CN1038498C - 玻璃组合物 - Google Patents
玻璃组合物 Download PDFInfo
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- CN1038498C CN1038498C CN93119049A CN93119049A CN1038498C CN 1038498 C CN1038498 C CN 1038498C CN 93119049 A CN93119049 A CN 93119049A CN 93119049 A CN93119049 A CN 93119049A CN 1038498 C CN1038498 C CN 1038498C
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- 239000011521 glass Substances 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 239000005355 lead glass Substances 0.000 claims abstract description 21
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 9
- 230000004927 fusion Effects 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- -1 refractive index Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0028—Compositions for glass with special properties for crystal glass, e.g. lead-free crystal glass
-
- 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
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S501/00—Compositions: ceramic
- Y10S501/90—Optical glass, e.g. silent on refractive index and/or ABBE number
- Y10S501/903—Optical glass, e.g. silent on refractive index and/or ABBE number having refractive index less than 1.8 and ABBE number less than 70
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Glass Compositions (AREA)
- Table Devices Or Equipment (AREA)
Abstract
本发明提供完全不含铅,而密度和光的折射率、色散值等与已往的含铅晶质玻璃相等或较高的玻璃组合物,以重量百分比计,含SiO250-60%、K2O5-13%、TiO25-8%、BaO10-15%、ZnO5-10%、Na2O3-10%、CaO1-5%、Sb2O30.3-0.8%。
Description
本发明是涉及不含铅但仍为晶质玻璃组合物的适用于食具等的玻璃组合物。
以往作为在食具等上使用的晶质玻璃,一般使用含铅的晶质玻璃。这种玻璃中含铅量高,其特性即“有重量感”、“光的折射率高、色散大”、“易熔融”等特性主要可能是由于PbO的缘故。PbO的含量各异,按重量百分比一般约为24~26%。
但是,对人体特别有害的铅从含铅晶质玻璃溶出这一点最近成了问题,例如在***合众国加利福尼亚州,对于供食具、细颈盛水瓶等使用的铅晶质玻璃,公共机关以“未对铅接触作出明确警告”被起诉,因而该国FDA(食品和药品管理委员会)标准中,铅溶出量的限制值被重新作了严格规定。
在日本国内,“食品卫生法厚生省告示第84号”中对含铅晶质玻璃的铅溶出量作了限制,含铅晶质玻璃制品厂商即使是PbO含量为24~26%以内的含铅晶质玻璃,也按未超过限制值的标准来制造,但估计此限制值在国内也将越来越变得严格起来。
因此,为抑制从含铅晶质玻璃溶出铅,日本专利公开平3-205325号公报上记载的技术中,用以氧化硅为主成分的保护膜涂复含铅晶质玻璃食具的表面,但由于在玻璃加工后必须再作二次加工,制造费用的升高是不可避免的。
在日本专利公开平2-141434号公报上还揭示了用无铅玻离层涂复高级玻璃容器表面的技术,但因同时熔融两种玻璃并吹制成形,故存在成形效率低且不能压制成形等问题。
在日本专利公开平4-50133号公报上记载的技术通过限定相对于PbO、碱土类金属和ZnO总量的碱金属的添加量而减少铅溶出,但减少停留在约1/2的程度。
本发明的目的在于提供新型的玻璃组合物,它完全不含铅、与已往含铅晶质玻璃发挥同等或较高的含铅晶质玻璃所特有的“有重量感”、“光的折射率高、色散大”、“易熔融”的特性。
为了达到上述目的,本发明提供了具有与晶质玻璃类似性质但不含铅的玻璃组合物,它含有SiO2 50-60重量%、K2O 5-13重量%、TiO2 5-8重量%、BaO 10-15重量%、ZnO 5-10重量%、Na2O 3-10重量%、Sb2O3 0.3-0.8重量%。
本发明的玻璃组合物还可含有占组合物总重量1-5%的CaO。
本发明的玻璃组合物可进一步含有Li2O 0-1.0重量%、ZrO20-2.0重量%和B2O3 1.0-2.0重量%。
各成分的含量列于表1。要说明的是,%全部以重量百分比表示。
表1
成分 | 含有率Wt% |
SiO2 | 50.0-60.0 |
CaO | 1.0-5.0 |
BaO | 10.0-15.0 |
Na2O | 3.0-10.0 |
K2O | 5.0-13.0 |
Li2O | 0-1.0 |
TiO2 | 5.0-8.0 |
ZnO | 5.0-10.0 |
ZrO2 | 0-2.0 |
B2O3 | 1.0-2.0 |
Sb2O3 | 0.3-0.8 |
在本发明中,使用TiO2和BaO作替代PbO的原料,在用TiO2时光的折射率和色散增大,在用BaO时密度和折射率增大。
TiO2具有同时增大折光率和色散(阿贝数变小)的效果,在本发明中作为替代PbO的物质是必不可少的。TiO2不到5.0%时,不能达到折射率、色散的目的;若超过8.0%,带黄色的倾向增强,对于注重透明度的晶质玻璃来说不太适宜。
SiO2不足50.0%时,化学耐久性差;若超过60.0%,就有必要提高熔融温度,而且密度也降低。作为碱土类,合并使用BaO和CaO,但从密度变大这点及折光率变大这点出发,以BaO为好。BaO不足10.0%时,不能达到密度2.90%以上的目标。BaO超过15.0%,脱泡难以进行,而且炉材的侵蚀加剧,熔融变得困难。CaO具有降低高温下粘度的效果,为使作业温度范围内的固化速度加快,CaO以1.0-5.0%为宜。
为使熔融温度降低,使用碱成分即K2O、Na2O、Li2O。特别是,K2O具有抑制玻璃中杂质Fe离子发色的效果,是重要的成分。它在5.0%以下时这种效果减小,若超过13.0%,则耐火材料的侵蚀加剧。Na2O为补充降低熔融温度的效果,至少需加3.0%。若K2O和Na2O合计超过18.0%,玻璃的化学耐久性变差,因此必须控制在18.0%以下。添加微量Li2O,降低熔融温度的效果大,1.0%以下即足够。
ZnO使玻璃的硬度不提高及使化学耐久性增大,使粘性温度曲线平缓,具有容易进行成形作业的效果。其添加量在5.0-10.0%的范围内即足够。
由于B2O3的少量添加不提高热膨胀系数而有降低熔融温度的效果,因此添加1.0-2.0%。
Sb2O3作为低温熔融的配方的脱泡剂,即便0.3-0.8%的微量也有效。
ZrO2是为提高化学耐久性的目的而添加的,但由于玻璃的硬度大,对进行切割和研磨加工多的晶质玻璃来说不理想,因此其添加量有必要限于最小量。
根据以上各成分的作用,可得到充分满足诸如以下晶质玻璃必要条件的玻璃组合物:
1.表示重量感的物理性质值的密度为2.90g/cm3以上;
2.折光率Nd为1.55以上;
3.表示色散的物理性质值的阿贝数为47以下;
4.在1370-1380℃左右的低温下可容易地熔融;
5.考虑到作为食具使用的情况多,热膨胀系数可在100×10-7/℃以下。
另外,添加微量氧化铬等着色剂,当然也可制造着色晶质玻璃。
实施例
在白金坩埚中分别加入按表2所示玻璃配方配制而成的例1至例7的样品,在电炉内于1375℃温度熔融约6小时。然后,取出白金坩埚,将熔融玻璃流出到钢板上,在徐冷炉中缓慢冷却。然后,切出各测定用试样,测定密度、折光率、阿贝数、热膨胀系数。该测定结果列于表2中。
已往一般的含铅晶质玻璃密度为2.95-3.00g/cm3、折光率Nd为1.555-1.565、阿贝数为45-47、热膨胀系数为96-100×10-7/℃。
表2
成分·性质 | 例1 | 例2 | 例3 | 例4 | 例5 | 例6 | 例7 |
SiO2 | 54.95 | 54.60 | 51.15 | 51.80 | 50.10 | 55.50 | 55.20 |
CaO | 4.00 | 3.50 | 5.00 | 4.00 | 3.00 | 1.50 | 1.50 |
BaO | 12.00 | 12.50 | 14.00 | 13.00 | 14.50 | 13.00 | 13.30 |
Na2O | 3.00 | 3.50 | 3.00 | 5.00 | 3.00 | 6.00 | 9.50 |
K2O | 9.00 | 10.00 | 11.00 | 8.00 | 12.50 | 7.00 | 5.00 |
Li2O | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 | ||
TiO2 | 7.50 | 7.00 | 5.00 | 8.00 | 7.00 | 6.50 | 5.00 |
ZnO | 7.50 | 8.00 | 7.50 | 8.00 | 7.00 | 9.00 | 9.00 |
ZrO2 | 1.00 | 1.00 | 1.00 | ||||
B2O3 | 1.25 | 1.00 | 1.50 | 1.30 | 1.00 | 1.00 | 1.00 |
Sb2O3 | 0.30 | 0.40 | 0.35 | 0.40 | 0.40 | 0.50 | 0.50 |
密度(g/cm3) | 2.885 | 2.908 | 2.951 | 2.940 | 2.955 | 2.902 | 2.906 |
折光率Nd | 1.589 | 1.590 | 1.588 | 1.600 | 1.601 | 1.582 | 1.577 |
阿贝数 | 46.5 | 46.8 | 48.2 | 45.5 | 46.5 | 47.0 | 47.0 |
热膨胀率系数(×10-7/℃) | 92.6 | 97.0 | 101.4 | 98.3 | 105.5 | 94.3 | 99.5 |
按照本发明,可得到尽管完全不含铅,也保持与含铅晶质玻璃同等或同等以上的密度、折光率、色散值的晶质玻璃。而且,原料也比较廉价,此外由于在比较低温下可熔融,因而是经济的。
对铅的限制,不仅仅限于从玻璃制品溶出的问题,如果考虑到从原料调制到熔融炉的粉尘,烟雾飞散所致作业环境与公害这点,预料也会越来越严,则完全不含毒性极强的铅这一点是很大的优点。
Claims (3)
1.具有与晶质玻璃类似性质但不含铅的玻璃组合物,其特征在于:含有SiO2 50-60重量%、K2O 5-13重量%、TiO2 5-8重量%、BaO 10-15重量%、ZnO 5-10重量%、Na2O 3-10重量%、Sb2O3 0.3-0.8重量%。
2.如权利要求1所述的玻璃组合物,还含有CaO 1-5重量%。
3.如权利要求2所述的玻璃组合物,还含有Li2O 0-1.0重量%、ZrO2 0-2.0重量%和B2O3 1.0-2.0重量%。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP306222/92 | 1992-10-20 | ||
JP30622292 | 1992-10-20 | ||
JP183375/93 | 1993-06-30 | ||
JP5183375A JP2906104B2 (ja) | 1992-10-20 | 1993-06-30 | 鉛を含まないクリスタルなガラス組成物 |
Publications (2)
Publication Number | Publication Date |
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CN1086196A CN1086196A (zh) | 1994-05-04 |
CN1038498C true CN1038498C (zh) | 1998-05-27 |
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CN93119049A Expired - Fee Related CN1038498C (zh) | 1992-10-20 | 1993-10-20 | 玻璃组合物 |
Country Status (7)
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US (1) | US5376597A (zh) |
EP (1) | EP0594422B1 (zh) |
JP (1) | JP2906104B2 (zh) |
KR (1) | KR960010093B1 (zh) |
CN (1) | CN1038498C (zh) |
DE (1) | DE69311668T2 (zh) |
DK (1) | DK0594422T3 (zh) |
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US5694139A (en) * | 1994-06-28 | 1997-12-02 | Sony Corporation | Short-distance communication antenna and methods of manufacturing and using the short-distance communication antenna |
IT1268814B1 (it) * | 1994-12-13 | 1997-03-06 | Calp Spa | Miscela vetrificabile per vetri di qualita' |
DE19638380B4 (de) * | 1995-09-22 | 2004-11-04 | Murata Manufacturing Co., Ltd., Nagaokakyo | Verwendung einer Glasmasse mit einer niedrigen Dielektrizitätskonstante für Hochfrequenzstromkreise |
JP2881573B2 (ja) * | 1996-06-07 | 1999-04-12 | 東洋ガラス株式会社 | 鉛を含まないクリスタルなガラス組成物の製造方法 |
TW402579B (en) * | 1996-06-07 | 2000-08-21 | Toyo Glass K K | Production method for lead- free crystal glass composition |
CN1071288C (zh) * | 1997-07-31 | 2001-09-19 | 东洋玻璃株式会社 | 无铅晶体玻璃组合物的制备方法 |
CN1312778A (zh) * | 1998-08-14 | 2001-09-12 | 康宁股份有限公司 | 无铅玻璃 |
BR0300042A (pt) * | 2003-01-14 | 2004-10-13 | Cbmm Sa | Composições de vidro para a produção de peças de vidro isentas de chumbo |
CN101356127B (zh) * | 2006-05-19 | 2011-12-28 | 东洋佐佐木玻璃股份有限公司 | 水晶玻璃物品 |
ITFI20070291A1 (it) | 2007-12-28 | 2009-06-29 | Rcr Cristalleria Italiana S P | "vetro sonoro superiore senza piombo ad alta trasparenza ed alta brillantezza adatto per fusioni elettriche a coperta fredda con elettrodi in ossido di stagno" |
CN104108872B (zh) * | 2013-04-18 | 2019-09-17 | 成都光明光电股份有限公司 | 环保光学玻璃、玻璃预制件、光学元件及光学仪器 |
CN103524042B (zh) * | 2013-09-24 | 2016-06-01 | 河北省沙河玻璃技术研究院 | 一种环保型高透高折射晶质玻璃及其制备方法 |
CN105347687B (zh) * | 2015-11-30 | 2018-06-12 | 武汉理工大学 | 一种高折射率铜红晶质玻璃及其制备方法 |
CN105837045B (zh) * | 2016-03-18 | 2019-07-30 | 成都光明光电股份有限公司 | 晶质玻璃 |
CN109942184A (zh) * | 2019-04-12 | 2019-06-28 | 和县晶晶玻璃制品有限公司 | 一种高透高折射晶质玻璃及其生产工艺 |
CN110981189A (zh) * | 2020-01-08 | 2020-04-10 | 山东理工大学 | 一种氧化锌基无铅水晶玻璃及其制备方法 |
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FR2627768B1 (fr) * | 1988-02-29 | 1990-06-29 | Baccarat Cristalleries | Recipient en cristal traite pour empecher la migration du plomb vers son contenu |
JPH03205325A (ja) * | 1989-12-28 | 1991-09-06 | Hoya Corp | 鉛含有クリスタルガラス食器 |
JP2515041B2 (ja) * | 1990-06-15 | 1996-07-10 | 佐々木硝子株式会社 | 鉛溶出の少ないクリスタルガラス食器 |
JP2747938B2 (ja) * | 1990-08-03 | 1998-05-06 | 株式会社オハラ | 樹脂充填用ガラス |
SK277737B6 (en) * | 1991-05-08 | 1994-10-12 | Ladislav Sasek | Leadless crystal glass |
-
1993
- 1993-06-30 JP JP5183375A patent/JP2906104B2/ja not_active Expired - Fee Related
- 1993-10-11 KR KR1019930021024A patent/KR960010093B1/ko not_active IP Right Cessation
- 1993-10-20 US US08/138,062 patent/US5376597A/en not_active Expired - Fee Related
- 1993-10-20 DE DE69311668T patent/DE69311668T2/de not_active Expired - Fee Related
- 1993-10-20 DK DK93308367.7T patent/DK0594422T3/da active
- 1993-10-20 EP EP93308367A patent/EP0594422B1/en not_active Expired - Lifetime
- 1993-10-20 CN CN93119049A patent/CN1038498C/zh not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5860641A (ja) * | 1981-10-02 | 1983-04-11 | Nippon Electric Glass Co Ltd | ガラス繊維組成物 |
EP0500325A1 (en) * | 1991-02-19 | 1992-08-26 | Nippon Electric Glass Company., Ltd. | Chemically resistant glass fiber composition |
US5270269A (en) * | 1992-06-08 | 1993-12-14 | Corning Incorporated | Lead-free fine crystal glassware |
EP0575758A1 (en) * | 1992-06-08 | 1993-12-29 | Corning Incorporated | Lead-free fine crystal glassware |
US5468693A (en) * | 1993-12-10 | 1995-11-21 | Corning Incorporated | Lead-free glasses exhibiting characteristics of crystal |
Also Published As
Publication number | Publication date |
---|---|
CN1086196A (zh) | 1994-05-04 |
EP0594422A1 (en) | 1994-04-27 |
KR940009084A (ko) | 1994-05-16 |
KR960010093B1 (ko) | 1996-07-25 |
EP0594422B1 (en) | 1997-06-18 |
DK0594422T3 (da) | 1998-01-05 |
US5376597A (en) | 1994-12-27 |
JP2906104B2 (ja) | 1999-06-14 |
JPH06183774A (ja) | 1994-07-05 |
DE69311668T2 (de) | 1997-12-18 |
DE69311668D1 (de) | 1997-07-24 |
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