CN110156463B - A kind of compound refractory material and preparation method thereof - Google Patents

A kind of compound refractory material and preparation method thereof Download PDF

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Publication number
CN110156463B
CN110156463B CN201910649219.7A CN201910649219A CN110156463B CN 110156463 B CN110156463 B CN 110156463B CN 201910649219 A CN201910649219 A CN 201910649219A CN 110156463 B CN110156463 B CN 110156463B
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refractory material
raw material
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barium zirconate
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CN110156463A (en
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戴燎元
陈显祥
谢耀明
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Zaozhuang Xinda Energy Saving Technology Development LLC
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Hunan 352 Environmental Protection & Technology Co Ltd
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Abstract

The invention belongs to titanium alloy smelting crucible fire resisting material fields, specially a kind of compound refractory material and preparation method thereof, the compound refractory material include made by the following raw material by weight: 50~60 parts of barium zirconate powder, 5~10 parts of bleeding agent, 6~8 parts of octanol, 10~15 parts of binder, 5~8 parts of yttrium oxide, 6~10 parts of calcium oxide, 10~20 parts of zirconium dioxide；The preparation method of the compound refractory material, include the following steps: grouping mixing, dry, sintering and heat treatment, when the present invention prepares refractory material, is mixed by the way of gradually adding raw materials, its mixing is more uniform, the agglomerating phenomenon for reducing raw material increases the intergranular contact area of each reactant, so that finer and close using melting crucible prepared by the refractory material, also have sintering temperature low simultaneously, the advantages of easy sinter molding, open defect is few, high yield rate.

Description

A kind of compound refractory material and preparation method thereof
Technical field
The invention belongs to titanium alloy smelting crucible fire resisting material field, specially a kind of compound refractory material and its preparation Method.
Background technique
Barium zirconate is a kind of extremely stable refractory material, is to prepare high quality single crystal Yt-Ba-Cu-O superconductor material at present The ideal crucible material of material.When barium zirconate is used for crucible smelting titanium alloy, barium zirconate refractory material and titanium alloy show compared with The wetability of difference has no that crucible element is spread into melt without transition zone between melt and crucible, illustrates that barium zirconate is that one kind has The casting titanium alloy smelting mold refractory material of potentiality.
But there is also some problems to need to solve as refractory material for barium zirconate, and the forming temperature of barium zirconate is higher, because This is sintered in preparation process at it, it is difficult to which the temperature of sinter molding, sintering is often higher；Simultaneously because barium zirconate quality is more crisp, Product splits caused by it is easy the extension because of fine cracks during the sintering process, and product is not fine and close enough, influences the use of product, most Whole yield rate is lower.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, this application provides a kind of compound refractory material and its preparation sides Method.
Technical scheme is as follows:
A kind of compound refractory material, including made by the following raw material by weight: 50~60 parts of barium zirconate powder, 5~10 parts of bleeding agent, 6~8 parts of octanol, 10~15 parts of binder, 5~8 parts of yttrium oxide, 6~10 parts of calcium oxide, zirconium dioxide 10 ~20 parts.
The average particle size of the barium zirconate powder is 160~180 microns, and the barium zirconate powder is electric smelting barium zirconate powder Body.
The bleeding agent is one in fatty alcohol polyoxyethylene ether, isomeric alcohol polyethenoxy ether or alkyl phenol polyoxyethylene ether Kind.
The binder includes yttrium colloidal sol and acidic silicasol, and the mixed proportion of the yttrium colloidal sol and acidic silicasol is 2: 1。
The preparation method of the compound refractory material, includes the following steps:
Step 1: grouping mixing: bleeding agent, octanol and binder are first group, barium zirconate powder, yttrium oxide, calcium oxide And zirconium dioxide is second group, is respectively uniformly mixed two groups of raw materials, and a small amount of second group of original is gradually added into first group of raw material Material is added next time again after so that two groups of raw material mixing is uniformly dispersed, until having added all second group of raw materials, is added every time Amount is the 10~20% of second group of total weight；
Step 2: dry: step 1 is grouped mixed raw material and stands 6~8 hours, it is sufficiently dry to it；
Step 3: sintering: the raw material obtained after step 2 is sufficiently dried carries out high temperature under 1080~1200 degrees Celsius Sintering；
Step 4: heat treatment: after the material that step 3 obtains is cooling, by it at 1100~1300 degrees Celsius and 100,000,000 High-temperature process is carried out under conditions of pa, up to compound refractory material after cooling down again.
After having added second group of raw material in the step 1 every time, dispersion is stirred to it using ultrasonic stirrer.
When step 4 high temperature processing, first heated 10 minutes under 1100 degrees celsius, it is Celsius 1300 later 2~4 hours are kept the temperature under the conditions of degree.
The present invention is beneficial to be had the technical effect that
1. compound refractory material of the invention is for preparing titanium alloy smelting crucible, by being added simultaneously in the feed The yttrium oxide and calcium oxide of special ratios utilize the synergistic effect of yttrium oxide and calcium oxide and zirconium dioxide sinter molding, a side Cation in the yttrium oxide of face can cation in substitutionary oxydation calcium, form Substitutional type solid solution, play stable calcium oxide Effect, so that sintered finished product is not easy decalcification unstability, on the other hand there are two types of crystal for formation in sintered finished product: tetragonal Body and cubic crystal, two kinds of crystal Uniform Dopeds are in the refractory material based on barium zirconate, when generating fine cracks, two kinds of crystalline substances Body is transformed into a kind of monoclinic crystal, and volume " expansion ", which becomes larger, to be filled in crackle, and pressure is also induced along with volume expansion Stress under compression plays a part of reducing crack driving force for propagation, to prevent the extension of crackle, while carrying out after material sintering to it Corresponding heat treatment, reduces the generation of bubble and crackle in material, so that the yield of final products is greatly promoted, and most The toughness of final shaping unit material is higher；
2. binder, octanol and bleeding agent three to be carried out to the combination of special ratios, carried out with barium zirconate powder sufficiently mixed After conjunction, octanol forms functionally complementary as surfactant and bleeding agent, and binder can preferably infiltrate into barium zirconate In powder, so that granule number when sintering in material unit volume is larger, intergranular active force is also increased accordingly, and viscosity becomes Greatly, it is sintered in preparation process and is more easier to form, while also reducing sintering temperature；
3. grouping mixing when mixed by the way of gradually adding raw materials, mix it is more uniform, reduce raw material at Group's phenomenon, increases the intergranular contact area of each reactant, so that more being caused using melting crucible prepared by the refractory material It is close.
Specific embodiment
Below with reference to embodiment, the present invention is specifically described.Obviously, described embodiment is only the present invention one Section Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not doing Every other embodiment obtained under the premise of creative work out, shall fall within the protection scope of the present invention.
Embodiment 1
A kind of compound refractory material, including made by the following raw material by weight: 50 parts of barium zirconate powder, fat 5 parts of alcohol polyoxyethylene ether, 6 parts of octanol, the yttrium colloidal sol that mixed proportion is 2:1 and 10 parts of acidic silicasol, 5 parts of yttrium oxide, oxidation 6 parts of calcium, 10 parts of zirconium dioxide.
The preparation method of compound refractory material in the present embodiment, includes the following steps:
Step 1: weighing the raw material of above-mentioned parts by weight meter, mixing is grouped to it, wherein bleeding agent, octanol and bonding Agent is first group, and barium zirconate powder, yttrium oxide, calcium oxide and zirconium dioxide are second group, is respectively uniformly mixed two groups of raw materials, A small amount of second group of raw material is gradually added into first group of raw material, is mixed two groups of raw materials using JY-Y202G type ultrasonic stirrer It is added next time again after being uniformly dispersed, until having added all second group of raw materials, each additional amount is second group of total weight 10%；
Step 2: dry: step 1 is grouped mixed raw material and stands 6 hours, it is sufficiently dry to it；
Step 3: sintering: it is small that the raw material obtained after step 2 is sufficiently dried carries out high temperature sintering 4 under 1080 degrees Celsius When；
Step 4: heat treatment: after material that step 3 obtains is cooling, place it in vacuum drying oven, adjust pressure to 100 megapascal first heat 10 minutes under 1100 degrees celsius, keep the temperature 2 hours under 1300 degrees celsius later, cold again But up to compound refractory material after.
Embodiment 2
A kind of compound refractory material, including made by the following raw material by weight: 55 parts of barium zirconate powder, isomery 8 parts of alcohol polyoxyethylene ether, 7 parts of octanol, the yttrium colloidal sol that mixed proportion is 2:1 and 13 parts of acidic silicasol, 7 parts of yttrium oxide, oxidation 7 parts of calcium, 15 parts of zirconium dioxide.
The preparation method of compound refractory material in the present embodiment, includes the following steps:
Step 1: weighing the raw material of above-mentioned parts by weight meter, mixing is grouped to it, wherein bleeding agent, octanol and bonding Agent is first group, and barium zirconate powder, yttrium oxide, calcium oxide and zirconium dioxide are second group, is respectively uniformly mixed two groups of raw materials, A small amount of second group of raw material is gradually added into first group of raw material, is mixed two groups of raw materials using JY-Y202G type ultrasonic stirrer It is added next time again after being uniformly dispersed, until having added all second group of raw materials, each additional amount is second group of total weight 15%；
Step 2: dry: step 1 is grouped mixed raw material and stands 7 hours, it is sufficiently dry to it；
Step 3: sintering: it is small that the raw material obtained after step 2 is sufficiently dried carries out high temperature sintering 4 under 1150 degrees Celsius When；
Step 4: heat treatment: after material that step 3 obtains is cooling, place it in vacuum drying oven, adjust pressure to 100 megapascal first heat 10 minutes under 1100 degrees celsius, keep the temperature 3 hours under 1300 degrees celsius later, cold again But up to compound refractory material after.
Embodiment 3
A kind of compound refractory material, including made by the following raw material by weight: 60 parts of barium zirconate powder, alkyl 10 parts of phenol polyethenoxy ether, 8 parts of octanol, the yttrium colloidal sol that mixed proportion is 2:1 and 15 parts of acidic silicasol, 8 parts of yttrium oxide, oxidation 10 parts of calcium, 20 parts of zirconium dioxide.
The preparation method of compound refractory material in the present embodiment, includes the following steps:
Step 1: weighing the raw material of above-mentioned parts by weight meter, mixing is grouped to it, wherein bleeding agent, octanol and bonding Agent is first group, and barium zirconate powder, yttrium oxide, calcium oxide and zirconium dioxide are second group, is respectively uniformly mixed two groups of raw materials, A small amount of second group of raw material is gradually added into first group of raw material, is mixed two groups of raw materials using JY-Y202G type ultrasonic stirrer It is added next time again after being uniformly dispersed, until having added all second group of raw materials, each additional amount is second group of total weight 20%；
Step 2: dry: step 1 is grouped mixed raw material and stands 8 hours, it is sufficiently dry to it；
Step 3: sintering: it is small that the raw material obtained after step 2 is sufficiently dried carries out high temperature sintering 4 under 1200 degrees Celsius When；
Step 4: heat treatment: after material that step 3 obtains is cooling, place it in vacuum drying oven, adjust pressure to 100 megapascal first heat 10 minutes under 1100 degrees celsius, keep the temperature 4 hours under 1300 degrees celsius later, cold again But up to compound refractory material after.
Reference examples 1
Difference with embodiment 3 is: all have disposably been added in the step of preparing the compound refractory material one Two groups of raw materials.
Prepare the following raw material: 60 parts of barium zirconate powder, 10 parts of alkyl phenol polyoxyethylene ether, 8 parts of octanol, mixed proportion 2: 1 15 parts of yttrium colloidal sol and acidic silicasol, 8 parts of yttrium oxide, 10 parts of calcium oxide, 20 parts of zirconium dioxide.
Preparation step is as follows:
Step 1: weighing the raw material of above-mentioned parts by weight meter, mixing is grouped to it, wherein bleeding agent, octanol and bonding Agent is first group, and barium zirconate powder, yttrium oxide, calcium oxide and zirconium dioxide are second group, is disposably added into first group of raw material Enter all second group of raw materials, two groups of raw materials are mixed using JY-Y202G type ultrasonic stirrer and are uniformly dispersed；
Step 2: dry: step 1 is grouped mixed raw material and stands 8 hours, it is sufficiently dry to it；
Step 3: sintering: it is small that the raw material obtained after step 2 is sufficiently dried carries out high temperature sintering 4 under 1200 degrees Celsius When；
Step 4: heat treatment: after material that step 3 obtains is cooling, place it in vacuum drying oven, adjust pressure to 100 megapascal first heat 10 minutes under 1100 degrees celsius, keep the temperature 4 hours under 1300 degrees celsius later, cold again But up to compound refractory material after.
Reference examples 2
Difference with embodiment 3 is: yttrium oxide and calcium oxide are not added in the preparation of the compound refractory material.
Prepare the following raw material: 60 parts of barium zirconate powder, 10 parts of alkyl phenol polyoxyethylene ether, 8 parts of octanol, mixed proportion 2: 1 15 parts of yttrium colloidal sol and acidic silicasol, 20 parts of zirconium dioxide.
Step 1: weighing the raw material of above-mentioned parts by weight meter, mixing is grouped to it, wherein bleeding agent, octanol and bonding Agent is first group, and barium zirconate powder and zirconium dioxide are second group, is respectively uniformly mixed two groups of raw materials, into first group of raw material A small amount of second group of raw material is gradually added, two groups of raw materials are mixed using JY-Y202G type ultrasonic stirrer after being uniformly dispersed again into Row adds next time, until having added all second group of raw materials, each additional amount is the 20% of second group of total weight；
Step 2: dry: step 1 is grouped mixed raw material and stands 8 hours, it is sufficiently dry to it；
Step 3: sintering: it is small that the raw material obtained after step 2 is sufficiently dried carries out high temperature sintering 4 under 1200 degrees Celsius When；
Step 4: heat treatment: after material that step 3 obtains is cooling, place it in vacuum drying oven, adjust pressure to 100 megapascal first heat 10 minutes under 1100 degrees celsius, keep the temperature 4 hours under 1300 degrees celsius later, cold again But up to compound refractory material after.
Reference examples 3
Difference with embodiment 3 is: not being heat-treated in the preparation of the compound refractory material.
Prepare the following raw material: 60 parts of barium zirconate powder, 10 parts of alkyl phenol polyoxyethylene ether, 8 parts of octanol, mixed proportion 2: 1 15 parts of yttrium colloidal sol and acidic silicasol, 8 parts of yttrium oxide, 10 parts of calcium oxide, 20 parts of zirconium dioxide.
Preparation step is as follows:
Step 1: weighing the raw material of above-mentioned parts by weight meter, mixing is grouped to it, wherein bleeding agent, octanol and bonding Agent is first group, and barium zirconate powder, yttrium oxide, calcium oxide and zirconium dioxide are second group, is respectively uniformly mixed two groups of raw materials, A small amount of second group of raw material is gradually added into first group of raw material, is mixed two groups of raw materials using JY-Y202G type ultrasonic stirrer It is added next time again after being uniformly dispersed, until having added all second group of raw materials, each additional amount is second group of total weight 20%；
Step 2: dry: step 1 is grouped mixed raw material and stands 8 hours, it is sufficiently dry to it；
Step 3: sintering: it is small that the raw material obtained after step 2 is sufficiently dried carries out high temperature sintering 4 under 1200 degrees Celsius When, up to compound refractory material after cooling.
Reference examples 4
Difference with embodiment 3 is: binder, octanol and infiltration are not added in the preparation of the compound refractory material Agent, and add conventional titanium dioxide and be sintered as fluxing agent.
Prepare the following raw material: 50 parts of barium zirconate powder, 5 parts of yttrium oxide, 6 parts of calcium oxide, 10 parts of zirconium dioxide, titanium dioxide 10 parts.
Preparation step is as follows:
Step 1: weighing the raw material of above-mentioned parts by weight meter, it is carried out to be sufficiently mixed uniformly；
Step 2: sintering: it is small that the raw material that step 1 is obtained after mixing carries out high temperature sintering 4 under 1800 degrees Celsius When；
Step 3: heat treatment: after material that step 2 obtains is cooling, place it in vacuum drying oven, adjust pressure to 100 megapascal first heat 10 minutes under 1100 degrees celsius, keep the temperature 2 hours under 1300 degrees celsius later, cold again But up to compound refractory material after.
Material prepared by above-described embodiment 1-3 and reference examples 1-3 is carried out to the test of appearance and physical property, test knot Fruit is as shown in table 1 below:
Table 1
Figure 225853DEST_PATH_IMAGE001
(remarks: in table " obvious crackle " refer to not by it is microscopical under the conditions of, what can visually be observed splits Line.)
From table 1 it follows that embodiment 3 for reference examples 1, is mixed by gradually adding raw materials, institute The bulk density for obtaining refractory material is bigger, and finally formed refractory material is finer and close；Embodiment 3 for reference examples 2, By addition yttrium oxide and calcium oxide raw material, the bend resistance intensity of material is improved, refractory material toughness obtained is more preferable；Implement Example 3, by increasing the step for being heat-treated in the preparation process of refractory material, significantly reduces for reference examples 3 The porosity of obtained refractory material and obvious crackle accounting, greatly reduce open defect；
Cation using the synergistic effect of yttrium oxide and calcium oxide and zirconium dioxide sinter molding, in one side yttrium oxide Can cation in substitutionary oxydation calcium, form Substitutional type solid solution, play the role of stable calcium oxide so that it is sintered at Product are not easy decalcification unstability, and on the other hand there are two types of crystal for formation in sintered finished product: tetragonal crystal and cubic crystal, two kinds of crystalline substances Body Uniform Doped is in the refractory material based on barium zirconate, and when generating fine cracks, two kinds of crystalline transformations are at a kind of monoclinic crystal Body, volume " expansion ", which becomes larger, to be filled in crackle, and also induces compression stress along with volume expansion, plays reduction crackle The effect of external drive power to prevent the extension of crackle, while being heat-treated it after material sintering accordingly, reduced The generation of bubble and crackle in material so that the yield of final products is greatly promoted, and the toughness of final molding material compared with It is high.
Above-described embodiment 1-3 and reference examples 4 are sintered to the test of temperature and fire resistance, test result is as follows table 2 It is shown:
Table 2
From Table 2, it can be seen that embodiment 1-3 for reference examples 4, is ensureing refractory material items fire resistance Under the premise of, by the addition of binder, octanol and bleeding agent, significantly reduce the forming temperature of refractory material；
Binder, octanol and bleeding agent three carry out the combination of special ratios, after being sufficiently mixed with barium zirconate powder, Octanol forms functionally complementary as surfactant and bleeding agent, and octanol and bleeding agent coat after mixing with barium zirconate powder On barium zirconate powder granule surface, binder is enable preferably to infiltrate into barium zirconate powder, material unit volume when sintering Interior granule number is larger, and intergranular active force also increases accordingly, and viscosity becomes larger, and is sintered in preparation process and is more easier to form, Sintering temperature is also reduced simultaneously；
In conclusion the refractory material prepared through the invention, has sintering temperature low, it is easy sinter molding, material is more Add densification, the advantages of open defect is few, high yield rate.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, for ability For the those of ordinary skill in domain, these embodiments can be carried out without departing from the principles and spirit of the present invention more Kind change, modification, replacement and modification, therefore without departing from the general concept defined in the claims and the equivalent scope, this hair It is bright to be not limited to specific details.

Claims (6)

1. a kind of compound refractory material, which is characterized in that including made by the following raw material by weight: barium zirconate powder 50~60 parts, 5~10 parts of bleeding agent, 6~8 parts of octanol, 10~15 parts of binder, 5~8 parts of yttrium oxide, 6~10 parts of calcium oxide, 10~20 parts of zirconium dioxide.
2. a kind of compound refractory material according to claim 1, it is characterised in that: the average grain of the barium zirconate powder Degree is 160~180 microns, and the barium zirconate powder is electric smelting barium zirconate powder.
3. a kind of compound refractory material according to claim 1, it is characterised in that: the bleeding agent is fatty alcohol polyoxy One of vinethene, isomeric alcohol polyethenoxy ether or alkyl phenol polyoxyethylene ether.
4. a kind of preparation method of compound refractory material as described in claim 1, which comprises the steps of:
Step 1: grouping mixing: bleeding agent, octanol and binder are first group, barium zirconate powder, yttrium oxide, calcium oxide and two Zirconium oxide is second group, is respectively uniformly mixed two groups of raw materials, a small amount of second group of raw material is gradually added into first group of raw material, makes Two groups of raw material mixing are added next time again after being uniformly dispersed, until having added all second group of raw materials, each additional amount is The 10~20% of second group of total weight；
Step 2: dry: step 1 is grouped mixed raw material and stands 6~8 hours, it is sufficiently dry to it；
Step 3: sintering: the raw material obtained after step 2 is sufficiently dried carries out high temperature sintering under 1080~1200 degrees Celsius；
Step 4: heat treatment: after material that step 3 obtains is cooling, by it in 1100~1300 degrees Celsius and 100 megapascal Under the conditions of carry out high-temperature process, up to compound refractory material after cooling down again.
5. a kind of preparation method of compound refractory material according to claim 4, which is characterized in that in the step 1 After having added second group of raw material every time, dispersion is stirred to it using ultrasonic stirrer.
6. a kind of preparation method of compound refractory material according to claim 4, which is characterized in that in the step 4 When high-temperature process, is first heated under 1100 degrees celsius 10 minutes, keep the temperature 2~4 hours under 1300 degrees celsius later.
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