CN104909562A - High-refractivity environment-friendly ruby glass and preparation method thereof - Google Patents

High-refractivity environment-friendly ruby glass and preparation method thereof Download PDF

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CN104909562A
CN104909562A CN201510327691.0A CN201510327691A CN104909562A CN 104909562 A CN104909562 A CN 104909562A CN 201510327691 A CN201510327691 A CN 201510327691A CN 104909562 A CN104909562 A CN 104909562A
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glass
ruby
preparation
ruby glass
bao
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CN104909562B (en
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袁坚
程金树
彭志钢
杜晓欧
郑伟宏
楼贤春
姜倩
陈晖�
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Hebei shahe glass technology research institute
Wuhan University of Technology WUT
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Hebei shahe glass technology research institute
Wuhan University of Technology WUT
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Abstract

The invention relates to a high-refractivity environment-friendly ruby glass and a preparation method thereof. The ruby glass mainly comprises the following components in percentage by mass: 40-55% of SiO2, 10-20% of BaO, 7-20% of TiO2, 3-9% of ZnO, 0-5% of ZrO2, 2-5% of K2O, 1-9% of B2O3, 1-3% of CaO, 0.8-2.5% of CdS used as a colorant, 0.6-1.8% of Se powder used as a colorant and 0.1-0.5% of C powder used as a reducer. The glass solves the problem of influence of coloration of TiO2 on the glass color by using a special technique instead of any decolorant. The BaO and K2O are introduced in the form of carbonates, and no oxidizing atmosphere is introduced. The refractivity of the ruby glass is up to 1.62-1.7. The ruby glass is free of lead, arsenium and other harmful substances, and is free of expensive rare-earth oxides for regulating the refractivity and gloss of glass, thereby greatly saving the cost.

Description

A kind of high refraction environmental protection ruby glass and preparation method
Technical field
The present invention relates to a kind of high refraction environmental protection ruby glass and preparation method.
Technical background
Jewel obtains the reason valued of people and is not only that rare is expensive characteristic, be more its can present after processing polishing bright colour and from from different color and lusters, shown that it is magnificent and noble.Jewel rareness natural is after all limited, expensive, and the general population is difficult to accept.Just because of jewel price is high, imitative diamond material is occurred in a large number, the development of Industrial materials and production and processing technology thereupon, market occurs a large amount of imitative diamond material occurs, some is even enough to mix the spurious with the genuine, and the general population also can be allowed can to have bought the ornament matched in excellence or beauty with true jewel with lower price simultaneously.
Imitative cameo glass kind is more in the market, as lead crystal glass, milkiness and half emulsion opal glass etc., but containing lead crystal glass owing to there being higher lead tolerance, and in use there will be stripping problem, have impact on HUMAN HEALTH, in addition, various disease is caused by human body suction body after the volatilization of lead crystal glass in melting process enters air.Milkiness and half emulsion opal glass and cameo glass difference large, opaque, do not reach the effect of cameo glass.Imitative cameo glass quality is not high enough, uneven in the market, though there is better sample, as opticglass, is with high plumbous or rare earth for main component mostly, environmental problem and cost price very big.
Color crystal has been enriched constantly the kind of crystal glass, also its decorative effect is strengthened, serve very important effect, in addition national have unique liking to redness, the exploitation of red crystal glass will be main flow kind, but red crystal glass, particularly the red crystal glass of environment-friendly type height refraction is not also reported at present, the meaning of the red serial crystal of exploitation environmental protection height refraction is self-evident, and market outlook are very wide.
Patent CN101381202A discloses a kind of stibium-containing ruby glass formula and preparation method, though be environment-friendly type, but its specific refractory power is low, and color is pure not, is difficult to the cameo glass color effect reaching high-quality.
D. Shi Hualuo Shi Qi limited partnership of internationally famous crystal glass company application publication number CN 102858703 A, introduce a kind of red coloration glass and preparation method thereof, described red coloration glass comprises parent glass composition, color additive, reductive agent, stablizer, wherein said color additive has copper oxide and neodymium oxides, and wherein said reductive agent has tin-oxide, and wherein said stablizer has sb oxide, it is characterized in that, the content of described copper oxide in described red coloration glass is between 0.02-0.08 % by weight.But this kind of red glass specific refractory power is not high, and be difficult to reach the pure redness of cadmium sulfoselenide.
Summary of the invention
The object of the invention is to for above technical problem, one cadmium sulfoselenide painted height refraction environment-friendly type ruby glass and preparation method thereof is provided, the detrimental oxide such as the not leaded and arsenic of this ruby glass, its specific refractory power is up to 1.62-1.7, visible region transmitance is high, and chemical stability is good, bright-colored pure, quality better, can play good decorative effect.
The technical solution used in the present invention is as follows:
A kind of high refraction environmental protection ruby glass, comprise parent glass and tinting material, it comprises following component by percentage to the quality: SiO 240-55%, BaO 10-20%, TiO 27-20%, ZnO 3-9%, ZrO 20-5%, K 2o 2-5%, B 2o 31-9%, CaO1-3%.
Further, described ruby glass is also with accounting for the Se of CdS and 0.6-1.8% of described parent glass mass percent 0.8-2.5% as tinting material.
Further, described ruby glass is also by the atmosphere of C powder as reductive agent control glass smelting accounting for described parent glass mass percent 0.1-0.5%.
Preferably, TiO 2be 20-35% with the content sum of BaO, wherein BaO is entirely with BaCO 3introduce, K 2o is entirely with K 2cO 3introduce, TiO 2introduce with industrial chemical oxide form.
The preparation method of described ruby glass, is characterized in that its step is as follows:
(1) each component of precise;
(2) each for the parent glass mixed component is added platinum crucible stove at 1000 DEG C, rise to 1350-1450 DEG C of insulation 4h by the heat-up rate of 5 DEG C/min and found;
(3) glass melted is poured into shrend in 10-20 DEG C of clean water and become glass particle, move in 150 DEG C of baking ovens and dry;
(4) frit of having dried is added described tinting material CdS, Se and reductive agent C powder mixes, in platinum crucible, 1300-1350 DEG C of secondary founds 2h, stir in melting process, sealed crucible, after furnace temperature is down to 1250-1300 DEG C of insulation 0.5h after to pour forming mould into shaping, move in 450-550 DEG C of annealing furnace the 0.5-3h that anneals, close stove and cool.
Further, after step (4) terminates, prepared glass carries out secondary heating color development treatment more in the lehr, and color development treatment temperature is 650-750 DEG C, and the time is 0.5-2.5h.
Preferably, the temperature of founding in step (2) is 1350-1380 DEG C, and melting time is 3-3.5h.
Preferably, in step (4), Annealing Temperature of Glass is 480-520 DEG C, and annealing time is 0.5-1.5h.
Preferably, described secondary heating color development treatment temperature is 660-720 DEG C, and the treatment time is 0.5-2h.
Cameo glass composition all produces great impact to its quality or performance and cost.Glass ingredient and production technique substantial connection, usually assign to select production technique according to the one-tenth of design, Glass Composition Design is improper, causes fusing difficulty, when founding, the defects such as calculus, striped, bubble occurs, happen occasionally in actual production.Further, Glass Composition Design must consider processing performance needs.Usually make design glass ingredient reach and be easy to fusing, meet the operational requirements such as shaping, processing and annealing.Finally, the quality stability of raw material and a large amount of supply problem must be considered when design mix.
In said components, SiO 2be important network former, form irregular contiguous network with the structural component of silicon-oxy tetrahedron, become the skeleton of glass.It not only can form glass, and can improve the physical strength, chemical stability, thermostability etc. of glass, but it is again more infusibilized material, therefore SiO 2content has its optimum value.If content is lower than 40%, cannot obtain this effect fully, the poor chemical stability of glass, become glass difficulty, quality can not be guaranteed.On the other hand, if containing ratio is more than 55%, then the temperature of fusion of cameo glass is high, and viscosity rises, and is difficult to glass is homogenized.So SiO of the present invention 2content 45 ~ 53% is preferably suitable, is more preferably 48 ~ 52%.
K 2o is network modifying oxide, can make silicon-oxy tetrahedron ［ SiO after introducing 4the network that formed is lax, fracture, thus solve SiO 2infusibilized problem, can, as fusing assistant, make glass melting temperature decline, preferred mass mark more than 2%.When potassium oxide content is too low, cause glass to melt difficulty, and need the K adding necessary content during preparation carbuncle of the present invention 2o ensures the bright-coloured pure of color.Therefore in this cameo glass, potassium oxide should have suitable content, preferred K in the present invention 2o 2.5-5%, be more preferably 3-5%.
TiO 2, also can increase the dispersion of glass simultaneously, be the main oxides of alternative PbO in the present invention and essential.TiO 2content less than 7% time, the specific refractory power of glass does not reach requirement; If more than 20%, can glass coloring be made and devitrification of glass tendency becomes and is difficult to greatly control, owing to making glass yellow tendency strengthen to ultraviolet strong absorption, simultaneously TiO 2can make again the painted enhancing of the Fe in glass, this prepares carbuncle glass to cadmium sulfoselenide is disadvantageous.
BaO substitutes the main oxides of PbO in the present invention and essential, there is the effect increasing glass refraction and glass density, the matter double infection of refraction effect and crystal glass can not be reached less than 10%, BaO is more than 20%, and the deaeration of glass in thaw process is difficult to carry out, and aggravates the erosion of kiln refractory materials, melting becomes difficulty, glass defect increases, degradation, is difficult to the crystal glass arriving high-quality.
CaO has the effect reducing glass high temperature viscosity and increase glass low-temperature viscosity, and in the present invention, for making the curing speed in the range of working temperature of glass accelerate, glass material property lengthens, and CaO content is better at 1-3%, and preferred content is 1.5-2.5%.
Very crucial in ZnO the present invention, chemical stability and the thermostability of glass can be improved, the viscosity curve of glass is made to become mild, be conducive to glass and form operation, and the introducing of ZnO plays vital effect to the painted of cadmium sulfoselenide, mainly prevent the volatilization of tinting material Se and S, play a part fixing S and Se.The content of ZnO of the present invention is better in 3-9% effect, and preferred content is 6-9%.
B 2o 3mainly play the speed accelerating glass smelting and clarifying process in the present invention, but work as B 2o 3massfraction when being greater than 10%, manufacture red glass very difficult.B is introduced in the present invention 2o 3with boric acid as raw material, the glass that the color ratio borax of fusion cast glass is founded is more bright-coloured.
ZrO 2mainly play in glass of the present invention and improve glass refraction and chemical stability effect, add the crystallization that effectively can prevent glass in right amount simultaneously.
Tinting material CdS and Se prepares carbuncle glass neccessary composition, its consumption and ratio directly determine the bright-colored and pure of glass, tinting material too much can be caused to sink to crucible bottom, the few color of amount cannot show, but both ratios are also crucial, in the present invention, colorant concentrations CdS 0.8-2.5%, Se 0.6-1.8, CdS/Se are at 1/0.6-1/0.8.Reductive agent C mainly plays manufacture reducing atmosphere in the present invention, is conducive to the preparation of ruby glass, and in the present invention, the consumption of control C is at 0.1-0.5%.
The preparation of carbuncle glass of the present invention adopts secondary to found the melting quality ensureing glass, is fully mixed by color additive, in covered crucible, found a few hours with glass powder.
Embodiment
Embodiment 1
The height of the present embodiment reflects consisting of (mass percent) of environment-friendly type ruby glass: SiO 255%, BaO 20%, TiO 27%, ZnO 9%, ZrO 25%, K 2o 2%, B 2o 31%, CaO1%, additive adopts outer addition, tinting material CdS 2.5%, Se 1.8%, reductive agent C powder 0.3%.
The preparation method of the present embodiment height refraction environment-friendly type ruby glass is as follows:
(1) each component of precise parent glass mixing;
(2) each for the parent glass mixed component is added platinum crucible stove at 1000 DEG C, rise to 1400 DEG C of insulation 4h by the heat-up rate of 5 DEG C/min and found;
(3) glass melted is poured into shrend in 20 DEG C of clean water and become glass particle, move in 150 DEG C of baking ovens and dry;
(4) frit of having dried is added tinting material CdS, Se and reductive agent C powder to mix 1350 DEG C of secondaries in platinum crucible and found 2h, stir in melting process, sealed crucible, after furnace temperature is down to 1250 DEG C of insulation 0.5h after to pour forming mould into shaping, close stove cooling after moving in 550 DEG C of annealing furnaces the 1h that anneals;
(5) prepared glass is carried out secondary heating color development treatment after terminating by cooling more in the lehr, and colour developing thermal treatment temp is 750 DEG C, and the time is 0.5h.
The present embodiment height refraction environment-friendly type ruby glass is bright-colored pure, specific refractory power 1.63, transmitance 88%.
The weight percent of each component of embodiment 2-7 is in table 1, and its preparation method is basic identical with embodiment 1, and difference is only the change of each control condition shown in table, and concrete technology condition is in table 1.
Table 1

Claims (9)

1. a high refraction environmental protection ruby glass, comprises parent glass and tinting material, it is characterized in that described parent glass comprises following component by percentage to the quality: SiO 240-55%, BaO 10-20%, TiO 27-20%, ZnO 3-9%, ZrO 20-5%, K 2o 2-5%, B 2o 31-9%, CaO1-3%.
2. ruby glass according to claim 1, is characterized in that the additional Se accounting for CdS and 0.6-1.8% of described parent glass mass percent 0.8-2.5% is as tinting material.
3. ruby glass according to claim 2, is characterized in that the additional C powder accounting for described parent glass mass percent 0.1-0.5% controls the atmosphere of glass smelting as reductive agent.
4. ruby glass according to claim 1, is characterized in that TiO 2be 20-35% with the content sum of BaO, wherein BaO is entirely with BaCO 3introduce, TiO 2introduce with industrial oxidation titanium form.
5. the preparation method of the ruby glass described in claim 3 or 4, is characterized in that its step is as follows:;
(1) each component of precise;
(2) each for the parent glass mixed component is added platinum crucible stove at 1000 DEG C, rise to 1350-1450 DEG C of insulation 3-4h by the heat-up rate of 5 DEG C/min and found;
(3) glass melted is poured into shrend in 10-20 DEG C of clean water and become glass particle, move in 150 DEG C of baking ovens and dry to obtain frit;
(4) frit of having dried in step (3) is added described tinting material CdS, Se and reductive agent C powder mixes, in platinum crucible, 1300-1350 DEG C of secondary founds 2h, stir in melting process, sealed crucible, after furnace temperature is down to 1250-1300 DEG C of insulation 0.5h after to pour forming mould into shaping, move in 450-550 DEG C of annealing furnace the 0.5-3h that anneals, close stove and cool.
6. ruby glass preparation method according to claim 5, is characterized in that: after step (4) terminates, described parent glass carries out secondary heating color development treatment more in the lehr, and color development treatment temperature is 650-750 DEG C, and the time is 0.5-2.5h.
7. the ruby glass preparation method according to claim 5 or 6, is characterized in that: the temperature of founding in step (2) is 1350-1380 DEG C, and melting time is 3-3.5h.
8. the ruby glass preparation method according to claim 5 or 6, is characterized in that: in step (4), Annealing Temperature of Glass is 480-520 DEG C, and annealing time is 0.5-1.5h.
9. ruby glass preparation method according to claim 6, is characterized in that: described secondary heating color development treatment temperature is 660-720 DEG C, and the treatment time is 0.5-2h.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105347687A (en) * 2015-11-30 2016-02-24 武汉理工大学 High-refraction-index copper red crystal glass and preparation method thereof
CN107445481A (en) * 2017-09-08 2017-12-08 蚌埠玻璃工业设计研究院 A kind of anti-blue light high transmission glass and preparation method thereof
CN109761579A (en) * 2019-03-26 2019-05-17 成都奇彩珠宝有限公司 Height refraction, high density colour synthetic jewel
CN110143758A (en) * 2019-06-24 2019-08-20 鲁米星特种玻璃科技股份有限公司 A kind of synthetic sapphire jade glass and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0624793A (en) * 1992-05-28 1994-02-01 Toshinori Kokubu White opal glass transmitting red light and its production
CN101913762A (en) * 2010-08-12 2010-12-15 安徽盛世光学玻璃有限公司 Method for preparing superconcentrate glass pigment and color crystal glass plate
CN104445925A (en) * 2014-12-01 2015-03-25 河北省沙河玻璃技术研究院 Ultra-high-refractivity environment-friendly cameo glass and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0624793A (en) * 1992-05-28 1994-02-01 Toshinori Kokubu White opal glass transmitting red light and its production
CN101913762A (en) * 2010-08-12 2010-12-15 安徽盛世光学玻璃有限公司 Method for preparing superconcentrate glass pigment and color crystal glass plate
CN104445925A (en) * 2014-12-01 2015-03-25 河北省沙河玻璃技术研究院 Ultra-high-refractivity environment-friendly cameo glass and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105347687A (en) * 2015-11-30 2016-02-24 武汉理工大学 High-refraction-index copper red crystal glass and preparation method thereof
CN105347687B (en) * 2015-11-30 2018-06-12 武汉理工大学 A kind of high refractive index copper red crystal glass and preparation method thereof
CN107445481A (en) * 2017-09-08 2017-12-08 蚌埠玻璃工业设计研究院 A kind of anti-blue light high transmission glass and preparation method thereof
CN109761579A (en) * 2019-03-26 2019-05-17 成都奇彩珠宝有限公司 Height refraction, high density colour synthetic jewel
CN110143758A (en) * 2019-06-24 2019-08-20 鲁米星特种玻璃科技股份有限公司 A kind of synthetic sapphire jade glass and preparation method thereof
CN110143758B (en) * 2019-06-24 2022-05-17 鲁米星特种玻璃科技股份有限公司 Artificial sapphire jade glass and preparation method thereof

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