CN1015443B - Microcrystal glass made from goose cord rock - Google Patents

Microcrystal glass made from goose cord rock

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Publication number
CN1015443B
CN1015443B CN 87108208 CN87108208A CN1015443B CN 1015443 B CN1015443 B CN 1015443B CN 87108208 CN87108208 CN 87108208 CN 87108208 A CN87108208 A CN 87108208A CN 1015443 B CN1015443 B CN 1015443B
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CN
China
Prior art keywords
glass
goose
rock
cord
ceramic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CN 87108208
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Chinese (zh)
Other versions
CN1034704A (en
Inventor
方之耀
陈学贤
朱亚娟
陈铁姗
沈崇德
李家治
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Ceramics of CAS filed Critical Shanghai Institute of Ceramics of CAS
Priority to CN 87108208 priority Critical patent/CN1015443B/en
Publication of CN1034704A publication Critical patent/CN1034704A/en
Publication of CN1015443B publication Critical patent/CN1015443B/en
Expired legal-status Critical Current

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Classifications

    • 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
    • C03C10/0018—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 monovalent metal oxide as main constituents
    • C03C10/0027—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 monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents

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

Abstract

The present invention discloses low swelling microcrystal glass made from goose marrow rock, and a making technique thereof. The cost can be reduced in vast scale by using goose marrow rock as a principal raw material to make the low swelling microcrystal glass, the fusion temperature of the glass is reduced by 40 to 50 DEG C. The glass is characterized in that the thermal expansion coefficient is from 9 to 15*10<-7>/DEC C, the mechanical strength is from 1200 to 1900 kg/cm<2>, and the hardness is from 750 to 950 kg/mm<2>. The novel microcrystalline glass is composed of 50 to 90 % of goose marrow rock, 3 to 6 % of lithium carbonate, 2 to 8 % of aluminum oxide (or aluminum hydroxide), 2 to 5 % of magnesium carbonate, 1 to 3 % of titanium pigment, 1 to 4 % phosphate, 0 to 3 % of zirconium oxide and a right amount of clarificant.

Description

Microcrystal glass made from goose cord rock
Involved in the present invention is a kind of glass material and manufacture method thereof.Particularly relate to a kind of goose cord rock of using *Low-expansion glass-ceramic and the technology thereof made.
Low-expansion glass-ceramic has splendid cold-resistant hot acute degeneration, and high physical strength and hardness and good saturating microwave property are a kind of glass materials that using value is arranged very much.In modern industry and daily life, its application surface is quite extensive, be mainly used in and make heat-resisting devitrified glass vessel, microwave oven utensil, microwave oven and electromagnetic stove plate, and other industrial low bulk high hardness material such as devitrified glass jewel and infrared radiant material etc.
Known low-expansion glass-ceramic all uses industrial chemicals production.((1) S.D.Stookey, " Method of Making Ceramics and Product Thereof; " U.S.Patent 2,920,97) (January 12,1960) S.D.Stookey .(2), " Low-Expansion Glass-Ceramic and Method of Making It ", U.S.Patent3,157,522.(November G.P.Smith 17,1964) .(3), " Method of Making Ceramic Atticle " U.S.Patent 3,246,972, (Aptil 19,1966) .) it is by Li 2The O(Lithium Oxide 98min)-Al 2O 3(aluminum oxide)-SiO 2(silicon-dioxide) is major ingredient, adds a certain amount of nucleus agent such as TiO 2(titanium dioxide), ZrO 2(zirconium dioxide) or phosphoric acid salt, and fusing assistant Na 2O(K 2O), MgO, in high-temperature smelting pot, be melt into uniform glass liquid, make devitrified glass through crystallization control again after the moulding.Because its used expensive raw material price up to 1.8 ten thousand yuan/ton, has limited its development as the industrial chemicals Quilonum Retard.Moreover, for Li 2O content be about 4% glass melting temperature up to 1600 ℃ about, energy consumption is big in the production, brings a series of problems also for simultaneously furnace refractories and molding device.Thereby, how to reduce cost and temperature of fusion has become the problem that presses for solution in the low-expansion glass-ceramic production.
In general, be applicable to that the raw mineral materials of making low-expansion glass-ceramic is except that should containing Lithium Oxide 98min, aluminum oxide and silicon-dioxide, the content of its detrimental impurity-potassium, na oxide and iron should lack, the former too high levels will cause the increase of devitrified glass thermal expansivity, and ferric oxide surpasses the whiteness that allowance (as greater than 0.06%) can seriously influence product.In fact, the raw mineral materials that can satisfy above-mentioned two conditions is few for number on earth, reason that low-expansion glass-ceramic still produces with industrial chemicals so far that Here it is.
The object of the present invention is to provide novel method and the goods thereof of making low-expansion glass-ceramic with goose cord rock.Goose cord rock is newfound a kind of
* the place of production: near volcanic rock Tongan City, Yifeng County, Jiangxi Province, can reduce devitrified glass cost and temperature of fusion with it significantly as the main raw material of manufacturing low-expansion glass-ceramic.
The method of manufacturing low-expansion glass-ceramic of the present invention mainly comprises following content:
1. adopt goose cord rock as the main raw material of making low-expansion glass-ceramic.This goose cord rock contains Lithium Oxide 98min (Li 2O), aluminum oxide (Al 2O 3), silicon oxide (SiO 2), potassium oxide (K 2O) and fluorine Chemical Composition such as (F), reserve through initial estimate more than 600,000 tons.Main petrofacies are lithionite, quartz and plagioclase.The chemical ingredients of goose cord rock is listed in table 1.
The Chemical Composition of table 1 goose cord rock
Sample ore SiO 2Al 2O 3Li 2O K 2O Fe 2O 3F
1 66.25 20.50 1.90 3.62 0.02 2.22
2 66.05 20.21 1.79 3.78 0.02 2.33
This mineral iron-holder is low, and color and luster is pure white, contains the main component Li that constitutes low-expansion glass-ceramic 2O, Al 2O 3And SiO 2, be a kind of raw material of splendid manufacturing low-expansion glass-ceramic.Goose cord rock as raw material needs through being crushed to the 80-100 order.
2. the batching of the low-expansion glass-ceramic made from goose cord rock involved in the present invention form and chemical composition range as follows:
Batching is formed (weight percentage) scope:
Goose cord rock 50-90, aluminum oxide or aluminium hydroxide 0-8, Quilonum Retard 4-8, magnesiumcarbonate 1-5, titanium dioxide 1-4, aluminum phosphate or primary ammonium phosphate 1-5, zirconium dioxide 0-4, quartz sand 0-16, white arsenic (As 2O 3) 0.3-1.
Chemical Composition (weight percentage) scope is:
SiO 2Al 2O 3Li 2OK 2O MgO TiO 2ZrO 2P 2O 5F As 2O 3
50-72 16-28 3.5-5 1.5-3.8 0-3 1-4 0-3 0-5 1.5-2.5 0.3-1
Chemical ingredients contains the F of 1.5-2.5% among the present invention, and more K 2O, this is the present invention and the marked difference of in the past similar glass.
Technical process is: pulverize goose cord rock (80-100 order)-adding nucleus agent (TiO 2, ZrO 2, P 2O 5) fusing assistant (MgCO 3, K 2O or Na 2O)-glass melting-moulding-crystallization and thermal treatment.
3. the glass melting temperature is 1540-1570 ℃, is incubated 8-12 hour.
4. the glass forming operation temperature is 1380-1480 ℃.Can adopt blowing, drawing, drawing method moulding.
5. the crystallization and thermal treatment technology of devitrified glass is: be warming up to 700-800 ℃ with 1 ℃/minute～4 ℃/minute speed, be incubated 0.5-2 hour, make and form nucleus in the glass.Rise to 840-920 ℃ with 1 ℃/minute～4 ℃/minute speed again, be incubated 1-4 hour, so that crystal grows up, then with 3～10 ℃/minute speed cooling.
Optimum treatment condition is: 2 hours nucleation of 740-800 ℃ of insulation, 850-900 ℃ of crystal growth.
Method of the present invention and goods thereof have following advantage:
1. can reduce raw materials cost significantly
The used goose cord rock of the present invention contains the major ingredient Li that constitutes low-expansion glass-ceramic 2O, Al 2O 3, SiO 2, can reduce raw materials cost significantly thus.Calculate with 1000 tons of goose cord rocks of year usage quantity (daily output glass about 3 tons of raw materials used amounts), compare, surplus only expense of raw materials can save 50 an every year ten thousand yuan with using industrial chemicals.
2. can reduce by 40～50 ℃ of temperature of fusion behind the glass employing goose cord rock raw material with composition.This is because seldom use refractory oxide SiO among the present invention 2And Al 2O 3, replace the aluminium silicate mineral that is in combined form.Moreover, contain a certain amount of K in the mineral 2O and F, this all helps to quicken fusing, thereby makes glass melting temperature reduce 40-50 ℃.Reach the minimizing energy consumption, prolong smelting furnace and the purpose of die life.
3. the low-expansion glass-ceramic of the method for the invention manufacturing has good physical properties (table 2).Can be used for making heat-resisting devitrified glass vessel, microwave oven and electromagnetic stove base plate, infrared radiant material etc. with this.
The low-expansion glass-ceramic rerum natura that table 2 is made with goose cord rock
The petrofacies composition % of table 3 goose cord rock
Quartzy 45
Lithionite 40
Plagioclase 8
Topaz 2
Example 1, low-expansion glass-ceramic preparation flow
Goose cord rock pulverizing-adding nucleus agent and fusing assistant are by prescription batching-glass melting-moulding-crystallization and thermal treatment.
By above-mentioned schema, goose cord rock is pressed batching through being crushed to 80 mesh sieves
Weight %
Goose cord rock 83.3
Aluminium hydroxide 4.0
Quilonum Retard 4.0
Magnesiumcarbonate 3.4
Titanium dioxide 2.1
Primary ammonium phosphate 2.7
White arsenic 0.4
The composition that is incorporated in the glass by goose cord rock accounts for 87% of total composition.The glass melting temperature is 1540 ℃-1550 ℃, is incubated 8 hours.The crystallization and thermal treatment temperature is: nucleation temperature is 780 ℃ of insulations 2 hours, and crystal growth temperature is 860 ℃ of insulations 2 hours.Recording thermal expansion coefficient of glass is 13 ± 2 * 10 -7/ ℃, folding strength is 1900kg/cm 2
Example 2, different is that the composition that goose cord rock is introduced accounts for 75% of glass assembly with glass part with example 1.
The batching composition of glass is as follows: weight %
Goose cord rock 71
Quilonum Retard 5.2
Magnesiumcarbonate 3.9
Titanium dioxide 2.6
Phosphoric acid salt 2.8
Quartz sand 9
Aluminum oxide 3.4
White arsenic 0.4
The F surplus
The temperature of fusion of glass is 1550-1560 ℃ of insulation 10 hours, and crystallization and thermal treatment technology is: nucleation temperature 750-760 ℃ is incubated 2 hours, and crystal growth temperature is: 850-860 ℃ is incubated 2 hours.The hot expansion system that obtains glass is 11 ± 2 * 10 -7/ ℃.
Different is with TiO in the glass for example 3. and embodiment 1,2 2And ZrO 2Do the nucleus agent.The composition that goose cord rock is introduced accounts for 86% of glass assembly with glass part.The glass melting temperature is 1550-1560 ℃, is incubated 8-10 hour, and nucleation temperature is 780 ℃ of insulations 2 hours, and crystal growth temperature is 860 ℃ of insulations 2 hours.The thermal expansivity that makes glass is 12 ± 2 * 10 -7/ ℃.
The batching composition of glass is as follows:
Goose cord rock 81.2%
Aluminium hydroxide 5.0%
Quilonum Retard 4.6%
Magnesiumcarbonate 3.9%
Titanium dioxide 3.4%
Zirconium dioxide 1.7%
The white arsenic surplus
Chemical Composition (weight percentage) scope is:
SiO 2Al 2O 3Li 2O K 2O MgO TiO 2ZrO 2P 2O 5F As 2O 3
50-72 16-28 3.5-5 1.5-3.8 0-3 1-4 0-3 0-5 1.5-2.5 0.3-1
The low-expansion glass-ceramic rerum natura that table 2 is made with goose cord rock
Thermal expansivity folding strength hardness water-resistant stability *Density
9-15 kg/cm 2kg/mm 2mg/g g/cm 3
×10 -7/℃ 1200- 750- 0.008-0.016 2.53
1900 950
The Chemical Composition of each embodiment products obtained therefrom of table 4
Instance number Chemical Composition %
SiO 2Al 2O 3LiO 3MgO K 2O TiO 2P 2O 5ZrO 2F by the goose cord rock introducing
1 63.5 23.5 3.9 1.3 2.8 3.0 2.0 1 1.8
2 64 23.5 3.9 1.4 2.3 3.0 2.0 2 1.6
3 63 23.2 3.8 1.4 2.6 4 2 3 1.7

Claims (4)

1, a kind of method with goose cord rock manufacturing low-expansion glass-ceramic is characterized in that:
A. selecting petrofacies for use is that the goose cord rock of quartz, lithionite, plagioclase, topaz is made main raw material, is crushed to the 80-100 order;
The main chemical compositions of goose cord rock is SiO 2, Al 2O 3, Li 2O, K 2O, Fe 2O 3And F;
B. by following formulation raw material: (weight %)
Goose cord rock 50-90 phosphoric acid salt 1-5 (nucleus agent)
Quilonum Retard 4-8 titanium dioxide 1-4 (nucleus agent)
Aluminum oxide (or aluminium hydroxide) 0-8 zirconium white 0-4 (nucleus agent)
Quartz sand 0-16 magnesiumcarbonate 1-5 (fusing assistant)
White arsenic 0.3-1
C. make in proper order by following processing condition:
(1) melting raw materials
Temperature 1540-1580 ℃, be incubated 8-12 hour
(2) the mold temperature 1380-1480 of glass ℃
(3) moulding
(4) crystallization and thermal treatment
Nucleation temperature 700-800 ℃, be incubated 0.5-3 hour
Crystal growth 840-920 ℃, be incubated 1-4 hour
(5) thermal expansivity of the low-expansion glass-ceramic of gained is 9-15 * 10 -7/ ℃.
2, according to the method for the manufacturing low-expansion glass-ceramic of claim 1, it is characterized in that the devitrified glass that described method makes, it has following feature:
A. the glass composition contains (weight %):
SiO 250-72 Li 2O 3.5-5
Al 2O 316-28 TiO 21-4
K 2O 1.5-3.8 ZrO 20-3
MgO 0-3 P 2O 50-5
As 2O 30.3-1 F -1.5-2.5
B. the physical parameter of glass:
A. folding strength 1200-1900Kg/cm 2
B. hardness 750-950Kg/mm 2
C. density 2.53g/cm 3
3, according to the manufacture method of claim 1, it is characterized in that: the method for glass ware forming is: blowing, drawing, compacting.
4, according to the manufacture method of claim 1, it is characterized in that: the optimum treatment process condition is 740-800 ℃, is incubated 2 hours nucleation, 850-900 ℃ of crystal growth.
CN 87108208 1987-12-26 1987-12-26 Microcrystal glass made from goose cord rock Expired CN1015443B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 87108208 CN1015443B (en) 1987-12-26 1987-12-26 Microcrystal glass made from goose cord rock

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 87108208 CN1015443B (en) 1987-12-26 1987-12-26 Microcrystal glass made from goose cord rock

Publications (2)

Publication Number Publication Date
CN1034704A CN1034704A (en) 1989-08-16
CN1015443B true CN1015443B (en) 1992-02-12

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Application Number Title Priority Date Filing Date
CN 87108208 Expired CN1015443B (en) 1987-12-26 1987-12-26 Microcrystal glass made from goose cord rock

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CN (1) CN1015443B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2980457B2 (en) * 1992-08-04 1999-11-22 東陶機器株式会社 Base for sanitary ware and its manufacturing method
AU2002367931A1 (en) * 2001-08-02 2003-12-22 3M Innovative Properties Company Alumina-yttria-zirconium oxide/hafnium oxide materials, and methods of making and using the same
CN101723587B (en) * 2009-11-16 2012-01-25 戴洪明 Manufacture method of igneous rock crystal glass material
CN102795773B (en) * 2012-08-28 2015-03-11 山东建筑大学 Method for preparing glass ceramic through compounding white clay and fly ash
CN108863058A (en) * 2018-07-31 2018-11-23 合肥利裕泰玻璃制品有限公司 A kind of Wear-resistant, high-temperature resistant glass and preparation method thereof
CN110903033B (en) * 2019-11-13 2022-03-25 蒙娜丽莎集团股份有限公司 Crystal nucleating agent and positioning crystal pattern ceramic tile prepared by using same

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