150 μm of the average grain diameter of granulation material.
By granulation material isostatic pressing, briquetting pressure 300MPa.
Shaping green compact are dried, and are sintered 30 hours at 1650 DEG C.The porosity of sintered specimen is about 0.2%.
Wherein, the preparation process of coated by titanium dioxide zirconium dioxide fine powder is as follows：
Zirconium dioxide raw material average grain diameter is 0.1 μm, and dispersant modified polycarboxylic acid salt AN-2000 consumptions are zirconium dioxide matter
The 0.4% of amount, zirconium dioxide powder is 25 with the volume ratio of water:75, by above-mentioned metering ratio, dispersant A N-2000 is dissolved in
It is 5 with the pH value of newborn acid-conditioning solution in water, adds zirconium dioxide powder, ball milling disperses 48 hours, obtains zirconium dioxide and hang
Supernatant liquid.
Above-mentioned suspension is stirred, TiO 2 sol is slowly added dropwise.In terms of titanium dioxide, zirconium dioxide and two in suspension
The mass ratio of titanium oxide is 90:10.Completion of dropping, continues to stir 4 hours, and suspension then is heated into 80 DEG C, stirs drying,
It is placed in again in drying box and is dried 8 hours at 200 DEG C, then will dry powder and be heat-treated 10 hours at 600 DEG C, is down to room temperature.
Powder after grinding heat treatment, crosses 200 mesh sieves, obtains coated by titanium dioxide zirconium dioxide powder.
Claims (8)
1. a kind of zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material, it is characterised in that：By zirconium
Diamond stone fine powder and coated by titanium dioxide zirconium dioxide fine powder are made；
The preparation method of the coated by titanium dioxide zirconium dioxide fine powder is comprised the following steps：
（1）Prepare zirconium dioxide suspension：
Dispersant modified polycarboxylic acid salt AN-2000 is dissolved in the water, lactic acid adjusts its pH value between 4-5, adds titanium dioxide
Zirconium powder body, obtains the zirconium dioxide suspension of stable suspersion after ball milling；
（2）Prepare coated by titanium dioxide zirconium dioxide fine powder：
Stirring zirconium dioxide suspension, to TiO 2 sol is added dropwise in zirconium dioxide suspension, continues to stir after completion of dropping,
Sol particles is adsorbed on zirconium dioxide particle surface, then suspension is heated and is kept stirring for, make moisture evaporation；Then it is first right
It is dried, then is heat-treated, and titanium dioxide is closely coated on zirconium dioxide particle surface, last ground, sieving,
Obtain coated by titanium dioxide zirconium dioxide fine powder.
2. the zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material according to claim 1,
It is characterized in that：Zircon fine powder accounts for 70-97 wt %, and coated by titanium dioxide zirconium dioxide fine powder accounts for 3-30 wt %.
3. the zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material according to claim 1,
It is characterized in that：The average grain diameter of zircon fine powder between 1-10mm, the average grain of coated by titanium dioxide zirconium dioxide fine powder
Footpath is between 0.1-3mm.
4. the zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material according to claim 1,
It is characterized in that：Content of titanium dioxide in coated by titanium dioxide zirconium dioxide fine powder is the 1-10wt% of coated powder.
5. the zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material according to claim 1,
It is characterized in that：Step（1）The consumption of middle dispersant is the 0.2-0.4 wt% of zirconium dioxide powder, zirconium dioxide powder and water
Volume ratio be 25-50:50-75, Ball-milling Time is 24-48h.
6. the zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material according to claim 1,
It is characterized in that：Step（2）Middle dropwise addition TiO 2 sol continues to stir 4-8h after finishing；Step（2）It is middle to heat suspension
To 80-90 DEG C and it is kept stirring for；Drying temperature is 200-250 DEG C, and drying time is 4-8h；Heat treatment temperature is 600-1000
DEG C, heat treatment time is 4-10h；Step（2）Powder after middle grinding heat treatment crosses 200 mesh sieves, obtains coated by titanium dioxide two
Zirconium powder.
7. a kind of any described zircon/zirconium oxides based on coated by titanium dioxide zirconium dioxide powder of claim 1-6 are multiple
The preparation method of phase material, it is characterised in that comprise the following steps：
（1）Zircon fine powder and the mixing fine powders of coated by titanium dioxide powdered zirconium oxide that ball milling has been weighed by metering, are mixed
Close uniform slurry；
（2）Dry slurry obtain for be molded mixed powder；
（3）Mixed powder is shaped to green compact；
（4）Sintering green compact obtain composite diphase material.
8. the zircon based on coated by titanium dioxide zirconium dioxide powder/zirconium oxide composite diphase material according to claim 7
Preparation method, it is characterised in that：Step（2）Middle drying process is using drying or mist projection granulating；Step（3）Middle moulding process is adopted
With isostatic pressing or dry-pressing formed；Step（4）Middle green compact sinter 20-30h at 1550-1650 DEG C.
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| GB2589905A (en) * | 2019-12-12 | 2021-06-16 | Univ Exeter | Refractory materials and methods of manufacture thereof |
| CN112063040B (en) * | 2020-07-21 | 2021-06-01 | 西安交通大学 | Preparation method of core-shell nano titanium oxide @ zirconium oxide particle-polypropylene maleic anhydride grafted polypropylene composite material |
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| CN1631844A (en) * | 2003-12-22 | 2005-06-29 | 宝山钢铁股份有限公司 | Zircon carbon brick |
| CN1657499A (en) * | 2003-12-16 | 2005-08-24 | 康宁股份有限公司 | Creep resistant zircon refractory material used in a glass manufacturing system |
| CN103992120A (en) * | 2014-04-01 | 2014-08-20 | 浙江立鑫高温耐火材料有限公司 | Supporting brick for glass kiln |
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- 2015-08-21 CN CN201510519042.0A patent/CN105130411B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657499A (en) * | 2003-12-16 | 2005-08-24 | 康宁股份有限公司 | Creep resistant zircon refractory material used in a glass manufacturing system |
| CN1631844A (en) * | 2003-12-22 | 2005-06-29 | 宝山钢铁股份有限公司 | Zircon carbon brick |
| CN103992120A (en) * | 2014-04-01 | 2014-08-20 | 浙江立鑫高温耐火材料有限公司 | Supporting brick for glass kiln |
Non-Patent Citations (1)
| Title |
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| 氧化锆_氧化钛复合粉体的制备与性能;周坤等;《中国粉体技术》;20130831;第19卷(第4期);第10-13，17页 * |
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