CN1285326A - A kind of phosphate glass - Google Patents

A kind of phosphate glass Download PDF

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Publication number
CN1285326A
CN1285326A CN 00125304 CN00125304A CN1285326A CN 1285326 A CN1285326 A CN 1285326A CN 00125304 CN00125304 CN 00125304 CN 00125304 A CN00125304 A CN 00125304A CN 1285326 A CN1285326 A CN 1285326A
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glass
chemical stability
bao
cao
temperature
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CN1108279C (en
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程继健
梁文
周赛玉
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East China University of Science and Technology
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East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus

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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)
  • Glass Compositions (AREA)

Abstract

The present invention discloses a kind of phosphate glass, and is characterized by that three kinds of alkali metal oxides and mixture of CaO and BaO are introduced in the general glass, so the migration of alkali metal ion can be stopped, and the chemical stability of the glass can be raised, and then Al2O3, B2O3 and GeO2 also can be added accerding to a certain proportion so as to further raise the chemical stability of glass. Said invented glass not only possesses proper thermal expansion coefficient, low transition temp. and softening temp., but also possesses excellent chemical stability to make it applicable to precision die-pressing forming process, also can be used for making special optical glass with special refractive index and dispersion and various sealing glasses.

Description

A kind of phosphate glass
The present invention relates to a kind of phosphate glass.
As everyone knows, for most of silicate glasses, phosphate glass particularly alkali metal phosphate glass has higher thermal expansivity, therefore lower transition temperature and melt temperature can be used to that sealing-in has the metal or alloy of high thermal expansion coefficient such as aluminium, aluminium alloy, stainless steel etc. and as basic glass of preparation optical waveguide material or the like.Specifically, phosphate glass also is suitable for making non-spherical lens, a kind of best lens of handling laser beam with precise compression molding technology.Yet in actual application, phosphate glass is often owing to poor chemical stability is subjected to certain limitation.For this reason, relevant scientific worker improves its chemical stability by adjusting glass ingredient with on the basis that keeps the phosphate glass advantage, comparatively typically has:
(1) United States Patent (USP) P5153151 discloses a kind of phosphate glass, and its mole consists of Li 2O:0-15%, Na 2O:0-20%, K 2O:0-10%, ZnO:0-45%, Ag 2O:0-25%, Tl 2O:0-25%, PbO:0-20%, CuO:0-5%, CaO:0-20%, SrO:0-20%, P 2O 5: 24-36%, Al 2O 3: 0-5%, CeO 2: 0-2%, BaO:0-20%, SnO:0-5%, Sb 2O 3: 0-61%, Bi 2O 3: 0-10%, B 2O 3: 0-10%, the performance index that glass reached are: glass transformation temperature is 300-340 ℃, thermal expansivity is 135-180 * 10 -7/ ℃, specific refractory power is greater than 1.65, and glass is suitable for precise compression molding technology.The shortcoming of this glass is Tl 2O is the bigger univalent oxide of a kind of toxicity, and the introducing of CuO etc. makes glass coloring easily.
(2) Japanese Patent JP10316448 discloses a kind of phosphate glass, and its molar percentage is P 2O 5: 17-31%, B 2O 3: 0-7% (P 2O 5+ B 2O 319-31%), TeO 2: 10-25%, BaO:0-20%, Li 2O:0-6%, Na 2O:6-16% (Li 2O+Na 2O9-17%), Nd 2O 5: 19-50%, WO 3: 0-25%, the softening temperature of this glass are 560 ℃, and specific refractory power is 1.73, and Abbe number is 28.5, are suitable for low-temperature precise compression molding non-spherical lens etc.Yet, introduce Nd in this glass 2O 3Make glass coloring easily, a large amount of TeO 2And WO 3Introducing make the volatilization aggravation of glass, thereby cause the final component of glass to be difficult to control.
(3) United States Patent (USP) P5021366 discloses a kind of phosphate glass, its molar percentage Li 2O:5-10%, Na 2O:5-15%, K 2O:0-6%, ZnO:10-15%, CaO:0-20%, BaO:0-20%, SrO:0-20%, P 2O 5: 30-36%, Al 2O 3: 0-5%, CeO 2: 0-2%, SnO:0-20%, PbO:0-20%, Sb 2O 3: 0-12%, Bi 2O 3: 0-6%, the performance index that glass reached are: glass transformation temperature is 300-340 ℃, thermal expansivity is 145-170 * 10 -7/ ℃, specific refractory power is 1.605, glass is suitable for precise compression molding technology.Yet, by our wherein CeO that experiment showed, 2The introducing amount can not be up to 2%, otherwise can cause the devitrification and the scum silica frost of glass.
The objective of the invention is to disclose the novel phosphate glass of a class, this glass not only has higher thermal expansion coefficient, low transition temperature and softening temperature, also has higher chemical stability, can be applicable to precise compression molding technology preferably.
Design of the present invention is as follows:
The contriver is on the basis of being engaged in the phosphate glass research work for a long time, by repeatedly practising, be found to be and make phosphate glass have higher thermal expansion coefficient, low softening temperature and the high chemical stability of changing, can form by adjusting glass, and utilize the synergy of the following aspects to reach.At first, introduced three kinds of alkalimetal oxides in the glass, produced " polybase effect "; Secondly, add the mixture of a certain proportion of CaO and BaO, cause " constraining effect " of glass, these two kinds of effects have all played and stoped the effect of the migration of alkalimetal ion, thereby have improved the chemical stability of glass, and are last, certain proportion Al 2O 3And B 2O 3Mixing introduce and GeO 2Introducing will further improve the chemical stability of glass.
The component of the said glass of the present invention and molar content are: Li 2O+Na 2O+K 2O 10～40%, wherein: Li 2O: Na 2O: K 2O=1: (1～4): 1ZnO 10～40%CaO+BaO 10～30%, wherein: CaO: BaO=1: (1～4) Sb 2O 30～10%Al 2O 3+ B 2O 3In 1～10%: Al 2O 3: B 2O 31: (1～5) GeO 20～10%P 2O 520～60%F 0～5%.Through a large amount of experiments, preferred ingredients and molar content are: Li 2O+Na 2O+K 2O 15～30%, wherein: Li 2O: Na 2O: K 2O=1: (2～3): 1ZnO 20～30%CaO+BaO 10～20%, wherein: CaO: BaO=1: (2～3) Sb 2O 30～5%Al 2O 3+ B 2O 31～5%, wherein: Al 2O 3: B 2O 3=1: (1～4) GeO 20～5%P 2O 530～50%F 0～1%.Best component and molar content are: Li 2O 6%Na 2O 7%K 2O 5%ZnO 23.8%BaO 3.8%CaO 10.3%Sb 2O 34%Al 2O 30.4%B 2O 31.3%F 0.2%GeO 20.1%P 2O 538.1%; And: Li 2O 6%Na 2O 8%K 2O 5%ZnO 23%BaO 4.3%CaO 10.2%Sb 2O 34%Al 2O 30.4%B 2O 30.4%F 0.1%GeO 20.2%P 2O 538.4%; Or: Li 2O 6%Na 2O 8%K 2O 5%ZnO 23.4%BaO 4%CaO 11%Sb 2O 34%Al 2O 30.4%B 2O 30.6%F 0.1%GeO 20.2%P 2O 537.3%.
The melting method of glass carries out in two steps, is summarized as follows:
(1) pre-treatment of raw material.Consider the volatility of phosphoric acid, the introducing mode of Vanadium Pentoxide in FLAKES has been carried out a series of research.The contrast experiment finds, with solid metaphosphoric acid (HPO 3) when introducing, raw material is easy to deliquescence, the weighing poor accuracy is difficult for pulverizing, have no way of uniform mixing and be heated and during fusion of powder when it, and the generation demixing phenomenon, volatilization loss is big.With phosphoric acid (H 3PO 4) impouring powder and directly founding, because phosphoric acid salt forms not exclusively, free phosphoric acid is easy to volatilization, and easily infiltrates when low temperature in the pore of sidewall of crucible, reinforcement is to the erosion of refractory materials, and produced moisture behind the phosphoric acid chemical reaction, causes foamed phenomenon.As for synthetic phosphoric acid salt,, often can not make required glass ingredient because the content of Vanadium Pentoxide in FLAKES is higher in the glass.Discover, the most favourable with partial synthesis phosphoric acid salt and the common introducing of Vanadium Pentoxide in FLAKES to founding of glass.The preprocessing process of raw material is as follows: carry out accurate weighing by glass formula, and load weighted raw material stirring is even, in the quartz crucible of packing into, in retort furnace, be warming up to 180～250 ℃ with 1～2 ℃/min of temperature rise rate slowly, be incubated 4 hours.The purpose of raw materials pretreatment is the moisture of introducing in the raw material in order to remove (some raw material such as Vanadium Pentoxide in FLAKES be the moisture absorption very easily); Make the raw material pre-reaction, prevent the excessive volatilization of Vanadium Pentoxide in FLAKES in the high temperature melting process of next step glass.The blocks of solid of thermal treatment gained promptly can be used for founding after crushed.
(2) glass founds.After the raw materials pretreatment, from quartz crucible, take out pulverizing and be ground to certain fineness, found.Glass melting temperature is 800 ℃～1000 ℃, and soaking time is 2～4 hours, and annealing temperature is 280～350 ℃, and annealing time is 2～4 hours.The tentative experimental result of founding shows, during about 900 ℃ of phosphate glass, viscosity has reached the required numerical value of clarification, is the volatilization that reduces Vanadium Pentoxide in FLAKES, and in conjunction with the characteristics of phosphate glass, it is suitable taking to found fast.The result shows that also when soaking time was no more than 1 hour, the glass of founding gained had defectives such as scum silica frost, calculus and bubble.When in the time of 900 ℃, prolonging more than the soaking time to 2 hour, can eliminate above-mentioned phenomenon substantially.When cast molding, glass is easy to explosion, must the preheating mould.Place the glass block on the quartz plate to place the temperature control holding furnace to anneal, annealing schedule is 12～15 ℃/hour.
The thermal expansivity of glass, transition temperature, softening temperature and specific refractory power all are to adopt the conventional test methodologies of glass industry to test.The chemical stability of glass is that mentioned standard compares among the reference United States Patent (USP) P5021366, if glass soaks percentage loss of weight after 6 hours less than 0.1% and at 60 ℃ in 100 ℃ of deionized waters, place 500 hours basic no changes of rear surface pattern under 100% humidity, then show the chemical stability of this glass.
Phosphate glass of the present invention is on the basis of a large amount of experiments, with the theory is according to the novel phosphate glass of creating of a class, test result shows, not only have suitable thermal expansivity, low transition temperature and softening temperature, also has excellent chemical stability, be applicable to precise compression molding technology fully, also different with the phosphate glass component of foreign patent, thereby broken the constraint of traditional glass moulding process, the opticglass that can also be used for special specific refractory power of requirement and chromatic dispersion, fields such as extraordinary seal glass have market development prospect widely.
Below will be by further illustrating related content of the present invention in conjunction with the embodiments, but embodiment does not limit its protection domain:
Embodiment 1
According to the accurate raw materials weighing of ratio of components shown in the table 1, pre-sintering temperature is 200 ℃, and the time is 4 hours, and cooling is founded after grinding.Glass melting temperature is 910 ℃, and soaking time is 3 hours, found finish after, melten glass is taken out mould top casting moulding in preheating, put into the temperature control holding furnace subsequently and anneal, annealing temperature is 330 ℃, annealing time is 3 hours.Glass after the annealing is product of the present invention.
The sample (being conventional technical requirements) that glass specimen cutting, grinding, polishing is had certain thickness and diameter.The test result of glass properties is shown in table 2.
Embodiment 2
According to the accurate raw materials weighing of ratio of components shown in the table 1, except pre-sintering temperature is 190 ℃, glass melting temperature is 900 ℃, and soaking time is 2.5 hours, and annealing temperature is 320 ℃, and annealing time is outside 2 hours, and all the other are identical with embodiment 1.Testing method is identical with embodiment 1, the results are shown in table 2.
Embodiment 3
According to the accurate raw materials weighing of ratio of components shown in the table 1, except pre-sintering temperature is 210 ℃, glass melting temperature is 920 ℃, and soaking time is 3.5 hours, and annealing temperature is 330 ℃, and annealing time is outside 3 hours, and all the other are identical with embodiment 1.Testing method is identical with embodiment 1, the results are shown in table 2.
Glass ingredient (mol%) Embodiment 1 Embodiment 2 Embodiment 3
????Li 2O ????6 ????6 ????6
????Na 2O ????7 ????8 ????8
????K 2O ????5 ????5 ????5
????ZnO ????23.8 ????23 ????23.4
????BaO ????3.8 ????4.3 ????4
????CaO ????10.3 ????10.2 ????11
????Sb 2O 3 ????4 ????4 ????4
????Al 2O 3 ????0.4 ????0.4 ????0.4
????B 2O 3 ????1.3 ????0.4 ????0.6
????F ????0.2 ????0.1 ????0.1
????GeO 2 ????0.1 ????0.2 ????0.2
????P 2O 5 ????38.1 ????38.4 ????37.3
Table 1
Glass properties Embodiment 1 Embodiment 2 Embodiment 3
Specific refractory power (n D) 1.600 1.600 1.603
Thermal expansivity (10 -7/℃，30-300℃) 152 149 145
Glass transformation temperature (℃) 313 318 321
Glass chemistry stability (weightless %) 0.084 0.072 0.032
Surface topography The surface no change The surface no change The surface no change
Table 2

Claims (5)

1. a kind of phosphate glass is characterized in that, the component of glass and molar content are:
Li 2O+Na 2O+K 2O 10～40%, wherein: Li 2O: Na 2O: K 2O=1: (1～4): 1
ZnO??????????????????10～40％
CaO+BaO 10～30%, wherein: CaO: BaO=1: (1～4)
Sb 2O 3??????????????0～10％
Al 2O 3+ B 2O 31～10%, wherein: Al 2O 3: B 2O 3=1: (1～5)
GeO 2????????????????0～10％
P 2O 5???????????????20～60％
F????????????????????0～5％。
2. glass as claimed in claim 1 is characterized in that, component and molar content are:
Li 2O+Na 2O+K 2O 15～30%, wherein: Li 2O: Na 2O: K 2O=1: (2～3): 1
ZnO??????????????????20～30％
CaO+BaO 10～20%, wherein: CaO: BaO=1: (2～3)
Sb 2O 3??????????????0～5％
Al 2O 3+ B 2O 315%, wherein: Al 2O 3: B 2O 3=1: (1～4)
GeO 2????????????????0～5％
P 2O 5???????????????30～50％
F????????????????????0～1％。
3. glass as claimed in claim 2 is characterized in that, component and molar content are:
Li 2O????????????????6％
Na 2O????????????????7％
K 2O?????????????????5
ZnO??????????????????2
BaO??????????????????3
CaO??????????????????10.3％
Sb 2O 3??????????????4％
Al 2O 3??????????????0.4％
B 2O 3???????????????1.3％
F????????????????????0.2％
GeO 2????????????????0.1％
P 2O 5???????????????38.1％。
4. glass as claimed in claim 2 is characterized in that, component and molar content are:
Li 2O????????????????6％
Na 2O????????????????8％
K 2O?????????????????5％
ZnO??????????????????23％
BaO??????????????????4.3％
CaO??????????????????10.2％
Sb 2O 3??????????????4％
Al 2O 3??????????????0.4％
B 2O 3???????????????0.4％
F????????????????????0.1％
GeO 2????????????????0.2％
P 2O 5???????????????38.4％。
5. glass as claimed in claim 2 is characterized in that, component and molar content are:
Li 2O????????????????6％
Na 2O????????????????8％
K 2O?????????????????5％
ZnO??????????????????23.4％
BaO??????????????????4％
CaO??????????????????11％
Sb 2O 3??????????????4％
Al 2O 3??????????????0.4％
B 2O 3???????????????0.6％
F????????????????????0.1％
GeO 2????????????????0.2％
P 2O 5???????????????37.3％。
CN00125304A 2000-09-21 2000-09-21 A kind of phosphate glass Expired - Fee Related CN1108279C (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1304315C (en) * 2002-02-20 2007-03-14 株式会社小原 Optical glass
CN100432662C (en) * 2004-10-29 2008-11-12 Tdk株式会社 Carbon dioxide sensor
CN101070222B (en) * 2007-06-16 2010-12-01 河北理工大学 Phosphorus silicate yellow-green long afterglow glass and preparing method
CN1867521B (en) * 2003-10-17 2011-01-12 雷克特本克斯尔荷兰有限公司 Water-soluble glass composition
CN102211870A (en) * 2011-04-11 2011-10-12 金招娣 Leadless low melting point phosphate glass
CN104402219A (en) * 2014-11-10 2015-03-11 湖北新华光信息材料有限公司 Preparation method of phosphate optical glass and phosphate optical glass produced by the preparation method
CN106746611A (en) * 2017-01-05 2017-05-31 中国科学院上海光学精密机械研究所 With the larger phosphate laser neodymium glass for bearing hot light path coefficient and high-gain
CN116477839A (en) * 2023-03-13 2023-07-25 华南理工大学 Low-dielectric phosphate glass suitable for high-frequency microwave communication and preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5122484A (en) * 1991-05-23 1992-06-16 Corning Incorporated Zinc phosphate low temperature glasses

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1304315C (en) * 2002-02-20 2007-03-14 株式会社小原 Optical glass
CN1867521B (en) * 2003-10-17 2011-01-12 雷克特本克斯尔荷兰有限公司 Water-soluble glass composition
CN100432662C (en) * 2004-10-29 2008-11-12 Tdk株式会社 Carbon dioxide sensor
CN101070222B (en) * 2007-06-16 2010-12-01 河北理工大学 Phosphorus silicate yellow-green long afterglow glass and preparing method
CN102211870A (en) * 2011-04-11 2011-10-12 金招娣 Leadless low melting point phosphate glass
CN104402219A (en) * 2014-11-10 2015-03-11 湖北新华光信息材料有限公司 Preparation method of phosphate optical glass and phosphate optical glass produced by the preparation method
CN104402219B (en) * 2014-11-10 2017-02-15 湖北新华光信息材料有限公司 Preparation method of phosphate optical glass and phosphate optical glass produced by the preparation method
CN106746611A (en) * 2017-01-05 2017-05-31 中国科学院上海光学精密机械研究所 With the larger phosphate laser neodymium glass for bearing hot light path coefficient and high-gain
CN116477839A (en) * 2023-03-13 2023-07-25 华南理工大学 Low-dielectric phosphate glass suitable for high-frequency microwave communication and preparation method and application thereof

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