CN102701589A - Red germanate glass and preparation method thereof - Google Patents

Abstract

The invention discloses a red germanate glass which comprises the following oxide components in percentage by mol: 49-99% of GeO2, 0-35% of Li2O, 0-10% of Na2O, 0-10% of K2O, 0-9% of B2O3, 0-9% of Al2O3, 0-10% of MgO, 0-10% of CaO, 0-10% of BaO, 0-10% of Ta2O5, 0.01-5% of Bi2O3, 0-10% of ZnO and 0-10% of SrO. The invention also discloses a preparation method of the red germanate glass. By using the cheap bismuth as a colorant, the preparation process is simple and easy to implement, and the prepared red glass has the advantages of uniform coloration and high heat stability. The components can be adjusted to change the color of glass; and the invention is hopeful to be used in the fields of glasswork, optical filters, decorating materials and the like.

Description

A kind of red bismuth germanate glass and preparation method thereof

Technical field

The present invention relates to the glass preparation technology, particularly a kind of red bismuth germanate glass and preparation method thereof.

Background technology

Coloured glass has very widely in daily life to be used, for example at aspects such as door and window, ceramic tile glaze, finished faced material and artworks.The glass art works of exotic shape because the use of coloured glass more has expressive force and infectivity and become, bring different visual experience and life to experience to the audience.The pleasant perfume of fragrance, because the playing up of bottle moulding and glass colour, and show fully elegant and poised.Coloured glass also can be applicable to optical field such as spectral filter.Red glass in the coloured glass, because of its gorgeous color, especially noticeable.Existing red glass mainly contains: ruby gold ruby glass, orange red Containing Sulfur cadmium glass, large red contain cadmium selenide glass, brick-red copper glass, the bright cherry-red glass of Containing Sulfur antimony, pink and contain erbium glass.Except that contain erbium glass come from erbium ion absorb painted, other red glass are to come from semi-conductor or metallic colloid is painted basically.Found at mother glass, after the moulding, these glass need extra subsequent heat treatment, make these painted groups assemble, grow up, and with the difference of group size, can produce differing absorption to visible light, and then show as different redness.These red glass that what's frequently heard can be repeated in detail, otherwise adopt severe toxicity like cadmium, selenium, copper, antimony, sulphur, or adopt expensive metals like gold or rare earth ion, as coloring element.To based on the painted glass of colloid, need later stage thermal treatment, induce the glass colour developing.

Summary of the invention

In order to overcome the deficiency of prior art, the object of the present invention is to provide a kind of red bismuth germanate glass, with the bismuth of cheapness as tinting material.

Another object of the present invention is to provide the preparation method of red bismuth germanate glass, do not need the later stage additional heat treatment.

The object of the invention is realized through following technical scheme:

A kind of red bismuth germanate glass, the molar percentage of each oxide component is:

GeO ₂ 49~99%；

Li ₂O 0~35%；

Na ₂ O 0~10%；

K ₂O 0~10%；

B ₂O ₃ 0~9%；

Al ₂ O ₃ 0~9%；

MgO 0~10%；

CaO 0~10%；

BaO 0~10%；

Ta ₂ O ₅ 0~10%；

Bi ₂O ₃ 0.01~5%；

ZnO 0~10%；

SrO 0~10%。

A kind of preparation method of red bismuth germanate glass may further comprise the steps:

(1) molar percentage by each oxide component takes by weighing raw material:

GeO ₂ 49~99%；

Li ₂O 0~35%；

Na ₂ O 0~10%；

K ₂O 0~10%；

B ₂O ₃ 0~9%；

Al ₂ O ₃ 0~9%；

MgO 0~10%；

CaO 0~10%；

BaO 0~10%；

Ta ₂ O ₅ 0~10%；

Bi ₂O ₃ 0.01~5%；

ZnO 0~10%；

SrO 0~10%；

(2) load weighted raw material is placed on crucible and compacting through milling mixing in the step (1), is to found under 1300 ~ 1550 ° of C 15 minutes ~ 5 hours in temperature;

(3) melt that step (2) is obtained casts in the mould, and after the cooling, unrelieved stress is removed in annealing, promptly makes red bismuth germanate glass.

Said founding in the process stirred, and to remove bubble, improves the homogeneity of glass.

Compared with prior art, the present invention has the following advantages and beneficial effect:

(1) the present invention adopts bismuth as tinting material, and non-precious metal gold or rare earth ion or hypertoxic ion such as cadmium etc. are made tinting material, have reduced production cost;

(2) of the present inventionly utilize high-temperature melting method once shaped, colour developing, no longer need loaded down with trivial details thermal treatment control colloidal solid size colour developing of later stage, the preparation process is simple;

(3) the present invention can realize that through the adjustment component glass colour is pink, purplish red, orange red, reddish brown, interval variations such as wine is red, brown, black;

(4) red glass that makes of the present invention, uniform coloring, Heat stability is good, high temperature (600 ° of C) and handle nondiscoloration, put for a long time under the room temperature and do not move back or variable color.

Description of drawings

Fig. 1 sees through graphic representation for the typical case of the reddish-brown glass of present embodiment preparation.

Fig. 2 sees through graphic representation for the typical case of the red-purple glass of present embodiment preparation.

Fig. 3 sees through graphic representation for the typical case of the brown glass of present embodiment preparation.

Fig. 4 sees through graphic representation for the typical case of the pink glass of present embodiment preparation.

Embodiment

Below in conjunction with embodiment and accompanying drawing, the present invention is done to specify further, but embodiment of the present invention is not limited thereto, the processing parameter for not indicating especially can carry out with reference to routine techniques.

Embodiment

The preparation process of the red bismuth germanate glass of present embodiment is following:

(1) be raw material with germanium dioxide, Quilonum Retard, yellow soda ash, salt of wormwood, boron trioxide (or boric acid), Natural manganese dioxide, lime carbonate (or quicklime), Strontium carbonate powder (or strontium oxide), barium carbonate, aluminum oxide (or white lake), bismuthous oxide bismuth trioxide (or bismuth meal), tantalum pentoxide, zinc oxide; Press the mole described in the table 1 and form raw materials weighing, the control gross weight is 20g.

(2) load weighted raw material is placed on crucible and compacting through milling mixing in the step (1), founds according to the processing parameter described in the table 1; Found in the process and stir,, improve the homogeneity of glass to remove bubble;

(3) melt that step (2) is obtained casts in the mould, and after the cooling, unrelieved stress is removed in annealing, promptly makes red bismuth germanate glass.

Composition, processing parameter and the color of the glass sample of table 1 present embodiment preparation

The molar percentage (mol%) of forming the oxide compound of glass

Glass melting temperature/time

Glass colour

89GeO 2-10Ta 2O 5-1.0Bi 2O 3	1540 ° C/20 minute	Reddish brown
			79GeO 2-10Ta 2O 5-10Li 2O-1.0Bi 2O 3	1540 ° C/20 minute	Reddish brown
49GeO 2-10Ta 2O 5-35Li 2O-1.0Bi 2O 3	1400 ° C/5 hour	Reddish brown
			89.99GeO 2-10Ta 2O 5-0.01Bi 2O 3	1540 ° C/20 minute	Pink
89.95GeO 2-10Ta 2O 5-0.05Bi 2O 3	1540 ° C/20 minute	Purplish red
			79GeO 2-10Ta 2O 5-10Na 2O-1.0Bi 2O 3	1500 ° C/15 minute	Reddish brown
79GeO 2-10Ta 2O 5-10K 2O-1.0Bi 2O 3	1500 ° C/15 minute	Reddish brown
			94GeO 2-5Ta 2O 5-1.0Bi 2O 3	1550 ° C/20 minute	Reddish brown
89GeO 2-5Ta 2O 5-5.0Bi 2O 3	1500 ° C/15 minute	Reddish brown
			99GeO 2-1.0Bi 2O 3	1550 ° C/20 minute	Reddish brown
96GeO 2-3MgO-1.0Bi 2O 3	1550 ° C/20 minute	Reddish brown
			79GeO 2-9Ta 2O 5-1.0Na 2O-10MgO-1.0Bi 2O 3	1300 ° C/2 hour	Reddish brown
79GeO 2-5Ta 2O 5-4Al 2O 3-1.0Na 2O-10CaO-1.0Bi 2O 3	1500 ° C/15 minute	Wine is red
			79GeO 2-5Ta 2O 5-4Al 2O 3-1.0Na 2O-10ZnO-1.0Bi 2O 3	1500 ° C/15 minute	Reddish brown
79GeO 2-9B 2O 3-1.0K 2O-10SrO-1.0Bi 2O 3	1500 ° C/15 minute	Palm fibre
			79GeO 2-9Al 2O 3-1.0Na 2O-10BaO-1.0Bi 2O 3	1500 ° C/15 minute	Wine is red
79GeO 2-10Ga 2O 3-1.0B 2O 3-9BaO-1.0Bi 2O	1500 ° C/15 minute	Palm fibre
			87GeO 2-4B 2O 3-1.0Ga 2O 3-5.0CaO-1.0SrO-10ZnO-1.0Bi 2O 3	1500 ° C/15 minute	Reddish brown
84GeO 2-4B 2O 3-1.0Ga 2O 3-10.0ZnO-1.0Bi 2O 3	1500 ° C/15 minute	Reddish brown

Fig. 1 can know that by figure glass has tangible absorption at 500nm and 705nm for the typical case of the reddish-brown glass of present embodiment preparation sees through graphic representation, absorbs at the 400nm place and ends.

Fig. 2 can know that by figure glass has tangible absorption at 511nm and 694nm for the typical case of the red-purple glass of present embodiment preparation sees through graphic representation, absorbs at the 277nm place and ends.

Fig. 3 can be known by figure that for the typical case of the brown glass of present embodiment preparation sees through graphic representation glass absorbs at the 420nm place and ends.

Fig. 4 can know that by figure glass has tangible absorption at 563nm and 690nm for the typical case of the pink glass of present embodiment preparation sees through graphic representation, absorbs at the 267nm place and ends.

Glass thermal treatment under 100 ~ 600 ° of C of present embodiment preparation, nondiscoloration.

The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not limited by the examples; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (3)

1. a red bismuth germanate glass is characterized in that, the molar percentage of each oxide component is:

GeO ₂ 49~99%；

Li ₂O 0~35%；

Na ₂O 0~10%；

K ₂O 0~10%；

B ₂O ₃ 0~9%；

Al ₂O ₃ 0~9%；

MgO 0~10%；

CaO 0~10%；

BaO 0~10%；

Ta ₂O ₅ 0~10%；

Bi ₂O ₃ 0.01~5%；

ZnO 0~10%；

SrO 0~10%。

2. the preparation method of a red bismuth germanate glass is characterized in that, may further comprise the steps:

(1) molar percentage by each oxide component takes by weighing raw material:

GeO ₂ 49~99%；

Li ₂O 0~35%；

Na ₂O 0~10%；

K ₂O 0~10%；

B ₂O ₃ 0~9%；

Al ₂O ₃ 0~9%；

MgO 0~10%；

CaO 0~10%；

BaO 0~10%；

Ta ₂O ₅ 0~10%；

Bi ₂O ₃ 0.01~5%；

ZnO 0~10%；

SrO 0~10%；

(2) load weighted raw material is placed on crucible and compacting through milling mixing in the step (1), is to found under 1300 ~ 1550 ° of C 15 minutes ~ 5 hours in temperature;

(3) melt that step (2) is obtained casts in the mould, and after the cooling, unrelieved stress is removed in annealing, promptly makes red bismuth germanate glass.

3. the preparation method of red bismuth germanate glass according to claim 2 is characterized in that, said founding in the process stirred.

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