CN110156327A - A kind of high zirconium alkali-proof glass and its application - Google Patents
A kind of high zirconium alkali-proof glass and its application Download PDFInfo
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- CN110156327A CN110156327A CN201910570832.XA CN201910570832A CN110156327A CN 110156327 A CN110156327 A CN 110156327A CN 201910570832 A CN201910570832 A CN 201910570832A CN 110156327 A CN110156327 A CN 110156327A
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- glass
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- proof glass
- high zirconium
- zirconium alkali
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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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
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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
- C03C4/00—Compositions for glass with special properties
- C03C4/20—Compositions for glass with special properties for chemical resistant glass
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention discloses a kind of high zirconium alkali-proof glass materials and its application, the glass to be grouped as by the group of following weight percentage: 31.0-49.0%SiO2, 10.0-19.0%Al2O3, 0-5.0%Na2O, 0-2.0%MgO, 0-2.0%CaO, 0-2.0%BaO, 6.0-20.0%ZrO2, 0.5-5.0%TiO2, 0.5-10.0%Sc2O5, 9.0-14.0%La2O3, 6.0-24.0%Y2O3.A kind of high zirconium alkali-proof glass provided by the invention have excellent acid-alkali-corrosive-resisting, high temperature resistant, anti-high pressure, high mechanical strength, chemical stability is excellent, transparency is high, the advantages that being suitable for tempering, it can be used for manufacturing observation window, high-pressure bottle observation window of high temperature and pressure liquid level meter etc..
Description
Technical field
The present invention relates to special glass material and its preparation technical field, in particular to a kind of high zirconium alkali-proof glass and its answer
With.
Background technique
Alkali-proof glass is as special glass material, and widely used in industry and building material industry, alkali-proof glass is made mostly
It is used in alkaline environment at alkali-resistant glass fibre or block.Here alkaline environment generally refers to aqueous slkali environment, different
Country and company formulated different alkaline-resisting standards, such as 695 standard of DIN ISO that SCHOTT company executes, i.e., by glass
Surface is placed in the aqueous slkali (solution concentration: 1mol/L NaOH, 0.5mol/L Na of boiling2CO3) in 3 hours, according to the mistake of glass
Weight evaluates its alkali resistance, and weightlessness is less than 75mg/100cm2, it is determined as A1 grades, weightlessness is in 75~175mg/100cm2Between, it is determined as
A2 grades, weightlessness is greater than 175mg/100cm2, it is determined as A3 grades, other alkaline-resisting standards are similar.
Have more research to alkali-proof glass both at home and abroad, alkali-proof glass have light weight, intensity are high, corrosion resistance is strong,
Ingredient is not easy the features such as being precipitated, and can be used to prepare enhancing base materials of the alkali-resistant glass fibre as glass fiber reinforced cement；?
It can be used to the drug splendid attire for preparing glassware as field of medicaments；It can also be used to prepare high-pressure-resistant vessel glass vision panel.But
Be applied to the above standard alkali-proof glass strain point temperature and bending strength it is generally all lower, unbearable high temperature and superelevation
The environment of pressure uses.And in the prior art, it usually needs to show using the liquidometer connecting with water tank in boiler water tank
Show the liquid level etc. of boiler, the level condition under high-temperature and high-pressure conditions is monitored with this, for this purpose, sight glass used just needs at this time
Higher transmitance and the at high temperature under high pressure corrosion of high-temperature resistant water steam and high alkalinity to glass.
Summary of the invention
It is an object of the invention to overcome the shortcomings of currently available technology and technology there are the problem of, it is resistance to provide a kind of high zirconium
Alkali glass material and its application.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of high zirconium alkali-proof glass, is grouped as by the group of following weight percentage:
A kind of high zirconium alkali-proof glass, which is characterized in that be preferably grouped as by the group of following weight percentage:
Further, alkaline earth oxide MgO+CaO+BaO total content≤2.0%.
Further, also oxide and environmentally harmful metal oxide and tool without containing valence variation element in component
There is the oxide such as As of glass coloration function2O3、Sb2O5、PbO、CdO、Cr2O3、CuO、CoO、NiO、 BeO、CeO2、V2O5、
WO3、MoO3、MnO2、SnO2、Ag2O、Nd2O3Any one of Deng；
Further, bending strength is greater than 400MPa.
Further, thermal expansion coefficient is (55 ± 5) × 10-7/℃。
Further, 650 DEG C of glass transition point temperature >.
Further, above-mentioned glass can be applied in illumination or display technology.
Further, above-mentioned glass preparation can apply in concrete enhancing at glass fibre.
Further, above-mentioned glass can be using as the container glass in chemical erosion liquid.
Further, above-mentioned glass can apply observation window, the superhigh temperature resistant super-pressure in manufacture high temperature and pressure liquid level meter
In container viewing window.
Compared with prior art, alkali-proof glass of the invention has characteristics that
1, a kind of high zirconium alkali-proof glass proposed by the present invention, the glass can be in the environment of high-temperature high pressure waters or alkalies
Used in body, can liquidometer observation glazing corrode with liquid contact surface, for a long time use transparency do not decline,
Liquidometer observation window is used without in addition setting mica sheet and protects etc., therefore cost and easy to operate, easy to maintenance, has wide
Wealthy market application prospect.
2, a kind of high zirconium alkali-proof glass proposed by the present invention have excellent alkali resistance, A1 grades of alkali resistance；With excellent
Mechanical performance, bending strength are greater than 400MPa；With suitable thermal expansion coefficient, thermal expansion coefficient (55 ± 5) × 10-7/℃；
With good thermal stability, glass transition point temperature is greater than 650 DEG C.
3, a kind of high zirconium alkali-proof glass proposed by the present invention uses formula of the low alkali without boron, and cost substantially reduces, and has aluminium
The superior function of silicate glass has specific gravity lighter, and stable structure, chemical stability is good, has resistance to strong acid, strong alkali solution
Erosion, the prolonged stabilization of glass is never degenerated in humid conditions, which can observe material flows situation and pipeline, container
Interior situation, without environmental pollution, is conducive to environmental protection and improves production without containing environmentally harmful elements such as lead, arsenic, cadmiums
The features such as working condition, even if for a long time under heatproof condition of high voltage using corrosion it is few, be suitable for chemical industry, petroleum, water supply,
Heating etc. is industrially widely used, and can be also suitably used for the bad working environments of the high temperature and pressure such as thermoelectricity, petrochemical industry, deep-sea exploring equipment.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution in the embodiment of the present invention is clearly and completely retouched
It states, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the present invention
In embodiment, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, shall fall within the protection scope of the present invention.
In the present embodiment, a kind of high zirconium alkali-proof glass is grouped as by the group of following weight percentage:
In the present invention, SiO2It is the main body that glass forms skeleton structure, is the ingredient to play a major role in glass skeleton.
SiO2Weight percent (wt.%) be 31-49.SiO2Content is lower than 31.0wt.%, is not easy to obtain the glass of good heat stability
Glass, while the alkali resistance of glass can be reduced；SiO2When content is higher than 49.0wt.%, the high-temperature viscosity of glass be will increase, and cause glass
Glass glass melting temperature is excessively high, alkali resistance decline.
Al2O3For the intermediate oxide of glass, Al3+There are two types of co-ordination states, that is, are located in tetrahedron or octahedron, when
When oxygen is enough in glass, aluminum-oxygen tetrahedron [AlO is formed4], continuous network is formed with oxygen-octahedron, when oxygen is not in glass
When sufficient, alumina octahedral [AlO is formed6], it is in for network outer body in the hole of silica structure network, so in certain content
In range can and SiO2It is the main body that glass network is formed, by introducing appropriate Al2O3, internal suspension structure can be repaired,
The chemical stability for improving glass is conducive to the alkali resistance for improving glass.Al2O3Be improve glass bending strength necessary at
Point, Al2O3Content is more, and the Young's modulus of glass is bigger, and mechanical strength is higher, Al2O3Content is preferably 10.0-
19.0wt.%, Al2O3When content is higher than 19.0wt.%, it will increase the high-temperature viscosity of glass, cause glass smelting temperature excessively high,
Al2O3When content is lower than 10.0wt.%, the bending strength and alkali resistance of glass can decline.
Na2O is glass structure network modifying oxide, is alkali metal oxide, can reduce the melting temperature of glass, is promoted
Into being melted for glass, Na2The weight percent (wt.%) of O is 0-5, Na2The content of O is greater than 5wt.%, can reduce the resistance to of glass
Alkalinity.
MgO, CaO, BaO are alkaline earth oxides, are all glass structure network modifying oxide, the weight percent of MgO
It is 0-2 than (wt.%), the weight percent (wt.%) of CaO is 0-2, and the weight percent (wt.%) of BaO is 0-2, the alkali
Soil metal oxide MgO+CaO+BaO total content is not more than 2.0%, and alkaline earth oxide can improve glass modulus, answer
Height and surface tension, but total content is greater than 2wt.%, can reduce glass chemical-resistant stability, increase the tendency towards devitrification of glass.
ZrO2It is ingredient necessary to improving glass alkali resistance, ZrO2Also can be improved the elasticity modulus of glass, hardness, viscosity,
Chemical stability reduces the coefficient of expansion, ZrO2Weight percent (wt.%) be 6.0-20.0%, when content is less than
When 6.0wt.%, it cannot get the alkali-proof glass of alkali resistance excellent effect, when content is greater than 20wt.%, the high-temperature viscosity of glass
It will increase, cause glass smelting temperature excessively high, and the easy crystallization of glass.
TiO2It is ingredient necessary to reducing thermal expansion coefficient of glass, TiO2The alkali resistance of glass, TiO can also be improved2
Weight percent (wt.%) be 0.5-5.0.SiO2Content is lower than 0.5wt.%, is not easy to obtain the glass of good heat stability,
The alkali resistance of glass can be reduced simultaneously；TiO2When content is higher than 5.0wt.%, then the transmitance of glass can decline and increase glass
Tendency towards devitrification.
La2O3It is lanthanide rare earth oxide, is ingredient necessary to improving alkali resistance, La3+Ionic radius is big, electric-field strength,
So that generate in glass it is very strong gather effect, can increase the alkali resistance of glass, La2O3Weight percent (wt.%) be
9.0-14.0 but La2O3Then alkali resistance declines when content is less than 9.0wt%, La2O3Content will cause glass when being greater than 14.0wt%
The thermal expansion coefficient of glass increases.
Y2O3It is ingredient necessary to improving glass alkali resistance, glass chemical-resistant stability, Y can be improved2O3Weight percent
It is 6.0-24.0, Y than (wt.%)2O3Less than 6.0wt%, then alkali resistance declines, Y2O3It then will increase glass analysis more than 24.0wt%
Crystalline substance tendency.
Sc2O3It is the oxide of similar group of the lanthanides, Sc2O3Physico-chemical property and rare earth oxide (such as La2O3、Y2O3) close,
It is all III B race oxide, Sc2O3Advantage with high temperature resistant, corrosion resistance, raising stability etc., Sc2O5Weight hundred
Dividing than (wt.%) is 0.5-10.0%, Sc2O5Less than 0.5wt%, then alkali resistance declines, Sc2O5Can then it increase more than 24.0wt%
Devitrification of glass is added to be inclined to.
A kind of high zirconium alkali-proof glass of the present invention belongs to zirconium yttrium lanthanum alumina silicate glass, contains substantially no oxide
B2O3；Substantially also without containing valence variation element oxide and environmentally harmful metal oxide and have glass coloration function
The oxide such as As of energy2O3、Sb2O5、PbO、CdO、Cr2O3、CuO、CoO、NiO、BeO、 CeO2、V2O5、WO3、MoO3、MnO2、
SnO2、Ag2O、Nd2O3Any one of Deng；Here the specific ingredient that contains substantially no refers to that does not add intentionally contains
Justice, it is not excluded that be inevitably mixed into extremely micro impurity from raw material impurity etc., shadow will not be caused to desired characteristic
Loud degree contains, even if the amount containing extremely pettiness is also due to other glass raw materials and is brought into, but to glass former material
The content of these valence variation elements will be strict controlled in 1ppm or less when the introducing of material.
List the glass chemistry composition (wt.%) and glass properties of embodiment in detail in table 1.Wherein, sample according to
Test request carries out various physical and chemical performance tests, the thermalexpansioncoefficientα of glass after surface grinding, polishing treatment30/300For
30-300 DEG C of the coefficient of mean linear thermal expansion is measured using horizontal expander instrument, is indicated with average linear expansion coefficient, using ISO
The measurement of method as defined in 7991；Bending strength is negative by 3 static bucklings using size and shape as defined in JC/T676-1997
Load fractures, and using electronic material universal testing machine by calculating its cross-section maximum stress in bend for bearing load, can obtain
The bending strength of sample out；Alkali resistance is evaluated using 695 standard testing of ISO, and alkali corrosion resistance amount uses a ten thousandth precision balance
Weighing evaluation.
The chemical composition (wt.%) and glass properties of 1 embodiment of table
Embodiment 1
A kind of high zirconium alkali-proof glass, is grouped as by the group of following weight percentage:
Firstly, selecting glass raw material by 1 embodiment of table, 1 glass composition, ingredient requirement, (high-purity, 150 μm are sieved quartz sand
Object be 1% or less, 45 μm of screenings be 30% or less, Fe2O3Content is less than 1PPm), aluminium hydroxide (50 μm of average grain diameter), carbon
Sour sodium (analysis is pure), basic magnesium carbonate (analysis is pure), calcium carbonate (analyzing pure, 250 μm of average grain diameter), (analysis is pure, pure for barium carbonate
Degree >=99.0%), zirconium oxide (analysis pure), titanium oxide (analysis is pure), scandium oxide (5N), lanthana (5N), yttrium oxide (5N), will
The requirement of test article as defined in being cast into after glass smelting is uniform, then anneals, test performance is as shown in table 1, (1)
30-300 DEG C of average linear expansion coefficient 52 × 10-7/℃；(2) bending strength 408MPa；(3) alkali resistance A1 grades.
Embodiment 2
A kind of high zirconium alkali-proof glass, is grouped as by the group of following weight percentage:
The practical composition of glass using raw material and ingredient requirement same as Example 1, and is taken referring to 1 embodiment 2 of table
Test condition same as Example 1 shows the basic performance of sample in table 1, and the average line that 30-300 DEG C of (1) expands system
Number 49 × 10-7/℃；(2) bending strength 410MPa；(3) alkali resistance A1 grades.
Embodiment 3
A kind of high zirconium alkali-proof glass, is grouped as by the group of following weight percentage:
The practical composition of glass using raw material and ingredient requirement same as Example 1, and is taken referring to 1 embodiment 3 of table
Test condition same as Example 1 shows the basic performance of sample in table 1, and the average line that 30-300 DEG C of (1) expands system
Number 59 × 10-7/℃；(2) bending strength 412MPa；(3) alkali resistance A1 grades.
Embodiment 4
A kind of high zirconium alkali-proof glass, is grouped as by the group of following weight percentage:
The practical composition of glass using raw material and ingredient requirement same as Example 1, and is taken referring to 1 embodiment 4 of table
Test condition same as Example 1 shows the basic performance of sample in table 1, and the average line that 30-300 DEG C of (1) expands system
Number 57 × 10-7/℃；(2) bending strength 432MPa；(3) alkali resistance A1 grades.
Embodiment 5
A kind of high zirconium alkali-proof glass, is grouped as by the group of following weight percentage:
The practical composition of glass using raw material and ingredient requirement same as Example 1, and is taken referring to 1 embodiment 5 of table
Test condition same as Example 1 shows the basic performance of sample in table 1, and the average line that 30-300 DEG C of (1) expands system
Number 56 × 10-7/℃；(2) bending strength 420MPa；(3) alkali resistance A1 grades.
Embodiment 6
A kind of high zirconium alkali-proof glass, is grouped as by the group of following weight percentage:
The practical composition of glass using raw material and ingredient requirement same as Example 1, and is taken referring to 1 embodiment 6 of table
Test condition same as Example 1 shows the basic performance of sample in table 1, and the average line that 30-300 DEG C of (1) expands system
Number 54 × 10-7/℃；(2) bending strength 424MPa；(3) alkali resistance A1 grades.
Therefore, high zirconium alkali-proof glass material provided by the invention and its application, stable structure high with zirconia content,
Chemical stability is good, and the erosion with resistance to strong acid, strong alkali solution, the prolonged stabilization of glass is never degenerated in humid conditions, glass
Transparent to observe situation in material flows situation and pipeline, container, specific gravity is lighter, and high mechanical strength, chemical-resistance is excellent, and
Without containing the environmentally harmful element such as lead, arsenic, cadmium, without environmental pollution, is conducive to environmental protection and improves productive labor item
The features such as part, corrosion is few using under heatproof condition of high voltage for a long time, observes glazing suitable for liquidometer,
It is industrial suitable for chemical industry, petroleum, water supply, heating etc., it can be also suitably used for the high temperature such as thermoelectricity, petrochemical industry, deep-sea exploring equipment height
The bad working environments of pressure.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of high zirconium alkali-proof glass, which is characterized in that be grouped as by the group of following weight percentage:
2. a kind of high zirconium alkali-proof glass according to claim 1, which is characterized in that preferably by following weight percentage
Group is grouped as:
3. a kind of high zirconium alkali-proof glass according to claim 1, which is characterized in that the alkaline earth oxide MgO+
CaO+BaO total content≤2.0%.
4. a kind of high zirconium alkali-proof glass according to claim 1, which is characterized in that also do not contain valence variation element in component
Oxide and environmentally harmful metal oxide and oxide such as As with glass coloration function2O3、Sb2O5、PbO、
CdO、Cr2O3、CuO、CoO、NiO、BeO、CeO2、V2O5、WO3、MoO3、MnO2、SnO2、Ag2O、Nd2O3Any one of Deng.
5. a kind of high zirconium alkali-proof glass according to claim 1, which is characterized in that can be applied and illuminated by above-mentioned glass
Or in display technology.
6. a kind of high zirconium alkali-proof glass according to claim 1, which is characterized in that by above-mentioned glass preparation at glass fibers
Dimension can be applied in concrete enhancing.
7. a kind of high zirconium alkali-proof glass according to claim 1, which is characterized in that can be applied and be used as by above-mentioned glass
The container glass of chemical erosion liquid.
8. a kind of high zirconium alkali-proof glass according to claim 1, which is characterized in that can be applied and manufactured by above-mentioned glass
In the observation window of high temperature and pressure liquid level meter, superhigh temperature resistant ultrahigh pressure vessel observation window.
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| CN201910570832.XA CN110156327B (en) | 2019-06-28 | 2019-06-28 | High-zirconium alkali-resistant glass and application thereof |
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| CN201910570832.XA CN110156327B (en) | 2019-06-28 | 2019-06-28 | High-zirconium alkali-resistant glass and application thereof |
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| CN110156327B CN110156327B (en) | 2022-05-17 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125528A (en) * | 2020-10-06 | 2020-12-25 | 青岛蓝创科信新能源科技有限公司 | High modulus glass fiber with excellent alkali resistance and preparation method thereof |
| CN113880427A (en) * | 2021-10-20 | 2022-01-04 | 怀化市吉驷玻璃有限公司 | Alkali-resistant glass |
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| US4088023A (en) * | 1974-03-18 | 1978-05-09 | Corning Glass Works | Liquid level gauge |
| CN102092938A (en) * | 2009-12-09 | 2011-06-15 | 文化贸易工业株式会社 | Glass used for liquid level observation window of level gauge and level gauge |
| CN106800370A (en) * | 2016-09-23 | 2017-06-06 | 南京神童特种玻璃技术有限公司 | A kind of high pressure liquid level gauge alkali-free aluminosilicate glass of high temperature high voltage resistant |
| CN106810067A (en) * | 2016-09-23 | 2017-06-09 | 南京神童特种玻璃技术有限公司 | A kind of alkaline-resisting high temperature resistant overpressure resistant zirconium yttrium lanthanum zinc-aluminium silica glass |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4088023A (en) * | 1974-03-18 | 1978-05-09 | Corning Glass Works | Liquid level gauge |
| CN102092938A (en) * | 2009-12-09 | 2011-06-15 | 文化贸易工业株式会社 | Glass used for liquid level observation window of level gauge and level gauge |
| CN106800370A (en) * | 2016-09-23 | 2017-06-06 | 南京神童特种玻璃技术有限公司 | A kind of high pressure liquid level gauge alkali-free aluminosilicate glass of high temperature high voltage resistant |
| CN106810067A (en) * | 2016-09-23 | 2017-06-09 | 南京神童特种玻璃技术有限公司 | A kind of alkaline-resisting high temperature resistant overpressure resistant zirconium yttrium lanthanum zinc-aluminium silica glass |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112125528A (en) * | 2020-10-06 | 2020-12-25 | 青岛蓝创科信新能源科技有限公司 | High modulus glass fiber with excellent alkali resistance and preparation method thereof |
| CN112125528B (en) * | 2020-10-06 | 2021-09-10 | 滨州信泰节能科技有限公司 | High modulus glass fiber with excellent alkali resistance and preparation method thereof |
| CN113880427A (en) * | 2021-10-20 | 2022-01-04 | 怀化市吉驷玻璃有限公司 | Alkali-resistant glass |
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