CN1158321A - Crystallized glass microball and its prodn. tech. - Google Patents

Crystallized glass microball and its prodn. tech. Download PDF

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Publication number
CN1158321A
CN1158321A CN 96120575 CN96120575A CN1158321A CN 1158321 A CN1158321 A CN 1158321A CN 96120575 CN96120575 CN 96120575 CN 96120575 A CN96120575 A CN 96120575A CN 1158321 A CN1158321 A CN 1158321A
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Prior art keywords
crystallization
microballon
glass
balling
crystallized glass
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CN 96120575
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CN1055905C (en
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刘凤英
方明虎
周嶅
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China Building Materials Academy CBMA
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China Building Materials Academy CBMA
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
    • C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

A process for producing crystallized fine glass beads uses glass containing cyrstal nucleus as raw material and includes forming glass beads conventionally, nucleation, and crystallization. Obtained glass beads has high strength, antiwear nature and chemical stability. Its bead forming temp is 850-1550 deg.C. Sinter time is less than 60 min. The temp for nucleation and crystallization is 350-1350 deg.C. Its crystallization time is less than 60 min.

Description

Crystallized glass microball and production technique thereof
The present invention relates to a kind of glass microballon.
Glass microballon is to develop infant industry material faster in recent years both at home and abroad.It is widely used in industrial sectors such as chemical industry, weaving, light industry, electronics, mine, coal, traffic, shipping, precision optical machinery processing.
The glass microballon that uses as grinding medium, weighting agent and shot-peening polishing is that glass is raw material with common sodium calcium all at present, and particle diameter is generally between 45 μ m～6mm.Only with regard to grinding medium is used glass microballon, be mainly used in dyestuff in the industries such as light industry, chemical industry, electronics, coating, printing ink, paint, tinting material, medicine, all series products production of food papermaking and use as grinding medium.But in the face of some chemical stabilities to grinding medium, wear resistance require higher, stricter industry, as industries such as electron trade, drug and food, papermaking, then common soda-lime glass microballon just seems and has not met the demands.The Ministry of Chemical Industry once organized " grinding medium " investigation, finding points out, only as main grinding medium---the glass microballon of dyestuff, coatings industry, home products is common, and to exist intensity lower, shortcomings such as wear resistance is relatively poor, and in the quality that influences Chemicals in varying degrees.Therefore, the glass microballon of high strength, high abrasion has become an urgent demand of the industrial sector of application grinding medium.At present, the application alumina balls that have in these industries, zirconia ball and agate ball are as grinding medium.But alumina balls are owing to be subjected to the restriction of its moulding process, and particle diameter can not be too little, can only be more than φ 10mm.And zirconia ball is as a kind of high-grade grinding medium, and its physical and chemical index is relatively very high, but its cost is quite expensive, has limited it and has used widely.Therefore it is very necessary developing a kind of grinding medium glass microballon novel, low-cost and high-performance.
Domesticly improving the intensity of grinding medium with glass microballon, the research of glass microballon tempering enhanced was once carried out in aspects such as wear resistance, with the method for tempering, and the physicochemical property that to improve common sodium calcium be glass microballon, but effect is undesirable.
Devitrified glass is a kind of based on the simple glass component, adds the nucleus agent, through the fusion cooling, and passes through coring at a certain temperature, after the crystallization treatment, has microcrystal and equally distributed residual glass matrix material mutually.It has many special functions, as quality densification, pore-free, airtight, waterproof, physical strength than glass, pottery all much higher, resistance to impact shock is 8 times of simple glass approximately, ultimate compression strength is 2 times of simple glass approximately, wear resistance chemical stability, electrical property etc. all are better than simple glass.The application of devitrified glass in the past is mostly as sheet material, tubing, bearing, mechanical part, and uses such as vessel, at present, Shang Weijian is abroad to the report of crystallization microballon aspect research.
The objective of the invention is to invent a kind of crystallized glass microball and production technique thereof, so that this microballon when using as grinding medium, weighting agent and shot-peening polishing, has good wear resistance, physical strength and chemical stability.
It is raw material that the present invention adopts the glass contain nucleus, utilizes the bead-forming process Cheng Zhu of simple glass microballon, will become microballon behind the pearl to carry out coring again, crystallization treatment is made high-strength, wear-resisting crystallized glass microball of the present invention.
Accompanying drawing is the schema of production technique of the present invention.
Crystallized glass microball of the present invention can be made by chemical raw material or mineral material, and the raw materials used chemical composition of this crystallization microballon is:
SiO 2   37～84％，Al 2O 3 2.5～38％，CaO   4～58％，
MgO?????2～65％，Fe 2O 3?0.1～36％，FeO?0.1～28％，
K 2O???0.2～10％，Na 2O??0.3～9％，?MnO?0.1～5％，
TiO 2?0.03～10％，ZrO 2??0～11％，Cr 2O 3?1.3～14％
F?0～6％，S -2?0～5％，P 2O 5?0～5％，CuO?0～6％，
Li 2O?0～25％，ZnS?0～6％
Above per-cent all is weight percentage.
As shown in drawings, to make the raw materials used fragmentation of pearl, cleaning, drying, grinding, sieve, make＜φ 8mm particulate material, should expect to drop into balling-up in the balling-up stove, become 800～1550 ℃ of bulb temperatures, balling-up time＜60 minute, the microballon particle diameter of making is 45 μ m～6mm, and the microballon after the balling-up is put into the crystallization furnace crystallization, and the coring Tc is 350～1350 ℃, crystallization time＜60 minute, be cooled to 40～80 ℃ again and come out of the stove, promptly make described crystallization microballon, its crystalline content is 30～98%.Its performance sees Table 1.
Table 1
Performance Index
Unit weight (g/cm 3) ????2.5～3.0
Particle diameter ????45μm?6mm
Microhardness (MPa) ????60～80
Folding strength (MPa) ????60～130
Mohs' hardness (level) ????6～8
Acid resistance (HCl 0.5mol/L, vector %) ????0.01
Alkali resistance (NaOH 1mol/L, weightless %) ????0.01
Wear rate (%) ????＜1
Example one
Get chemical constitution frit as described below and produce microballon of the present invention:
Chemical constitution: SiO 249%, Al 2O 315.3%, CaO 7.1%, and MgO 8.6%, and FeO 11.5%, Fe 2O 32.5% RO 6%.
(annotate: RO is a metal oxide)
Raw material crushing to 14～18 orders (standard sieve) cleaning, the oven dry of above-mentioned chemical constitution are mixed with separant (graphite etc.), drop in 1240 ℃ of balling-up stoves (well-type electric furnace), sintering 20 minutes, enter crystallization in the crystallization furnace (retort furnace) after the balling-up, crystallization temperature is 870 ℃, and crystallization time is 20 minutes, and the φ 0.6～1.0mm crystallization microballon balling ratio that makes reaches more than 85%, the volume crystallization rate reaches more than 60%, table 1 requirement before performance satisfies.
Example two
Identical raw material crushing to 18～20 orders of example on the orientation, clean, oven dry back sintering 15 minutes in 1230 ℃ balling-up stove, enter crystallization furnace after the balling-up, 600 ℃ of crystallization temperatures, crystallization time are 15 minutes, are cooled to 40～60 ℃ again and come out of the stove and make the crystallization microballon, the bead diameter φ 0.4～0.8mm that makes, balling ratio reaches more than 85%, volume crystallization rate＞60%, table 1 requirement before performance satisfies.Crystallized glass microball of the present invention has the physical strength height, and is wear-resistant, the advantage that chemical stability is good.Can be used as grinding medium, weighting agent and shot-peening polishing are used, and are widely used in industrial sectors such as light industry, chemical industry, weaving, electronics, mine, coal, precision optical machinery processing.

Claims (2)

1. crystallized glass microball is characterized in that: making its chemical ingredients with the glass that contains nucleus or raw mineral materials is: SiO 237～84%, Al 2O 32.5～38%, CaO 4～58%, MgO 2～65%, Fe 2O 30.1～36%, FeO 0.1～28%, K 2O 0.2～10%, Na 2O 0.3～9%, and MnO 0.1～5%, TiO 20.03～10%, ZrO 20～11%, Cr 2O 31.3～14%, F 0～6%, S -20～5%, P 2O 50～5%, CuO 0～6%, Li 2O 0～25%, and ZnS 0～6%, and described microballon particle diameter is 45 μ m～6mm, and crystalline content is 30～98%.
2. the production technique of the described crystallized glass microball of claim 1, it is characterized in that: utilize the balling technique balling-up of simple glass microballon, become 850～1550 ℃ of bulb temperatures, sintering time＜60 minute, microballon after the balling-up drops into crystallization in the crystallization furnace, and the coring Tc is 350～1350 ℃, crystallization time＜60 minute, be cooled to 40～80 ℃ again and come out of the stove, promptly make described crystallized glass microball.
CN96120575A 1996-11-21 1996-11-21 Crystallized glass microball and its prodn. tech. Expired - Fee Related CN1055905C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN96120575A CN1055905C (en) 1996-11-21 1996-11-21 Crystallized glass microball and its prodn. tech.

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Application Number Priority Date Filing Date Title
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CN1158321A true CN1158321A (en) 1997-09-03
CN1055905C CN1055905C (en) 2000-08-30

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1071721C (en) * 1997-09-18 2001-09-26 中国科学院感光化学研究所 High-refractive index transparent ceramic micro-bead and its manufacture method and use
NL1017444C2 (en) * 2001-02-26 2002-08-27 Ceramtrade Hk Ltd Three-dimensional object covered by glass.
CN101781083A (en) * 2009-12-21 2010-07-21 浙江通达实业有限公司 Hydrophobic hollow glass microsphere preparation method and prepared hydrophobic hollow glass microsphere thereof
CN101857355A (en) * 2010-06-02 2010-10-13 天台精工西力玻璃珠有限公司 Method for producing glass beads used for curing high-level nuclear wastes
CN103265170A (en) * 2013-05-06 2013-08-28 朱晓明 Novel industrial grinding ball and manufacturing process thereof
CN114014536A (en) * 2021-10-20 2022-02-08 杭州乾智坤达新材料科技有限公司 Preparation method of enhanced high-roundness glass polishing/shot blasting, product and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59174540A (en) * 1983-03-24 1984-10-03 Toshiba Glass Co Ltd Wear resistant glass bead
US4615987A (en) * 1985-04-15 1986-10-07 Corning Glass Works Reinforcement of alkaline earth aluminosilicate glass-ceramics

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1071721C (en) * 1997-09-18 2001-09-26 中国科学院感光化学研究所 High-refractive index transparent ceramic micro-bead and its manufacture method and use
NL1017444C2 (en) * 2001-02-26 2002-08-27 Ceramtrade Hk Ltd Three-dimensional object covered by glass.
WO2002068355A1 (en) * 2001-02-26 2002-09-06 Ceramtrade (Hk) Ltd. Three-dimensional article enclosed by glass
CN101781083A (en) * 2009-12-21 2010-07-21 浙江通达实业有限公司 Hydrophobic hollow glass microsphere preparation method and prepared hydrophobic hollow glass microsphere thereof
CN101781083B (en) * 2009-12-21 2011-12-28 浙江通达机械有限公司 Hydrophobic hollow glass microsphere preparation method and prepared hydrophobic hollow glass microsphere thereof
CN101857355A (en) * 2010-06-02 2010-10-13 天台精工西力玻璃珠有限公司 Method for producing glass beads used for curing high-level nuclear wastes
CN101857355B (en) * 2010-06-02 2012-09-05 天台精工西力玻璃珠有限公司 Method for producing glass beads used for curing high-level nuclear wastes
CN103265170A (en) * 2013-05-06 2013-08-28 朱晓明 Novel industrial grinding ball and manufacturing process thereof
CN103265170B (en) * 2013-05-06 2016-06-29 朱晓明 A kind of industry mill ball and processing technology thereof
CN114014536A (en) * 2021-10-20 2022-02-08 杭州乾智坤达新材料科技有限公司 Preparation method of enhanced high-roundness glass polishing/shot blasting, product and application thereof
CN114014536B (en) * 2021-10-20 2023-07-07 杭州乾智坤达新材料科技有限公司 Preparation method of enhanced high-roundness glass polishing/shot blasting, product and application thereof

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