CN102320743B - High strength aluminosilicate hollow glass microsphere and preparation method thereof - Google Patents

High strength aluminosilicate hollow glass microsphere and preparation method thereof Download PDF

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CN102320743B
CN102320743B CN 201110292306 CN201110292306A CN102320743B CN 102320743 B CN102320743 B CN 102320743B CN 201110292306 CN201110292306 CN 201110292306 CN 201110292306 A CN201110292306 A CN 201110292306A CN 102320743 B CN102320743 B CN 102320743B
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hollow glass
glass
glass microsphere
hollow
glass micropearl
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CN102320743A (en
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彭寿
王芸
彭小波
彭程
仲召进
董为勇
钱学君
王华文
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China Triumph International Engineering Co Ltd
China Building Materials Glass New Materials Research Institute Group Co Ltd
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China Triumph International Engineering Co Ltd
Bengbu Glass Industry Design and Research Institute
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Abstract

The invention discloses a high strength aluminosilicate hollow glass microsphere and a preparation method thereof. The hollow glass microsphere is characterized by comprising the following chemical components by mass percent: 60-75% of SiO2, 10-15% of Al2O3, 10-15% of Na2O, 1-3% of CaO, 0-1% of MgO, 0.02-0.5% of S, 0-3% of R2O and 0-3% of Fe2O3, wherein R in R2O is an alkali metal except Na. The density of the hollow glass microsphere is 0.2-0.6g/cm<3>, the compressive strength is 3-130MPa, the grain size is not greater than 80mu m, the floating rate is not less than 95%, and the softening temperature is not less than 750 DEG C. The hollow glass microsphere disclosed by the invention not only can be used in the fields in which common hollow glass microspheres are applied, but also is suitable for the high temperature and high pressure fields having special requirements in which the common hollow glass microspheres can not be applied. The hollow glass microsphere can be the hollow glass microsphere solid buoyancy material used 1000m, 2000m, 4500m and below under water, the hollow glass microsphere used for cementing wells with depth beyond 6000m during oil drilling and the hollow glass microsphere used for plastic hot extrusion molding.

Description

Aluminosilicate high strength hollow glass micropearl and preparation method thereof
Technical field:
The purpose of this invention is to provide a kind of aluminosilicate high strength hollow glass micropearl, this hollow glass micropearl has superstrength and high softening temperature performance, can use in the field that present commercial hollow glass micropearl can't be suitable for, as deep-sea detecting, ultra deep well petroleum prospecting and plastic extruding forming etc.
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, and, 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 solid buoyancy material, petrochemical complex, emulsion explosive, heat-insulating fire-proofing material, stealthy deadener, high-grade insulating materials, Chemicals additive, low density ablator.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 based on 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 by industrially producing, and mainly based on borosilicate, its ultimate compression strength is low, can't satisfy the service requirements of special dimension.
Yet, along with the continuous development and the new Application Areas of science and technology are continually developed, performance requriements to hollow glass micropearl is more and more higher, especially ultimate compression strength performance, as when adding polymer materials to and being prepared into low close material, especially solid buoyancy material, because hollow glass micropearl ultimate compression strength is low, hollow glass micropearl is broken easily, causes additive effect not obvious, does not have effect; And for example when oil drilling, some oil well depth is more than 6000 meters, even last myriametre, the low close grout that needs the adjusting of superstrength hollow glass is cemented the well, present commercial hollow glass micropearl is difficult to reach its service requirements, to help to expand the hollow glass micropearl Application Areas on the one hand so develop the strong hollow glass micropearl of a kind of high-strength, superelevation, will help on the other hand to improve with the matrix material overall performance of hollow glass micropearl as additive.
Summary of the invention:
The purpose of this invention is to provide a kind of aluminosilicate high strength hollow glass micropearl and preparation method thereof, this hollow glass micropearl has superstrength and high softening temperature performance, can use in the field that present commercial hollow glass micropearl can't be suitable for, as fields such as deep-sea detecting, ultra deep well petroleum prospecting and plastic extruding formings.
The present invention is feedstock production high strength hollow glass micropearl with the alumina silicate glass, and alumina silicate glass has better chemical stability, electrical insulating property, physical strength, lower thermal expansivity [(30~60) * 10 -7-1], water-tolerant, with other glassy phase ratios, the very high (of softening temperature ≧ 750 ℃).
Aluminosilicate high strength hollow glass micropearl, by mass percentage, the chemical constitution of described hollow glass micropearl is as follows:
SiO 2 60%~75%
Al 2O 3 10%~15%
Na 2O 10%~15%
CaO 1%~3%
MgO 0~1%
S 0.02%~0.5%
R 2O 0~3%
Fe 2O 3 0~3%
Described R 2R is the basic metal beyond the Na among the O;
Described hollow glass micropearl, density 0.2~0.6g/cm 3, ultimate compression strength 3~130MPa, size≤80 μ m, floating rate ≧ 95%, softization Wen Du ≧ 750 ℃.This product can be applied to and require hollow glass micropearl to have the Application Areas of superstrength.
Prioritization scheme of the present invention is, aluminosilicate high strength hollow glass micropearl, and by mass percentage, the chemical constitution of described hollow glass micropearl is as follows: SiO 2-65%, Al 2O 3-14%, Na 2O-15%, CaO-3%, MgO-1.0%, S-0.3%, Li 2O-1.5%, Fe 2O 3-0.5%.
SiO 2Be the main component among the present invention, mass percent is in 60%~75% the best, if SiO 2Be reduced to less than 60%, the intensity of microballon can reduce; If SiO 2Be increased to greater than 75%, form for best glass microballon, the glass melting temperature improves, and glass viscosity improves, and significantly reduces the output of glass microballon.
Na among the present invention 2O helps SiO 2Fusing reduces the temperature of fusion that glass forms, and reduces the glass metal viscosity, increases temperature flowing simultaneously, is good fusing assistant.But too high levels can reduce physical strength, chemical stability and the thermostability of glass.
Al among the present invention 2O 3Can reduce the crystallization tendency of glass, improve chemical stability, thermostability, physical strength, hardness and the specific refractory power etc. of glass.
CaO, MgO can improve physical strength, hardness and the chemical stability of glass among the present invention.
S is as forming the hollow glass micropearl whipping agent among the present invention, it is the key component of preparation hollow glass micropearl, select a certain amount of S(such as vitriol, sulphite etc.) be included in and can obtain ideal in the glass particle and expand, thus and in final hollow glass micropearl, obtain ideal density and wall thickness.By content, heating glass particulate quantity and length heat-up time (as delivering glass particle quantity, the length of flame etc.) of sulphur in the feed glass particle, thereby feed glass grain expansion size is controlled wall thickness.
Fe among the present invention 2O 3Can make in the glass forming process to be under the oxidizing atmosphere, thus the content of S in the more effective feed glass.
A kind of preparation method of aluminosilicate high strength hollow glass micropearl is characterized in that by mass percentage, proportioning raw materials is as follows;
Quartz sand 50%~70%
Aluminum oxide 6%~12%
Soda ash 18%~25%
Lime carbonate 3%~10%
Feldspar 0~3%
Saltcake 1%~5%
Quilonum Retard 0~3%
Ferric oxide 0~3%
Found putting in the electric smelting crucible after the confected materials mixing, glass melting temperature is 1400 ℃~1600 ℃, and melting time is 5~8 hours; Then with the glass metal shrend that melts, 200 ℃~300 ℃ oven dry 5~8 hours; The glass cullet of oven dry are worn into the particle of 0.8~1.2mm, 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=3~6 μ m, D 50=12~23 μ m, D 90=25~45 μ m, maximum particle diameter≤60 μ m, the glass powder that classification is good is sent into balling furnace, the nodularization temperature is controlled at 1250 ℃~1450 ℃, the nodularization time is 0.4~1 second, and the glass powder of the hollow nodularization of process is collected hollow glass micropearl by swimming on the water surface after collector is collected.
As mentioned above, the density range of prepared hollow glass micropearl is 0.2~0.6g/cm 3, strength range is 3~130MPa, and density is high more, and intensity is high more.Density is at 0.2~0.4 g/cm 3Hollow glass micropearl is mainly used solid buoyancy material, emulsion explosive, heat-insulating fire-proofing material, stealthy deadener, high-grade insulating materials, Chemicals additive, low density ablator etc.; Density is at 0.5~0.6 g/cm 3Hollow glass micropearl mainly be used in ultra deep well well cementation with the hollow glass micropearl light weight cement be used for hollow glass micropearl matrix material that the plastic hot extrusion moulding uses etc.
The particle diameter of hollow glass micropearl of the present invention is best below 80 μ m, realizes the heat-up time in the time of can expanding into hollow glass by sulphur content in the feed glass particle and glass particle.
Hollow glass micropearl of the present invention not only can be used for the every field that common hollow glass micropearl is used, and be applicable to that common hollow glass micropearl is beyond one's reach, high temperature, high pressure field that particular requirement is arranged, the well cementation that surpasses 6000m as well depth in the hollow glass micropearl solid buoyancy material of 1000m, 2000m, 4500m and following use under water, the oil drilling are with hollow glass micropearl and be used for hollow glass micropearl that the plastic hot extrusion moulding uses etc.
Embodiment
The invention will be further described below by our company's closed test example.
Embodiment 1
Calculate quartz sand 52.4kg, feldspar 1.94kg, lime carbonate 8.15kg, aluminum oxide 9.14kg, soda ash 17.5kg, Quilonum Retard 3kg, saltcake 1.8kg, ferric oxide 0.8kg by weight.The frit that mixes is put in the electric smelting crucible 1400 ℃ to be founded 5 hours, then with the glass metal shrend that melts, 200 ℃~300 ℃ oven dry 5 hours, the glass cullet of oven dry are worn into 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=6 μ m, D 50=23 μ m, D 90=45 μ m, maximum particle diameter is no more than 60 μ m, the good glass powder of classification is sent into balling furnace with charging machine several times with 8kg/h, the nodularization temperature is controlled between 1250 ℃~1450 ℃, and the nodularization time is 0.8 second, and the glass powder of the hollow nodularization of process is after collector is collected, collect hollow glass micropearl on the water surface by swimming in, the particle diameter of cenosphere concentrates between 10 ~ 80 μ m substantially, and showy rate is 99%, and density is 0.20g/cm 3, its chemical ingredients is SiO by analysis 260%, Al 2O 315%, Na 2O 13.5%, and CaO 3%, and MgO 1.0%, Li 2O 3%, Fe 2O 33% and microballon in contain S 0.5%.When being subjected to 3MPa hydrostatics pressure, cenosphere volume broken rate of grinding ball is less than 10%.
Embodiment 2
Calculate quartz sand 56.4kg, feldspar 1.74kg, lime carbonate 8.15kg, aluminum oxide 8.14kg, soda ash 20.145kg, Quilonum Retard 1.98kg, saltcake 1.41kg, ferric oxide 0.3kg by weight.The frit that mixes is put in the electric smelting crucible 1450 ℃ to be founded 5 hours, then with the glass metal shrend that melts, 200 ℃~300 ℃ oven dry 5 hours, the glass cullet of oven dry are worn into 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=5.99 μ m, D 50=23 μ m, D 90=45 μ m, maximum particle diameter is no more than 60 μ m, the good glass powder of classification is sent into balling furnace with charging machine several times with 8kg/h, the nodularization temperature is controlled between 1250 ℃~1450 ℃, and the nodularization time is 0.5 second, and the glass powder of the hollow nodularization of process is after collector is collected, collect hollow glass micropearl on the water surface by swimming in, the particle diameter of cenosphere concentrates between 10 ~ 80 μ m substantially, and showy rate is 98%, and density is 0.23g/cm 3, its chemical ingredients is SiO by analysis 265%, Al 2O 314%, Na 2O 15%, CaO3%, MgO1.0%, Li 2O 1.5%, Fe 2O 30.5% and microballon in contain S 0.4%.When being subjected to 5MPa hydrostatics pressure, cenosphere volume broken rate of grinding ball is less than 10%.
Embodiment 3
Weight proportion is identical with embodiment 2, unique different be that the composition of sulphur in the composition is dropped to 0.3% weight ratio.The frit that mixes is put in the electric smelting crucible 1450 ℃ to be founded 5 hours, then with the glass metal shrend that melts, 200 ℃~300 ℃ oven dry 5 hours, the glass cullet of oven dry are worn into 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=5.99 μ m, D 50=23 μ m, D 90=45 μ m, maximum particle diameter is no more than 60 μ m, the good glass powder of classification is sent into balling furnace with charging machine several times with 8kg/h, the nodularization temperature is controlled between 1250 ℃~1450 ℃, and the nodularization time is 0.5 second, and the glass powder of the hollow nodularization of process is after collector is collected, collect hollow glass micropearl on the water surface by swimming in, the particle diameter of cenosphere concentrates between 10 ~ 80 μ m substantially, and showy rate is 98%, and density is 0.38g/cm 3, its chemical ingredients is SiO by analysis 265%, Al 2O 314%, Na 2O 15%, CaO3%, MgO1.0%, Li 2O 1.5%, Fe 2O 30.5% and microballon in contain S 0.3%.When being subjected to 32MPa hydrostatics pressure, cenosphere volume broken rate of grinding ball is less than 10%.
Embodiment 4
Calculate quartz sand 65.474kg, feldspar 1.74kg, lime carbonate 2.35kg, aluminum oxide 6.14kg, soda ash 16.45kg, Quilonum Retard 2.85kg, saltcake 0.8kg, ferric oxide 0.3kg by weight.The frit that mixes is put in the electric smelting crucible 1600 ℃ to be founded 7 hours, then with the glass metal shrend that melts, 200 ℃~300 ℃ oven dry 5 hours, the glass cullet of oven dry are worn into 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=5.99 μ m, D 50=23 μ m, D 90=45 μ m, maximum particle diameter is no more than 60 μ m, the good glass powder of classification is sent into balling furnace with charging machine several times with 8kg/h, the nodularization temperature is controlled between 1250 ℃~1450 ℃, and the nodularization time is 0.5 second, and the glass powder of the hollow nodularization of process is after collector is collected, collect hollow glass micropearl on the water surface by swimming in, the particle diameter of cenosphere concentrates between 10 ~ 80 μ m substantially, and showy rate is 98%, and density is 0.32g/cm 3, its chemical ingredients is SiO by analysis 275%, Al 2O 310%, Na 2O 10%, and CaO 1.5%, and MgO 0.5%, Li 2O 2.5%, Fe 2O 30.5% and microballon in contain S 0.35%.When being subjected to 16MPa hydrostatics pressure, cenosphere volume broken rate of grinding ball is less than 10%.
Embodiment 5
Calculate quartz sand 60.474kg, feldspar 1.74kg, lime carbonate 7.15kg, aluminum oxide 8.14kg, soda ash 20.145kg, Quilonum Retard 1.98kg, saltcake 0.71kg, ferric oxide 0.5kg by weight.The frit that mixes is put in the electric smelting crucible 1500 ℃ to be founded 5 hours, then with the glass metal shrend that melts, 200 ℃~300 ℃ oven dry 5 hours, the glass cullet of oven dry are worn into 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=15.38 μ m, D 90=30.4 μ m, maximum particle diameter is no more than 38 μ m, the good glass powder of classification is sent into balling furnace with charging machine several times with 8kg/h, the nodularization temperature is controlled between 1250 ℃~1450 ℃, and the nodularization time is 0.5 second, and the glass powder of the hollow nodularization of process is after collector is collected, collect hollow glass micropearl on the water surface by swimming in, the particle diameter of cenosphere concentrates between 10 ~ 50 μ m substantially, and showy rate is 98%, and density is 0.50g/cm 3, its chemical ingredients is SiO by analysis 267%, Al 2O 313%, Na 2O 14%, CaO 2%, MgO1.0%, Li 2O 1.5%, Fe 2O 31.0% and microballon in contain S 0.15%.When being subjected to 63MPa hydrostatics pressure, cenosphere volume broken rate of grinding ball is less than 10%.
Embodiment 6
Calculate by weight, quartz sand 62.474kg, feldspar 1.9kg, lime carbonate 5.15kg, aluminum oxide 7.14kg, soda ash 18.145kg, Quilonum Retard 0.98kg, saltcake 0.41kg, ferric oxide 0.6kg, the frit that mixes is put in the electric smelting crucible 1550 ℃ to be founded 5 hours, then with the glass metal shrend that melts,, the glass cullet of oven dry are worn into particle about 1mm 200 ℃~300 ℃ oven dry 5 hours, 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=3.1 μ m, D 50=12.38 μ m, D 90=28.6 μ m, maximum particle diameter is no more than 32 μ m, the good glass powder of classification is sent into balling furnace with charging machine several times with 8kg/h, the nodularization temperature is controlled between 1250 ℃~1450 ℃, and the nodularization time is 0.5 second, and the glass powder of the hollow nodularization of process is after collector is collected, collect hollow glass micropearl on the water surface by swimming in, the particle diameter of cenosphere concentrates between 10 ~ 40 μ m substantially, and showy rate is 96%, and density is 0.60g/cm 3, its chemical ingredients is SiO by analysis 268%, Al 2O 313.5%, Na 2O 14%, CaO1.8%, MgO1.0%, Li 2O 0.4%, Fe 2O 31.0% and microballon in contain S 0.08%.When being subjected to 130MPa hydrostatics pressure, cenosphere volume broken rate of grinding ball 10%.

Claims (2)

1. aluminosilicate high strength hollow glass micropearl is characterized in that, by mass percentage, the chemical constitution of described hollow glass micropearl is as follows:
SiO 2 60%~75%
Al 2O 3 10%~15%
Na 2O 10%~15%
CaO 1%~3%
MgO 0~1%
S 0.02%~0.5%
R 2O 0~3%
Fe 2O 3 0~3%
Described R 2R is the basic metal beyond the Na among the O;
Described hollow glass micropearl, density 0.2~0.6g/cm 3, ultimate compression strength 3~130MPa, size≤80 μ m, floating rate ≧ 95%, softization Wen Du ≧ 750 ℃.
2. prepare the method for the described aluminosilicate high strength of claim 1 hollow glass micropearl, it is characterized in that, by mass percentage, proportioning raw materials is as follows;
Quartz sand 50%~70%
Aluminum oxide 6%~12%
Soda ash 18%~25%
Lime carbonate 3%~10%
Feldspar 0~3%
Saltcake 1%~5%
Quilonum Retard 0~3%
Ferric oxide 0~3%
Found putting in the electric smelting crucible after the confected materials mixing, glass melting temperature is 1400 ℃~1600 ℃, and melting time is 5~8 hours; Then with the glass metal shrend that melts, 200 ℃~300 ℃ oven dry 5~8 hours; The glass cullet of oven dry are worn into the particle of 0.8~1.2mm, 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=3~6 μ m, D 50=12~23 μ m, D 90=25~45 μ m, maximum particle diameter≤60 μ m, the glass powder that classification is good is sent into balling furnace, the nodularization temperature is controlled at 1250 ℃~1450 ℃, the nodularization time is 0.4~1 second, and the glass powder of the hollow nodularization of process is collected hollow glass micropearl by swimming on the water surface after collector is collected.
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