CN109320074A - A kind of neutral boron silica glass material and preparation method thereof - Google Patents
A kind of neutral boron silica glass material and preparation method thereof Download PDFInfo
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- CN109320074A CN109320074A CN201811287963.9A CN201811287963A CN109320074A CN 109320074 A CN109320074 A CN 109320074A CN 201811287963 A CN201811287963 A CN 201811287963A CN 109320074 A CN109320074 A CN 109320074A
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
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Abstract
The invention belongs to acceptable packaging material technical fields, especially a kind of neutral boron silica glass material and preparation method thereof, it is bad to solve pharmaceutical pack glass material intensity, chemical resistance and hydrolytic stability in the prior art, there are problems that neutrality is unqualified, mixes with drug, flake, the neutral boron silica glass material, the raw material including following weight percent: silica 74~77%, aluminum oxide 3.8~5.5%, diboron trioxide 9~11%, di-iron trioxide 4~5%, glass agent 0.3~0.8%, surplus are composition.Inventive formulation science, proportion is rigorous, and neutral boron silica glass obtained has the characteristics that chemical resistance is good, hydrolytic stability is good, thermal stability is good, high mechanical strength, is suitable for all kinds of pharmaceutical packings, storage.
Description
Technical field
The present invention relates to acceptable packaging material technical field more particularly to a kind of neutral boron silica glass material and its production sides
Method.
Background technique
Medicinal neutral boron silicate glass is the preferred glass of acceptable packaging material generally acknowledged in the world, due to resisting for this glass
Water, antiacid, alkali resistant ability are level-ones, it may be said that there is excellent chemical stability and thermal stability, as pack package material,
To drug quality is ensured, there is incomparable superiority.By the effort of decades, China's pharmaceutical pack industry achieves length
The progress of foot, but compared with world level, larger gap is still had in some aspects.By taking medicinal pipe-produced glass bottle as an example, mesh
It is 5.0 neutral density glass glass tube vials that preceding developed country in the world generallys use the coefficient of expansion already, and China is produced due to pharmaceutical glass
Industry starting is than later, by many-sided conditionality, is up to the present only capable of the low borosilicate glass that the production coefficient of expansion is 7.0 or more
Glass, 3.3 high-boron-silicon glass and soda-lime glass, above-mentioned packaging material is in terms of intensity, water-fast, resistance to jelly, chemical stabilization and shock resistance
It is not so good as neutral boron silica glass, 1 grade and HC1 grade standard is not achieved in glass particle method water resistance and inner surface Water Resistance Test,
In practical applications generally existing neutrality it is unqualified, with drug mix, flake phenomena such as, flake in medical fluid be in fish scale-shaped, pine
It is needle-shaped, seriously injure the drug safety of the people；When containing the high drug of pH value, potassium sodium amount of precipitation is exceeded, and drug and glass are sent out
The raw reaction that mixes, causes liquid drugs injection clarity not up to standard, and medicine stability reduces.
In recent years, with the fast development of medical and health cause, people are higher and higher to the quality requirement of medical product, right
The quality requirement of acceptable packaging material is also higher and higher therewith.Therefore it researches and develops a kind of high-intensitive, high chemical resistance and high hydrolysis is steady
Qualitative neutral boron silica glass becomes very urgent.Based on above statement, the invention proposes a kind of neutral boron silica glass materials
And preparation method thereof.
Summary of the invention
The purpose of the present invention is to solve pharmaceutical pack glass material intensity in the prior art, chemical resistance and hydrolysis are steady
It is qualitative bad, there are problems that it is neutral it is unqualified, mix with drug, flake, and a kind of neutral boron silica glass material that proposes and
Its production method.
A kind of neutral boron silica glass material, the raw material including following weight percent: silica 74~77%, three aoxidizes
Two aluminium 3.8~5.5%, diboron trioxide 9~11%, di-iron trioxide 4~5%, glass agent 0.3~0.8%, surplus are group
Close object；
The composition be praseodymium neodymium oxide, sodium oxide molybdena, barium bromide and silicon nitride compound, and praseodymium neodymium oxide, sodium oxide molybdena,
The mass ratio of barium bromide and silicon nitride is 1:6~9:3~5:2~3；
The glass agent is made by following methods:
S1, by weight, weighs 4~8 parts of sodium molybdate, 2~5 parts of zinc sulfate, 5~7 parts of prodan, strontium carbonate powder 1
~3 parts, 5~10 parts of Paris white, 2~5 parts of potassium stannate, 3~8 parts of graphite powder it is spare；
S2, will be cooled to after sodium molybdate, zinc sulfate, prodan and potassium stannate heating melting 210~240 DEG C heat preservation 1~
2h obtains mixture I；
S3, into mixture I be added 3.5~4.5 times of mixture I mass water make its quenching, then be added strontium carbonate powder,
Paris white and graphite powder are dispersed with stirring the dilute salt for being uniformly added that the mass fraction of 0.4~0.7 times of mixture I mass is 12%
Acid after continuing 0.5~1h of stirring, adds alkali to adjust pH value to neutrality, obtains mixtures II；
S4, mixtures II is added in whizzer, fluidized drying is carried out in centrifugal force field, after completing drying
Add zirconium oxide bead to carry out ball milling, 220~280 meshes are crossed after 4~6h of ball milling to get glass agent.
Preferably, the neutral boron silica glass material, the raw material including following weight percent: silica 75~
76%, aluminum oxide 4~5%, diboron trioxide 9.5~10.5%, di-iron trioxide 4.2~4.8%, glass agent 0.4
~0.7%, surplus is composition.
Preferably, the neutral boron silica glass material, the raw material including following weight percent: silica 75.5%,
Aluminum oxide 4.5%, diboron trioxide 10%, di-iron trioxide 4.5%, glass agent 0.6%, surplus are composition.
Preferably, the composition be praseodymium neodymium oxide, sodium oxide molybdena, barium bromide and silicon nitride compound, and praseodymium neodymium oxide,
The mass ratio of sodium oxide molybdena, barium bromide and silicon nitride is 1:7.5:4:2.5.
The invention also provides a kind of production methods of neutral boron silica glass material, comprising the following steps:
S1, the weight percent is pressed, weighs starting silica, aluminum oxide, diboron trioxide, three oxidations two
Glass agent 7:3 in mass ratio is divided into two parts by iron, glass agent and composition, respectively glass agent I and glass agent II
It is spare；
S2, by starting silica, aluminum oxide, diboron trioxide and di-iron trioxide ball milling mixing it is uniform after pour into
In alumina crucible, after being at the uniform velocity warming up to 850 DEG C, glass agent I and composition is added, is continuously heating to 1450 DEG C of heat preservation fusings
0.5h is cooled to 1250 DEG C of heat preservations with the rate of 8 DEG C/min, and glass agent II is added, and clarification 3h obtains glass metal；
S3, crucible is taken out, glass metal is poured into the graphite jig for being preheated to 640~680 DEG C, after glass molding material
Add water quenching to be cooled to room temperature, the glass material after quenching is warming up to 160~190 DEG C of 1~3h of heat preservation, then proceedes to be warming up to 220
~260 DEG C, 2~5h of heat preservation is air-cooled to room temperature to get neutral boron silica glass material.
A kind of neutral boron silica glass material proposed by the present invention, has the advantages that
1, the present invention is uniformly pre- using silica, aluminum oxide, diboron trioxide and di-iron trioxide ball milling mixing
Heat adds glass agent I and composition to heat up and melts, and cooling plus glass agent II clarification finally form obtained neutral boron silica glass
Material；Inventive formulation science, proportion is rigorous, and neutral boron silica glass obtained is with chemical resistance is good, hydrolytic stability is good, hot
The characteristics of stability is good, high mechanical strength is suitable for all kinds of pharmaceutical packings, storage, solves pharmaceutical pack in the prior art
Glass material intensity, chemical resistance and hydrolytic stability are bad, there are problems that neutrality is unqualified, mixes with drug, flake,
Production method is simple, and safe preparation process environmental protection, product quality obtained is high, is suitble to industrialized production, is worthy to be popularized.
2, the present invention compounds sodium molybdate, zinc sulfate, prodan, strontium carbonate powder, Paris white, potassium stannate and graphite powder
Glass agent is made, obtained glass agent is environmentally protective, nontoxic, and the present invention is in such a way that gradation is added, by glass
Glass auxiliary agent can effectively inhibit raw material respectively at fusing and clarification stage addition in neutral boron silica glass material manufacturing process
The volatilization of boron in fusion process discharges air pocket, moreover it is possible to and it is effective to absorb the minute bubbles for not having release in clarifying process, to make
Glass metal obtained is transparent, without calculus, bubble-free, without striped, meet production standard.
3, the present invention is in the melting stage of neutral boron silica glass material manufacturing process, common addition glass agent I and combination
Object makes the two that synergy occur, and so as to effectively reduce the fusing in manufacturing process, clarification and forming temperature, reduces
The coefficient of linear thermal expansion of neutral boron silica glass material improves its thermal stability, chemical stability and hydrolytic stability, while significant
Improve its mechanical strength.
Specific embodiment
Combined with specific embodiments below the present invention is made further to explain.
Embodiment one
A kind of neutral boron silica glass material proposed by the present invention, the raw material including following weight percent: silica
74%, aluminum oxide 3.8%, diboron trioxide 9%, di-iron trioxide 4%, glass agent 0.3%, surplus are composition；
The composition be praseodymium neodymium oxide, sodium oxide molybdena, barium bromide and silicon nitride compound, and praseodymium neodymium oxide, sodium oxide molybdena,
The mass ratio of barium bromide and silicon nitride is 1:6:3:2；
The glass agent is made by following methods:
S1, by weight, weighs 4 parts of sodium molybdate, 2 parts of zinc sulfate, 5 parts of prodan, 1 part of strontium carbonate powder, calcium carbonate
5 parts of powder, 2 parts of potassium stannate, 3 parts of graphite powder it is spare；
S2, it will be cooled to 210 DEG C of heat preservation 1h after sodium molybdate, zinc sulfate, prodan and potassium stannate heating melting must mix
Object I；
S3, the water that 3.5 times of mixture I mass is added into mixture I make its quenching, and strontium carbonate powder, carbonic acid is then added
Calcium powder and graphite powder are dispersed with stirring the dilute hydrochloric acid for being uniformly added that the mass fraction of 0.4 times of mixture I mass is 12%, continue to stir
After mixing 0.5h, adds alkali to adjust pH value to neutrality, obtain mixtures II；
S4, mixtures II is added in whizzer, fluidized drying is carried out in centrifugal force field, after completing drying
Add zirconium oxide bead to carry out ball milling, 220 meshes are crossed after ball milling 4h to get glass agent.
A kind of production method of neutral boron silica glass material, comprising the following steps:
S1, the weight percent is pressed, weighs starting silica, aluminum oxide, diboron trioxide, three oxidations two
Glass agent 7:3 in mass ratio is divided into two parts by iron, glass agent and composition, respectively glass agent I and glass agent II
It is spare；
S2, by starting silica, aluminum oxide, diboron trioxide and di-iron trioxide ball milling mixing it is uniform after pour into
In alumina crucible, after being at the uniform velocity warming up to 850 DEG C, glass agent I and composition is added, is continuously heating to 1450 DEG C of heat preservation fusings
0.5h is cooled to 1250 DEG C of heat preservations with the rate of 8 DEG C/min, and glass agent II is added, and clarification 3h obtains glass metal；
S3, crucible is taken out, glass metal is poured into the graphite jig for being preheated to 640 DEG C, water is added after glass molding material
Glass material after quenching is warming up to 160 DEG C of heat preservation 1h, then proceedes to be warming up to 220 DEG C, heat preservation 2h is air-cooled by quenching to room temperature
To room temperature to get neutral boron silica glass material.
Embodiment two
A kind of neutral boron silica glass material proposed by the present invention, the raw material including following weight percent: silica
75.5%, aluminum oxide 4.5%, diboron trioxide 10%, di-iron trioxide 4.5%, glass agent 0.6%, surplus are group
Close object；
The composition be praseodymium neodymium oxide, sodium oxide molybdena, barium bromide and silicon nitride compound, and praseodymium neodymium oxide, sodium oxide molybdena,
The mass ratio of barium bromide and silicon nitride is 1:7.5:4:2.5；
The glass agent is made by following methods:
S1, by weight, weighs 6 parts of sodium molybdate, 3.5 parts of zinc sulfate, 6 parts of prodan, 2 parts of strontium carbonate powder, carbonic acid
8 parts of calcium powder, 3.5 parts of potassium stannate, 5 parts of graphite powder it is spare；
S2, it will be cooled to 225 DEG C of heat preservation 1.5h after sodium molybdate, zinc sulfate, prodan and potassium stannate heating melting must mix
Close object I；
S3, the water that 4 times of mixture I mass is added into mixture I make its quenching, and strontium carbonate powder, calcium carbonate is then added
Powder and graphite powder are dispersed with stirring the dilute hydrochloric acid for being uniformly added that the mass fraction of 0.5 times of mixture I mass is 12%, continue to stir
After 0.8h, adds alkali to adjust pH value to neutrality, obtain mixtures II；
S4, mixtures II is added in whizzer, fluidized drying is carried out in centrifugal force field, after completing drying
Add zirconium oxide bead to carry out ball milling, 250 meshes are crossed after ball milling 5h to get glass agent.
A kind of production method of neutral boron silica glass material, comprising the following steps:
S1, the weight percent is pressed, weighs starting silica, aluminum oxide, diboron trioxide, three oxidations two
Glass agent 7:3 in mass ratio is divided into two parts by iron, glass agent and composition, respectively glass agent I and glass agent II
It is spare；
S2, by starting silica, aluminum oxide, diboron trioxide and di-iron trioxide ball milling mixing it is uniform after pour into
In alumina crucible, after being at the uniform velocity warming up to 850 DEG C, glass agent I and composition is added, is continuously heating to 1450 DEG C of heat preservation fusings
0.5h is cooled to 1250 DEG C of heat preservations with the rate of 8 DEG C/min, and glass agent II is added, and clarification 3h obtains glass metal；
S3, crucible is taken out, glass metal is poured into the graphite jig for being preheated to 660 DEG C, water is added after glass molding material
Glass material after quenching is warming up to 175 DEG C of heat preservation 2h, then proceedes to be warming up to 240 DEG C, heat preservation 3.5h is empty by quenching to room temperature
It is cooled to room temperature to get neutral boron silica glass material.
Embodiment three
A kind of neutral boron silica glass material proposed by the present invention, the raw material including following weight percent: silica
77%, aluminum oxide 5.5%, diboron trioxide 11%, di-iron trioxide 5%, glass agent 0.8%, surplus are composition；
The composition be praseodymium neodymium oxide, sodium oxide molybdena, barium bromide and silicon nitride compound, and praseodymium neodymium oxide, sodium oxide molybdena,
The mass ratio of barium bromide and silicon nitride is 1:9:5:3；
The glass agent is made by following methods:
S1, by weight, weighs 8 parts of sodium molybdate, 5 parts of zinc sulfate, 7 parts of prodan, 3 parts of strontium carbonate powder, calcium carbonate
10 parts of powder, 5 parts of potassium stannate, 8 parts of graphite powder it is spare；
S2, it will be cooled to 240 DEG C of heat preservation 2h after sodium molybdate, zinc sulfate, prodan and potassium stannate heating melting must mix
Object I；
S3, the water that 4.5 times of mixture I mass is added into mixture I make its quenching, and strontium carbonate powder, carbonic acid is then added
Calcium powder and graphite powder are dispersed with stirring the dilute hydrochloric acid for being uniformly added that the mass fraction of 0.7 times of mixture I mass is 12%, continue to stir
After mixing 1h, adds alkali to adjust pH value to neutrality, obtain mixtures II；
S4, mixtures II is added in whizzer, fluidized drying is carried out in centrifugal force field, after completing drying
Add zirconium oxide bead to carry out ball milling, 280 meshes are crossed after ball milling 6h to get glass agent.
A kind of production method of neutral boron silica glass material, comprising the following steps:
S1, the weight percent is pressed, weighs starting silica, aluminum oxide, diboron trioxide, three oxidations two
Glass agent 7:3 in mass ratio is divided into two parts by iron, glass agent and composition, respectively glass agent I and glass agent II
It is spare；
S2, by starting silica, aluminum oxide, diboron trioxide and di-iron trioxide ball milling mixing it is uniform after pour into
In alumina crucible, after being at the uniform velocity warming up to 850 DEG C, glass agent I and composition is added, is continuously heating to 1450 DEG C of heat preservation fusings
0.5h is cooled to 1250 DEG C of heat preservations with the rate of 8 DEG C/min, and glass agent II is added, and clarification 3h obtains glass metal；
S3, crucible is taken out, glass metal is poured into the graphite jig for being preheated to 680 DEG C, water is added after glass molding material
Glass material after quenching is warming up to 190 DEG C of heat preservation 3h, then proceedes to be warming up to 260 DEG C, heat preservation 5h is air-cooled by quenching to room temperature
To room temperature to get neutral boron silica glass material.
Comparative example one
A kind of neutral boron silica glass material proposed by the present invention, the raw material including following weight percent: silica
74%, aluminum oxide 3.8%, diboron trioxide 9%, di-iron trioxide 4%, surplus are composition；
The composition be praseodymium neodymium oxide, sodium oxide molybdena, barium bromide and silicon nitride compound, and praseodymium neodymium oxide, sodium oxide molybdena,
The mass ratio of barium bromide and silicon nitride is 1:6:3:2；
A kind of production method of neutral boron silica glass material, comprising the following steps:
S1, the weight percent is pressed, weighs starting silica, aluminum oxide, diboron trioxide, three oxidations two
Iron, glass agent and composition are spare；
S2, by starting silica, aluminum oxide, diboron trioxide and di-iron trioxide ball milling mixing it is uniform after pour into
In alumina crucible, after being at the uniform velocity warming up to 850 DEG C, composition is added, is continuously heating to 1450 DEG C of heat preservations and melts 0.5h, with 8 DEG C/
The rate of min is cooled to 1250 DEG C of heat preservations, and clarification 3h obtains glass metal；
S3, crucible is taken out, glass metal is poured into the graphite jig for being preheated to 640 DEG C, water is added after glass molding material
Glass material after quenching is warming up to 160 DEG C of heat preservation 1h, then proceedes to be warming up to 220 DEG C, heat preservation 2h is air-cooled by quenching to room temperature
To room temperature to get neutral boron silica glass material.
Comparative example two
A kind of neutral boron silica glass material proposed by the present invention, the raw material including following weight percent: silica
74%, aluminum oxide 3.8%, diboron trioxide 9%, di-iron trioxide 4%, glass agent 0.3%, surplus are composition；
The composition be praseodymium neodymium oxide, sodium oxide molybdena, barium bromide and silicon nitride compound, and praseodymium neodymium oxide, sodium oxide molybdena,
The mass ratio of barium bromide and silicon nitride is 1:6:3:2；
The glass agent is made by following methods:
S1, by weight, weighs 4 parts of sodium molybdate, 2 parts of zinc sulfate, 5 parts of prodan, 1 part of strontium carbonate powder, calcium carbonate
5 parts of powder, 2 parts of potassium stannate, 3 parts of graphite powder it is spare；
S2, it will be cooled to 210 DEG C of heat preservation 1h after sodium molybdate, zinc sulfate, prodan and potassium stannate heating melting must mix
Object I；
S3, the water that 3.5 times of mixture I mass is added into mixture I make its quenching, and strontium carbonate powder, carbonic acid is then added
Calcium powder and graphite powder are dispersed with stirring the dilute hydrochloric acid for being uniformly added that the mass fraction of 0.4 times of mixture I mass is 12%, continue to stir
After mixing 0.5h, adds alkali to adjust pH value to neutrality, obtain mixtures II；
S4, mixtures II is added in whizzer, fluidized drying is carried out in centrifugal force field, after completing drying
Add zirconium oxide bead to carry out ball milling, 220 meshes are crossed after ball milling 4h to get glass agent.
A kind of production method of neutral boron silica glass material, comprising the following steps:
S1, the weight percent is pressed, weighs starting silica, aluminum oxide, diboron trioxide, three oxidations two
Iron, glass agent and composition are spare；
S2, by starting silica, aluminum oxide, diboron trioxide and di-iron trioxide ball milling mixing it is uniform after pour into
In alumina crucible, after being at the uniform velocity warming up to 850 DEG C, glass agent and composition is added, is continuously heating to 1450 DEG C of heat preservation fusings
0.5h is cooled to 1250 DEG C of heat preservations with the rate of 8 DEG C/min, and clarification 3h obtains glass metal；
S3, crucible is taken out, glass metal is poured into the graphite jig for being preheated to 640 DEG C, water is added after glass molding material
Glass material after quenching is warming up to 160 DEG C of heat preservation 1h, then proceedes to be warming up to 220 DEG C, heat preservation 2h is air-cooled by quenching to room temperature
To room temperature to get neutral boron silica glass material.
Comparative example three
A kind of neutral boron silica glass material proposed by the present invention, the raw material including following weight percent: silica
74%, aluminum oxide 3.8%, diboron trioxide 9%, di-iron trioxide 4%, glass agent 0.3%, surplus are composition；
The composition be praseodymium neodymium oxide, sodium oxide molybdena, barium bromide and silicon nitride compound, and praseodymium neodymium oxide, sodium oxide molybdena,
The mass ratio of barium bromide and silicon nitride is 1:6:3:2；
The glass agent is made by following methods:
S1, by weight, weighs 4 parts of sodium molybdate, 2 parts of zinc sulfate, 5 parts of prodan, 1 part of strontium carbonate powder, calcium carbonate
5 parts of powder, 2 parts of potassium stannate, 3 parts of graphite powder it is spare；
S2, it will be cooled to 210 DEG C of heat preservation 1h after sodium molybdate, zinc sulfate, prodan and potassium stannate heating melting must mix
Object I；
S3, the water that 3.5 times of mixture I mass is added into mixture I make its quenching, and strontium carbonate powder, carbonic acid is then added
Calcium powder and graphite powder are dispersed with stirring the dilute hydrochloric acid for being uniformly added that the mass fraction of 0.4 times of mixture I mass is 12%, continue to stir
After mixing 0.5h, adds alkali to adjust pH value to neutrality, obtain mixtures II；
S4, mixtures II is added in whizzer, fluidized drying is carried out in centrifugal force field, after completing drying
Add zirconium oxide bead to carry out ball milling, 220 meshes are crossed after ball milling 4h to get glass agent.
A kind of production method of neutral boron silica glass material, comprising the following steps:
S1, the weight percent is pressed, weighs starting silica, aluminum oxide, diboron trioxide, three oxidations two
Glass agent 7:3 in mass ratio is divided into two parts by iron, glass agent and composition, respectively glass agent I and glass agent II
It is spare；
It is S2, starting silica, aluminum oxide, diboron trioxide, di-iron trioxide and composition ball milling mixing is equal
It is poured into alumina crucible after even, after being at the uniform velocity warming up to 850 DEG C, glass agent I is added, be continuously heating to 1450 DEG C of heat preservation fusings
0.5h is cooled to 1250 DEG C of heat preservations with the rate of 8 DEG C/min, and glass agent II is added, and clarification 3h obtains glass metal；
S3, crucible is taken out, glass metal is poured into the graphite jig for being preheated to 640 DEG C, water is added after glass molding material
Glass material after quenching is warming up to 160 DEG C of heat preservation 1h, then proceedes to be warming up to 220 DEG C, heat preservation 2h is air-cooled by quenching to room temperature
To room temperature to get neutral boron silica glass material.
The neutral boron silica glass material prepared in the embodiment of the present invention one~tri- and comparative example one~tri- is cut or ground
Wear into the bulk of predetermined size, strip, sheet, graininess or powdered samples in YBB00022005-2,98 DEG C of water-fast test institutes
The size for needing sample is 300~500 μm, and the size of sample needed for 121 DEG C of water-fast tests is 600~1000 μm, acid resistance test
The total surface area of required sample is 100 ± 10cm2, the total surface area of sample needed for alkali resistance is tested is 10~15cm2, line heat is swollen
The size of sample needed for swollen coefficient is 4*4*24.5mm.
The performance of the neutral boron silica glass material prepared in testing example one~tri- and comparative example one~tri- respectively, obtains
Following result out:
Table:
In table: 98 DEG C of particle methods are water-fast to be tested by YBB00362004, and 121 DEG C of particle methods are water-fast to be surveyed by YBB00252003
Examination, acid resistance are tested by YBB00342004, and alkali resistance is tested by YBB00352004, and thermal expansion coefficient presses standard GB/T16920-
1997 tests, number of bubbles refer to diameter >=0.02mm bubble number in every square metre of neutral boron silica glass material.
As seen from the above table: water resistance, the acid resistance of the neutral boron silica glass material prepared in the embodiment of the present invention one~tri-
1 grade standard is reached with alkali resistance, bubble is practically free of in glass material, comprehensive performance, which is much better than in comparative example one~tri-, to be made
Standby neutral boron silica glass material.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (5)
1. a kind of neutral boron silica glass material, which is characterized in that the raw material including following weight percent: silica 74~
77%, aluminum oxide 3.8~5.5%, diboron trioxide 9~11%, di-iron trioxide 4~5%, glass agent 0.3~
0.8%, surplus is composition；
The composition be praseodymium neodymium oxide, sodium oxide molybdena, barium bromide and silicon nitride compound, and praseodymium neodymium oxide, sodium oxide molybdena, bromination
The mass ratio of barium and silicon nitride is 1:6~9:3~5:2~3；
The glass agent is made by following methods:
S1, by weight, weighs 4~8 parts of sodium molybdate, 2~5 parts of zinc sulfate, 5~7 parts of prodan, strontium carbonate powder 1~3
Part, 5~10 parts of Paris white, 2~5 parts of potassium stannate, 3~8 parts of graphite powder it is spare；
S2, it will be cooled to 210~240 DEG C of 1~2h of heat preservation after sodium molybdate, zinc sulfate, prodan and potassium stannate heating melting obtains
Mixture I；
S3, the water that 3.5~4.5 times of mixture I mass is added into mixture I make its quenching, and strontium carbonate powder, carbonic acid is then added
Calcium powder and graphite powder are dispersed with stirring the dilute hydrochloric acid for being uniformly added that the mass fraction of 0.4~0.7 times of mixture I mass is 12%, after
After 0.5~1h of continuous stirring, adds alkali to adjust pH value to neutrality, obtain mixtures II；
S4, mixtures II is added in whizzer, fluidized drying is carried out in centrifugal force field, complete oxygenation after drying
Change zirconium pearl and carry out ball milling, 220~280 meshes are crossed after 4~6h of ball milling to get glass agent.
2. a kind of neutral boron silica glass material according to claim 1, which is characterized in that including following weight percent
Raw material: silica 75~76%, aluminum oxide 4~5%, diboron trioxide 9.5~10.5%, di-iron trioxide 4.2~
4.8%, glass agent 0.4~0.7%, surplus are composition.
3. a kind of neutral boron silica glass material according to claim 1 or 2, which is characterized in that including following weight percent
The raw material of ratio: silica 75.5%, aluminum oxide 4.5%, diboron trioxide 10%, di-iron trioxide 4.5%, glass help
Agent 0.6%, surplus are composition.
4. a kind of neutral boron silica glass material according to claim 1 or 2, which is characterized in that the composition is oxidation
Praseodymium neodymium, sodium oxide molybdena, barium bromide and silicon nitride compound, and praseodymium neodymium oxide, sodium oxide molybdena, barium bromide and silicon nitride mass ratio be
1:7.5:4:2.5。
5. the production method of neutral boron silica glass material according to any one of claims 1 to 4, which is characterized in that including
Following steps:
S1, the weight percent is pressed, weighs starting silica, aluminum oxide, diboron trioxide, di-iron trioxide, glass
Glass agent 7:3 in mass ratio is divided into two parts by glass auxiliary agent and composition, and respectively glass agent I and glass agent II are spare；
S2, by starting silica, aluminum oxide, diboron trioxide and di-iron trioxide ball milling mixing it is uniform after pour into oxidation
In aluminium crucible, after being at the uniform velocity warming up to 850 DEG C, glass agent I and composition is added, is continuously heating to 1450 DEG C of heat preservation fusings
0.5h is cooled to 1250 DEG C of heat preservations with the rate of 8 DEG C/min, and glass agent II is added, and clarification 3h obtains glass metal；
S3, crucible is taken out, glass metal is poured into the graphite jig for being preheated to 640~680 DEG C, water is added after glass molding material
Glass material after quenching is warming up to 160~190 DEG C of 1~3h of heat preservation, then proceedes to be warming up to 220~260 by quenching to room temperature
DEG C, 2~5h of heat preservation is air-cooled to room temperature to get neutral boron silica glass material.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61146735A (en) * | 1984-12-19 | 1986-07-04 | Fujitsu Ltd | Manufacture of glass ceramic |
| CN1537085A (en) * | 2001-08-02 | 2004-10-13 | 3M | Al2O3-rare earth oxide-ZrO2/HfO2 materials and methods of making and using the same |
| CN103011240A (en) * | 2012-12-24 | 2013-04-03 | 赣州虔东稀土集团股份有限公司 | Bulky-grain rare earth carbonate and preparation method and application of carbonate |
| CN104860540A (en) * | 2015-06-03 | 2015-08-26 | 苏州靖羽新材料有限公司 | Heat-resistant glass and preparation method thereof |
| CN105036553A (en) * | 2015-08-04 | 2015-11-11 | 沧州四星玻璃股份有限公司 | Medicinal neutral borosilicate glass tube and preparing method thereof |
| CN105819689A (en) * | 2016-05-19 | 2016-08-03 | 台玻安徽玻璃有限公司 | Heat-shock-resistant float glass |
| CN106957151A (en) * | 2016-01-11 | 2017-07-18 | 沈兰 | Soda lime borosilicate hollow glass micropearl and its production method containing rare earth |
-
2018
- 2018-10-31 CN CN201811287963.9A patent/CN109320074A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61146735A (en) * | 1984-12-19 | 1986-07-04 | Fujitsu Ltd | Manufacture of glass ceramic |
| CN1537085A (en) * | 2001-08-02 | 2004-10-13 | 3M | Al2O3-rare earth oxide-ZrO2/HfO2 materials and methods of making and using the same |
| CN103011240A (en) * | 2012-12-24 | 2013-04-03 | 赣州虔东稀土集团股份有限公司 | Bulky-grain rare earth carbonate and preparation method and application of carbonate |
| CN104860540A (en) * | 2015-06-03 | 2015-08-26 | 苏州靖羽新材料有限公司 | Heat-resistant glass and preparation method thereof |
| CN105036553A (en) * | 2015-08-04 | 2015-11-11 | 沧州四星玻璃股份有限公司 | Medicinal neutral borosilicate glass tube and preparing method thereof |
| CN106957151A (en) * | 2016-01-11 | 2017-07-18 | 沈兰 | Soda lime borosilicate hollow glass micropearl and its production method containing rare earth |
| CN105819689A (en) * | 2016-05-19 | 2016-08-03 | 台玻安徽玻璃有限公司 | Heat-shock-resistant float glass |
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