CN106282635A - A kind of alloyed oxide complex phase thermal storage refractory and preparation method thereof - Google Patents
A kind of alloyed oxide complex phase thermal storage refractory and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of alloyed oxide complex phase thermal storage refractory and preparation method thereof.Its technical scheme is: with silica flour and aluminium powder as raw material, silica flour content being incremented to by the 3wt% of the 1st grade the 39wt% of the 6th grade step by step, content of aluminium powder also changes with silica flour content, obtains the raw material of 6 ranks.6 rank raw materials are stirred evenly respectively, respectively electric smelting under the conditions of 600 ~ 1500 DEG C, cold-drawn, prepare the B alloy wire of 6 ranks in advance.Being coiled into successively along the equal alloying pellet of radial direction thickness with the B alloy wire of the 1st grade to n-th grade, n is the natural number of 3 ~ 6.At one layer of silane coupler of alloying pellet surface spraying, then spray one layer of compound slip, obtain green-ball base；Green-ball base is dried, burns till at 1200 ~ 1500 DEG C, obtain alloyed oxide complex phase thermal storage refractory.Goods prepared by the present invention have high temperature resistant, resistance to deteriorate, commutating period is short, heat exchange property is high, the good and free of contamination feature of length in service life, reusability.
Description
Technical field
The invention belongs to complex phase thermal storage refractory technical field.It is specifically related to a kind of alloy-oxide complex phase accumulation of heat resistance to
Fire material and preparation method thereof.
Background technology
Refractory material directly applies to the height in the field such as iron and steel, coloured, cement, glass, pottery, chemical industry, mechanically and electrically power
In temperature industrial production process, it is to ensure that the above-mentioned industry requisite basic material of operation and development.China is energy consumption big country, with
The anxiety of environmental requirement and fuel supply, energy-saving and emission-reduction are own is classified as great technological improvement engineering by country.Heat accumulating type waste heat
Recovery technology 19th-century begins to for the scales such as glass furnace, blast funnace hot blast stove, open hearth and coke oven are big and temperature is high mid-term
Stove.
In recent years, the heating furnace of China will develop to the direction of recuperative heater rapidly, except newly-built heating furnace will be more
Coming outside the most employing regenerative heat technology, the most online heating furnace also will progressively transform recuperative heater as.In order to adapt to
This change, improves the serviceability of recuperative heater refractory material further, and recuperative heater will with refractory material
Can be developed further and be applied.Recuperative heater energy-saving effect is notable, environmentally friendly protection and becoming of improving steel
Material rate, is the prior development direction of modern later heating furnace in period.
Since nineteen nineties, research and application aspect in regenerative combustion technology obtain to enter the most greatly in the world
Exhibition, combines energy-conservation and environmental protection, is promoted to " HTAC (HTAC) ".Japan will application heat storage type combustion skill
The industrial furnace of art is referred to as " high performance industrial furnace ", is classified as national great new industrial research problem and application, and obtains notable
Effect.On soda-lime-silica glass kiln, flue gas leaves the temperature the highest (up to more than 1400 DEG C) of flame space, and flue gas is so
Leave kiln at a temperature of height, substantial amounts of heat will be taken away, typically account for the 50～70% of kiln heating load.Therefore, for improving
The thermal efficiency of kiln, reasonable energy utilization, in the structure of glass furnace designs, all have the waste heat utilization equipments such as regenerator.With
Time, for flame temperature required in reaching kiln, in addition to the heat energy that fuel combustion provides, also need to preheat combustion air,
This also one of free-revving engine being introduced into regenerator.
Heat storage be high-temperature heat accumulation equipment in critical component, directly affect the miniaturization of regenerative apparatus, heat exchange efficiency and
Economic benefit.Traditional regenerator uses checker brick to make heat storage, and heat transfer efficiency is low, and regenerator is bulky, and the commutation cycle is long,
Limit its application on other industrial furnace.Nineteen eighty-two, Hotwork Development company of Britain and British Gas
Institute cooperation, succeeds in developing First and uses ceramic bead to make the New Regenerative glass furnace of heat storage.Heat-storing sphere exists
Though being used widely on recuperative heater, but its shortcoming is that thermal efficiency ratio honeycomb ceramics is low, and the heating furnace of equal production volume is filled
The heat storage tank of bead is bigger than the heat storage tank volume of filled honeycomb body, i.e. the area of section of regenerator wants big, and casing number to increase
Add.Ceramic honey comb as heat storage, advantage is that refractoriness specific surface area high, regenerator is big, volume is little, be beneficial to low oxygen combustion,
The most even heat transfer of furnace temperature is rapid, shortcoming be thermal storage density low and by hot and cold air alternating action service life short.
Summary of the invention
It is contemplated that overcome prior art defect, it is therefore an objective to provide a kind of high temperature resistant, intensity is high, resistance to deteriorate, when commutating
Between short, heat exchange property is high, length in service life, reusability are good, low cost and free of contamination alloy-oxide complex phase accumulation of heat resistance to
Fire material and preparation method thereof.
For realizing above-mentioned task, the technical solution adopted in the present invention is:
Step one, with the silica flour of 3 ~ 39wt% and the aluminium powder of 61 ~ 97wt% as raw material, by silica flour content by the 1st grade 3wt% step by step
Being incremented to the 39wt% of the 6th grade, correspondingly, content of aluminium powder is then decremented to the 61wt% of the 6th grade step by step by the 97wt% of the 1st grade, successively
Obtain silica flour is 3wt% and aluminium powder is 97wt% the 1st grade of raw material ..., silica flour be 39wt% and aluminium powder is 61wt% the 6th grade former
Material.
Step 2, by uniform for described 1st grade of raw material stirring, electric smelting under the conditions of 600 ~ 1500 DEG C, cold-drawn, prepare the 1st grade
B alloy wire；Identical with the preparation technology of the 1st grade of B alloy wire, respectively obtain by the 2nd grade of raw material ... with the 6th grade of raw material successively
The 2nd grade of B alloy wire ... preparing and the 6th grade of B alloy wire；The diameter of described B alloy wire is identical, a diameter of 0.1 ~ 1mm.
Step 3, the 1st grade of B alloy wire prepared in advance by step 2, the 2nd grade of B alloy wire ..., thenLevel B alloy wire depends on
The secondary alloying pellet that is coiled into, n is the natural number of 3 ~ 6, and the radius of described alloying pellet is 2 ~ 12mm；1st grade of B alloy wire, the 2nd grade of alloy
Silk ..., n-th grade of B alloy wire along described alloying pellet radial direction to be coiled into thickness equal.
Step 4, the first silane coupler thick at one layer of 0.1 ~ 0.5mm of the alloying pellet surface even application being coiled into, more uniformly
Spray the thick compound slip of one layer of 0.2 ~ 2mm；Described compound slip is having of the metal-oxide by 85 ~ 95wt% and 5 ~ 15wt%
Machine alcohol mixes.
Step 5, by described green-ball base under the conditions of 60 ~ 150 DEG C be dried 24 ~ 36 hours, then at 1200 ~ 1500 DEG C of bars
It is incubated 1 ~ 3 hour under part, obtains alloy-oxide complex phase thermal storage refractory.
The Al content of described aluminium powder > 99.4wt%, particle diameter is 13 ~ 150 μm.
The Si content of described silica flour > 99.5wt%, particle diameter is 13 ~ 88 μm.
Described metal-oxide is more than one in aluminium oxide, magnesium oxide, silicon oxide, the particle diameter of described metal-oxide
<88μm。
Described Organic Alcohol is more than one in ethanol, polyvinyl alcohol, the tert-butyl alcohol.
Owing to using technique scheme, the present invention compared with prior art has a following good effect:
The present invention utilizes the phase transition temperature difference of different content alusil alloy, according to heat conductivility under composite diphase material different conditions with
Dependency between the heat of transformation, it is thus achieved that material thermal conductivity, heat storage capacity and the relation of Temperature Distribution, builds heat storage capacity maximum
Change the Gradient distribution alloy material rapid with exchange capability of heat so that heat conduction and accumulation of heat maximize balance；Utilize metal-oxide
High temperature resistant, high intensity, anti-thermal shock protect alloy spheroid, in conjunction with silane coupler, energy after high-temperature process with decay resistance
Forming microgap to separate without destroying with alloying pellet body, the overall thermal neither affecting alloy-oxide complex phase thermal storage refractory passes
Lead, also improve the anti-fatigue performance of alloy-oxide complex phase thermal storage refractory, thus reach to commutate soon, high heat exchange, longevity
The purpose of life.
Alloy prepared by the present invention-oxide complex phase thermal storage refractory is after testing: bulk density is 2.75 ~ 3.05g/
cm3, closed porosity accounts for total porosity ratio > and 55%, average pore size is 0.1 ~ 0.5 μm.
In-situ alloy prepared by the present invention-oxide complex phase thermal storage refractory main performance is: thermal storage density (△ T=
100 DEG C) it is 424.8 ~ 366.2J/g, heat conductivity is 77.5 ~ 67.3W/ (m DEG C), and compressive resistance is 35 ~ 60MPa, thermal shock
The compressive strength retention that (1000 DEG C) air-cooled 300 times is 95 ~ 99%.
Therefore, the alloy prepared by the present invention-oxide complex phase thermal storage refractory have high temperature resistant, intensity is high, anti-corrosion
Damage, commutating period is short, heat exchange property is high, length in service life, reusability are good, low cost and free of contamination feature.
Alloy prepared by the present invention-oxide complex phase thermal storage refractory, both directly can be used for cigarette as heat storage
The waste heat recovery of gas, it is also possible to as preparing the refractory aggregate of the heat accumulating type refractory product such as checker brick, honeycomb ceramic heat accumulator, suitable
Wide by scope, strong adaptability.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described, not limiting of its scope:
For avoiding repeating, the preparation method Unify legislation of the B alloy wire of the 6 kinds of ranks first this detailed description of the invention prepared in advance
As follows:
With the silica flour of 3 ~ 39wt% and the aluminium powder of 61 ~ 97wt% as raw material, silica flour content is incremented to step by step by the 3wt% of the 1st grade
The 39wt% of 6 grades, correspondingly, content of aluminium powder is then decremented to the 61wt% of the 6th grade step by step by the 97wt% of the 1st grade.1st grade to the 6th grade
Silica flour and the content of aluminium powder of raw material are followed successively by: silica flour is 3 ~ 9wt% and aluminium powder is 91 ~ 97wt%；Silica flour is 9 ~ 15wt% and aluminium powder is
85~91wt%；Silica flour is 15 ~ 21wt% and aluminium powder is 79 ~ 85wt%；Silica flour is 21 ~ 27wt% and aluminium powder is 73 ~ 79wt%；Silica flour is
27 ~ 33wt% and aluminium powder are 67 ~ 73wt%；Silica flour is 33 ~ 39wt% and aluminium powder is 61 ~ 67wt%.
Then described 1st grade of raw material stirring is uniform, electric smelting under the conditions of 600 ~ 750 DEG C, cold-drawn, prepare the 1st grade of alloy
Silk；2nd grade of raw material stirring is uniform, electric smelting under the conditions of 700 ~ 850 DEG C, cold-drawn, prepare the 2nd grade of B alloy wire；By 3rd level raw material
Stir, electric smelting under the conditions of 800 ~ 1000 DEG C, cold-drawn, prepare 3rd level B alloy wire；4th grade of raw material stirring is uniform,
Electric smelting under the conditions of 950 ~ 1200 DEG C, cold-drawn, prepare the 4th grade of B alloy wire；5th grade of raw material stirring is uniform, at 1150 ~ 1350 DEG C of bars
Electric smelting under part, cold-drawn, prepare the 5th grade of B alloy wire；6th grade of raw material stirring is uniform, electric smelting under the conditions of 1300 ~ 1500 DEG C, cold
Pull out, prepare the 6th grade of B alloy wire.The diameter of described B alloy wire is identical, a diameter of 0.1 ~ 1mm.
Again by as follows to the raw material involved by this detailed description of the invention and technological parameter Unify legislation:
The Al content of described aluminium powder > 99.4wt%, particle diameter is 13 ~ 150 μm.
The Si content of described silica flour > 99.5wt%, particle diameter is 13 ~ 88 μm.
Described metal-oxide is more than one in aluminium oxide, magnesium oxide, silicon oxide, the particle diameter of described metal-oxide
<88μm。
Described Organic Alcohol is more than one in ethanol, polyvinyl alcohol, the tert-butyl alcohol.
Above description, repeats no more in each embodiment.
Embodiment 1
A kind of alloy-oxide complex phase thermal storage refractory and preparation method thereof.Described preparation method is:
Step one, with this detailed description of the invention in advance prepare the 1st grade of B alloy wire, the 2nd grade of B alloy wire and 3rd level B alloy wire successively
Being coiled into alloying pellet, the radius of described alloying pellet is 2 ~ 6mm；1st grade of B alloy wire, the 2nd grade of B alloy wire and 3rd level B alloy wire are along described
Alloying pellet radial direction to be coiled into thickness equal.
Step 2, the first silane coupler thick at one layer of 0.1 ~ 0.25mm of the alloying pellet surface even application being coiled into, more all
The compound slip that one layer of 0.2 ~ 0.75mm of even spraying is thick, obtains the green-ball base that radius is 2.3 ~ 7.0mm；Described compound slip be by
The metal-oxide of 85 ~ 95wt% and the Organic Alcohol of 5 ~ 15wt% mix.
Step 3, by described green-ball base under the conditions of 60 ~ 90 DEG C be dried 24 ~ 30 hours, then 1200 ~ 1300 DEG C of conditions
Lower insulation 1 ~ 1.5 hour, obtains alloy-oxide complex phase thermal storage refractory.
Alloy prepared by the present embodiment-oxide complex phase thermal storage refractory main performance is: thermal storage density (△ T=
100 DEG C) it is 424.8 ~ 406.8J/g；Heat conductivity is 77.5 ~ 74.1W/ (m DEG C)；Compressive resistance is 35 ~ 45MPa；Thermal shock
The compressive strength retention that (1000 DEG C) air-cooled 300 times is 95 ~ 96.5%.
Embodiment 2
A kind of alloy-oxide complex phase thermal storage refractory and preparation method thereof.Described preparation method is:
Step one, the 1st grade of B alloy wire, the 2nd grade of B alloy wire, 3rd level B alloy wire and the 4th grade that prepare in advance by this specific embodiment party
B alloy wire is coiled into alloying pellet successively, and the radius of described alloying pellet is 4 ~ 8mm；1st grade of B alloy wire, the 2nd grade of B alloy wire, 3rd level close
Spun gold and the 4th grade of B alloy wire along described alloying pellet radial direction to be coiled into thickness equal.
Step 2, the first silane coupler thick at one layer of 0.2 ~ 0.35mm of the alloying pellet surface even application being coiled into, more all
The compound slip that one layer of 0.5 ~ 1.15mm of even spraying is thick, obtains the green-ball base that radius is 4.7 ~ 9.5mm；Described compound slip be by
The metal-oxide of 85 ~ 95wt% and the Organic Alcohol of 5 ~ 15wt% mix.
Step 3, by described green-ball base under the conditions of 80 ~ 110 DEG C be dried 26 ~ 32 hours, then at 1250 ~ 1350 DEG C of bars
It is incubated 1.5 ~ 2 hours under part, obtains alloy-oxide complex phase thermal storage refractory.
Alloy prepared by the present embodiment-oxide complex phase thermal storage refractory main performance is: thermal storage density (△ T=
100 DEG C) it is 398.2 ~ 385.8J/g；Heat conductivity is 72.5 ~ 70.4W/ (m DEG C)；Compressive resistance is 40 ~ 50MPa；Thermal shock
The compressive strength retention that (1000 DEG C) air-cooled 300 times is 96 ~ 97.5%.
Embodiment 3
A kind of alloy-oxide complex phase thermal storage refractory and preparation method thereof.Described preparation method is:
Step one, the 1st grade of B alloy wire, the 2nd grade of B alloy wire ... and the 5th grade of B alloy wire that prepare in advance by this specific embodiment party
Being coiled into alloying pellet successively, the radius of described alloying pellet is 6 ~ 10mm.1st grade of B alloy wire, the 2nd grade of B alloy wire ... and the 5th grade of conjunction
Spun gold along described alloying pellet radial direction to be coiled into thickness equal.
Step 2, the first silane coupler thick at one layer of 0.3 ~ 0.45mm of the alloying pellet surface even application being coiled into, more all
The compound slip that one layer of 0.8 ~ 1.45mm of even spraying is thick, obtains the green-ball base that radius is 7.1 ~ 11.9mm；Described compound slip is
Mixed by the metal-oxide of 85 ~ 95wt% and the Organic Alcohol of 5 ~ 15wt%.
Step 3, by described green-ball base under the conditions of 100 ~ 130 DEG C be dried 28 ~ 34 hours, then at 1300 ~ 1400 DEG C of bars
It is incubated 2 ~ 2.5 hours under part, obtains alloy-oxide complex phase thermal storage refractory.
Alloy prepared by the present embodiment-oxide complex phase thermal storage refractory main performance is: thermal storage density (△ T=
100 DEG C) it is 389.9 ~ 383.3J/g；Heat conductivity is 71.1 ~ 70.0W/ (m DEG C)；Compressive resistance is 45 ~ 55MPa；Thermal shock
The compressive strength retention that (1000 DEG C) air-cooled 300 times is 97 ~ 98.5%.
Embodiment 4
A kind of alloy-oxide complex phase thermal storage refractory and preparation method thereof.Described preparation method is:
Step one, the 1st grade of B alloy wire, the 2nd grade of B alloy wire ... and the 6th grade of B alloy wire that prepare in advance by this specific embodiment party
Being coiled into alloying pellet successively, the radius of described alloying pellet is 8 ~ 12mm；1st grade of B alloy wire, the 2nd grade of B alloy wire ... and the 6th grade of conjunction
Spun gold along described alloying pellet radial direction to be coiled into thickness equal.
Step 2, the first silane coupler thick at one layer of 0.4 ~ 0.5mm of the alloying pellet surface even application being coiled into, more uniformly
Spray the thick compound slip of one layer of 1.2 ~ 2.0mm, obtain the green-ball base that radius is 9.6 ~ 14.5mm；Described compound slip is by 85
The metal-oxide of ~ 95wt% and the Organic Alcohol of 5 ~ 15wt% mix.
Step 3, by described green-ball base under the conditions of 120 ~ 150 DEG C be dried 30 ~ 36 hours, then at 1350 ~ 1500 DEG C of bars
It is incubated 2.5 ~ 3 hours under part, obtains alloy-oxide complex phase thermal storage refractory.
Alloy prepared by the present embodiment-oxide complex phase thermal storage refractory main performance is: thermal storage density (△ T=
100 DEG C) it is 373.8 ~ 366.2J/g；Heat conductivity is 68.5 ~ 67.3W/ (m DEG C)；Compressive resistance is 50 ~ 60MPa；Thermal shock
The compressive strength retention that (1000 DEG C) air-cooled 300 times is 98 ~ 99%.
This detailed description of the invention compared with prior art has a following good effect:
This detailed description of the invention utilizes the heat conductivility of difference composition alusil alloy and regenerative capacity to constitute Gradient distribution alloy material
Material so that heat conduction and accumulation of heat maximize balance；The high temperature resistant of metal-oxide and high-intensity performance is utilized to protect alloy spheroid, knot
Close silane coupler, microgap can be formed with alloying pellet body after high-temperature process and separate without destroying, neither affect alloy-oxide
The overall thermal conduction of complex phase thermal storage refractory, also improves the anti-fatigue performance of material, thus reach to commutate soon, high heat exchange,
Long-life purpose.
Alloy prepared by this detailed description of the invention-oxide complex phase thermal storage refractory is after testing: bulk density is
2.75~3.05g/cm3, closed porosity accounts for total porosity ratio > and 55%, average pore size is 0.1 ~ 0.5 μm.
In-situ alloy prepared by this detailed description of the invention-oxide complex phase thermal storage refractory main performance is: accumulation of heat
Density (△ T=100 DEG C) is 424.8 ~ 366.2J/g, and heat conductivity is 77.5 ~ 67.3W/ (m DEG C), compressive resistance is 35 ~
60MPa, the compressive strength retention that thermal shock (1000 DEG C) is air-cooled 300 times is 95 ~ 99%.Therefore, prepared by this detailed description of the invention
Alloy-oxide complex phase thermal storage refractory have high temperature resistant, intensity is high, resistance to deteriorate, commutating period is short, heat exchange property is high,
Service life length, reusability is good, low cost and free of contamination feature.
Alloy prepared by this detailed description of the invention-oxide complex phase thermal storage refractory, both can be directly as accumulation of heat
Body is for the waste heat recovery of flue gas, it is also possible to as preparing the resistance to of the heat accumulating type refractory product such as checker brick, honeycomb ceramic heat accumulator
Fire aggregate, applied widely, strong adaptability.
Claims (6)
1. the preparation method of alloy-oxide complex phase thermal storage refractory, it is characterised in that:
Step one, with the silica flour of 3 ~ 39wt% and the aluminium powder of 61 ~ 97wt% as raw material, by silica flour content by the 1st grade 3wt% step by step
Being incremented to the 39wt% of the 6th grade, correspondingly, content of aluminium powder is then decremented to the 61wt% of the 6th grade step by step by the 97wt% of the 1st grade, successively
Obtain silica flour is 3wt% and aluminium powder is 97wt% the 1st grade of raw material ..., silica flour be 39wt% and aluminium powder is 61wt% the 6th grade former
Material；
Step 2, by uniform for described 1st grade of raw material stirring, electric smelting under the conditions of 600 ~ 1500 DEG C, cold-drawn, prepare the 1st grade of alloy
Silk；Identical with the preparation technology of the 1st grade of B alloy wire, respectively obtain and prepared successively by the 2nd grade of raw material ... and the 6th grade of raw material
The 2nd grade of B alloy wire ... and the 6th grade of B alloy wire；The diameter of described B alloy wire is identical, a diameter of 0.1 ~ 1mm；
Step 3, the 1st grade of B alloy wire prepared in advance by step 2, the 2nd grade of B alloy wire ..., thenLevel B alloy wire successively around
Becoming alloying pellet, n is the natural number of 3 ~ 6, and the radius of described alloying pellet is 2 ~ 12mm；1st grade of B alloy wire, the 2nd grade of alloy
Silk ..., n-th grade of B alloy wire along described alloying pellet radial direction to be coiled into thickness equal；
Step 4, the first silane coupler thick at one layer of 0.1 ~ 0.5mm of the alloying pellet surface even application being coiled into, then even application
One layer of compound slip thick for 0.2 ~ 2mm；Described compound slip is the metal-oxide by 85 ~ 95wt% and the Organic Alcohol of 5 ~ 15wt%
Mix；
Step 5, by described green-ball base under the conditions of 60 ~ 150 DEG C be dried 24 ~ 36 hours, then under the conditions of 1200 ~ 1500 DEG C
It is incubated 1 ~ 3 hour, obtains alloy-oxide complex phase thermal storage refractory.
The preparation method of alloy the most according to claim 1-oxide complex phase thermal storage refractory, it is characterised in that described
The Al content of aluminium powder > 99.4wt%, particle diameter is 13 ~ 150 μm.
The preparation method of alloy the most according to claim 1-oxide complex phase thermal storage refractory, it is characterised in that described
The Si content of silica flour > 99.5wt%, particle diameter is 13 ~ 88 μm.
The preparation method of alloy the most according to claim 1-oxide complex phase thermal storage refractory, it is characterised in that described
Metal-oxide is more than one in aluminium oxide, magnesium oxide, silicon oxide, particle diameter < 88 μm of described metal-oxide.
The preparation method of alloy the most according to claim 1-oxide complex phase thermal storage refractory, it is characterised in that described
Organic Alcohol is more than one in ethanol, polyvinyl alcohol, the tert-butyl alcohol.
6. alloy-oxide complex phase thermal storage refractory, it is characterised in that described alloy-oxide complex phase accumulation of heat is fire-resistant
Material is the preparation method according to the alloy according to any one of claims 1 ~ 5-oxide complex phase thermal storage refractory
Prepared alloy-oxide complex phase thermal storage refractory.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107988506A (en) * | 2017-11-29 | 2018-05-04 | 武汉科技大学 | A kind of composite material phase change heat storage balls and preparation method thereof |
| CN110976836A (en) * | 2019-11-11 | 2020-04-10 | 武汉科技大学 | Low-heat-dissipation long-life steel ladle lining body and preparation method thereof |
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| CN105670601A (en) * | 2016-01-05 | 2016-06-15 | 清华大学深圳研究生院 | High-efficiency phase change energy storage microcapsule with thermochromic function, and preparation method thereof |
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| CN102319903A (en) * | 2011-08-05 | 2012-01-18 | 北京北矿锌业有限责任公司 | Preparation method for hollow microspheres |
| JP2015048393A (en) * | 2013-08-30 | 2015-03-16 | 株式会社金星 | Heat reservoir |
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| CN107988506A (en) * | 2017-11-29 | 2018-05-04 | 武汉科技大学 | A kind of composite material phase change heat storage balls and preparation method thereof |
| CN110976836A (en) * | 2019-11-11 | 2020-04-10 | 武汉科技大学 | Low-heat-dissipation long-life steel ladle lining body and preparation method thereof |
| CN110976836B (en) * | 2019-11-11 | 2021-09-14 | 武汉科技大学 | Low-heat-dissipation long-life steel ladle lining body and preparation method thereof |
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