CN101704632B - Preparation method of high-strength low-density hollow glass bead - Google Patents

Preparation method of high-strength low-density hollow glass bead Download PDF

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Publication number
CN101704632B
CN101704632B CN200910185799A CN200910185799A CN101704632B CN 101704632 B CN101704632 B CN 101704632B CN 200910185799 A CN200910185799 A CN 200910185799A CN 200910185799 A CN200910185799 A CN 200910185799A CN 101704632 B CN101704632 B CN 101704632B
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China
Prior art keywords
glass
hollow glass
density
hollow
classification
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CN200910185799A
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CN101704632A (en
Inventor
彭寿
王芸
彭小波
彭程
鲍田
王华文
倪嘉
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China Triumph International Engineering Co Ltd
Bengbu Glass Industry Design and Research Institute
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China Triumph International Engineering Co Ltd
Bengbu Glass Industry Design and Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/10—Forming beads
    • C03B19/107—Forming hollow beads
    • C03B19/1075—Forming hollow beads by blowing, pressing, centrifuging, rolling or dripping
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Abstract

The invention provides a high-strength low-density hollow glass bead and a preparation method thereof. The hollow glass bead comprises the following chemical compositions: SiO2 (70%-80%), Na2O (8%-12%), CaO (5%-9%), B2O3 (2%-6%), SO3 (0.02%-1.25%), R2O (0-5% excepting Na2O), RO (0-5% excepting CaO) and R2O3 (0-5% excepting B2O3); and the density of the obtained hollow glass bead is less than or equal to 0.3g/cm3, the compressive strength thereof is more than or equal to 12MPa, the size of particle diameter thereof is 10-60 mum, and the rate of floatage thereof is more than or equal to 95%. The high-strength low-density hollow glass bead is applied in the industries such as petrochemical industry, automobiles and ships, aerospace and the like and the military field as light-weight filler, especially in the fields with high-strength low-density requirements such as aerospace ablative materials and deep-sea diving equipment materials.

Description

A kind of preparation method of high-strength low-density hollow glass bead
Technical field:
The present invention relates to mineral filler, particularly a kind of hollow glass micropearl, it is widely used in fields such as oil, chemical industry, shipbuilding, space flight and aviation, radiotelegraphy, especially is applied in the aerospace low density ablator.
Background technology:
Hollow glass micropearl is a hollow; Include the miniature spherical material of rare gas element; It is a kind of unique properties and stable hollow minute particle;, characteristics such as heat conductivility low, specific inductivity little, resistance to chemical attack little owing to its density are widely used in military, civilian and other high-tech areas such as petrochemical complex, emulsion [explosive, heat-insulating fire-proofing material, stealthy deadener, high-grade insulating materials, Chemicals additive, low density ablator; Especially in aerospace material, become very useful material; Can be used for preparing that density is low, intensity is high, modulus is high, proportion is low, the material of heat-resisting burn-out proof and high electric insulation property, and have good processing characteristics, generally do not need special processing units.Microballoon only mixes with liquid organic material can obtain homogeneous material with common stirring means, and this light material is much easier than the technology of sponge made from chemicalfoaming or porous plastics, and quality also is easy to control.
Mainly contain two kinds of products in the market, a kind of is the cenosphere that coal dust produces in combustion processes, the appearance gray, and chemical constitution is main with silicon-dioxide and aluminum oxide, and the composition fluctuation is big, and ultimate compression strength is low.Another kind is the hollow glass micropearls of people through industrially producing, and is main with borosilicate and aluminosilicate mainly, and outward appearance is white in color, and can design the hollow glass micropearl of various performances according to the market requirement.Because its hardness height, light weight, fire prevention, insulation, ultimate compression strength is high, thermal conductivity is low, dispersed, mobile, all good advantageous characteristic of stability, adds modification and obtains very big development as material.
Patents such as U.S. US3365315, US4391646, US5217928 and Russian R2059574 have been introduced the chemical constitution and the method for hollow glass micropearl preparation, and the density of its cenosphere is at 0.1～0.7g/cm 3Between, the different ultimate compression strength of density are also different, and the pairing ultimate compression strength of different densities model is respectively between 2～120Mpa, but the density≤0.3g/cm that on low density ablator, uses 3, the hollow glass micropearl of ultimate compression strength>=12MPa does not appear in the newspapers, though China has produced hollow glass micro-ball at present; But of less types, specification is incomplete yet, to the microballoon of some properties; Like electronic-grade. hollow glass micro-ball high intensity level, the ocean level and different sphere diameters; The further development of still needing, the hollow glass micropearl that uses on the especially manned engineering low density ablator is blank especially, this big limitations the development of China's aerospace cause.Facts have proved, obtained effect preferably,, more should pay attention to and quicken hollow glass micro-ball research in today of aviation and aerospace industry develop rapidly with the light material that hollow glass micro-ball is processed.
Summary of the invention:
One of the object of the invention is exactly the defective that density is higher, intensity is lower that exists to existing hollow glass micropearl; A kind of high-strength low-density hollow glass bead that provides; This product not only can be used on the manned return capsule ablator, but also can be used on many product for civilian use industries such as oil high temperature deep well, light weight cement, emulsion [explosive.
Another object of the present invention is to provide a kind of preparation method of high-strength low-density hollow glass bead, this method obtains the needs that hollow glass micropearl can satisfy aerospace material.
To achieve these goals, the hollow glass micropearl of a kind of high-strength low-density provided by the invention, its composition comprises the following weight proportion raw material:
SiO 270%～80%, Na 2O 8%～12%, and CaO 5%～9%, B 2O 32%～6%, SO 30.2%～0.5%, R 2O (removes Na 2O is outer) 0～5%, RO (except that CaO) 0～5%, R 2O 3(remove B 2O 3Outward) 0～3%,
SiO 2Be the staple of microballon of the present invention, account for 60%～90% of weight ratio usually, for mass percent of the present invention in 70%～80% the best.If SiO 2Reduce to 60%～70% of mass percent, the intensity of microballon can reduce, and density can increase.If but SiO 2Be increased to 80%～90% of mass percent, form for best glass microballon, the glass melting temperature improves, and glass viscosity improves, and significantly reduces the output of glass microballon.
Na 2O can reduce the temperature of fusion of glass, reduces the glass metal viscosity greatly, increases temperature flowing property simultaneously, is good fusing assistant.But too high levels can reduce the physical strength chemicalstability and the thermostability of glass, thus the content of sodium oxide be controlled at mass percent 8%～12% between.
The CaO mass percent is between 5%～9%, and its effect is physical strength, hardness and the chemicalstability that improves glass.
B 2O 3Mass percent is between 2%～6%, and it mainly acts on is to be used for reducing melt temperature, improves chemical durability and low heat expansion property.
SO 3Effect is as whipping agent, selects a certain amount of SO 3Be included in and obtain the ideal expansion in the glass particle, thereby obtain the hollow glass micropearl of certain density.The rational SO of the present invention 3Scope is 0.2%～0.5%.
R 2O comprises except that Na 2Alkalimetal oxide K beyond the O 2O and Li 2O, it is favourable adding multiple alkalimetal oxide, can produce the alkali resistance that " two alkali effect " improves hollow glass micropearl, in addition, Li 2The introducing of O can reduce the temperature of fusion of glass, plays better fluxing action, and its content is controlled in 5%.
RO in the glass (except that CaO) is oxide compound ZnO and BaO, and mass percent is between 0～5%.An amount of adding of these oxide compounds can improve and in than large-temperature range, keeps SO in the glass smelting process 3
R in the glass 2O 3(remove B 2O 3Oxide compound Al preferably outward) 2O 3, mass percent is between 0～3%, and it can improve the chemicalstability of glass microballon, but add-on is crossed conference and is made SO in the glass particle 3Content reduces, so its content is no more than 3%.
Another characteristics of the present invention provide a kind of preparation method of said hollow glass micropearl, and said method may further comprise the steps successively:
1. batching: take by weighing raw material and mix according to the chemical constitution prescription of frit;
2. melt shrend: the frit that mixes is dropped in the melting furnaces found, glass melting temperature is 1350 ℃～1450 ℃, and melting time is 1～2 hour, pours the glass metal that melts in watch-quench tank shrend then;
3. dry crushing and classification: the frit oven dry that shrend is good, through the jet mill grinding machine, grinding is classified as the glass powder of 5 ~ 40 μ m then;
4. hollow nodularization: good frit is put into feed hopper will to process classification; Opening for feed is located at the burner bottom; From bottom centre's charging; Converge through feeding-passage entering quirk and burning state air-flow, combustion gas is sprayed by nozzle through blast tube, and combustion air flows into the combustion gas mixing and the burning of furnace chamber and ejection at spinning disk effect underspin through air passageways.The flow direction of glass microballon is consistent with the flow direction of combustion gas flowing; The glass microballon particle is in burned flame after the fusion endways under the induced draft fan effect; Can only flow vertically upward and cooling rapidly, thereby avoid fused glass microballon and furnace wall or the collision of other devices, thereby improve the bead yield rate of glass microballon; Color and luster and rounding property also improve greatly, and the temperature of balling furnace is 1100 ℃～1300 ℃.
5. collect sorting: the glass powder through balling furnace heated is collected through rotoclone collector and cloth bag scoop, and the principle of work of rotoclone collector is for after getting into scoop when dust-contained airflow by tangential inlet, and air-flow rotates in scoop; Grit in the air-flow is outside move under centrifugal action; Arrive wall, and fall into ash bucket and reach isolating purpose, and the cloth bag scoop is mainly collected dust through sieving effect, inertial collision effect and diffusional effect at air-flow and action of gravity lower edge wall; Dust to 1.0 μ m; Efficient reaches 98%-99%, and its equipment is known products, and tail gas is discharged through the traction blower fan.Collected glass powder is isolated hollow glass micropearl through floating method.
Adopt its granularity of hollow glass micropearl of preparing method's gained of the present invention to concentrate on 10 ~ 60 μ m, density≤0.3g/cm 3, ultimate compression strength>=12Mpa, its floatability:>=95%.Like this, to hollow glass micropearl intensity and density requirements than higher like industries such as the high pressure resistance lightweight of space flight and aviation tackiness agent, low density ablator and the high deep drillings of oil, reliable high-quality product is provided.
Below in conjunction with embodiment the present invention is described particularly.
Embodiment one:
1, batching: silica sand 293.18kg, feldspar 36.38kg, lime carbonate 53.42kg, boric acid 22.72kg, zinc oxide 6.35kg, yellow soda ash 62.43kg, Quilonum Retard 14.59kg, saltcake 11.38kg.With above material thorough mixing.
2, put into the frit that mixes in the electric smelting crucible, founded 1-2 hour for 1450 ℃, through sample examination, the glass chemistry composition after the fusing is SiO 275%, Na 2O 10%, and CaO 7%, B 2O 33%, ZnO1.5%, Al 2O 31.5%, Li 2O 1.5% and SO 30.5%.
3, pour the glass metal that melts in watch-quench tank shrend; Then the glass cullet of shrend were dried 5 hours at 200 ℃～300 ℃.
4, the glass cullet of oven dry are worn into the particle about 1mm, and then in the jet mill grinding machine, with the glass particle crushing and classification, the granular powder particle diameter D behind the crushing and classification 10=3.99 μ m, D 50=19.38 μ m, D 90=39.06 μ m, maximum particle diameter is no more than 70 μ m.
5, the glass powder that classification is good is sent into balling furnace with the speed of 8kg/h with charging machine; The nodularization temperature is controlled at 1250 ℃, and the nodularization time is 0.5 second, and the glass powder of the hollow nodularization of process is after scoop is collected; Sub-elect hollow glass micropearl with showy method; The particle diameter of the hollow glass micropearl that sub-elects concentrates between 10 ~ 60 μ m basically, and showy rate is 98%, and density is 0.28g/cm 3, it is 16MPa that calculating crushing by volume accounts for volume 5% cenosphere crushing strength.
Embodiment two:
1, batching: calculate by weight, silica sand 291.6kg, feldspar 23.04kg, lime carbonate 60.89kg, boric acid 22.66kg, zinc oxide 6.33kg, yellow soda ash 77.61kg, Quilonum Retard 15.02kg, saltcake 11.35kg is with above material thorough mixing.
2, put in the electric smelting crucible 1400 ℃ to the frit that mixes and founded 1-2 hour, through sample examination, the glass chemistry composition after the fusing is SiO 273%, Na 2O 11%, and CaO 8%, B 2O 33%, ZnO 1.5%, Al 2O 31.0%, Li 2O 1.5% and SO 30.4%.
3, pour the glass metal that melts in watch-quench tank shrend; Then the glass cullet of shrend were dried 5 hours at 200 ℃～300 ℃.
4, with the oven dry glass cullet wear into the particle about 1mm, and then in the jet mill grinding machine with the glass particle crushing and classification, the granular powder particle diameter D behind the crushing and classification 10=4.07 μ m, D 50=19.59 μ m, D 90=41.80 μ m, maximum particle diameter is no more than 70 μ m.
5, the glass powder after the classification is sent into balling furnace with charging machine several times with 8kg/h; The nodularization temperature is controlled at 1200 ℃, and the nodularization time is 0.5 second, and the glass powder of the hollow nodularization of process is after scoop is collected; Sub-elect hollow glass micropearl with showy method; The particle diameter of the hollow glass micropearl that sub-elects concentrates between 10 ~ 60 μ m basically, and showy rate is 97%, and density is 0.3g/cm 3, it is 23MPa that calculating crushing by volume accounts for volume 5% cenosphere crushing strength.

Claims (1)

1. the preparation method of a high-strength low-density hollow glass bead is characterized in that may further comprise the steps:
1. prepare burden, frit is made up of the following weight proportion raw material:
SiO 270%～80%, Na 2O 8%～12%, and CaO 5%～9%, B 2O 32%～6%, SO 30.2%～0.5%, K 2O or Li 2O 0～5%, ZnO or BaO 0～5%, Al 2O 30～3%;
Take by weighing raw material and mix according to the chemical constitution prescription of frit;
2. melt shrend: the frit that mixes is dropped in the melting furnaces found, the glass smelting temperature is 1350 ℃～1450 ℃, and melting time is 1～2 hour, pours the glass metal that melts in watch-quench tank shrend then;
3. dry crushing and classification: the frit oven dry that shrend is good, grinding classification then, crushing and classification adopts jet mill grinding, and used glass powder particle size range is 4～40 μ m;
4. hollow nodularization: the glass powder that classification is good is through becoming the hollow nodularization of pearl stove; Hollow nodularization temperature is 1100 ℃～1300 ℃;
5. collect sorting: will collect through the glass powder that becomes the pearl stove to heat, and isolate hollow glass micropearl through floating method then; Its granularity of gained hollow glass micropearl concentrates on 10～60 μ m, density≤0.3g/cm 3, ultimate compression strength>=12Mpa, its floatability:>=95%.
CN200910185799A 2009-11-30 2009-11-30 Preparation method of high-strength low-density hollow glass bead Expired - Fee Related CN101704632B (en)

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