CN1155524A - 含有氧化锆和氧化锂的具有高化学稳定性和低粘度的硼硅酸盐玻璃 - Google Patents
含有氧化锆和氧化锂的具有高化学稳定性和低粘度的硼硅酸盐玻璃 Download PDFInfo
- Publication number
- CN1155524A CN1155524A CN96113360A CN96113360A CN1155524A CN 1155524 A CN1155524 A CN 1155524A CN 96113360 A CN96113360 A CN 96113360A CN 96113360 A CN96113360 A CN 96113360A CN 1155524 A CN1155524 A CN 1155524A
- Authority
- CN
- China
- Prior art keywords
- glass
- sio
- oxide
- zro
- borosilicate glass
- 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.)
- Granted
Links
- 239000005388 borosilicate glass Substances 0.000 title claims abstract description 16
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910001947 lithium oxide Inorganic materials 0.000 title claims abstract description 13
- 239000000126 substance Substances 0.000 title claims abstract description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title abstract description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 title abstract 2
- 239000011521 glass Substances 0.000 claims abstract description 67
- 239000000203 mixture Substances 0.000 claims abstract description 30
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003708 ampul Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000005022 packaging material Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003518 caustics Substances 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract 1
- 150000007513 acids Chemical class 0.000 abstract 1
- 239000011129 pharmaceutical packaging material Substances 0.000 abstract 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 239000011734 sodium Substances 0.000 description 13
- 239000000292 calcium oxide Substances 0.000 description 9
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 7
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 6
- 229910001950 potassium oxide Inorganic materials 0.000 description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 6
- 229910001948 sodium oxide Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 229910052810 boron oxide Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- -1 Al (OH) 3 Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005292 fiolax Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000005356 container glass Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/508—Containers for the purpose of retaining a material to be analysed, e.g. test tubes rigid containers not provided for above
- B01L3/5082—Test tubes per se
-
- 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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
- A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
- A61J1/06—Ampoules or carpules
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Hematology (AREA)
- Clinical Laboratory Science (AREA)
- Glass Compositions (AREA)
Abstract
本发明涉及一种硼硅酸盐玻璃，它具有高化学稳定性和低粘度，含有氧化锆和氧化锂，该玻璃具有一级抗水解性—根据DINISO719、一级耐酸性—根据DIN12116、一级抗苛性碱性—根据DINISO659，低的工作点VA为1180-1230℃并且线性热膨胀系数α20/300=4.9×10-6K-1，具有下列组成(重量百分比，基于氧化物)：SiO273.0-75.0，B2O37.0-10.0，Al2O35.0-7.0，ZrO21.0-3.0，Li2O0.5-1.5，Na2O0-10.0，K2O0-10.0，MgO0-3.0，CaO0-3.0，BaO0-3.0，SrO0-3.0，ZnO0-3.0，其SiO2/B2O3大于或等于7.5，∑SiO2+Al2O3+ZrO280.0-83.0，∑MgO+CaO+BaO+SrO+ZnO小于或等于3.0以及氟化物0-3。该玻璃特别适用于用作通用的主要医药包装材料，如安瓿玻璃。
Description
本发明涉及含有氧化锆和氧化锂的硼硅酸盐玻璃，该玻璃具有一级抗水解性、耐酸性和耐苛性碱性并且具有低粘度，特别是在处理范围内。
作为主要包装材料，例如作为安瓿玻璃，医药工业要求玻璃具有极高的化学稳定性。迄今为至，已知的工业医药安瓿玻璃具有一级(H)的抗水解性(根据DIN ISO 719)、一级(S)的耐酸性(根据DIN 12116)和二级(L)的耐苛性碱性(根据DIN ISO 695)。现有技术的代表是透明玻璃FiolaxTM，编号为8412(SiO274.7，B2O310.0，Al2O35.0，Na2O6.5，CaO1.5，BaO2.0，氟化合物0.3，百分重量)以及JENA仪器玻璃Ggl490/5(SiO273.2，B2O311.0，Al2O35.3，Na2O7.0，K2O0.2，CaO0.8，BaO 2.5，百分重量)，它们具有100mg/dm2的失重(根据DIN ISO 695)。一级耐苛性碱性，即失重小于75mg/dm2至今通过工业医药安瓿玻璃还不能达到。
但是，医药工业的一个重要要求是提供具有明显改进的抗苛性碱性的主要包装材料，从而可以包装新近开发出的对容器具有强碱性作用的注射液。实际经验表明要想保证在生产工艺中的抗苛性碱性，就要求在实验室中开发出失重小于65-70mg/dm2，即在一级苛性碱范围内的玻璃。
当然，达到这个要求必需不能损害其它重要的玻璃和玻璃生产性能。举例来说，必需保持H＝1和S＝1。此外，对于透明工业玻璃FiolaxTM，编号8412和Ggl490/5来说，线性热膨胀系数α20/300大约为4.9×10-6K-1，并且出于质量和成本原因，其粘度在整个熔化、处理和冷却范围内不能太高。
评价玻璃的可操作性的一个基本参数是工作点(VA)，在该点下玻璃的粘度为104dPas。对于医药安瓿玻璃来说，该VA值应该不超过1220-1230℃，以防止发生玻璃成分，主要是碱金属氧化物和硼酸的不利的蒸发现象以及在玻璃管生产中以及在随后的将玻璃管转变成安瓿瓶的过程中节约能量。在玻璃的热形成过程中发生的蒸发将使安瓿瓶变得不适用。
在冷却区中的玻璃粘度的特征在于玻璃的转变温度Tg，该温度对应的粘度大约为1013dPas。为了在冷却区中节能，同样它不能太高。
在专利说明书中DE3722130 C2和DD301821 A7中所说的医药容器玻璃不满足这些高要求。
具有在DE3722130 C2中所说的组成的玻璃不属于一级苛性碱中。
描述了灯：玻璃和防火玻璃的专利说明书DE4230607 C1所要求的范围仅仅指出了一种具有一级抗苛性碱性的特定组合物。虽然通过具有在DD301821 A7中所说的组合物的某些玻璃可以达到L＝1，但是很显然首先是仅仅达到一级苛性碱性，其次在抗苛性碱性试验中的失重当将具有一定组成的熔体重复多次时呈现出发散数值，因此L＝1不是总能达到。这就需要进行改进以获得可靠的抗苛性碱性。
本发明的目的在于开发出具有高化学稳定性和低粘度的硼硅酸盐玻璃，特别是具有一级抗水解性(根据DIN ISO 719)、一级耐酸性(根据DIN 12116)，特别是一级抗苛性碱性(根据DIN ISO 659)，其失重＜65-70mg/dm2，工作点＜1220-1230℃并且线性热膨胀系数α20/300＝4.8-5.0×10-6K-1。
根据本发明，该目的是通过权利要求1所说的玻璃而实现的，该玻璃含有一定量的氧化锆和氧化锂。
具有H＝1、S＝1、L＝1(失重小于65-70mg/dm2)、VA值小于1230℃和α20/300＝4.8-5.0×10-6K-1的玻璃可以在下列组合物范围内制造(重量百分比，基于氧化物)，SiO273.0-75.0(优选地为73.5-75.0)，B2O37.0-10.0(优选地为8.0-10.0)，Al2O35.0-7.0(优选地为5.0-6.0)，ZrO21.0-3.0(优选地为1.0-2.5)，Li2O0.5-1.5，Na2O0-10.0，K2O0-10.0，MgO0-3.0，CaO0-3.0，BaO0-3.0，SrO0-3.0，ZnO0-3.0和氟化物0-3.0，玻璃形成体SiO2和B2O3之间的比值为大于或等于7.5，SiO2+Al2O3+ZrO2的和为80.0-83.0％重量并且二价添加物的和(MgO+CaO+BaO+SrO+ZnO)小于或等于3.0％重量。碱金属氧化物的和(Li2O+Na2O+K2O)优选地限制为7.0-10.0％重量。
下列组合物范围(重量百分比，基于氧化物)是特别优选的：SiO273.5-75.0，B2O38.0-10.0，Al2O35.0-6.0，ZrO21.0-2.5，Li2O 0.5-1.5，Na2O0.5-5.0，K2O0.5-5.0，CaO0.5-2.0，SiO2/B2O3大于或等于7.5，∑SiO2+Al2O3+ZrO281.0-83.0，而∑Li2O+Na2O+K2O7.0-9.5。
这些玻璃还具有一些对于无缺陷和廉价批量生产是必需的优点。例如，它们满足涉及熔化行为的所需条件、结晶和分层稳定性、导电性、作为耐火材料的腐蚀性能、澄清性能、蒸发性能等。
从普通容器玻璃组合物开始(重量百分比，基于氧化物)，SiO275，B2O311，Al2O35，∑Na2O3+K2O7，∑BaO+CaO2，导致该新组合物的优化过程如下：
为了达到失重小于65-70mg/dm2的一级抗苛性碱性同时获得相当的低的工作点，VA＜1220-1230℃，必须向上述硼硅酸盐玻璃中加入1-3％重量的氧化锆和0.5-1.5％重量的氧化锂(在DE3722130C2中完全不存在)。此外，玻璃形成体二氧化硅和三氧化二硼的比必须大于或等于7.5。该新型组合物在该比值或相当低的氧化硼含量(7.0-10.0％重量)方面不同于DE3722130C2和DD301821A7。
通过改变其它的成分(氧化铝、碱金属氧化物、碱土金属氧化物或氧化锌)，可以将该组合物优化，而且其它的重要玻璃或玻璃生产性能可以能得到改进或相匹配。
由于一般的硼硅酸盐玻璃SiO2-B2O3-Al2O3-M2O-MO-AC(＝其它的组分)已经有一段时间为人们所已知了，并且在多种情况下进行了科学的研究以及实际用于多种用途，因此，所发现的溶液是极其出乎人们意外的。
另外，基于线性模式的优化计算对于确定具有高抗苛性碱性的组合物范围是不适用的，这是因为玻璃的抗苛性碱性不会随着SiO2/B2O3比值的增加而线性增加，因此这种技术不能确定失重的范围。
加入二氧化锆和少量的氧化硼可以改进抗水、酸和苛性碱性。但是氧化锆的加入受到其在玻璃中的低溶解性和玻璃粘度增加的限制。氧化硼含量的降低也会引起粘度的增加，但是这可以通过加入碱金属氧化物，特别是氧化锂而得到补偿。
当选择碱金属氧化物时，应该考虑多种因素：玻璃熔体中的氧化锂的含量过大将会对熔化端的耐火材料产生难以接受的强烈攻击，因此0.5-1.5％重量的氧化锂是最佳的。正象氧化锂与氧化钠相比在所说的硼硅酸盐玻璃熔体中的蒸发要小那样，氧化钠的蒸汽压力比氧化钾的要小。这就告诉我们要单单使用或主要使用氧化钠(在所给定的最大氧化锂含量下)。氧化钠原料的低成本也是一个优势。
在该新型玻璃的特殊应用中，例如制造光电倍增管中，完全不用氧化钾是不利的。这是因为氧化钾原料可含极少量的放射性杂质，这些杂质在某些条件下会使光电倍增管的噪音量增加。
与其相反，在低氧化钙和没有氧化钙的合成变化形式中，必须采用相当大量的氧化钾，以产生所需的α20/300值。
对于没有氧化钙的合成来说，下列组合物范围是有利的(％重量，基于氧化物)：SiO273.5-75.0，B2O38.0-10.0，Al2O35.0-6.0，ZrO21.0-2.5，Li2O0.5-1.5，Na2O0-3.0，K2O4.0-7.0，SiO2/B2O3大于或等于7.5，∑SiO2+Al2O3+ZrO281.0-83.0，∑Li2O+Na2O+K2O7.0-10.0。
已经知道在通过将玻璃在高成型温度下再加热而将玻璃管转变成安瓿瓶的过程中较高的氧化钠含量将会导致玻璃表面风化得特别快。但是这点可以通过加入氧化锆和氧化锂并且还可以通过仅仅使用氧化钾或同时使用氧化钾和氧化钠以及加入少量的氧化锌而使VA值降低来消除。
由于在工业硼硅酸盐玻璃中的蒸发产物，通常是偏硼酸盐与所用的碱金属氧化物(M2O)的类型无关，在高温下具有下列硼酸模数：￥＝B2O3/(B2O3+M2O)(摩尔％)为0.53-0.58，该数值非常接近于玻璃组合物的硼酸模数，这使得蒸发很容易，因此必须通过其它手段，即通过大量增加粘度而降低熔化过程中的蒸发。
这一点可以通过相当高的氧化硅(73.0-75.0％重量)和氧化铝(5.0-7.0％重量)含量而实现。
这种水平的氧化铝含量表示该新型玻璃组合物进一步区别于DD301821A7的组合物。DE4230607C1的玻璃组合物也含有相当少量的氧化铝，1.5-4.0％重量。
如果氧化硅和氧化铝的比例增加甚至超过了所要求的范围，其粘度和VA值将增加太多，这将不利于澄清。高氧化铝含量还会使耐酸性得到显著地降低。
考虑到这种高质量通用的药物安瓿玻璃的组分的全部优点和不利影响，已经证明下列玻璃组合物是特别有利的(％重量，基于氧化物)：SiO274.9-74.5，B2O38.5-9.5(特别优选的是9.0-9.5)，Al2O35.3-6.0(特别优选的是5.3-5.8)，ZrO21.6-2.0，Li2O0.7-1.3(特别优选的是0.9-1.1)，Na2O3.0-5.0.K2O2.0-5.0(特别优选的是2.0-4.0)，CaO0.5-1.6(特别优选的是0.8-1.2)，∑SiO2+Al2O3+ZrO281.3-82.0，而∑Li2O+Na2O+K2O7.0-9.5(特别优选的是7.0-9.0)。
因此，在α值约为4.9×10-6K-1时，可以达到特别好的H＝1、S＝1和L＝1(失重＜65mg/dm2)的化学稳定性并且VA值低到小于或等于1200℃。
由于氧化钙对耐酸性具有稳定作用，因此，如果可以的话，可以向玻璃中加入少量氧化钙。类似地，少量氧化钡有助于进一步降低粘度并降低熔点。另一方面，该玻璃还必须含有很少量的氧化钙和氧化钡，或几乎没有，这是因为已经知道这些成分会以不合适的形式与某些特定的射入溶液起反应。
如果有代表性的医药和工业应用领域在化学稳定性方面没有很高的要求，那通过加入二价成分SrO、MgO和ZnO并改变CaO和BaO含量而进一步改变玻璃性能。
但是，它们的总含量必须保持在最高3.0％重量，该新型组合物通过该值而区别于DE4230607 C1中所述的组合物，(∑MgO+CaO+BaO+ZnO+SrO+ZrO2＝6-10＝∑ MgO+CaO+BaO+ZnO+SrO＝3-9.5，如果ZrO2＝0.5-3)。
此外，可以向该新型玻璃组合物中加入少量氟化物以加速熔化或降低粘度，或已知的澄清剂，如氯化物和Sb2O3。
操作实施例：
表1表示与本发明有关的新型玻璃组合物及其基本性能。
可以看出，如果获得所定义的热膨胀系数α20/300＝4.9×10-6K-1时，抗苛性碱性L(用低失重值58-65mg/dm2表示)非常稳定地在一级中，工作点较低，VA值为1180-1220℃。表1新型玻璃的例子以重量百分比计的玻璃组合物玻璃编号 1 2 3 4 5SiO2 74.3 74.2 74.3 74.3 74.3B2O3 9.3 8.8 9.3 9.3 9.3Al2O3 5.5 5.8 5.5 5.5 5.5ZrO2 1.8 1.8 1.8 1.8 1.8Li2O 1.0 1.0 1.0 1.0 1.0Na2O 4.0 3.0 3.5 3.0 2.0K2O 3.0 4.0 3.8 4.6 6.1CaO 1.1 1.4 0.8 0.5 -SiO2/B2O3 8.0 8.4 8.0 8.0 8.0∑ SiO2+Al2O3+ZrO281.6 81.8 81.6 81.6 81.6∑Li2O+Na2O+K2O 8.0 8.0 8.3 8.6 9.1基本玻璃性能 1 2 3 4 5α20/300(10-6K-1) 4.9 4.9 4.9 4.9 4.9L(mg/dm2) 62 58 63 64 65VA(℃) 1180 1200 1190 1200 1220
下列数据是针对实施例1给出，以证明进一步的有利性能：密度ρ：2.36g/cm3玻璃转变温度Tg：540℃退火点A.P.：550℃软化点Ew：785℃结晶和分层稳定性：适用于当批量生产产品时无缺陷地生产玻璃。
Tg和A.P.证实该玻璃即使在冷却区中也具有相当低的和良好的粘度，因此可以廉价地冷却。
以常规方式，在用煤气加热的实验炉中、在1620℃中、在0.5升坩埚中、在约4小时内制备玻璃，然后浇铸在金属模中成块并冷却。所用的原料为砂子，H3BO3，Al(OH)3，碱金属和碱土金属碳酸盐和硝酸盐，二氧化锆和ZnO。该玻璃具有良好的熔化性能。所用的原料还可以是常用于工业玻璃的。
该新型玻璃主要适用于用作通用的主要医药包装材料，如安瓿玻璃。它还可以作为仪器玻璃而用于实验或其它技术领域。
Claims (7)
1.硼硅酸盐玻璃，它具有高化学稳定性和低粘度，含有氧化锆和氧化锂，其特征在于为下列组合物(重量百分比，基于氧化物)：SiO2 73.0-75.0B2O3 7.0-10.0Al2O3 5.0-7.0ZrO2 1.0-3.0Li2O 0.5-1.5Na2O 0-10.0K2O 0-10.0MgO 0-3.0CaO 0-3.0BaO 0-3.0SrO 0-3.0ZnO 0-3.0氟化物 0-3.0SiO2/B2O3 大于或等于7.5∑SiO2+Al2O3+ZrO2 80.0-83.0∑MgO+CaO+BaO+SrO+ZnO 小于或等于3.0。
2.根据权利要求1的含有氧化锆和氧化锂的硼硅酸盐玻璃，其特征在于下列组合物(重量百分比，基于氧化物)：SiO2 73.5-75.0B2O3 8.0-10.0Al2O3 5.0-6.0ZrO2 1.0-2.5Li2O 0.5-1.5Na2O 0-10.0K2O 0-10.0MgO 0-3.0CaO 0-3.0BaO 0-3.0SrO 0-3.0ZnO 0-3.0SiO2/B2O3 大于或等于7.5∑SiO2+Al2O3+ZrO2 80.0-83.0∑Li2O+Na2O+K2O 7.0-10.0∑MgO+CaO+BaO+SrO+ZnO 小于或等于3.0。
3.根据权利要求1或2的硼硅酸盐玻璃，其特征在于下列组合物(重量百分比，基于氧化物)：SiO2 73.5-75.0B2O3 8.0-10.0Al2O3 5.0-6.0ZrO2 1.0-2.5Li2O 0.5-1.5Na2O 0.5-5.0K2O 0.5-5.0CaO 0.5-2.0SiO2/B2O3 大于或等于7.5∑ SiO2+Al2O3+ZrO2 81.0-83.0∑ Li2O+Na2O+K2O 7.0-9.5。
4.根据权利要求1或2的硼硅酸盐玻璃，其特征在于下列组合物(重量百分比，基于氧化物)：SiO2 73.5-75.0B2O3 8.0-10.0Al2O3 5.0-6.0ZrO2 1.0-2.5Li2O 0.5-1.5Na2O 0-3.0K2O 4.0-7.0SiO2/B2O3 大于或等于7.5∑ SiO2+Al2O3+ZrO2 81.0-83.0∑ Li2O+Na2O+K2O 7.0-10.0。
5.根据权利要求1-3至少一个的硼硅酸盐玻璃，其特征在于下列组合物(重量百分比，基于氧化物)：SiO2 74.0-74.5B2O3 8.5-9.5Al2O3 5.3-6.0ZrO2 1.6-2.0Li2O 0.7-1.3Na2O 3.0-5.0K2O 2.0-5.0CaO 0.5-1.6∑ SiO2+Al2O3+ZrO2 81.3-82.0∑ Li2O+Na2O+K2O 7.0-9.5。
6.根据权利要求5的硼硅酸盐玻璃，其特征在于下列组合物(重量百分比，基于氧化物)：SiO2 74.0-74.5B2O3 9.0-9.5Al2O3 5.3-5.8ZrO2 1.6-2.0Li2O 0.9-1.1Na2O 3.0-5.0K2O 2.0-4.0CaO 0.8-1.2∑ SiO2+Al2O3+ZrO2 81.3-82.0∑ Li2O+Na2O+K2O 7.0-9.0。
7.根据前面权利要求中至少一个的硼硅酸盐玻璃的用途，该玻璃具有一级抗水解性一根据DIN ISO 719、一级耐酸性一根据DIN 12116、一级抗苛性碱性-根据DIN ISO 659，其失重＜70mg/dm2，最大工作点VA＜1230℃并且线性热膨胀系数α20/300＝4.8-5.0×10-6K-1，它被用作主要医药包装材料，如安瓿玻璃，作为仪器玻璃用于实验室或其它技术领域。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19536708A DE19536708C1 (de) | 1995-09-30 | 1995-09-30 | Zirkon- und lithiumoxidhaltiges Borosilicatglas hoher chemischer Beständigkeit und geringer Viskosität und dessen Verwendung |
| DE19536708.1 | 1995-09-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1155524A true CN1155524A (zh) | 1997-07-30 |
| CN1101348C CN1101348C (zh) | 2003-02-12 |
Family
ID=7773842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96113360A Expired - Lifetime CN1101348C (zh) | 1995-09-30 | 1996-09-30 | 含有氧化锆和氧化锂的具有高化学稳定性和低粘度的硼硅酸盐玻璃 |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5736476A (zh) |
| EP (1) | EP0765847B1 (zh) |
| JP (1) | JP4215176B2 (zh) |
| CN (1) | CN1101348C (zh) |
| AR (1) | AR003754A1 (zh) |
| BR (1) | BR9603894A (zh) |
| DE (2) | DE19536708C1 (zh) |
| ES (1) | ES2135828T3 (zh) |
| HU (1) | HU214878B (zh) |
| RU (1) | RU2127709C1 (zh) |
| UA (1) | UA55368C2 (zh) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102578791A (zh) * | 2010-10-19 | 2012-07-18 | 波米奥利鲁吉股份公司 | 由包覆成型复合材料制造的制品及其相关的制备 |
| CN104261676A (zh) * | 2014-09-04 | 2015-01-07 | 东莞市长安东阳光铝业研发有限公司 | 一种中性硼硅玻璃及其应用 |
| CN104445926A (zh) * | 2014-11-07 | 2015-03-25 | 河北省沙河玻璃技术研究院 | 一种玻璃组合物及其制成的适合化学增强的硼硅酸盐玻璃 |
| CN105263875A (zh) * | 2013-06-06 | 2016-01-20 | 日本电气硝子株式会社 | 药物容器用玻璃 |
| CN106430953A (zh) * | 2016-08-31 | 2017-02-22 | 山东省药用玻璃股份有限公司 | 耐碱药用玻璃及其制备方法 |
| CN110683758A (zh) * | 2018-07-06 | 2020-01-14 | 肖特股份有限公司 | 具有提高的离子可交换性的玻璃 |
| CN112028475A (zh) * | 2020-09-11 | 2020-12-04 | 成都光明光电股份有限公司 | 光学玻璃和光学元件 |
| CN112028474A (zh) * | 2020-09-11 | 2020-12-04 | 成都光明光电股份有限公司 | 光学玻璃 |
| CN113860729A (zh) * | 2021-10-25 | 2021-12-31 | 北京工业大学 | 一种中硼硅药用玻璃 |
Families Citing this family (100)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19617344C1 (de) * | 1996-04-30 | 1997-08-07 | Schott Glaswerke | Alkalifreies Aluminoborosilicatglas und seine Verwendung |
| DE19842942C2 (de) | 1998-09-18 | 2001-05-23 | Schott Glas | Borosilicatglas hoher chemischer Beständigkeit und dessen Verwendung |
| US20040142810A1 (en) * | 1999-03-23 | 2004-07-22 | Christian Kunert | Use of a glass for thermal shock-resistant beverage containers |
| DE19913227C1 (de) * | 1999-03-23 | 2000-07-27 | Schott Glas | Verwendung eines Glases für temperaturwechselbeständige Getränkebehälter |
| US6475573B1 (en) | 1999-05-03 | 2002-11-05 | Guardian Industries Corp. | Method of depositing DLC inclusive coating on substrate |
| US6261693B1 (en) | 1999-05-03 | 2001-07-17 | Guardian Industries Corporation | Highly tetrahedral amorphous carbon coating on glass |
| US6461731B1 (en) | 1999-05-03 | 2002-10-08 | Guardian Industries Corp. | Solar management coating system including protective DLC |
| US6312808B1 (en) | 1999-05-03 | 2001-11-06 | Guardian Industries Corporation | Hydrophobic coating with DLC & FAS on substrate |
| US6335086B1 (en) | 1999-05-03 | 2002-01-01 | Guardian Industries Corporation | Hydrophobic coating including DLC on substrate |
| US6280834B1 (en) | 1999-05-03 | 2001-08-28 | Guardian Industries Corporation | Hydrophobic coating including DLC and/or FAS on substrate |
| US6368664B1 (en) | 1999-05-03 | 2002-04-09 | Guardian Industries Corp. | Method of ion beam milling substrate prior to depositing diamond like carbon layer thereon |
| US6447891B1 (en) | 1999-05-03 | 2002-09-10 | Guardian Industries Corp. | Low-E coating system including protective DLC |
| US6277480B1 (en) | 1999-05-03 | 2001-08-21 | Guardian Industries Corporation | Coated article including a DLC inclusive layer(s) and a layer(s) deposited using siloxane gas, and corresponding method |
| DE10025465C2 (de) * | 1999-05-25 | 2003-03-27 | Eckhart Watzke | Lithiumoxidarmes Borosilicatglas und seine Verwendung |
| DE10027699B4 (de) * | 2000-06-03 | 2008-12-24 | Schott Ag | Borosilicatglas hoher chemischer Beständigkeit und dessen Verwendung |
| DE10035801B4 (de) | 2000-07-22 | 2008-04-03 | Schott Ag | Borosilicatglas hoher chemischer Beständigkeit und dessen Verwendungen |
| DE10238915B3 (de) * | 2002-08-24 | 2004-04-29 | Schott Glas | Borosilicatglas mit hoher hydrolytischer Beständigkeit und Verwendungen |
| DE10238930C1 (de) | 2002-08-24 | 2003-11-20 | Schott Glas | Borosilicatglas und seine Verwendungen |
| EP1426345A1 (en) * | 2002-12-03 | 2004-06-09 | Corning Incorporated | Borosilicate glass compositions and uses therof |
| US7488538B2 (en) * | 2005-08-08 | 2009-02-10 | Guardian Industries Corp. | Coated article including soda-lime-silica glass substrate with lithium and/or potassium to reduce sodium migration and/or improve surface stability and method of making same |
| CN100463634C (zh) * | 2007-07-20 | 2009-02-25 | 胡伟添 | 一种电饭煲用玻璃内胆及其加工工艺 |
| US9017991B2 (en) | 2009-03-13 | 2015-04-28 | Tufts University | Methods tip assemblies and kits for introducing material into cells |
| DE102010006331A1 (de) * | 2010-01-29 | 2011-08-04 | Schott Ag, 55122 | Aluminosilikatgläser mit hoher thermischer Beständigkeit, niedriger Verarbeitungstemperatur und hoher Kristallisationsbeständigkeit |
| US8973405B2 (en) | 2010-06-17 | 2015-03-10 | Johns Manville | Apparatus, systems and methods for reducing foaming downstream of a submerged combustion melter producing molten glass |
| US8769992B2 (en) | 2010-06-17 | 2014-07-08 | Johns Manville | Panel-cooled submerged combustion melter geometry and methods of making molten glass |
| US10322960B2 (en) | 2010-06-17 | 2019-06-18 | Johns Manville | Controlling foam in apparatus downstream of a melter by adjustment of alkali oxide content in the melter |
| US9032760B2 (en) | 2012-07-03 | 2015-05-19 | Johns Manville | Process of using a submerged combustion melter to produce hollow glass fiber or solid glass fiber having entrained bubbles, and burners and systems to make such fibers |
| US8991215B2 (en) | 2010-06-17 | 2015-03-31 | Johns Manville | Methods and systems for controlling bubble size and bubble decay rate in foamed glass produced by a submerged combustion melter |
| US8707740B2 (en) | 2011-10-07 | 2014-04-29 | Johns Manville | Submerged combustion glass manufacturing systems and methods |
| US8875544B2 (en) | 2011-10-07 | 2014-11-04 | Johns Manville | Burner apparatus, submerged combustion melters including the burner, and methods of use |
| US8997525B2 (en) | 2010-06-17 | 2015-04-07 | Johns Manville | Systems and methods for making foamed glass using submerged combustion |
| US9776903B2 (en) | 2010-06-17 | 2017-10-03 | Johns Manville | Apparatus, systems and methods for processing molten glass |
| US8707739B2 (en) | 2012-06-11 | 2014-04-29 | Johns Manville | Apparatus, systems and methods for conditioning molten glass |
| US9096452B2 (en) | 2010-06-17 | 2015-08-04 | Johns Manville | Methods and systems for destabilizing foam in equipment downstream of a submerged combustion melter |
| US9021838B2 (en) | 2010-06-17 | 2015-05-05 | Johns Manville | Systems and methods for glass manufacturing |
| US8973400B2 (en) | 2010-06-17 | 2015-03-10 | Johns Manville | Methods of using a submerged combustion melter to produce glass products |
| US8650914B2 (en) | 2010-09-23 | 2014-02-18 | Johns Manville | Methods and apparatus for recycling glass products using submerged combustion |
| DE202010014985U1 (de) | 2010-10-30 | 2010-12-30 | Schott Ag | Bororsilicatglas hoher chemischer Beständigkeit und geringer Entglasungsneigung |
| CN102178463A (zh) * | 2011-04-01 | 2011-09-14 | 胡伟添 | 一种电饭煲用玻璃内胆及其制作方法 |
| DE102011084543B4 (de) | 2011-10-14 | 2017-04-27 | Schott Ag | Borosilicatglas mit hoher hydrolytischer Beständigkeit |
| US10350139B2 (en) | 2011-10-25 | 2019-07-16 | Corning Incorporated | Pharmaceutical glass packaging assuring pharmaceutical sterility |
| WO2013063283A1 (en) | 2011-10-25 | 2013-05-02 | Corning Incorporated | Delamination resistant pharmaceuticals glass containers containing active pharmaceutical ingredients |
| CA2966274C (en) | 2011-10-25 | 2020-02-18 | Corning Incorporated | Glass compositions with improved chemical and mechanical durability |
| CN109704566B (zh) | 2011-10-25 | 2022-08-26 | 康宁股份有限公司 | 具有改善的化学和机械耐久性的碱土金属铝硅酸盐玻璃组合物 |
| US9517966B2 (en) | 2011-10-25 | 2016-12-13 | Corning Incorporated | Glass compositions with improved chemical and mechanical durability |
| US11497681B2 (en) | 2012-02-28 | 2022-11-15 | Corning Incorporated | Glass articles with low-friction coatings |
| US10737973B2 (en) | 2012-02-28 | 2020-08-11 | Corning Incorporated | Pharmaceutical glass coating for achieving particle reduction |
| DE202013012666U1 (de) | 2012-02-28 | 2018-04-26 | Corning Incorporated | Glaserzeugnisse mit reibungsarmen Beschichtungen |
| US9533905B2 (en) | 2012-10-03 | 2017-01-03 | Johns Manville | Submerged combustion melters having an extended treatment zone and methods of producing molten glass |
| US10273048B2 (en) | 2012-06-07 | 2019-04-30 | Corning Incorporated | Delamination resistant glass containers with heat-tolerant coatings |
| US9034442B2 (en) | 2012-11-30 | 2015-05-19 | Corning Incorporated | Strengthened borosilicate glass containers with improved damage tolerance |
| WO2014055199A1 (en) | 2012-10-03 | 2014-04-10 | Johns Manville | Methods and systems for destabilizing foam in equipment downstream of a submerged combustion melter |
| JP2014088293A (ja) * | 2012-10-31 | 2014-05-15 | Nippon Electric Glass Co Ltd | 医薬用ガラス及び医薬用ガラス管 |
| US9227865B2 (en) | 2012-11-29 | 2016-01-05 | Johns Manville | Methods and systems for making well-fined glass using submerged combustion |
| US10117806B2 (en) | 2012-11-30 | 2018-11-06 | Corning Incorporated | Strengthened glass containers resistant to delamination and damage |
| US9849066B2 (en) | 2013-04-24 | 2017-12-26 | Corning Incorporated | Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients |
| US9707155B2 (en) | 2013-04-24 | 2017-07-18 | Corning Incorporated | Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients |
| US9707154B2 (en) | 2013-04-24 | 2017-07-18 | Corning Incorporated | Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients |
| US9700486B2 (en) | 2013-04-24 | 2017-07-11 | Corning Incorporated | Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients |
| US9603775B2 (en) | 2013-04-24 | 2017-03-28 | Corning Incorporated | Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients |
| US9707153B2 (en) | 2013-04-24 | 2017-07-18 | Corning Incorporated | Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients |
| US9713572B2 (en) | 2013-04-24 | 2017-07-25 | Corning Incorporated | Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients |
| US9717648B2 (en) | 2013-04-24 | 2017-08-01 | Corning Incorporated | Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients |
| US9700485B2 (en) | 2013-04-24 | 2017-07-11 | Corning Incorporated | Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients |
| US9839579B2 (en) | 2013-04-24 | 2017-12-12 | Corning Incorporated | Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients |
| US9717649B2 (en) | 2013-04-24 | 2017-08-01 | Corning Incorporated | Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients |
| DE202013011766U1 (de) | 2013-04-26 | 2014-09-30 | Schott Ag | Borosilikatglas mit verbesserter hydrolytischer Beständigkeit zur bevorzugten Verwendung im Pharmabereich |
| US10138151B2 (en) | 2013-05-22 | 2018-11-27 | Johns Manville | Submerged combustion burners and melters, and methods of use |
| US10654740B2 (en) | 2013-05-22 | 2020-05-19 | Johns Manville | Submerged combustion burners, melters, and methods of use |
| US9777922B2 (en) | 2013-05-22 | 2017-10-03 | Johns Mansville | Submerged combustion burners and melters, and methods of use |
| US10131563B2 (en) | 2013-05-22 | 2018-11-20 | Johns Manville | Submerged combustion burners |
| PL2999923T3 (pl) | 2013-05-22 | 2019-02-28 | Johns Manville | Piec do topienia ze spalaniem pod powierzchnią cieczy z udoskonalonym palnikiem oraz odpowiadający sposób |
| EP3003997B1 (en) | 2013-05-30 | 2021-04-28 | Johns Manville | Submerged combustion burners with mixing improving means for glass melters, and use |
| PL3003996T3 (pl) | 2013-05-30 | 2020-12-28 | Johns Manville | Układy do topienia szkła ze spalaniem zanurzeniowym i sposoby ich zastosowania |
| JP6301176B2 (ja) * | 2014-04-01 | 2018-03-28 | クラレノリタケデンタル株式会社 | ガラスセラミック組成物及びガラスセラミック焼結体 |
| MX2017002898A (es) | 2014-09-05 | 2017-10-11 | Corning Inc | Artículos de vidrio y métodos para mejorar la confiabilidad de artículos de vidrio. |
| WO2016085867A1 (en) | 2014-11-26 | 2016-06-02 | Corning Incorporated | Methods for producing strengthened and durable glass containers |
| JP6532225B2 (ja) * | 2014-12-03 | 2019-06-19 | クラレノリタケデンタル株式会社 | ガラス材料及び歯科用補綴物 |
| WO2016093176A1 (ja) * | 2014-12-10 | 2016-06-16 | 日本電気硝子株式会社 | 医薬品容器用ガラス及び医薬容器用ガラス管 |
| US9751792B2 (en) | 2015-08-12 | 2017-09-05 | Johns Manville | Post-manufacturing processes for submerged combustion burner |
| US10041666B2 (en) | 2015-08-27 | 2018-08-07 | Johns Manville | Burner panels including dry-tip burners, submerged combustion melters, and methods |
| US10670261B2 (en) | 2015-08-27 | 2020-06-02 | Johns Manville | Burner panels, submerged combustion melters, and methods |
| US9815726B2 (en) | 2015-09-03 | 2017-11-14 | Johns Manville | Apparatus, systems, and methods for pre-heating feedstock to a melter using melter exhaust |
| US9982884B2 (en) | 2015-09-15 | 2018-05-29 | Johns Manville | Methods of melting feedstock using a submerged combustion melter |
| US10837705B2 (en) | 2015-09-16 | 2020-11-17 | Johns Manville | Change-out system for submerged combustion melting burner |
| US10081563B2 (en) | 2015-09-23 | 2018-09-25 | Johns Manville | Systems and methods for mechanically binding loose scrap |
| EP3150564B1 (en) | 2015-09-30 | 2018-12-05 | Corning Incorporated | Halogenated polyimide siloxane chemical compositions and glass articles with halogenated polylmide siloxane low-friction coatings |
| US10144666B2 (en) | 2015-10-20 | 2018-12-04 | Johns Manville | Processing organics and inorganics in a submerged combustion melter |
| BR112018008744B1 (pt) | 2015-10-30 | 2022-09-06 | Corning Incorporated | Artigos de vidro com revestimento de óxido metálico e polímero misto |
| DE102016101090A1 (de) | 2015-11-26 | 2017-06-01 | Schott Ag | Thermisch vorgespanntes Glaselement und seine Verwendungen |
| US10246362B2 (en) | 2016-06-22 | 2019-04-02 | Johns Manville | Effective discharge of exhaust from submerged combustion melters and methods |
| US10301208B2 (en) | 2016-08-25 | 2019-05-28 | Johns Manville | Continuous flow submerged combustion melter cooling wall panels, submerged combustion melters, and methods of using same |
| US10337732B2 (en) | 2016-08-25 | 2019-07-02 | Johns Manville | Consumable tip burners, submerged combustion melters including same, and methods |
| US10196294B2 (en) | 2016-09-07 | 2019-02-05 | Johns Manville | Submerged combustion melters, wall structures or panels of same, and methods of using same |
| EP3299347B1 (de) * | 2016-09-22 | 2018-09-26 | Schott AG | Aluminium-freies borosilikatglas |
| US10233105B2 (en) | 2016-10-14 | 2019-03-19 | Johns Manville | Submerged combustion melters and methods of feeding particulate material into such melters |
| DE102016226030B4 (de) | 2016-12-22 | 2018-07-05 | Schott Ag | Bariumfreies Borosilicatglas |
| WO2018121491A1 (zh) | 2016-12-29 | 2018-07-05 | 广东东阳光药业有限公司 | 高耐化学性的硼硅酸盐玻璃及其应用 |
| RU2646246C1 (ru) * | 2017-02-27 | 2018-03-02 | Юлия Алексеевна Щепочкина | Стекло |
| US11958771B1 (en) | 2021-10-19 | 2024-04-16 | Schott Ag | Glass, glass article, method of making the glass, use of the glass and flash lamp comprising the glass |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE301821C (zh) * | ||||
| DE2756555C3 (de) * | 1977-12-19 | 1982-12-02 | Schott Glaswerke, 6500 Mainz | Thermisch vorspannbare Gläser mit hoher Temperaturwechselfestigkeit und Wärmedehnungskoeffizienten im Temperaturbereich von 20 bis 300°C von 33,9 bis 53,2 mal 10↑-↑↑7↑/°C auf der Basis SiO↓2↓-B↓2↓O↓3↓-Al↓2↓O↓3↓-Na↓2↓O |
| US4386164A (en) * | 1981-12-14 | 1983-05-31 | Owens-Illinois, Inc. | Barium-free Type I, Class B laboratory soda-alumina-borosilicate glass |
| GB8623214D0 (en) * | 1986-09-26 | 1986-10-29 | Pilkington Brothers Plc | Glass compositions |
| DE3722130A1 (de) * | 1987-07-02 | 1989-01-12 | Schott Glaswerke | Borosilikatglas |
| DD301821A7 (de) * | 1990-03-23 | 1994-04-07 | Jenaer Glaswerk Gmbh | Zirkonhaltiges borosilikatglas |
| JPH0474731A (ja) * | 1990-07-06 | 1992-03-10 | Nippon Electric Glass Co Ltd | 医薬用硼珪酸ガラス |
| GB9106086D0 (en) * | 1991-03-22 | 1991-05-08 | Pilkington Plc | Glass composition |
| DE4230607C1 (de) * | 1992-09-12 | 1994-01-05 | Schott Glaswerke | Chemisch und thermisch hochbelastbares, mit Wolfram verschmelzbares Borosilikatglas und dessen Verwendung |
| DE4335204C1 (de) * | 1993-10-15 | 1995-04-06 | Jenaer Glaswerk Gmbh | Reduzierend erschmolzenes Borosilikatglas mit hoher Transmission im UV-Bereich und guter hydrolytischer Beständigkeit und seine Verwendung |
| DE4430710C1 (de) * | 1994-08-30 | 1996-05-02 | Jenaer Glaswerk Gmbh | Borsäurearmes Borosilikatglas und seine Verwendung |
| FR2728557A1 (fr) * | 1994-12-27 | 1996-06-28 | Corning France | Nouveaux verres et lentilles ophtalmiques |
-
1995
- 1995-09-30 DE DE19536708A patent/DE19536708C1/de not_active Expired - Fee Related
-
1996
- 1996-09-17 JP JP26503896A patent/JP4215176B2/ja not_active Expired - Lifetime
- 1996-09-21 EP EP96115187A patent/EP0765847B1/de not_active Expired - Lifetime
- 1996-09-21 ES ES96115187T patent/ES2135828T3/es not_active Expired - Lifetime
- 1996-09-21 DE DE59602322T patent/DE59602322D1/de not_active Expired - Lifetime
- 1996-09-26 BR BR9603894A patent/BR9603894A/pt not_active IP Right Cessation
- 1996-09-27 UA UA96093738A patent/UA55368C2/uk unknown
- 1996-09-27 RU RU96119747A patent/RU2127709C1/ru not_active IP Right Cessation
- 1996-09-27 HU HU9602656A patent/HU214878B/hu not_active IP Right Cessation
- 1996-09-30 AR ARP960104553A patent/AR003754A1/es unknown
- 1996-09-30 CN CN96113360A patent/CN1101348C/zh not_active Expired - Lifetime
- 1996-09-30 US US08/722,668 patent/US5736476A/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102578791A (zh) * | 2010-10-19 | 2012-07-18 | 波米奥利鲁吉股份公司 | 由包覆成型复合材料制造的制品及其相关的制备 |
| CN105263875A (zh) * | 2013-06-06 | 2016-01-20 | 日本电气硝子株式会社 | 药物容器用玻璃 |
| CN104261676A (zh) * | 2014-09-04 | 2015-01-07 | 东莞市长安东阳光铝业研发有限公司 | 一种中性硼硅玻璃及其应用 |
| CN104445926A (zh) * | 2014-11-07 | 2015-03-25 | 河北省沙河玻璃技术研究院 | 一种玻璃组合物及其制成的适合化学增强的硼硅酸盐玻璃 |
| CN106430953A (zh) * | 2016-08-31 | 2017-02-22 | 山东省药用玻璃股份有限公司 | 耐碱药用玻璃及其制备方法 |
| CN110683758A (zh) * | 2018-07-06 | 2020-01-14 | 肖特股份有限公司 | 具有提高的离子可交换性的玻璃 |
| CN110683758B (zh) * | 2018-07-06 | 2023-01-10 | 肖特股份有限公司 | 具有提高的离子可交换性的玻璃 |
| CN112028475A (zh) * | 2020-09-11 | 2020-12-04 | 成都光明光电股份有限公司 | 光学玻璃和光学元件 |
| CN112028474A (zh) * | 2020-09-11 | 2020-12-04 | 成都光明光电股份有限公司 | 光学玻璃 |
| CN113860729A (zh) * | 2021-10-25 | 2021-12-31 | 北京工业大学 | 一种中硼硅药用玻璃 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0765847A1 (de) | 1997-04-02 |
| JP4215176B2 (ja) | 2009-01-28 |
| BR9603894A (pt) | 1998-06-02 |
| JPH09118541A (ja) | 1997-05-06 |
| DE19536708C1 (de) | 1996-10-31 |
| AR003754A1 (es) | 1998-09-09 |
| EP0765847B1 (de) | 1999-06-30 |
| HU9602656D0 (en) | 1996-11-28 |
| HUP9602656A3 (en) | 1998-04-28 |
| CN1101348C (zh) | 2003-02-12 |
| HU214878B (hu) | 1998-07-28 |
| DE59602322D1 (de) | 1999-08-05 |
| ES2135828T3 (es) | 1999-11-01 |
| RU2127709C1 (ru) | 1999-03-20 |
| US5736476A (en) | 1998-04-07 |
| HUP9602656A2 (en) | 1997-04-28 |
| UA55368C2 (uk) | 2003-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1101348C (zh) | 含有氧化锆和氧化锂的具有高化学稳定性和低粘度的硼硅酸盐玻璃 | |
| CA1230349A (en) | Cladding glass for optical fiber | |
| CN1043987C (zh) | 玻璃纤维组合物 | |
| US4526874A (en) | Optical light weight glass with a refractive index of >1.70, an Abbe index of >22 and a density of <3.5 G/CM3 | |
| US4386163A (en) | Fluorophosphate optical glass | |
| DE69205370T2 (de) | Flache Anzeigevorrichtung mit einem Erdalkalialuminoborosilikat-Glassubstrat. | |
| JP2004083403A (ja) | ホウケイ酸ガラスおよびその使用 | |
| CN112811813B (zh) | 一种硼硅玻璃组合物、硼硅玻璃及其制备方法和应用 | |
| CA1183174A (en) | Thallium-containing optical glass | |
| CN1392868A (zh) | 高耐化学性的硼硅玻璃及其用途 | |
| CN1472154A (zh) | 无铅和优选无砷的镧重燧石玻璃 | |
| CN1200359A (zh) | 用于平面显示装置的铝硅酸盐玻璃 | |
| WO2002057195A1 (en) | Zinc phosphate glass compositions | |
| CN1099388C (zh) | 具有负向反常色散的光学玻璃 | |
| EP0559389A2 (en) | Alkali-free glass compositions | |
| JPH06199538A (ja) | ドープされた石英ガラス及びその製品 | |
| KR20050085384A (ko) | 붕규산 유리, 붕산염 및 결정성 붕소 함유 물질의 제조방법 | |
| JPH1143350A (ja) | 無アルカリガラス及びその製造方法 | |
| CN1105955A (zh) | 光学玻璃 | |
| CN1230395C (zh) | 无铅和无砷的性短燧石－特种玻璃 | |
| CN1155876A (zh) | 硼硅酸盐玻璃 | |
| CN107344813B (zh) | 包括耐化学性玻璃的医药包装 | |
| CN1286757C (zh) | 具有高水解稳定性的硼硅酸盐玻璃 | |
| SE429852B (sv) | Komposition for framstellning av glas med hogt brytningsindex | |
| CN101723585A (zh) | 具有高化学稳定性的硼硅酸盐玻璃及其应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SCHOTT AG Free format text: FORMER OWNER: SCHOTT-ROHRGLAS GMBH Effective date: 20120516 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20120516 Address after: Germany Mainz Patentee after: Schott AG Address before: German Bbe Roy Faith Patentee before: Schott-Rohrglas GmbH |
|
| CX01 | Expiry of patent term |
Granted publication date: 20030212 |
|
| EXPY | Termination of patent right or utility model |