CN116217090B - Coated glass tube and preparation method and application thereof - Google Patents
Coated glass tube and preparation method and application thereof Download PDFInfo
- Publication number
- CN116217090B CN116217090B CN202211105060.0A CN202211105060A CN116217090B CN 116217090 B CN116217090 B CN 116217090B CN 202211105060 A CN202211105060 A CN 202211105060A CN 116217090 B CN116217090 B CN 116217090B
- Authority
- CN
- China
- Prior art keywords
- glass tube
- washing
- coating
- coated
- weight
- 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.)
- Active
Links
- 239000011521 glass Substances 0.000 title claims abstract description 224
- 238000002360 preparation method Methods 0.000 title abstract description 56
- 239000000758 substrate Substances 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 56
- 239000011248 coating agent Substances 0.000 claims abstract description 51
- 238000000576 coating method Methods 0.000 claims abstract description 51
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000011787 zinc oxide Substances 0.000 claims abstract description 13
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 9
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- 239000007888 film coating Substances 0.000 claims description 67
- 238000009501 film coating Methods 0.000 claims description 67
- 238000005406 washing Methods 0.000 claims description 65
- 239000000843 powder Substances 0.000 claims description 53
- 238000005507 spraying Methods 0.000 claims description 51
- 238000000137 annealing Methods 0.000 claims description 33
- 239000011159 matrix material Substances 0.000 claims description 33
- 238000005245 sintering Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 238000004140 cleaning Methods 0.000 claims description 21
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000005361 soda-lime glass Substances 0.000 claims description 13
- 239000000292 calcium oxide Substances 0.000 claims description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- 238000005554 pickling Methods 0.000 claims description 12
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical group [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 12
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 11
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 8
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 238000005352 clarification Methods 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 6
- 238000002386 leaching Methods 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 3
- 239000003513 alkali Substances 0.000 abstract description 14
- 239000007921 spray Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 5
- 239000005388 borosilicate glass Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- RSCACTKJFSTWPV-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 RSCACTKJFSTWPV-UHFFFAOYSA-N 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007721 medicinal effect Effects 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B15/00—Drawing glass upwardly from the melt
- C03B15/14—Drawing tubes, cylinders, or rods from the melt
-
- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
-
- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
- C03C17/04—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass by fritting glass powder
-
- 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
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/17—Deposition methods from a solid phase
-
- 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
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Composite Materials (AREA)
- Surface Treatment Of Glass (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
本发明涉及药用玻璃管生产领域，公开了一种镀膜玻璃管及其制备方法和应用，该镀膜玻璃管包括玻璃管基体和设于所述玻璃管基体表面的镀膜涂层；所述镀膜涂层中含有：以镀膜涂层的总重量为100重量份计，氧化锌的含量为30‑35重量份，二氧化硅的含量为25‑35重量份，三氧化二硼的含量为17‑20重量份，氧化铝的含量为2‑3重量份，碱金属氧化物的含量为9‑14重量份，碱土金属氧化物的含量为4.5‑11重量份，二氧化锆的含量为1‑2重量份。本发明所提供的方法制备的镀膜玻璃管具有优异的耐酸性和耐碱性，其中，耐酸性符合1级，耐碱性符合1级。
The present invention relates to the field of production of medicinal glass tubes, and discloses a coated glass tube and a preparation method and application thereof, wherein the coated glass tube comprises a glass tube substrate and a coating provided on the surface of the glass tube substrate; the coating contains: based on the total weight of the coating as 100 parts by weight, the content of zinc oxide is 30-35 parts by weight, the content of silicon dioxide is 25-35 parts by weight, the content of boron trioxide is 17-20 parts by weight, the content of aluminum oxide is 2-3 parts by weight, the content of alkali metal oxide is 9-14 parts by weight, the content of alkaline earth metal oxide is 4.5-11 parts by weight, and the content of zirconium dioxide is 1-2 parts by weight. The coated glass tube prepared by the method provided by the present invention has excellent acid resistance and alkali resistance, wherein the acid resistance meets level 1 and the alkali resistance meets level 1.
Description
Technical Field
The invention relates to the field of preparation of medicinal glass tubes, in particular to a coated glass tube, and a preparation method and application thereof.
Background
At present, the medicinal injection bottles and ampoule bottles are produced by using medicinal glass tubes, so that the quality of the medicinal glass tubes has important influence on the medical effect. The medical glass tube is mainly divided into soda-lime glass and borosilicate glass, wherein the borosilicate glass is gradually used as a preferred material of the medical glass due to the low thermal expansion coefficient, good water resistance and acid/alkali resistance. However, the borosilicate glass has the advantages of complex production technology, high production cost and difficult popularization, thereby increasing the production cost of medicines.
CN113860729a discloses a medium borosilicate medicinal glass, the chemical composition of which comprises 2-4wt% of Al 2O3, 8-9wt% of B 2O3, 11-12wt% of Al 2O3+B2O3, 2-4wt% of ZnO, 1-2wt% of ZrO 2, 3-6wt% of ZnO+Zr 2, 6-8wt% of Li 2O+Na2O+K2 O, and Li 2O:Na2O:K2 O=3:6:1, 2-4wt% of CaO+SrO, and (6-8) of CaO: srO (2-4), the balance being SiO 2. Although the medium borosilicate medicinal glass has the advantages of high chemical stability, low-temperature melting, low volatilization of B 2O3 and low thermal expansion coefficient. However, the introduction of large amounts of diboron trioxide in production can result in excessive costs for preparing pharmaceutical glass.
However, no expensive borax pentahydrate (which is a source of diboron trioxide) is added to the soda lime glass, and the production cost is relatively low compared with borosilicate glass.
However, alkali metal ions in the soda lime glass can exchange with H + in water, so that the Si-O-Si network structure in the glass is damaged, and the soda lime glass is easy to corrode and has short service life.
Therefore, the preparation cost of the medicinal glass is reduced, the water resistance and acid and alkali resistance of the soda-lime glass material are improved, the research is worth of at present, the popularization of the application of the soda-lime glass is facilitated, and the cost of the medicine production industry is reduced.
Disclosure of Invention
The invention aims to overcome the defects of poor acid and alkali resistance and high preparation cost of medicinal glass existing in the existing soda-lime glass.
In order to achieve the above object, a first aspect of the present invention provides a coated glass tube comprising a glass tube substrate and a coated coating layer provided on a surface of the glass tube substrate;
The film coating contains the following components which are stored independently or stored by mixing more than two of the components:
based on 100 parts by weight of the total weight of the film coating, the zinc oxide content is 30-35 parts by weight, the silicon dioxide content is 25-35 parts by weight, the diboron trioxide content is 17-20 parts by weight, the aluminum oxide content is 2-3 parts by weight, the alkali metal oxide content is 9-14 parts by weight, the alkaline earth metal oxide content is 4.5-11 parts by weight, and the zirconium dioxide content is 1-2 parts by weight;
and the film coating is sprayed on the surface of the glass tube matrix at a spraying angle of 20-50 degrees with the wall of the glass tube matrix.
Preferably, the zirconia is contained in an amount of 1.5 to 2 parts by weight.
Preferably, the thickness of the plating coat is 10-30 μm.
Preferably, the alkali metal oxide is sodium oxide and/or potassium oxide.
Preferably, the alkaline earth metal oxide is at least one of calcium oxide, magnesium oxide, and barium oxide.
Preferably, the glass tube substrate is a soda lime glass tube.
Preferably, the film coating is sprayed on the surface of the glass tube substrate at a spraying angle of 30-45 degrees with the wall of the glass tube substrate.
A second aspect of the present invention provides a method of preparing a coated glass tube according to the first aspect, the method comprising the steps of:
(1) Melting each component in the film coating of the film-coated glass tube in the first aspect to obtain film-coated coating melt;
(2) Sequentially clarifying, annealing and grinding the film coating molten liquid to obtain film coating powder;
(3) Spraying the film-coating powder on the surface of a dry glass tube substrate to obtain a glass tube coated with the coating powder;
(4) And sintering the glass tube covered with the coating powder to obtain the coated glass tube.
Preferably, in step (1), the melting conditions are at least satisfied at a temperature of 1100-1200 ℃ for a time of 240-480min.
Preferably, in the step (2), the clarification treatment conditions are at least satisfied, wherein the temperature is 850-900 ℃ and the time is 60-120min.
Preferably, in the step (2), the annealing treatment condition at least satisfies that the annealing temperature is 480-520 ℃ and the annealing time is not less than 30min.
Preferably, in the step (3), the spraying condition at least meets the condition that the spraying speed is 50-100g/min, and the thickness of the coated film after spraying is 10-30 mu m.
In the step (4), the sintering condition at least meets the conditions that the sintering temperature is 560-610 ℃ and the sintering time is 20-40min.
Preferably, in step (2), the film-coating powder has an average particle size of less than 50 μm and a moisture content of less than 3wt%.
Preferably, the method further comprises the steps of sequentially carrying out a cleaning treatment and a drying treatment on the glass tube substrate to be applied before the step (3), and then using the glass tube substrate subjected to the drying treatment in the step (3) to carry out the spraying;
the step of the cleaning treatment comprises the following steps:
(A) Under the conditions of leaching and/or ultrasonic leaching, carrying out first washing on a glass tube matrix to be applied by using 0.4-0.6wt% of alkaline solution to obtain an alkaline washing glass tube matrix;
(B) Performing second washing on the alkali-washed glass tube by using 0.4-0.6wt% of acid solution to obtain an acid-washed glass tube matrix;
(C) And thirdly washing the pickled glass tube substrate with water.
Preferably, in the first washing, the alkaline solution is a sodium hydroxide solution.
Preferably, in the second washing, the acidic solution is a hydrochloric acid solution.
Preferably, the first washing is performed under ultrasonic immersion washing conditions.
Preferably, the ultrasonic pickling condition is at least satisfied that the ultrasonic frequency is 30-50KHz, the temperature of the first washing is 40-50 ℃, and the pickling time is 30-60s.
Preferably, the conditions in the second washing are at least satisfied that the temperature of the second washing is 40-50 ℃ and the washing time is 80-100s.
Preferably, in the third washing, the acid-washed glass tube substrate is washed with deionized water for 80-100 seconds and then distilled water until the conductivity of the washing solution is less than 5.1 mu s/cm.
A third aspect of the present invention provides the use of the coated glass tube according to the first aspect in the field of pharmaceutical injection bottles, ampoules.
The coated glass tube prepared by the method provided by the invention has excellent acid resistance and alkali resistance, wherein the acid resistance accords with the level 1, and the alkali resistance accords with the level 1.
Drawings
FIG. 1 is a process flow diagram of a process for preparing a coated glass tube;
FIG. 2 is a flow chart of a spray process for a coating of a plating film.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As previously described, a first aspect of the present invention provides a coated glass tube comprising a glass tube substrate and a coating of a coating film provided on a surface of the glass tube substrate;
The film coating contains the following components which are stored independently or stored by mixing more than two of the components:
based on 100 parts by weight of the total weight of the film coating, the zinc oxide content is 30-35 parts by weight, the silicon dioxide content is 25-35 parts by weight, the diboron trioxide content is 17-20 parts by weight, the aluminum oxide content is 2-3 parts by weight, the alkali metal oxide content is 9-14 parts by weight, the alkaline earth metal oxide content is 4.5-11 parts by weight, and the zirconium dioxide content is 1-2 parts by weight;
and the film coating is sprayed on the surface of the glass tube matrix at a spraying angle of 20-50 degrees with the wall of the glass tube matrix.
The spraying angle is an acute angle formed by the straight line where the spray gun is positioned and the wall of the glass tube substrate.
Preferably, in the film coating, the content of zinc oxide is 30 to 34 parts by weight, the content of silicon dioxide is 26 to 30 parts by weight, the content of diboron trioxide is 17 to 19 parts by weight, the content of aluminum oxide is 2.5 to 3 parts by weight, the content of alkali metal oxide is 11 to 13 parts by weight, the content of alkaline earth metal oxide is 6.5 to 9 parts by weight, and the content of zirconium dioxide is 1.5 to 2 parts by weight, based on 100 parts by weight of the total weight of the film coating. The inventors of the present invention found that, in this preferred case, the coated glass tube produced was better in acid resistance and alkali resistance.
In addition, the inventor finds that the alkali resistance of the coated glass tube can be improved by adding the zirconium dioxide, and when the content of the zirconium dioxide is 1.5-2 parts by weight, the alkali resistance of the coated glass tube obtained by the scheme can reach 1 level, and the glass crystallization phenomenon can not occur.
Preferably, the thickness of the film coating is 10-30 μm.
Preferably, the alkali metal oxide is sodium oxide and/or potassium oxide.
More preferably, the alkali metal oxide is sodium oxide and potassium oxide, and the content of sodium oxide is 7 to 8 parts by weight, and the content of potassium oxide is 4 to 5 parts by weight.
Preferably, the alkaline earth metal oxide is selected from at least one of calcium oxide, magnesium oxide, and barium oxide.
More preferably, the alkaline earth metal oxide is calcium oxide, magnesium oxide, and barium oxide, and the content of the calcium oxide is 2 to 3 parts by weight, the content of the magnesium oxide is 4 to 5 parts by weight, and the content of the barium oxide is 0.5 to 1 part by weight.
According to a preferred embodiment, the glass tube substrate is a soda lime glass tube. More preferably, the glass tube substrate contains 65 to 75 parts by weight of silica, 0 to 5 parts by weight of alumina, 9 to 18 parts by weight of sodium oxide, 0 to 5 parts by weight of potassium oxide, 2 to 10 parts by weight of calcium oxide, 2 to 5 parts by weight of magnesium oxide, 0 to 2 parts by weight of lithium oxide and 0 to 2 parts by weight of zinc oxide based on 100 parts by weight of the total weight of the glass tube substrate.
As previously mentioned, a second aspect of the present invention provides a method of preparing a coated glass tube according to the first aspect, the method comprising the steps of:
(1) Melting each component in the film coating of the film-coated glass tube in the first aspect to obtain film-coated coating melt;
(2) Sequentially clarifying, annealing and grinding the film coating molten liquid to obtain film coating powder;
(3) Spraying the film-coating powder on the surface of a dry glass tube substrate to obtain a glass tube coated with the coating powder;
(4) And sintering the glass tube covered with the coating powder to obtain the coated glass tube.
According to a preferred embodiment, as shown in FIG. 1, the method further comprises mixing the components of the film coating to be treated until the uniformity reaches 95% or more, drying the mixture so that the moisture content is less than 3wt% to obtain a mixture, and using the mixture for the film coating melt in the step (1).
Further, as shown in FIG. 1, the method further comprises the steps of drying the obtained film-coated coating powder after the spraying treatment in the step (2), spraying the dried film-coated coating powder on the surface of the cleaned and dried glass tube substrate to obtain a glass tube coated with the coating powder, and sintering and annealing the glass tube coated with the coating powder to obtain the film-coated glass tube.
According to a preferred embodiment, as shown in fig. 1, specifically includes:
Preparing a coating film, namely mixing, drying and melting all components of the coating film to obtain coating film melt, sequentially clarifying and annealing the coating film melt, and then grinding and drying to obtain coating film powder;
Preparing a glass tube matrix, namely mixing and melting all components of the glass tube matrix, sequentially clarifying and homogenizing the glass liquid I to obtain glass liquid II, drawing and forming the glass liquid II, and annealing to obtain the glass tube matrix;
and (3) preparing a coated glass tube, namely cleaning and drying the glass tube substrate, spraying the coated powder on the surface of the dried glass tube substrate, and sintering and annealing to obtain the glass tube coated with the coated powder.
It should be noted that the uniformity test in the present invention is not particularly limited, and may be performed by any means known in the art, for example, by using a conductivity test method.
The glass tube substrate according to the invention can be obtained by purchase or can be self-made by methods known in the art, which are not particularly required by the invention. The present invention hereinafter exemplarily provides a method for preparing a glass tube substrate, as shown in fig. 1, which comprises:
s1, mixing and melting the components of the glass tube matrix:
Mixing coating components containing silicon dioxide, aluminum oxide, sodium oxide, potassium oxide, calcium oxide, magnesium oxide, lithium oxide and zinc oxide, and melting at 1650-1700 ℃ for 240-480min to obtain glass liquid I;
S2, clarifying and homogenizing:
sequentially clarifying and homogenizing the glass liquid I to obtain glass liquid II, wherein the clarifying temperature is 1400-1600 ℃ and the time is 50-70min;
S3, drawing, forming and annealing:
And drawing and forming the glass liquid II by adopting a Danna method forming process, and annealing at 550-570 ℃ for at least 30min to obtain the glass tube matrix.
According to a preferred embodiment, the method further comprises mixing the components of the coating until the uniformity reaches 95% or more and drying the mixture to a moisture content of less than 3% by weight prior to the melt processing in step (1).
The invention has no special requirements on the specific operation method of the Dana method forming process, and the technical means known by the person skilled in the art can be adopted.
Preferably, in step (1), the melting conditions are at least satisfied at a temperature of 1100-1200 ℃ for a time of 240-480min.
Preferably, in the step (2), the clarification treatment conditions are at least satisfied, wherein the temperature is 850-900 ℃ and the time is 60-120min.
Preferably, in the step (2), the annealing treatment condition at least satisfies that the annealing temperature is 480-520 ℃ and the annealing time is not less than 30min.
Preferably, in the step (3), the spraying condition at least meets the condition that the spraying speed is 50-100g/min, and the thickness of the coated film after spraying is 10-30 mu m.
Preferably, in the step (2), the film-forming coating solution is clarified, annealed, cooled to room temperature, and then ground.
According to a preferred embodiment, the method further comprises, in step (2), subjecting the ground film-coating powder to a drying treatment to a moisture content of less than 3% by weight.
The spraying method is not particularly limited in the present invention, and those skilled in the art can use known techniques. In order to provide a tighter bond of the resulting film coating powder to the glass substrate, the present invention provides a preferred embodiment of the spray coating process hereinafter in conjunction with FIG. 2.
As shown in fig. 2, after the film coating powder passes through the gauge, compressed gas is pressed into an electrostatic spray gun to spray the surface of the glass tube substrate, so as to obtain the glass tube coated with the film coating powder, wherein the pressure of the compressed gas is 0.02-0.025Mpa, a discharge needle or an annular metal discharge nozzle for generating high-voltage static electricity is arranged at the head of the electrostatic spray gun, the distance between the nozzle of the electrostatic spray gun and the spraying center of the surface of the glass tube substrate is 12-15cm, and in the spraying process, the glass tube substrate is horizontally placed and continuously rotates, and the rotating speed is 5-10r/min, so that uniform spraying is realized.
Further, as shown in FIG. 2, the method further comprises sintering and annealing the glass tube covered with the coating powder to obtain a coated glass tube.
According to a preferred embodiment, as shown in fig. 2, the method further comprises collecting the coating powder residues generated during the spraying process in time and discharging the coating powder residues to a coating powder recycling device in the step (3) so as to be continuously used in the spraying of the glass tube substrate, thereby further reducing the preparation cost.
According to a preferred embodiment, as shown in fig. 2, the method further comprises the steps of spraying the surface of the glass tube substrate by pressing compressed gas into an electrostatic spray gun after the film coating powder passes through the meter to obtain the glass tube coated with the coating powder, and sintering and annealing the glass tube coated with the coating powder to obtain the film coating glass tube. And the method further comprises the step of timely collecting the coating powder residues generated in the spraying process, and discharging the residues to a coating powder recovery device so as to be continuously used in the spraying of the glass tube substrate.
Preferably, in the step (4), the sintering condition is at least satisfied that the sintering temperature is 560-610 ℃ and the sintering time is 20-40min.
According to a preferred embodiment, the method further comprises, prior to performing the sintering step in step (4), raising the temperature from room temperature to the sintering temperature at a rate of 2-4 ℃ per minute, sintering, and annealing to room temperature after sintering to obtain the coated glass tube.
The room temperature of the present invention was 25.+ -. 5 ℃ unless otherwise specified.
The specific mode of annealing is not particularly limited in the present invention and can be carried out by methods known in the art.
Preferably, in step (2), the film-coating powder has an average particle size of less than 50 μm and a moisture content of less than 3wt%.
Preferably, the method further comprises the steps of sequentially carrying out a cleaning treatment and a drying treatment on the glass tube substrate to be applied before the step (3), and then using the glass tube substrate subjected to the drying treatment in the step (3) to carry out the spraying;
the step of the cleaning treatment comprises the following steps:
(A) Under the conditions of leaching and/or ultrasonic leaching, carrying out first washing on a glass tube matrix to be applied by using 0.4-0.6wt% of alkaline solution to obtain an alkaline washing glass tube matrix;
(B) Performing second washing on the alkali-washed glass tube by using 0.4-0.6wt% of acid solution to obtain an acid-washed glass tube matrix;
(C) And thirdly washing the pickled glass tube substrate with water.
Preferably, in the first washing, the alkaline solution is a sodium hydroxide solution.
Preferably, in the second washing, the acidic solution is a hydrochloric acid solution.
Preferably, the first washing is performed under ultrasonic immersion washing conditions.
Preferably, the ultrasonic pickling condition is at least satisfied that the ultrasonic frequency is 30-50KHz, the temperature of the first washing is 40-50 ℃, and the pickling time is 30-60s.
Preferably, the conditions in the second washing are at least satisfied that the temperature of the second washing is 40-50 ℃ and the washing time is 80-100s.
The inventor found that the control of the first washing temperature and the second washing temperature in the invention can improve the cleaning effect and is not easy to corrode the wall of the glass tube substrate.
Preferably, in the third washing, the water is deionized water and distilled water. More preferably, in the third washing, the acid-washed glass tube substrate is washed with deionized water for 80 to 100 seconds and then with distilled water until the washing solution has a conductivity of less than 5.1. Mu.s/cm.
The inventor discovers that the method for cleaning can enable the film coating and the glass tube substrate to be tightly combined, so that the stability of the film coated glass tube is further improved.
A third aspect of the present invention provides the use of the coated glass tube according to the first aspect in the field of pharmaceutical injection bottles, ampoules.
The present invention will be described in detail by way of examples, and unless otherwise specified, all materials used are commercially available.
The glass tube substrate meets the requirement of YBB00282003-2015 pharmaceutical soda-lime glass tube.
In the examples below, unless otherwise specified, 100g is represented per "part" or per "part by weight".
The model of the electrostatic spraying equipment is KCI, and is purchased from Jining New coordinate mechanical equipment Co., ltd.
Preparing a glass tube substrate:
reference is made to the components and addition amounts of the glass tube matrix in Table 1
S1, mixing and melting the components of the glass tube matrix:
mixing coating components containing silicon dioxide, aluminum oxide, sodium oxide, potassium oxide, calcium oxide, magnesium oxide, lithium oxide and zinc oxide, and melting at 1670 ℃ for 300min to obtain glass liquid I;
S2, clarifying and homogenizing:
Sequentially clarifying and homogenizing the glass liquid I to obtain glass liquid II, wherein the clarifying temperature is 1500 ℃ and the time is 60min;
S3, drawing, forming and annealing:
and drawing and forming the glass liquid II by adopting a Danna method forming process, and annealing for 30min at 560 ℃ to obtain the glass tube matrix.
The following examples were carried out using the process flows shown in fig. 1 and 2, unless otherwise specified.
Preparation example 1 coated glass tube, number P1
This preparation example is intended to illustrate that the coated glass tube according to the present invention is prepared as follows.
The components and the addition amounts of the film coating are shown in Table 2.
Preparing a coated glass tube:
(1) Mixing and drying all components in the film coating, and then introducing the mixture into a kiln for melting to obtain film coating melt;
wherein, the components in the film coating are mixed until the uniformity is 97%, and the components are dried until the moisture content is 2wt%, and the melting condition is that the temperature is 1100 ℃ and the time is 240min;
(2) Sequentially clarifying, annealing, grinding and drying the film coating molten liquid to obtain film coating powder;
wherein, the temperature of clarification treatment is 900 ℃, the time is 60min, annealing is carried out for 30min at 480 ℃, cooling is carried out to room temperature after annealing, then the film-coating powder is ground to the average grain diameter of 45 mu m, and then drying is carried out until the moisture content is 2wt%;
Before the step (3), cleaning and drying the glass tube substrate to be applied in sequence, and then spraying the glass tube substrate after the drying treatment;
Wherein the step of the cleaning process comprises:
(A) Under the ultrasonic immersion cleaning condition, carrying out first cleaning on a glass tube substrate to be applied by using 0.5wt% sodium hydroxide solution to obtain an alkali-cleaned glass tube substrate;
The ultrasonic pickling condition is that the ultrasonic frequency is 40KHz, the temperature of the first washing is 45 ℃, and the pickling time is 30s;
(B) Performing second washing on the alkali-washed glass tube by using 0.5wt% hydrochloric acid solution to obtain an acid-washed glass tube matrix;
Wherein the temperature of the second washing is 40 ℃ and the washing time is 90s;
(C) Thirdly washing the acid-washed glass tube substrate by water;
Wherein, the acid-washing glass tube substrate is washed for 90s by deionized water, and then is washed by distilled water until the conductivity of the washing solution is 4.1 mu s/cm;
(3) Spraying the film-coating powder on the surface of the dried glass tube matrix to obtain a glass tube covered with the coating powder;
After passing through a meter, the film coating powder is pressed into an electrostatic spray gun by compressed gas to spray the surface of a glass tube substrate, wherein the pressure of the compressed gas is 0.02Mpa, the spraying angle is 30 ℃, a discharge needle for generating high-voltage static electricity is arranged at the head of the electrostatic spray gun, the distance between a nozzle of the electrostatic spray gun and the spraying center of the surface of the glass tube substrate is 14cm, the spraying speed is 50g/min, the thickness of the film coating after spraying is 20 mu m, and the glass tube substrate is horizontally placed and continuously rotated at the rotating speed of 10r/min during spraying;
(4) After the temperature is raised from room temperature to sintering temperature, sintering the glass tube coated with the coating powder to obtain a coated glass tube;
wherein the temperature rising rate is 3 ℃ per minute, the sintering temperature is 565 ℃ and the sintering time is 30 minutes.
Preparation example 2 preparation of coated glass tube, number P2
Coated glass tubes were prepared as described below, wherein the components and amounts of the coating in the coating are shown in Table 2.
Preparing a coated glass tube:
(1) Mixing and drying all components in the film coating, and then introducing the mixture into a kiln for melting to obtain film coating melt;
Wherein, the components in the film coating are mixed until the uniformity is 96%, and the moisture content is 2.5wt%, and the melting condition is 1180 ℃ for 300min;
(2) Sequentially clarifying, annealing, grinding and drying the film coating molten liquid to obtain film coating powder;
Wherein the temperature of the clarification treatment is 880 ℃, the time is 85min, the annealing is carried out at 480 ℃ for 40min, the annealing is carried out, the cooling is carried out to room temperature, the film coating powder is ground to the average particle size of 40 mu m, and then the drying is carried out until the moisture content is 2.5wt%;
Before the step (3), cleaning and drying the glass tube substrate to be applied in sequence, and then spraying the glass tube substrate after the drying treatment;
Wherein the step of the cleaning process comprises:
(A) Under the ultrasonic immersion cleaning condition, carrying out first cleaning on a glass tube substrate to be applied by using 0.5wt% sodium hydroxide solution to obtain an alkali-cleaned glass tube substrate;
the ultrasonic pickling condition is that the ultrasonic frequency is 30KHz, the temperature of the first washing is 50 ℃, and the pickling time is 60s;
(B) Performing second washing on the alkali-washed glass tube by using 0.5wt% hydrochloric acid solution to obtain an acid-washed glass tube matrix;
wherein the temperature of the second washing is 50 ℃ and the washing time is 90s;
(C) Thirdly washing the acid-washed glass tube substrate by water;
Wherein, the acid-washing glass tube substrate is washed for 90s by deionized water, and then is washed by distilled water until the conductivity of the washing solution is 4.6 mu s/cm;
(3) Spraying the film-coating powder on the surface of the dried glass tube matrix to obtain a glass tube covered with the coating powder;
After passing through a meter, the film coating powder is pressed into an electrostatic spray gun by compressed gas to spray the surface of a glass tube substrate, wherein the pressure of the compressed gas is 0.025Mpa, the spraying angle is 45 degrees, a discharge needle for generating high-voltage static electricity is arranged at the head of the electrostatic spray gun, the distance between a nozzle of the electrostatic spray gun and the spraying center of the surface of the glass tube substrate is 12cm, the spraying speed is 80g/min, the thickness of the film coating after spraying is 15 mu m, and the glass tube substrate is horizontally placed and continuously rotated at the rotating speed of 7r/min during spraying;
(4) After the temperature is raised from room temperature to sintering temperature, sintering the glass tube coated with the coating powder to obtain a coated glass tube;
Wherein the temperature rising rate is 4 ℃ per minute, the sintering temperature is 300 ℃ and the sintering time is 25 minutes.
PREPARATION EXAMPLE 3 preparation of coated glass tube, numbered P3
Coated glass tubes were produced in accordance with the method described below, wherein the amount of zirconium dioxide added to the coating film was 1 part by weight, and the other components and amounts added are shown in Table 2. The film coating is sprayed on the surface of the glass tube matrix at a spraying angle of 30 degrees with the wall of the glass tube matrix.
Preparing a coated glass tube:
(1) Mixing and drying all components in the film coating, and then introducing the mixture into a kiln for melting to obtain film coating melt;
Wherein, the components in the film coating are mixed until the uniformity is 98%, and the components are dried until the moisture content is 2wt%, and the melting condition is that the temperature is 1180 ℃ and the time is 400min;
(2) Sequentially clarifying, annealing, grinding and drying the film coating molten liquid to obtain film coating powder;
Wherein the temperature of clarification treatment is 860 ℃ and the time is 100min, annealing is carried out for 60min at 500 ℃, cooling is carried out to room temperature after annealing, then the film-coating powder is ground to the average grain diameter of 45 mu m, and then drying is carried out until the moisture content is 2.5wt%;
Before the step (3), cleaning and drying the glass tube substrate to be applied in sequence, and then spraying the glass tube substrate after the drying treatment;
Wherein the step of the cleaning process comprises:
(A) Under the ultrasonic immersion cleaning condition, carrying out first cleaning on a glass tube substrate to be applied by using 0.6wt% sodium hydroxide solution to obtain an alkali-cleaned glass tube substrate;
the ultrasonic pickling condition is that the ultrasonic frequency is 30KHz, the temperature of the first washing is 50 ℃, and the pickling time is 60s;
(B) Performing second washing on the alkali-washed glass tube by using 0.4wt% hydrochloric acid solution to obtain an acid-washed glass tube matrix;
wherein the temperature of the second washing is 45 ℃ and the washing time is 80s;
(C) Thirdly washing the acid-washed glass tube substrate by water;
Wherein, the acid-washing glass tube substrate is washed for 100s by deionized water, and then is washed by distilled water until the conductivity of the washing solution is 4.6 mu s/cm;
(3) Spraying the film-coating powder on the surface of the dried glass tube matrix to obtain a glass tube covered with the coating powder;
After passing through a meter, the film coating powder is pressed into an electrostatic spray gun by compressed gas to spray the surface of a glass tube substrate, wherein the pressure of the compressed gas is 0.025Mpa, the spraying angle is 30 ℃, a discharge needle for generating high-voltage static electricity is arranged at the head of the electrostatic spray gun, the distance between a nozzle of the electrostatic spray gun and the spraying center of the surface of the glass tube substrate is 12cm, the spraying speed is 80g/min, the thickness of the film coating after spraying is 15 mu m, and the glass tube substrate is horizontally placed and continuously rotated at the rotating speed of 7r/min during spraying;
(4) After the temperature is raised from room temperature to sintering temperature, sintering the glass tube coated with the coating powder to obtain a coated glass tube;
Wherein the temperature rising rate is 4 ℃ per minute, the sintering temperature is 300 ℃ and the sintering time is 25 minutes.
PREPARATION EXAMPLE 4 preparation of coated glass tube, numbered P4
This preparation was conducted in the same manner as in preparation example 1 except that the amount of zirconium dioxide added was 1 part by weight, and the other components and the amounts added were as shown in Table 2.
And obtaining the coated glass tube.
PREPARATION EXAMPLE 5 preparation of coated glass tube, numbered P5
The preparation example was carried out in the same manner as in preparation example 2, except that the plating coat was sprayed on the surface of the glass tube substrate at a spray angle of 25 degrees with respect to the wall of the glass tube substrate. The components and the addition amounts of the film coating are shown in Table 2.
And obtaining the coated glass tube.
Comparative example 1
The same procedure as in preparation example 1 was conducted except that the respective components and the addition amounts of the coating film used for preparing the coated glass tube were different, in which the addition amount of zirconium dioxide was 2.5 parts by weight. The remainder was the same as in preparation example 1, see in particular table 2.
The coated glass tube was obtained, number DP1.
Comparative example 2
The same procedure as in preparation example 1 was conducted except that the respective components and the addition amounts of the coating film used for preparing the coated glass tube were different, wherein the addition amount of zinc oxide was 20 parts by weight. The remainder was the same as in preparation example 1, see in particular table 2.
The coated glass tube was obtained, number DP2.
Comparative example 3
The same procedure as in preparation example 1 was conducted except that the plating coat was sprayed on the surface of the glass tube substrate at a spray angle of 55 degrees with respect to the wall of the glass tube substrate.
The components and the addition amounts of the coating film for preparing the coated glass tube are shown in Table 2.
The coated glass tube was obtained, number DP3.
Comparative example 4
The same procedure as in preparation example 1 was conducted except that the glass tube substrate was prepared in accordance with the composition and the addition amount of the glass tube substrate in Table 1, but the prepared glass tube substrate was not subjected to coating spray later. The glass tube substrate is a soda lime glass tube, number DP4.
TABLE 1
| Glass tube matrix composition | Additive amount, parts by weight |
| SiO2 | 70 |
| Al2O3 | 5 |
| Na2O | 10 |
| K2O | 1 |
| Li2O | 3 |
| MgO | 3 |
| CaO | 7 |
| ZnO | 1 |
TABLE 2
| Coating composition of film coating per weight portion | Preparation example 1 | Preparation example 2 | Preparation example 3 | Preparation example 4 | Preparation example 5 |
| ZnO | 31 | 34 | 35 | Same as in preparation example 2 | Same as in preparation example 1 |
| SiO2 | 28 | 34 | 27 | Same as in preparation example 2 | Same as in preparation example 1 |
| B2O3 | 17.5 | 20 | 18 | Same as in preparation example 2 | Same as in preparation example 1 |
| Al2O3 | 2.7 | 2 | 2 | Same as in preparation example 2 | Same as in preparation example 1 |
| K2O | 5 | 13 | 4 | Same as in preparation example 2 | Same as in preparation example 1 |
| Na2O | 6 | 0 | 6 | Same as in preparation example 2 | Same as in preparation example 1 |
| CaO | 2 | 3 | 2 | Same as in preparation example 2 | Same as in preparation example 1 |
| BaO | 3 | 5 | 2 | Same as in preparation example 2 | Same as in preparation example 1 |
| MgO | 3 | 2 | 3 | Same as in preparation example 2 | Same as in preparation example 1 |
| ZrO2 | 1.8 | 1.5 | 1 | Same as in preparation example 2 | 1 |
| Spray angle/° | 30 | 45 | Same as in preparation example 1 | 25 | Same as in preparation example 1 |
Table 2 continuous table
Test example 1
The following tests were conducted to obtain the performance by the following method:
(1) The alkali resistance is obtained by referring to the test of YBB00352004-2015 glass boiling-resistant mixed alkali aqueous solution etching determination method;
(2) The acid resistance is obtained by referring to the test of YBB00342004-2015 glass boiling hydrochloric acid etching resistance test method;
(3) Characteristic temperature points, namely Tm (melting temperature), tg (softening temperature) and Ts (transition point temperature) pass differential scanning calorimeter test (DSC);
(4) CTE (coefficient of thermal expansion) was measured by cutting and grinding a glass sample into 4mm by 25.40mm strips, measuring the coefficient of thermal expansion, and measuring the coefficient of thermal expansion of the glass by differential method, the measuring instrument being DIL2012STD dilatometer.
The products prepared in the above preparation examples and comparative examples were subjected to performance (characteristic temperature point, thermal expansion coefficient, alkali resistance, acid resistance) test, and the results are shown in Table 3.
TABLE 3 Table 3
The result shows that the comprehensive performance of the coated glass tube prepared by the method is greatly improved compared with that of soda lime glass, wherein the acid resistance is 1 level, the alkali resistance is 1 level, and in the method, borax pentahydrate (which is a source of diboron trioxide) with higher price is only added when a coated film is prepared, and the borax pentahydrate is not used in a glass tube matrix, so that the use amount of the diboron trioxide is very low, and the preparation cost is reduced.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The coated glass tube is characterized by comprising a glass tube substrate and a coated coating layer arranged on the surface of the glass tube substrate;
The raw materials of the film coating contain the following components which are stored independently or stored by mixing more than two of the following components:
Based on 100 weight parts of the total weight of the film coating raw material, the zinc oxide content is 30-34 weight parts, the silicon dioxide content is 26-30 weight parts, the diboron trioxide content is 17-19 weight parts, the aluminum oxide content is 2.5-3 weight parts, the alkali metal oxide content is 11-13 weight parts, the alkaline earth metal oxide content is 6.5-9 weight parts, and the zirconium dioxide content is 1.5-1.8 weight parts;
The film coating is sprayed on the surface of the glass tube matrix at a spraying angle of 30-45 degrees with the wall of the glass tube matrix.
2. The coated glass tube according to claim 1, wherein the thickness of the coating film is 10-30 μm, and/or
The alkali metal oxide is sodium oxide and/or potassium oxide, and/or
The alkaline earth metal oxide is at least one of calcium oxide, magnesium oxide and barium oxide, and/or
The glass tube substrate is a soda lime glass tube.
3. A method of making the coated glass tube of claim 1 or 2, comprising the steps of:
(1) Melting each component in the coating raw materials of the coated glass tube according to claim 1 or 2 to obtain a coating melt;
(2) Sequentially clarifying, annealing and grinding the film coating molten liquid to obtain film coating powder;
(3) Spraying the film-coating powder on the surface of a dry glass tube substrate to obtain a glass tube coated with the coating powder;
(4) And sintering the glass tube covered with the coating powder to obtain the coated glass tube.
4. A process according to claim 3, wherein in step (1) the conditions of melting are at least satisfied at a temperature of 1100-1200 ℃ for a time of 240-480min, and/or
In the step (2), the clarification treatment condition at least meets the condition that the temperature is 850-900 ℃ and the time is 60-120min, the annealing treatment condition at least meets the condition that the annealing temperature is 480-520 ℃ and the annealing time is not less than 30min, and/or
In the step (3), the spraying condition at least meets the conditions that the spraying speed is 50-100g/min, the thickness of the coated film after spraying is 10-30 mu m, and/or
In the step (4), the sintering condition at least meets the conditions that the sintering temperature is 560-610 ℃ and the sintering time is 20-40min.
5. The method according to claim 3 or 4, wherein in step (2), the film-coating powder has an average particle size of less than 50 μm and a moisture content of less than 3wt%.
6. The method according to claim 3 or 4, wherein the method further comprises, before performing the step (3), sequentially subjecting the glass tube substrate to be applied to a cleaning treatment and a drying treatment, and then using the glass tube substrate subjected to the drying treatment in the step (3) to perform the spraying;
the step of the cleaning treatment comprises the following steps:
(A) Under the conditions of leaching and/or ultrasonic leaching, carrying out first washing on a glass tube matrix to be applied by using 0.4-0.6wt% of alkaline solution to obtain an alkaline washing glass tube matrix;
(B) Performing second washing on the alkali-washed glass tube by using 0.4-0.6wt% of acid solution to obtain an acid-washed glass tube matrix;
(C) And thirdly washing the pickled glass tube substrate with water.
7. A process according to claim 6, wherein in the first washing the alkaline solution is sodium hydroxide solution, and/or
In the second wash, the acidic solution is a hydrochloric acid solution.
8. The process according to claim 6, wherein the first washing is carried out under ultrasonic immersion washing conditions, and/or
The ultrasonic pickling condition is at least satisfied that the ultrasonic frequency is 30-50kHz, the temperature of the first washing is 40-50 ℃, and the pickling time is 30-60s.
9. The process according to claim 6, wherein the conditions in the second washing are at least satisfied that the temperature of the second washing is 40-50 ℃ and the washing time is 80-100s, and/or
In the third washing, the acid-washed glass tube substrate is washed for 80-100s by deionized water, and then is washed by distilled water until the conductivity of the washing solution is less than 5.1 mu s/cm.
10. Use of the coated glass tube according to claim 1 or 2 in the field of pharmaceutical injection bottles, ampoules.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211105060.0A CN116217090B (en) | 2022-09-09 | 2022-09-09 | Coated glass tube and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211105060.0A CN116217090B (en) | 2022-09-09 | 2022-09-09 | Coated glass tube and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116217090A CN116217090A (en) | 2023-06-06 |
| CN116217090B true CN116217090B (en) | 2024-12-03 |
Family
ID=86575530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211105060.0A Active CN116217090B (en) | 2022-09-09 | 2022-09-09 | Coated glass tube and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116217090B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103552320A (en) * | 2013-10-28 | 2014-02-05 | 西南科技大学 | LZAS (Li2O-ZnO-Al2O3-SiO2) series microcrystalline glass gradient coating composite board and preparation method thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5279265A (en) * | 1975-12-25 | 1977-07-04 | Nippon Electric Co | Hybrid integrated circuit substrate |
| JP2937369B2 (en) * | 1989-12-08 | 1999-08-23 | 株式会社ナカシマ | Glass coating method |
| CA2020173A1 (en) * | 1990-06-29 | 1991-12-30 | Charles R. Coleman | Processing glass sheets with ceramic enamel bands |
| CN1084360C (en) * | 1997-09-02 | 2002-05-08 | 王卫中 | Glass hot sprayed film material and manufacture thereof |
| DE19834801C2 (en) * | 1998-08-01 | 2002-08-08 | Schott Glas | Lead and cadmium-free glass composition for glazing, enamelling and decorating glasses or glass ceramics as well as processes for the production of a glass ceramic coated with them |
| DE10116653A1 (en) * | 2001-04-04 | 2002-10-10 | Dmc2 Degussa Metals Catalysts Cerdec Ag | Conductivity paste, articles thus produced with a conductive coating on glass, ceramic and enamelled steel and process for their production |
| JP4226574B2 (en) * | 2005-06-27 | 2009-02-18 | 株式会社ノリタケカンパニーリミテド | Glass composition having acid resistance |
| CN101003419B (en) * | 2006-09-11 | 2010-09-01 | 福耀玻璃工业集团股份有限公司 | Gray coated glass and preparation method |
| FR2926544B1 (en) * | 2008-01-18 | 2011-04-22 | Eurokera | VITROCERAMIC ARTICLE AND EMAIL ADAPTED FOR ITS COATING |
| CN101497496B (en) * | 2008-02-02 | 2011-06-15 | 比亚迪股份有限公司 | Porcelain enamel glaze composition, film coating material and preparation thereof |
| CN204723400U (en) * | 2015-06-08 | 2015-10-28 | 双峰格雷斯海姆医药玻璃（丹阳）有限公司 | A kind of medical ampoule bottle |
| CN109354404A (en) * | 2018-12-10 | 2019-02-19 | 江苏孚日玻璃科技有限公司 | A kind of frosting lotion pump and its production technology |
| CN109867449A (en) * | 2019-04-23 | 2019-06-11 | 郑州知淘信息科技有限责任公司 | A kind of automobile glass printing ink lead-free glass powder with low melting point and preparation method thereof |
| GB201911367D0 (en) * | 2019-08-08 | 2019-09-25 | Johnson Matthey Plc | Composition, paste and methods |
-
2022
- 2022-09-09 CN CN202211105060.0A patent/CN116217090B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103552320A (en) * | 2013-10-28 | 2014-02-05 | 西南科技大学 | LZAS (Li2O-ZnO-Al2O3-SiO2) series microcrystalline glass gradient coating composite board and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116217090A (en) | 2023-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105948500B (en) | Frit for porcelain enamel, enamel slurry and its preparation method and application | |
| US7032412B2 (en) | Methods of manufacturing glass sheets with reduced blisters | |
| CN104556648B (en) | The intensifying method of alumina silicate glass | |
| CN107216032A (en) | A kind of glass composition and alumina silicate glass and its preparation method and application | |
| CN100582040C (en) | Porcelain enamel glaze for acid-resistant cast iron sanitary ware | |
| JPS6389435A (en) | Enamel composition and substrate coated with the composition | |
| CN108328927B (en) | Ultra-smooth white glaze and preparation method thereof | |
| CN108503213A (en) | Alumina silicate glass and strengthened glass | |
| CN116217090B (en) | Coated glass tube and preparation method and application thereof | |
| CN102352143B (en) | Glass coating and film technology for reducing platinum rhodium alloy bushing plate loss | |
| CN104556685A (en) | Alumina silicate glass and tempered glass | |
| CN113024124A (en) | Glass powder and preparation method thereof | |
| US3463646A (en) | Semi-crystalline ground coats having controlled p2o5/b2o3 ratio | |
| CN107216043A (en) | A kind of preparation method of high-strength armoured-glass | |
| US5198393A (en) | Rare earth-containing frits having a high glass transition temperature and their use for the production of enamels having improved heat resistance | |
| CN104118996B (en) | The preparation method of anti-dazzle glas | |
| JP4062236B2 (en) | ISLAND PROJECT MODIFIED COMPONENT, ITS MANUFACTURING METHOD, AND DEVICE USING THE SAME | |
| CN104098274B (en) | A kind of glass enamel and preparation method thereof for leadless environment-friendly easy cut ampule | |
| Wang et al. | Strengthening soda-lime-silica glass by a low-expansion coating applied by melt dipping | |
| CN112391594B (en) | Platinum channel with zirconia protective coating and preparation method thereof | |
| CN109305754B (en) | Preparation method of ground glass | |
| US3488216A (en) | Method for glazing | |
| CN102953060B (en) | Method for preparing enameled air conditioner bracket | |
| CN113213760A (en) | Corrosion-resistant glaze for ceramic pot and glazing method thereof | |
| US5264287A (en) | Rare earth-containing frits having a high glass transition temperature and their use for the production of enamels having improved heat resistance |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |