CN119774877A - Rare earth doped strong neutral medicinal glass and preparation method thereof - Google Patents
Rare earth doped strong neutral medicinal glass and preparation method thereof Download PDFInfo
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Abstract
本发明提出了一种稀土掺杂的强中性药用玻璃及其制备方法，按重量份计，包括如下原料：硅砂68‑72份、无水硼砂16.5‑18.5份、氧化铝4.5‑5.5份、石灰石1.5‑2.0份、氧化钇0.8‑2.0份、纯碱1.8‑4.0份、碳酸钾0‑1.5份、氧化镧‑碳酸钡混合料0.5‑1.5份和氯化钠0.2‑0.4份。本发明的药用玻璃具有耐酸性、耐碱性及耐水性三性1级的强中性性能，并具有较低的平均线热膨胀系数(α35‑300℃<5.30×10‑6K‑1)和较高的抗弯强度(σf>180MPa)等特性。同时，其制备熔制时间短，成本较低，且工艺简单，适合实际量产。The present invention proposes a rare earth doped strong neutral pharmaceutical glass and a preparation method thereof, which comprises the following raw materials by weight: 68-72 parts of silica sand, 16.5-18.5 parts of anhydrous borax, 4.5-5.5 parts of aluminum oxide, 1.5-2.0 parts of limestone, 0.8-2.0 parts of yttrium oxide, 1.8-4.0 parts of soda ash, 0-1.5 parts of potassium carbonate, 0.5-1.5 parts of lanthanum oxide-barium carbonate mixture and 0.2-0.4 parts of sodium chloride. The pharmaceutical glass of the present invention has a strong neutral performance of level 1 in acid resistance, alkali resistance and water resistance, and has characteristics such as a lower average linear thermal expansion coefficient (α 35-300℃ <5.30×10 ‑6 K ‑1 ) and a higher bending strength (σ f >180MPa). At the same time, the preparation melting time is short, the cost is low, and the process is simple, which is suitable for actual mass production.
Description
Technical Field
The invention relates to the technical field of medicinal glass, in particular to rare earth doped strong neutral medicinal glass and a preparation method thereof.
Background
As a glass container for packaging medicines, the medicines are directly contacted with the medicines for a long time, and the medicines have different acid and alkali corrosivity, the medicines can generate a small amount of chemical reaction through exchange, corrosion and adsorption processes between surfaces for a long time, so that the performances of the medicines are influenced, even the flaking of the inner surface of a glass packaging material is seriously generated, fine solid-phase particles are formed, once the glass is input into a human body, serious consequences are caused, and borosilicate glass has incomparable advantages of other glass products in the aspects of water resistance, acid resistance, alkali resistance and strength.
The medium boron silicon 5.0 glass is a neutral medicinal glass commonly used in the international market, but the production technology difficulty is high, the investment is high, and the international market is mainly controlled by several large companies such as German Schottky (Schott), corning and the like at present, and the capacity of the medium boron silicon 5.0 glass occupies about 80 percent of the total capacity.
And the medical glass packaging container for long-term production in China is called a semi-neutral borosilicate medical glass product in the industry. The expansion coefficient of the glass is 7.0 multiplied by 10 -6/DEGC, also called as 7.0 glass, the chemical stability of the glass cannot meet the neutrality requirement, the water resistance of 121 ℃ particles and the surface water resistance of the glass are usually between 1 and 2 levels, the requirement of the first-level water-resistant glass cannot be met, and when sensitive medicines are contained, acid and alkaline substances in the glass are easy to separate out, and severe flaking can occur, so that the quality of the medicines is influenced. The medicine has non-negligible potential safety hazard for containing meta-acid, meta-alkali and pH-value sensitive medicines, and is one of the main reasons that the medicinal glass in China depends on import for a long time.
In order to change this situation, further development of the glass for pharmaceutical use is necessary.
In the performance index of the medicinal glass, the acid resistance and the alkali resistance are often contradictory, and currently, products which can simultaneously meet the three-level 1 of acid resistance, alkali resistance and water resistance are fresh in the market.
Chinese patent CN201410448955.3 discloses neutral borosilicate glass and application thereof, wherein the weight percentage of glass composition is ：SiO2 70.0-80.0％,B2O3 7.0-12.0％,Al2O3 1.5-5.0％,Na2O 5.5-8.0％,K2O 0-1.0％,Li2O 0-1.5％,CaO 1.5-3.0％,BaO 0-3.5％,MgO 0-2.0％,NaCl 0.3-0.5％,Na2O+K2O+Li2O 6.0-9.5％,CaO+BaO+MgO 1.5-6％., the neutral borosilicate glass has the water resistance of 98 ℃ in a particle method of 1 level, the water resistance of 121 ℃ in a particle method of 1 level, the acid resistance of 1 level, but the alkali resistance of 2 levels, and the batch is heated to 1650 ℃ from room temperature according to the heating rate of 5 ℃ per minute and then clarified for 4 hours, so that the problems of overhigh melting temperature, overlong time consumption and the like exist.
Chinese patent CN201811314131.1 discloses a neutral boron silicon medicinal glass and a preparation method thereof, wherein the raw materials comprise, by weight, 57-66 parts of quartz sand, 4.5-6.8 parts of aluminum hydroxide, 20-26 parts of borax pentahydrate, 0-4 parts of sodium carbonate, 1.9-5 parts of barium nitrate, 1.5-4 parts of calcite, 2-4 parts of potassium carbonate, 1.5-5 parts of salt, 0-5 parts of manganese dioxide, 0.1-0.3 part of lithium carbonate, 0.1-0.3 part of cerium oxide, 0.1-0.4 part of zinc oxide, 0< cesium carbonate < 0.5 part, 0< indium carbonate < 0.3 part, and 0< sodium selenate < 0.2 part. Although the water resistance of the glass particles of the medicinal glass is 1 grade, the glass particles have acid resistance which is not detailed, the melting time is not less than 4 hours, expensive cesium, indium and the like are used in the raw materials, and the preparation cost is relatively high.
Chinese patent CN202311356573.3 discloses a neutral borosilicate glass medicinal tube and a preparation method thereof, wherein the glass raw materials comprise, by weight, 65-67 parts of quartz sand, 27-29 parts of borax, 3.5-5.5 parts of aluminum hydroxide, 1.8-2.0 parts of wollastonite, 6-8 parts of nepheline, 1.5-1.8 parts of diopside, 7-9 parts of spodumene, 1.2-1.5 parts of zirconia, 0.8-1.0 part of yttrium oxide, 0.6-0.8 part of pretreated red mud and 1.6-1.8 parts of sodium fluosilicate. The glass particles of the glass tube for medical use are 1 grade in water resistance at 98 ℃ and 1 grade in alkali resistance but not in detail in acid resistance, and the melting, clarifying and homogenizing time is as long as 6 hours.
Comprehensive comparison shows that the neutral medicinal glass disclosed at present has the common problems of overlong melting time, larger energy consumption, higher raw material cost and the like, is more or less acidic or alkaline, and cannot meet the strong neutral requirements of three levels 1 of acid resistance, alkali resistance and water resistance.
Therefore, research and development of the strong neutral medicinal glass tube which can simultaneously meet the three levels of acid resistance, alkali resistance and water resistance, has low raw material cost and uncomplicated melting process has important significance, meets the industrial development trend and market demand, and has good application prospect.
Disclosure of Invention
In view of the above, the invention aims to provide rare earth doped strong neutral medicinal glass and a preparation method thereof, so as to solve the problems that the existing medicinal glass is difficult to simultaneously consider the three grades 1 of acid resistance, alkali resistance and water resistance, and has difficult melting, higher production cost and the like.
The technical scheme of the invention is realized as follows:
the invention aims at providing rare earth doped strong neutral medicinal glass, which comprises, by weight, 68-72 parts of silica sand, 16.5-18.5 parts of anhydrous borax, 4.5-5.5 parts of alumina, 1.5-2.0 parts of limestone, 0.8-2.0 parts of yttrium oxide, 1.8-4.0 parts of sodium carbonate, 0-1.5 parts of potassium carbonate, 0.5-1.5 parts of lanthanum oxide-barium carbonate mixture and 0.2-0.4 part of sodium chloride.
Further, the material comprises the following raw materials in parts by weight: 70.2 parts of silica sand, 17.5 parts of anhydrous borax, 5.0 parts of alumina, 1.75 parts of limestone, 1.0 part of yttrium oxide, 2.0 parts of sodium carbonate, 1.4 parts of potassium carbonate, 0.9 part of lanthanum oxide-barium carbonate mixture and 0.3 part of sodium chloride.
In the raw material components of the rare earth doped strong neutral medicinal glass, the doped rare earth oxide is lanthanum oxide and yttrium oxide. Rare earth ions Y 3+ and La 3+ are positioned in the gaps of the glass network, have higher field intensity, and can promote the transformation from the [ BO 3 ] triangle to the [ BO 4 ] tetrahedron, so that the glass network structure is more compact.
The doping of yttrium oxide reduces the amount of non-bridging oxygen in the glass network structure, and obviously improves the alkali resistance of the glass while increasing the stability of the glass structure, but when the glass network structure is excessively added, Y 2O3 can force the bridging oxygen bond in the glass structure to break, thereby reducing the stability of the glass network structure, increasing the content of isolated hydroxyl groups and reducing the acid resistance of the glass network structure.
La 2O3 and BaO are introduced into the lanthanum oxide-barium carbonate mixture, so that the strength of the glass can be improved, the chemical stability of the glass can be improved, the viscosity and the melting temperature of the glass can be effectively reduced, and the glass melting time is shorter.
Further, in the lanthanum oxide-barium carbonate mixture, lanthanum oxide and barium carbonate are mixed according to any proportion, and the potassium carbonate is anhydrous potassium carbonate.
Further, the mass ratio of the lanthanum oxide to the barium carbonate is 1:8.
The second purpose of the invention is to provide the preparation method of the rare earth doped strong neutral medicinal glass, which comprises the following steps of weighing raw materials according to parts by weight, uniformly mixing, placing into a 1450 ℃ high-temperature furnace, preserving heat for 20min for preliminary melting, then heating to 1610-1620 ℃ according to the heating rate of 10 ℃ per min, preserving heat for 2h for clarification and homogenization. And then pouring the molten glass liquid into a mould for molding, transferring the molten glass liquid into an annealing furnace at 600 ℃, and directly annealing and cooling to room temperature to obtain the strong neutral medicinal glass.
Further, the preliminary melting temperature is 1450 ℃, and the heat preservation time is 20min.
Further, the clarifying and homogenizing temperature is 1610-1620 ℃, the heat preservation time is 2 hours, the annealing temperature is 600 ℃, and the temperature is directly reduced to room temperature along with the furnace.
Compared with the prior art, the invention has the beneficial effects that:
(1) The currently disclosed medicinal glass has the advantages that the alkali resistance and the acid resistance of the medicinal glass can simultaneously reach 1 grade, and the strong neutrality requirements of the three grades of acid resistance, alkali resistance and water resistance are more difficult to achieve. The strong neutral medicinal glass disclosed by the invention not only can simultaneously have the performance requirements of acid resistance, alkali resistance and water resistance of grade 1, but also has a lower linear expansion coefficient, higher bending strength and excellent comprehensive performance.
(2) The disclosed melting method of the medicinal glass generally has the problems of difficult melting and clarification, overlong melting time and higher energy and raw material cost. The strong neutral medicinal glass has the advantages of greatly shortened melting, clarifying and homogenizing time, reduced volatilization of boron, energy conservation, readily available raw materials, simple melting process and suitability for mass production.
(3) The strong neutral medicinal glass is innovatively doped with common rare earth oxide, so that the melt viscosity of the glass is effectively improved, the melting time is shortened, and the chemical stability of the glass is remarkably improved.
As described above, the invention realizes the strong neutral performance of the medicinal glass with acid resistance, alkali resistance and water resistance at level 1 through composition design and process optimization, can completely meet the higher requirement of medicine holding on glass neutrality, effectively shortens the melting time in the preparation process, simplifies the melting process, has lower cost and can realize standard mass production.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the embodiment of the invention are conventional methods unless otherwise specified.
Materials, reagents, and the like used in the examples of the present invention are commercially available unless otherwise specified.
Examples
The formulations of the rare earth doped strong neutral pharmaceutical glasses, examples and comparative examples are given in table 1 below:
table 1 composition and control requirements (Unit: parts) of each example and comparative example
The preparation method of the rare earth doped medicinal glass comprises the following specific steps:
(a) Proportioning materials
Raw materials are weighed according to the formula of the table 1, and the raw materials are uniformly mixed to be used as a batch.
(B) Smelting
Placing the batch into a high-temperature furnace at 1450 ℃ for heat preservation for 20min for preliminary melting, then heating to 1610-1620 ℃ at the heating rate of 10 ℃/min, and preserving heat for 2h for clarification and homogenization to obtain molten glass.
(C) Shaping and annealing
And pouring the molten glass liquid into a mould for molding, transferring to a 600 ℃ annealing furnace, and directly annealing and cooling to room temperature to obtain the medicinal glass.
Test case
Samples prepared in examples 1 to 5 and comparative examples 1 to 2 were tested for acid resistance according to the "YBB 00342004-2015 glass boiling hydrochloric acid etching resistance test", alkali resistance according to the "YBB 0035204-2015 glass boiling mixed alkali aqueous solution etching resistance test", 98 ℃ glass particle water resistance according to the "YBB 0036204-2015 glass particle water resistance test and classification at 98 ℃,121 ℃ glass particle water resistance according to the" GB/T12416.2-1990 glass particle water resistance test and classification at 121 ℃ and average linear thermal expansion coefficient according to the "YBB 00202003-2015 average linear thermal expansion coefficient test", bending strength according to the "GB/T6569-2006 fine ceramic bending strength test", and the obtained partial results are shown in Table 2.
Table 2 pharmaceutical glass performance parameters prepared in examples and comparative examples
As can be seen from the example data in Table 2, the pharmaceutical glasses of examples 1 to 5 of the present invention have the characteristics of acid resistance level 1, alkali resistance level 1, water resistance level 1 of 121 ℃ glass particles, low expansion (. Alpha. 35-300℃<5.30×10-6K-1), high bending strength (. Sigma. f >180 MPa), and the like.
In the case where the other raw material components are not changed much, as compared with example 3, comparative example 1 does not add yttrium oxide, and the alkali resistance is directly reduced to grade 2 although the produced medicinal glass is better in acid resistance.
Compared with example 1, the yttrium oxide dosage of comparative example 2 is directly increased from 1.4 parts to 2.4 parts, and the acid resistance is reduced to grade 2 although the prepared medicinal glass has better alkali resistance.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.
Claims (7)
1. The rare earth doped strong neutral medicinal glass is characterized by comprising, by weight, 68-72 parts of silica sand, 16.5-18.5 parts of anhydrous borax, 4.5-5.5 parts of alumina, 1.5-2.0 parts of limestone, 0.8-2.0 parts of yttrium oxide, 1.8-4.0 parts of sodium carbonate, 0-1.5 parts of potassium carbonate, 0.5-1.5 parts of lanthanum oxide-barium carbonate mixture and 0.2-0.4 part of sodium chloride.
2. The rare earth doped strong neutral medicinal glass according to claim 1 is characterized by comprising, by weight, 70.2 parts of silica sand, 17.5 parts of anhydrous borax, 5.0 parts of alumina, 1.75 parts of limestone, 1.0 part of yttrium oxide, 2.0 parts of sodium carbonate, 1.4 parts of anhydrous potassium carbonate, 0.9 parts of lanthanum oxide-barium carbonate mixture and 0.3 part of sodium chloride.
3. The rare earth doped strong neutral medicinal glass according to claim 1, wherein lanthanum oxide and barium carbonate are mixed according to any proportion in the lanthanum oxide-barium carbonate mixture, and the potassium carbonate is anhydrous potassium carbonate.
4. A rare earth doped strongly neutral pharmaceutical glass according to claim 2, wherein the mass ratio of lanthanum oxide to barium carbonate is 1:8.
5. The method for preparing the rare earth doped strong neutral medicinal glass according to any one of claims 1 to 4 is characterized by comprising the steps of weighing raw materials according to parts by weight, uniformly mixing, placing into a 1450 ℃ high-temperature furnace, preserving heat for 20min for preliminary melting, then raising the temperature to 1610-1620 ℃ at a temperature raising rate of 10 ℃ per min, and preserving heat for 2h for clarification and homogenization. And then pouring the molten glass liquid into a mould for molding, transferring the molten glass liquid into an annealing furnace at 600 ℃, and directly annealing and cooling to room temperature to obtain the strong neutral medicinal glass.
6. The method for preparing rare earth doped strong neutral pharmaceutical glass according to claim 5, wherein the preliminary melting temperature is 1450 ℃, and the holding time is 20min.
7. The method for preparing rare earth doped strong neutral medicinal glass according to claim 5, wherein the clarifying and homogenizing temperature is 1610-1620 ℃, the heat preservation time is 2h, the annealing temperature is 600 ℃, and the temperature is directly reduced to room temperature along with a furnace.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040152580A1 (en) * | 2002-12-03 | 2004-08-05 | Paulo Marques | Borsilicate glass compositions and uses thereof |
| US20120148770A1 (en) * | 2009-08-21 | 2012-06-14 | Momentive Performance Materials, Inc. | Fused quartz tubing for pharmaceutical packaging |
| US20190322569A1 (en) * | 2016-12-29 | 2019-10-24 | Sunshine Lake Pharma Co., Ltd. | Borosilicate glass with high chemical resistance and application thereof |
| CN114507010A (en) * | 2022-02-09 | 2022-05-17 | 湖南洪康新材料科技有限公司 | Medium borosilicate glass composition and preparation method and application thereof |
| CN116813197A (en) * | 2023-04-10 | 2023-09-29 | 中国科学院上海光学精密机械研究所 | A kind of borosilicate glass curing aid for the treatment of medium and low radioactive waste liquid and its use method |
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- 2024-12-30 CN CN202411961558.6A patent/CN119774877A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040152580A1 (en) * | 2002-12-03 | 2004-08-05 | Paulo Marques | Borsilicate glass compositions and uses thereof |
| US20120148770A1 (en) * | 2009-08-21 | 2012-06-14 | Momentive Performance Materials, Inc. | Fused quartz tubing for pharmaceutical packaging |
| US20190322569A1 (en) * | 2016-12-29 | 2019-10-24 | Sunshine Lake Pharma Co., Ltd. | Borosilicate glass with high chemical resistance and application thereof |
| CN114507010A (en) * | 2022-02-09 | 2022-05-17 | 湖南洪康新材料科技有限公司 | Medium borosilicate glass composition and preparation method and application thereof |
| CN116813197A (en) * | 2023-04-10 | 2023-09-29 | 中国科学院上海光学精密机械研究所 | A kind of borosilicate glass curing aid for the treatment of medium and low radioactive waste liquid and its use method |
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