CN110451808A - A method of improving fluoride opal glass whiteness - Google Patents
A method of improving fluoride opal glass whiteness Download PDFInfo
- Publication number
- CN110451808A CN110451808A CN201910761917.6A CN201910761917A CN110451808A CN 110451808 A CN110451808 A CN 110451808A CN 201910761917 A CN201910761917 A CN 201910761917A CN 110451808 A CN110451808 A CN 110451808A
- Authority
- CN
- China
- Prior art keywords
- opal glass
- rare earth
- glass
- earth oxide
- whiteness
- 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.)
- Pending
Links
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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- 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
-
- 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
- C03C10/16—Halogen containing crystalline phase
Landscapes
- 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
The invention discloses a kind of methods for improving fluoride opal glass whiteness.The primary raw material that fluoride opal glass is prepared in the invention patent is respectively as follows: quartz sand 58~63%, fluorite 4.5~5.5%, borax pentahydrate 4~6.5%, soda ash 14~21%, barium carbonate 1~2%, calcium carbonate 1.5~2.5%, potassium carbonate 1.5~3%, zinc oxide 0.5~3%, titanium dioxide 0.5~1%, aluminum oxide 1~2%, prodan 1.5~2.5% by weight percentage.All raw materials are put into crucible after weighing in proportion to be melted at a high temperature of 1430 DEG C~1450 DEG C.0.15%~0.25%La of basic material total weight will be pressed2O3、Nd2O3、Y2O3、CeO2After one or more of rare earth oxide briquettings, it is pressed into the glass precursor solution of melting, after being sufficiently stirred, clarifying, is cast in molding die, obtain opal glass afterwards after further treatment.Compared with the opal glass for not adding rare earth oxide, whiteness is increased to 92 or more from 85, and has preferable quality stability.
Description
Technical field
The invention belongs to glass making techniques fields, and in particular to a kind of to be improved by adding a small amount of rare earth oxide
The method of fluoride opal glass whiteness.
Background technique
Opal glass is also known as devitrified glass or glass-ceramic.Opal glass is higher than the brightness of ceramics, stronger than glass toughness, tool
Have high mechanical strength, excellent insulating property, dielectric loss is few, dielectric constant is stable, thermal expansion coefficient can very wide range adjust,
Resistant to chemical etching, wear-resisting, the advantages that thermal stability is good, high using temperature, the enthusiasm for receiving market is pursued.
As modern society people are to the pay attention to day by day of own health, the higher porcelain product of content of beary metal is gradually
It is substituted, the environment-friendly type opal glass for imitating porcelain or jade texture rises, to substitute traditional lacquer etc..But it is domestic at present
The generally existing performance of the opal glass of production is bad, is unable to reach the specified environmentally protective standard of European Union, there is also high investments, height
Several big problems such as cost, high price, lack competitiveness in the international market.
It is an object of the invention to improve opal glass whiteness and quality stability, huge economic benefit is brought to enterprise
And social benefit.Fluoride opal glass cardinal principle is that the fluoride fine particle by being precipitated in glass matrix is dissipated in light
The effect of penetrating is lower to generate opaque effect, but causes milkiness degree to send out often because of the volatilization of fluoride in practical fusion process
Changing, the case where causing product to become blue, turn yellow appearance, reduces quality stability.
The present invention preferably controls the size of the crystal of fluoride of precipitation, divides by adding a small amount of rare earth oxide
Cloth and form.Since the field strength of rare earth ion is larger, rare earth ion is filled primarily in the network gap of glass, so that glass
Structure is even closer, i.e. the potential barrier that the phase transition of glass to be overcome increases, and the crystalline size being precipitated is smaller, is evenly distributed more
It dissipates, improves the stability of opal glass.Secondly, the addition of rare earth facilitates the crystallization of fluoride opal glass and inhibits fluorine
Volatilization, this is because rare earth ion has biggish volume than oxygen-octahedron, provides condition for the formation of crystal of fluoride, from
And be conducive to crystallization.Opal glass whiteness is improved by adding a small amount of rare earth oxide, not only simple process, device quality are steady
It is fixed, also there is very strong practicability and generalization.
Summary of the invention
Goal of the invention: for the whiteness and quality stability for improving fluoride opal glass, the present invention provides a kind of raisings
The preparation method of fluoride opal glass whiteness and its quality stability.
Technical solution: in order to solve the above technical problems, the present invention adopts the following technical scheme:
A method of fluoride opal glass whiteness being improved, the fluoride opal glass is by including following weight percent
The raw material of ratio is prepared:
Quartz sand 58~63%, fluorite 4.5~5.5%, borax pentahydrate 4~6.5%, soda ash 14~21%, barium carbonate 1~
2%, calcium carbonate 1.5~2.5%, potassium carbonate 1.5~3%, zinc oxide 0.5~3%, the oxidation of titanium dioxide 0.5~1%, three two
Aluminium 1~2%, prodan 1.5~2.5%, rare earth oxide 0.15%~0.25%.The rare earth oxide is La2O3、
Nd2O3、Y2O3、CeO2One or more of mixture.Rare earth oxide is first pressed into bulk, then is pressed into the glass for being added to melting
In glass liquid, it is sufficiently stirred, after clarification and homogenization, then cooled down, opal glass is prepared.
The present invention changes the network structure of glass system, and influence the phosphorus being precipitated by adding a small amount of rare earth oxide
Size, distribution and the form of hydrochlorate crystal, so that the scattering behavior of refractive index and precipitation particle to glass matrix material generates
It influences, and then promotes the whiteness of opal glass and the stability of product quality.
Wherein, the partial size of the raw material is not more than 120 microns, it is preferable that raw material particle size is 80~100 microns.
A method of fluoride opal glass whiteness is improved, further comprising the steps of:
(1) by weight percentage: quartz sand 58~63%, fluorite 4.5~5.5%, borax pentahydrate 4~6.5%, soda ash 14
~21%, barium carbonate 1~2%, calcium carbonate 1.5~2.5%, potassium carbonate 1.5~3%, zinc oxide 0.5~3%, titanium dioxide
0.5~1%, aluminum oxide 1~2%, prodan 1.5~2.5% carry out ingredient, after ball milling mixing, cross 200 meshes.
Ingredient is put into crucible and carries out high temperature melting.
(2) by rare earth oxide La2O3、Nd2O3、Y2O3、CeO2It is preferably dilute according to mass percent 0.15%~0.25%
Native oxide is La2O3、Nd2O3And Y2O3Mixture, be placed in mold, using press machine, be pressed into rare earth oxide block, will
Rare earth oxide block is pressed into the glass precursor solution of step (1) melting, after stirring, clarification and homogenization, then is cooled down；
(3) through overcooled solution, the sample that required shape is made in mold will be poured into step (2)；
(4) opal glass stereotyped in step (3) is sent in furnace and is heat-treated, make it on the basis of opal glass
Upper further controlled micro crystallization, obtains the opal glass by controlled micro crystallization；
(5) opal glass that step (4) obtains is made annealing treatment.
In step (1), fusion temperature is 1430 DEG C~1450 DEG C.
In step (2), rare earth oxide addition manner, can to prevent from volatilizing under rare earth oxide high temperature using forced
Oxide is pressed into the bulk of rule, such as square, ball-type, cylindrical type, the middle part of melten glass liquid is pressed by tool
Or bottom.
In step (2), the cooling temperature is 1200 DEG C~1250 DEG C.
In step (4), the controlled micro crystallization treatment conditions be cool to 50 DEG C with the furnace by 750 DEG C, or with 2~10 DEG C/
Min is cooled to 50 DEG C, it is preferable that cooling velocity is controlled in 3~5 DEG C/min.
The condition of controlled micro crystallization is 750 DEG C~50 DEG C, furnace cooling, can also realize that temperature control is cooling, cooling velocity control 2~
Within the scope of 10 DEG C/min, it is preferable that cooling velocity is controlled in 3~5 DEG C/min.
In step (5), the annealing treating process is 500 DEG C~550 DEG C of temperature, the time 1~2 hour, it is preferable that
520 DEG C~540 DEG C, the time is 1 hour.
The utility model has the advantages that the whiteness of opal glass of the present invention is effectively improved, the addition of rare earth oxide can promote fluorine
Blue shift occurs for the wavelength of the precipitation of compound crystal, reflected light, while the uniformity of tissue also being made to be improved, and improves quality
Stability.Since rare earth oxide uses unique forced addition, direct rare earth oxide is added to raw material with traditional
In compare, not only can effectively avoid rare earth element and occur excessive scaling loss during prolonged high melt, reduce waste,
The secondary crystal size being precipitated in glass matrix can also be promoted to refine, and the disperse that is evenly distributed, the comprehensive of product is effectively promoted
Close performance.In addition, the present invention can also suitably reduce the dosage (about 50~65wt%) of aluminum oxide, melting sources temperature is reduced
10~20 DEG C.The product performance indexes as made from this technique production technology can reach the green ring of the newest formulation of European Union
The whiteness of guarantor's standard, opal glass is increased to 92 or more from 85, and has preferable quality stability, alternative traditional lacquer.
Detailed description of the invention
Rare earth oxide is pressed into the tool in glass precursor solution by Fig. 1.
Specific embodiment
The present invention is made combined with specific embodiments below and being elaborated.
Embodiment 1
The fluoride opal glass composition of raw materials for preparing of the present embodiment is (weight percent): quartz sand 58%, fluorite
5.5%, borax pentahydrate 6.5%, soda ash 14%, barium carbonate 2%, calcium carbonate 2.5%, potassium carbonate 3%, zinc oxide 3%, dioxy titanium
1%, aluminum oxide 2%, prodan 2.5%.The partial size of above-mentioned raw materials is not more than 120 microns, it is preferable that raw material particle size is
80~100 microns；
A kind of above-mentioned method for improving fluoride opal glass whiteness, further comprising the steps of:
(1) by weight percentage: quartz sand 58%, fluorite 5.5%, borax pentahydrate 6.5%, soda ash 14%, barium carbonate
2%, calcium carbonate 2.5%, potassium carbonate 3%, zinc oxide 3%, dioxy titanium 1%, aluminum oxide 2%, prodan 2.5% carry out
Ingredient crosses 200 meshes after ball milling mixing；Ingredient is put into crucible again and carries out high temperature melting.
(2) La is weighed again in the ratio of 0.15wt% in above-mentioned raw materials total weight2O3Rare earth oxide is placed in mold simultaneously
Formed under press machine, wherein the type chamber of mold be Cubic preferentially select at suitable pressures, briquetting pressure be 10~
50MPa, block is placed in dry container for use after molding.
(3) after the ingredient in step (1) is completely melt, then the 0.15wt%La that will be obtained in step (2)2O3Rare earth oxygen
Compound block is pressed into the middle part or bottom of melten glass liquid by a kind of band specific purpose tool with concave surfaces, is sufficiently stirred, is clear
After cleer and peaceful homogenizing, then cooled down；
(4) through overcooled melt, the sample that required shape is made in mold will be poured into step (2)；
(5) opal glass stereotyped in step (4) is sent to progress controlled micro crystallization processing in furnace, obtained by controlled micro crystallization
Opal glass；
(6) opal glass that step (5) obtains is made annealing treatment, the opal glass after being annealed.Opal glass
Whiteness be 92, compared with not adding rare earth oxide, whiteness is obviously improved.
In step (1), fusion temperature is 1430 DEG C~1450 DEG C.
In step (2), the bulk shape of rare earth oxide is square.
In step (3), rare earth oxide addition manner is using forced.Block is by a kind of band special tool with concave surfaces
Tool is pressed into the glass precursor solution of melting, and after standing 1~5min, mechanically or electrically magnetic stirs 5~10min.
In step (3), the cooling temperature of liquid is 1200 DEG C~1250 DEG C
In step (5), the condition of controlled micro crystallization is 750 DEG C~50 DEG C, furnace cooling, can also realize that temperature control is cooling, cooling speed
Degree control (preferably, cooling velocity control is in 3~5 DEG C/min) within the scope of 2~10 DEG C/min.
In step (6), annealing temperature is 500 DEG C~550 DEG C, and (preferably, 520 DEG C~540 DEG C) time is 1 hour.
Embodiment 2
The fluoride opal glass composition of raw materials for preparing of the present embodiment is (weight percent): quartz sand 60%, fluorite
5%, borax pentahydrate 5.5%, soda ash 17.5%, barium carbonate 1.5%, calcium carbonate 2%, potassium carbonate 2%, zinc oxide 2%, titanium dioxide
Titanium 1%, aluminum oxide 1.5%, prodan 2%.The partial size of above-mentioned raw materials is not more than 120 microns, it is preferable that raw material particle size
It is 80~100 microns；
A kind of above-mentioned method for improving fluoride opal glass whiteness, further comprising the steps of:
(1) by weight percentage: quartz sand 60%, fluorite 5%, borax pentahydrate 5.5%, soda ash 17.5%, barium carbonate
1.5%, calcium carbonate 2%, potassium carbonate 2%, zinc oxide 2%, titanium dioxide 1%, aluminum oxide 1.5%, prodan 2% into
Row ingredient crosses 200 meshes after ball milling mixing；Ingredient is put into crucible again and carries out high temperature melting.
(2) Nd is weighed again in the ratio of 0.2wt% in above-mentioned raw materials total weight2O3Rare earth oxide is placed in mold simultaneously
Formed under press machine, wherein the type chamber of mold be cylindrical type preferentially select at suitable pressures, briquetting pressure be 10~
50MPa, block is placed in dry container for use after molding.
(3) after the ingredient in step (1) now melts completely, then the 0.2wt%Nd that will be obtained in step (2)2O3Rare earth oxygen
Compound block is pressed into the middle part or bottom of melten glass liquid by a kind of band specific purpose tool with concave surfaces, is sufficiently stirred, is clear
After cleer and peaceful homogenizing, then cooled down；
(4) through overcooled melt, the sample that required shape is made in mold will be poured into step (2)；
(5) opal glass stereotyped in step (4) is sent to progress controlled micro crystallization processing in furnace, obtained by controlled micro crystallization
Opal glass；
(6) opal glass that step (5) obtains is made annealing treatment, the opal glass after being annealed.Opal glass
Whiteness be 92, compared with not adding rare earth oxide, whiteness is obviously improved.
In step (1), fusion temperature is 1430 DEG C~1450 DEG C.
In step (2), the bulk shape of rare earth oxide is cylindrical type.
In step (3), rare earth oxide addition manner is using forced.Block is by a kind of band special tool with concave surfaces
Tool is pressed into the glass precursor solution of melting, and after standing 1~5min, mechanically or electrically magnetic stirs 5~10min.
In step (3), the cooling temperature of liquid is 1200 DEG C~1250 DEG C
In step (5), the condition of controlled micro crystallization is 750 DEG C~50 DEG C, furnace cooling, can also realize that temperature control is cooling, cooling speed
Degree control (preferably, cooling velocity control is in 3~5 DEG C/min) within the scope of 2~10 DEG C/min.
In step (6), annealing temperature is 500 DEG C~550 DEG C, and (preferably, 520 DEG C~540 DEG C) time is 1 hour.
Embodiment 3
The fluoride opal glass composition of raw materials for preparing of the present embodiment is (weight percent): quartz sand 61%, fluorite
5%, borax pentahydrate 5%, soda ash 18%, barium carbonate 1.5%, calcium carbonate 2%, potassium carbonate 2%, zinc oxide 1.5%, titanium dioxide
0.5%, aluminum oxide 1.5%, prodan 2%.The partial size of above-mentioned raw materials is not more than 120 microns, it is preferable that raw material particle size
It is 80~100 microns；
A kind of above-mentioned method for improving fluoride opal glass whiteness, further comprising the steps of:
(1) by weight percentage: quartz sand 61%, fluorite 5%, borax pentahydrate 5%, soda ash 18%, barium carbonate 1.5%,
Calcium carbonate 2%, potassium carbonate 2%, zinc oxide 1.5%, titanium dioxide 0.5%, aluminum oxide 1.5%, prodan 2% carry out
Ingredient crosses 200 meshes after ball milling mixing；Ingredient is put into crucible again and carries out high temperature melting.
(2) Y is weighed again in the ratio of 0.25wt% in above-mentioned raw materials total weight2O3Rare earth oxide is placed in mold simultaneously
Formed under press machine, wherein the type chamber of mold be ball-type preferentially select at suitable pressures, briquetting pressure be 10~
50MPa, block is placed in dry container for use after molding.
(3) after the ingredient in step (1) now melts completely, then the 0.25wt%Y that will be obtained in step (2)2O3Rare earth oxygen
Compound block is pressed into the middle part or bottom of melten glass liquid by a kind of band specific purpose tool with concave surfaces, is sufficiently stirred, is clear
After cleer and peaceful homogenizing, then cooled down；
(4) through overcooled melt, the sample that required shape is made in mold will be poured into step (2)；
(5) opal glass stereotyped in step (4) is sent to progress controlled micro crystallization processing in furnace, obtained by controlled micro crystallization
Opal glass；
(6) opal glass that step (5) obtains is made annealing treatment, the opal glass after being annealed.Opal glass
Whiteness be 92, compared with not adding rare earth oxide, whiteness is obviously improved.
In step (1), fusion temperature is 1430 DEG C~1450 DEG C.
In step (2), the bulk shape of rare earth oxide is ball-type.
In step (3), rare earth oxide addition manner is using forced.Block is by a kind of band special tool with concave surfaces
Tool is pressed into the glass precursor solution of melting, and after standing 1~5min, mechanically or electrically magnetic stirs 5~10min.
In step (3), the cooling temperature of liquid is 1200 DEG C~1250 DEG C
In step (5), the condition of controlled micro crystallization is 750 DEG C~50 DEG C, furnace cooling, can also realize that temperature control is cooling, cooling speed
Degree control (preferably, cooling velocity control is in 3~5 DEG C/min) within the scope of 2~10 DEG C/min.
In step (6), annealing temperature is 500 DEG C~550 DEG C, and (preferably, 520 DEG C~540 DEG C) time is 1 hour.
Embodiment 4
The fluoride opal glass composition of raw materials for preparing of the present embodiment is (weight percent): quartz sand 62.5%, fluorite
4.5%, borax pentahydrate 4.5%, soda ash 20%, barium carbonate 1%, calcium carbonate 1.5%, potassium carbonate 2%, zinc oxide 1%, titanium dioxide
Titanium 0.5%, aluminum oxide 1%, prodan 1.5%.The partial size of above-mentioned raw materials is not more than 120 microns, it is preferable that raw material grain
Diameter is 80~100 microns；
A kind of above-mentioned method for improving fluoride opal glass whiteness, further comprising the steps of:
(1) by weight percentage: quartz sand 62.5%, fluorite 4.5%, borax pentahydrate 4.5%, soda ash 20%, barium carbonate
1%, calcium carbonate 1.5%, potassium carbonate 2%, zinc oxide 1%, titanium dioxide 0.5%, aluminum oxide 1%, prodan 1.5%
Ingredient is carried out, after ball milling mixing, crosses 200 meshes；Ingredient is put into crucible again and carries out high temperature melting.
(2) CeO is weighed again in the ratio of 0.2wt% in above-mentioned raw materials total weight2Rare earth oxide is placed in mold simultaneously
Formed under press machine, wherein the type chamber of mold be ball-type preferentially select at suitable pressures, briquetting pressure be 10~
50MPa, block is placed in dry container for use after molding.
(3) after the ingredient in step (1) now melts completely, then the 0.25wt%CeO that will be obtained in step (2)2Rare earth
Oxide block is pressed into the middle part or bottom of melten glass liquid by a kind of band specific purpose tool with concave surfaces, be sufficiently stirred,
After clarification and homogenization, then cooled down；
(4) through overcooled melt, the sample that required shape is made in mold will be poured into step (2)；
(5) opal glass stereotyped in step (4) is sent to progress controlled micro crystallization processing in furnace, obtained by controlled micro crystallization
Opal glass；
(6) opal glass that step (5) obtains is made annealing treatment, the opal glass after being annealed.Opal glass
Whiteness be 92, compared with not adding rare earth oxide, whiteness is obviously improved.
In step (1), fusion temperature is 1430 DEG C~1450 DEG C.
In step (2), the bulk shape of rare earth oxide is ball-type.
In step (3), rare earth oxide addition manner is using forced.Block is by a kind of band special tool with concave surfaces
Tool is pressed into the glass precursor solution of melting, and after standing 1~5min, mechanically or electrically magnetic stirs 5~10min.
In step (3), the cooling temperature of liquid is 1200 DEG C~1250 DEG C
In step (5), the condition of controlled micro crystallization is 750 DEG C~50 DEG C, furnace cooling, can also realize that temperature control is cooling, cooling speed
Degree control (preferably, cooling velocity control is in 3~5 DEG C/min) within the scope of 2~10 DEG C/min.
In step (6), annealing temperature is 500 DEG C~550 DEG C, and (preferably, 520 DEG C~540 DEG C) time is 1 hour.
Embodiment 5
The fluoride opal glass composition of raw materials for preparing of the present embodiment is (weight percent): quartz sand 63%, fluorite
4.5%, borax pentahydrate 4%, soda ash 21%, barium carbonate 1%, calcium carbonate 1.5%, potassium carbonate 1.5%, zinc oxide 0.5%, dioxy
Change titanium 0.5%, aluminum oxide 1%, prodan 1.5%.The partial size of above-mentioned raw materials is not more than 120 microns, it is preferable that raw material
Partial size is 80~100 microns；
A kind of above-mentioned method for improving fluoride opal glass whiteness, further comprising the steps of:
(1) by weight percentage: quartz sand 63%, fluorite 4.5%, borax pentahydrate 4%, soda ash 21%, barium carbonate 1%,
Calcium carbonate 1.5%, potassium carbonate 1.5%, zinc oxide 0.5%, titanium dioxide 0.5%, aluminum oxide 1%, prodan 1.5%
Ingredient is carried out, after ball milling mixing, crosses 200 meshes；Ingredient is put into crucible again and carries out high temperature melting.
(2) a certain amount of rare earth oxide (La is weighed again in the ratio of 0.2wt% in above-mentioned raw materials total weight2O3、
Nd2O3And Y2O3, triangular ratio can be any, but total weight is 0.2wt%, it may be preferable that triangular ratio is 1:1:1),
It is placed in mold and is formed under press machine, wherein the type chamber of mold is that ball-type preferentially selects at suitable pressures, is formed
Pressure is 10~50MPa, and block is placed in dry container for use after molding.
(3) after the ingredient in step (1) now melts completely, then the 0.25wt%Y that will be obtained in step (2)2O3Rare earth oxygen
Compound block is pressed into the middle part or bottom of melten glass liquid by a kind of band specific purpose tool with concave surfaces, is sufficiently stirred, is clear
After cleer and peaceful homogenizing, then cooled down；
(4) through overcooled melt, the sample that required shape is made in mold will be poured into step (2)；
(5) opal glass stereotyped in step (4) is sent to progress controlled micro crystallization processing in furnace, obtained by controlled micro crystallization
Opal glass；
(6) opal glass that step (5) obtains is made annealing treatment, the opal glass after being annealed.Opal glass
Whiteness be 93, compared with not adding rare earth oxide, whiteness is obviously improved.
In step (1), fusion temperature is 1430 DEG C~1450 DEG C.
In step (2), the bulk shape of rare earth oxide is ball-type.
In step (3), rare earth oxide addition manner is using forced.Block is by a kind of band special tool with concave surfaces
Tool is pressed into the glass precursor solution of melting, and after standing 1~5min, mechanically or electrically magnetic stirs 5~10min.
In step (3), the cooling temperature of liquid is 1200 DEG C~1250 DEG C
In step (5), the condition of controlled micro crystallization is 750 DEG C~50 DEG C, furnace cooling, can also realize that temperature control is cooling, cooling speed
Degree control (preferably, cooling velocity control is in 3~5 DEG C/min) within the scope of 2~10 DEG C/min.
In step (6), annealing temperature is 500 DEG C~550 DEG C, and (preferably, 520 DEG C~540 DEG C) time is 1 hour.
Comparative example 1: not plus rare earth oxide
It is (weight percent): quartz sand 58%, fluorite that this comparative example, which prepares fluoride opal glass composition of raw materials,
5.5%, borax pentahydrate 6.5%, soda ash 14%, barium carbonate 2%, calcium carbonate 2.5%, potassium carbonate 3%, zinc oxide 3%, dioxy titanium
1%, aluminum oxide 2%, prodan 2.5%.Above-mentioned raw materials partial size is 80~100 microns.
(1) by weight percentage: quartz sand 58%, fluorite 5.5%, borax pentahydrate 6.5%, soda ash 14%, barium carbonate
2%, calcium carbonate 2.5%, potassium carbonate 3%, zinc oxide 3%, dioxy titanium 1%, aluminum oxide 2%, prodan 2.5% carry out
Ingredient crosses 200 meshes after ball milling mixing.
(2) high temperature melting will be carried out in the ingredient investment crucible in step (1), be sufficiently stirred, after clarification and homogenization, then into
Row cooling；
(3) through overcooled melt, the sample that required shape is made in mold will be poured into step (2)；
(4) opal glass stereotyped in step (3) is sent in furnace and is heat-treated, make it on the basis of opal glass
Upper further controlled micro crystallization, obtains the opal glass by controlled micro crystallization；
(5) opal glass that step (4) obtains is made annealing treatment, the opal glass after being annealed.Opal glass
Whiteness be 85.
In step (2), fusion temperature is 1450 DEG C, and the cooling temperature of liquid is 1200 DEG C~1250 DEG C
In step (4), the condition of controlled micro crystallization is 750 DEG C~50 DEG C, furnace cooling, can also realize that temperature control is cooling, cooling speed
Degree control is within the scope of 3~5 DEG C/min.
In step (5), annealing temperature is 520 DEG C~540 DEG C, and the time is 1 hour.
Comparative example 2: the non-briquetting of rare earth oxide is mixed directly into raw material.
The fluoride opal glass composition of raw materials for preparing of the present embodiment is (weight percent): quartz sand 58%, fluorite
5.5%, borax pentahydrate 6.5%, soda ash 14%, barium carbonate 2%, calcium carbonate 2.5%, potassium carbonate 3%, zinc oxide 3%, dioxy titanium
1%, aluminum oxide 2%, prodan 2.5%.Above-mentioned raw materials partial size is 80~100 microns.The partial size of above-mentioned raw materials is little
In 120 microns, it is preferable that raw material particle size is 80~100 microns；
A kind of above-mentioned method for improving fluoride opal glass whiteness, further comprising the steps of:
(1) by weight percentage: quartz sand 58%, fluorite 5.5%, borax pentahydrate 6.5%, soda ash 14%, barium carbonate
2%, calcium carbonate 2.5%, potassium carbonate 3%, zinc oxide 3%, dioxy titanium 1%, aluminum oxide 2%, prodan 2.5%.On
Stating raw material particle size is 80~100 microns.In the ratio of raw material gross weight 0.2wt%, a certain amount of rare earth oxide La is weighed2O3、
Nd2O3And Y2O3, triangular ratio is 1:1:1.With above-mentioned ingredient together after ball milling mixing, 200 meshes are crossed.
(2) ingredient is put into crucible and carries out high temperature melting, be sufficiently stirred, after clarification and homogenization, then cooled down.
(3) through overcooled melt, the sample that required shape is made in mold will be poured into step (2)；
(4) opal glass stereotyped in step (3) is sent in furnace and is heat-treated, make it on the basis of opal glass
Upper further controlled micro crystallization, obtains the opal glass by controlled micro crystallization；
(5) opal glass that step (4) obtains is made annealing treatment, the opal glass after being annealed.Opal glass
Whiteness be 86, compared with not adding rare earth oxide, whiteness has obtained a small amount of promotion.
In step (2), fusion temperature is 1430 DEG C~1450 DEG C, and the cooling temperature of liquid is 1200 DEG C~1250 DEG C
In step (4), the condition of controlled micro crystallization is 750 DEG C~50 DEG C, furnace cooling, can also realize that temperature control is cooling, cooling speed
Degree control is within the scope of 3~5 DEG C/min.
In step (5), annealing temperature is 520 DEG C~540 DEG C, and the time is 1 hour.
Comparative example 3: rare earth oxide briquetting, but be not pressed into liquid.
The fluoride opal glass composition of raw materials for preparing of the present embodiment is (weight percent): quartz sand 58%, fluorite
5.5%, borax pentahydrate 6.5%, soda ash 14%, barium carbonate 2%, calcium carbonate 2.5%, potassium carbonate 3%, zinc oxide 3%, dioxy titanium
1%, aluminum oxide 2%, prodan 2.5%.The partial size of above-mentioned raw materials is not more than 120 microns, it is preferable that raw material particle size is
80~100 microns；
A kind of above-mentioned method for improving fluoride opal glass whiteness, further comprising the steps of:
(1) by weight percentage: quartz sand 58%, fluorite 5.5%, borax pentahydrate 6.5%, soda ash 14%, barium carbonate
2%, calcium carbonate 2.5%, potassium carbonate 3%, zinc oxide 3%, dioxy titanium 1%, aluminum oxide 2%, prodan 2.5% carry out
Ingredient crosses 200 meshes after ball milling mixing；Ingredient is put into crucible again and carries out high temperature melting.
(2) a certain amount of rare earth oxide (La is weighed again in the ratio of 0.2wt% in above-mentioned raw materials total weight2O3、
Nd2O3And Y2O3Triangular ratio is 1:1:1), it is placed in mold and is formed under press machine, wherein the type chamber of mold is ball
Type preferentially selects at suitable pressures, briquetting pressure be 10~50MPa, after molding block be placed in dry container to
With.
(3) after the ingredient in step (1) now melts completely, then the 0.25wt%Y that will be obtained in step (2)2O3Rare earth oxygen
Compound block, and throw into the glass precursor solution of melting, it is sufficiently stirred, after clarification and homogenization, then cooled down；
(4) through overcooled melt, the sample that required shape is made in mold will be poured into step (3)；
(5) opal glass stereotyped in step (4) is sent to progress controlled micro crystallization processing in furnace, obtains the milky white of controlled micro crystallization
Glass；
(6) opal glass that step (5) obtains is made annealing treatment, the opal glass after being annealed.Opal glass
Whiteness be 87, compared with not adding rare earth oxide, whiteness has obtained a small amount of promotion.
In step (1), fusion temperature is 1430 DEG C~1450 DEG C.
In step (2), the bulk shape of rare earth oxide is ball-type.
In step (3), block be directly thrown into the glass precursor solution of melting, and by mechanically or electrically magnetic stirring 5~
10min。
In step (3), the cooling temperature of liquid is 1200 DEG C~1250 DEG C
In step (5), the condition of controlled micro crystallization is 750 DEG C~50 DEG C, furnace cooling, can also realize that temperature control is cooling, cooling speed
Degree control (preferably, cooling velocity control is in 3~5 DEG C/min) within the scope of 2~10 DEG C/min.
In step (6), annealing temperature is 500 DEG C~550 DEG C, and (preferably, 520 DEG C~540 DEG C) time is 1 hour.
Claims (10)
1. a kind of method for improving fluoride opal glass whiteness, which is characterized in that the fluoride opal glass is by including such as
The weight percent of lower raw material is prepared:
Quartz sand 58~63%
Fluorite 4.5~5.5%
Borax pentahydrate 4~6.5%
Soda ash 14~21%
Barium carbonate 1~2%
Calcium carbonate 1.5~2.5%
Potassium carbonate 1.5~3%
Zinc oxide 0.5~3%
Titanium dioxide 0.5~1%
Aluminum oxide 1~2%
Prodan 1.5~2.5%
Rare earth oxide 0.15%~0.25%.
2. a kind of method for improving fluoride opal glass whiteness according to claim 1, which is characterized in that all raw materials
Partial size be not more than 120 microns.
3. a kind of method for improving fluoride opal glass whiteness according to claim 1, which is characterized in that described is dilute
Native oxide are as follows: La2O3、Nd2O3、Y2O3、CeO2One or more of mixture.
4. a kind of method for improving fluoride opal glass whiteness according to claim 1, which is characterized in that including following
Step:
(1) by weight percentage: quartz sand 58~63%, fluorite 4.5~5.5%, borax pentahydrate 4~6.5%, soda ash 14~
21%, barium carbonate 1~2%, calcium carbonate 1.5~2.5%, potassium carbonate 1.5~3%, zinc oxide 0.5~3%, titanium dioxide 0.5
~1%, aluminum oxide 1~2%, prodan 1.5~2.5% carry out ingredient, after ball milling mixing, cross 200 meshes；It will match
High temperature melting is carried out in material investment crucible；
(2) by rare earth oxide La2O3、Nd2O3、Y2O3、CeO2After being weighed according to mass percent 0.15%~0.25%, merging
In mold, using press machine, it is pressed into rare earth oxide block, rare earth oxide block is pressed into the glass of step (1) melting
In liquid, after stirring, clarification and homogenization, then cooled down；
(3) through overcooled solution, the sample that required shape is made in mold will be poured into step (2)；
(4) opal glass stereotyped in step (3) is sent to progress controlled micro crystallization processing in furnace, obtained by the milky white of controlled micro crystallization
Glass；
(5) the controlled micro crystallization opal glass that step (4) obtains is made annealing treatment.
5. a kind of method for improving fluoride opal glass whiteness according to claim 4, which is characterized in that step (1)
In, fusion temperature is 1430 DEG C~1450 DEG C.
6. a kind of method for improving fluoride opal glass whiteness according to claim 4, which is characterized in that step (2)
In, the bulk shape of rare earth oxide are as follows: square, ball-type or cylindrical type.
7. a kind of method for improving fluoride opal glass whiteness according to claim 4, which is characterized in that step (2)
In, rare earth oxide addition manner is using forced；Rare earth oxide block is pressed into the middle part or bottom of melten glass liquid
Portion.
8. a kind of method for improving fluoride opal glass whiteness according to claim 4, which is characterized in that step (2)
In, cooling temperature is 1200 DEG C~1250 DEG C.
9. a kind of method for improving fluoride opal glass whiteness according to claim 4, which is characterized in that step (4)
In, the controlled micro crystallization treatment conditions are to cool to 50 DEG C with the furnace by 750 DEG C, or to be cooled to 50 DEG C in 2~10 DEG C/min.
10. a kind of method for improving fluoride opal glass whiteness according to claim 4, which is characterized in that step (5)
In, the annealing keeps the temperature 1 hour at a temperature of being 500 DEG C~550 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910761917.6A CN110451808A (en) | 2019-08-19 | 2019-08-19 | A method of improving fluoride opal glass whiteness |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910761917.6A CN110451808A (en) | 2019-08-19 | 2019-08-19 | A method of improving fluoride opal glass whiteness |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110451808A true CN110451808A (en) | 2019-11-15 |
Family
ID=68487378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910761917.6A Pending CN110451808A (en) | 2019-08-19 | 2019-08-19 | A method of improving fluoride opal glass whiteness |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110451808A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115557700A (en) * | 2022-11-03 | 2023-01-03 | 广东健诚高科玻璃制品股份有限公司 | Surface-strengthened opal glass tableware and preparation method of surface-strengthened opal glass |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4977110A (en) * | 1990-01-12 | 1990-12-11 | Corning Incorporated | Beige-tinted glass-ceramics |
| CN104176935A (en) * | 2014-08-18 | 2014-12-03 | 江苏杰龙晶瓷科技有限公司 | Crystal-jade ceramic milk glass |
| CN107265854A (en) * | 2017-06-22 | 2017-10-20 | 合肥钢骨玻璃制品有限公司 | A kind of low fluorine opal glass product and preparation method thereof |
| CN107640889A (en) * | 2017-09-27 | 2018-01-30 | 江苏拜富科技有限公司 | Low temperature coloured glass aubergine colouring agent and preparation method thereof and application method |
| CN110104948A (en) * | 2019-05-07 | 2019-08-09 | 淮阴工学院 | It is the heat-resistant opal glass and preparation method thereof of raw material preparation using recessed soil |
-
2019
- 2019-08-19 CN CN201910761917.6A patent/CN110451808A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4977110A (en) * | 1990-01-12 | 1990-12-11 | Corning Incorporated | Beige-tinted glass-ceramics |
| CN104176935A (en) * | 2014-08-18 | 2014-12-03 | 江苏杰龙晶瓷科技有限公司 | Crystal-jade ceramic milk glass |
| CN107265854A (en) * | 2017-06-22 | 2017-10-20 | 合肥钢骨玻璃制品有限公司 | A kind of low fluorine opal glass product and preparation method thereof |
| CN107640889A (en) * | 2017-09-27 | 2018-01-30 | 江苏拜富科技有限公司 | Low temperature coloured glass aubergine colouring agent and preparation method thereof and application method |
| CN110104948A (en) * | 2019-05-07 | 2019-08-09 | 淮阴工学院 | It is the heat-resistant opal glass and preparation method thereof of raw material preparation using recessed soil |
Non-Patent Citations (1)
| Title |
|---|
| 马薇薇: "磷酸盐微晶玻璃的研制", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115557700A (en) * | 2022-11-03 | 2023-01-03 | 广东健诚高科玻璃制品股份有限公司 | Surface-strengthened opal glass tableware and preparation method of surface-strengthened opal glass |
| CN115557700B (en) * | 2022-11-03 | 2023-11-24 | 广东健诚高科玻璃制品股份有限公司 | Surface-reinforced opal glass tableware and preparation method of surface-reinforced opal glass |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106587634B (en) | A kind of direct speckle devitrified glass and preparation method thereof using molten blast furnace slag | |
| CN103524042B (en) | A kind of environment-friendly type height high refraction crystal glass and its preparation method thoroughly | |
| CN105236734B (en) | A kind of preparation method of the low lanthanum optical glass of high niobium of titaniferous | |
| CN105347685A (en) | Glass ceramic and preparation method thereof | |
| CN105060682A (en) | Process for preparing glass ceramics with melting method | |
| CN107244803A (en) | Flint optical glass with heavy lanthanum and preparation method thereof and optical element | |
| JP2005504708A (en) | High purity bioactive glass and method for producing the same | |
| CN105236733A (en) | Titanium-containing high-lanthanum and low-niobium optical glass preparation method | |
| CN109502983A (en) | A kind of preparation method of the canopy of the heavens blue glass ceramics with star spherical distribution | |
| CN108793728A (en) | High-aluminum alkali-free borosilicate glass fining agent and defecation method | |
| CN109704573B (en) | Red glass product and preparation method thereof | |
| CN110451808A (en) | A method of improving fluoride opal glass whiteness | |
| CN106892560A (en) | A kind of high finished product rate glass and its production technology | |
| CN102515524A (en) | Boroaluminosilicate glass substrate and preparation method thereof | |
| CN101407376B (en) | High brightness glass microbeads and preparation technique thereof | |
| CN110436786A (en) | A method of improving phosphate-opal glass whiteness | |
| CN106007371B (en) | Transparent float glass production method | |
| JP2003183047A (en) | Red color glass composition and transparent crystallized glass | |
| CN109502966A (en) | A kind of high rigidity high permeability glass and preparation method thereof | |
| CN113336438A (en) | Colored glaze and manufacturing method thereof | |
| CN110104948A (en) | It is the heat-resistant opal glass and preparation method thereof of raw material preparation using recessed soil | |
| CN107777881A (en) | A kind of method that milky white heat resistant glass is produced using lepidolite as raw material | |
| CN114538780B (en) | Front tooth facing ceramic material and preparation method thereof | |
| CN106946457A (en) | A kind of aubergine glass and its preparation method that once develops the color | |
| CN107902898A (en) | A kind of antibiotic glass ball and its production technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20191115 |