JP2002220254A - Method of manufacturing colored glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing blue colored and defoamed soda lime-base or potassium-base glass by effectively using volcanic ash of MIYAKE island as glass raw materials. SOLUTION: In the method, 1-100 pts.wt. of volcanic ash of MIYAKE island is added to 100 pts.wt. of the mixture of silica sand, soda ash or potassium carbonate, and limestone, melted in reducing atmosphere, and formed to give defoamed and blue colored soda lime-base or potassium-base glass having excellent heat ray absorbing property.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a colored soda-lime glass or a potassium-based glass, and more particularly to a method of effectively utilizing Miyakejima volcanic ash, which has excellent heat ray absorbability and has a defoamed and blue color. The present invention relates to a method for producing colored soda-lime glass or potassium glass.

[0002]

2. Description of the Related Art In general, soda-lime glass or potassium-based glass is obtained by adding silica, soda ash or potassium carbonate and limestone to aluminum hydroxide, As ₂ O ₃ or Sb.
A fining agent such as ₂ O ₃ and a metal ion such as Fe and Co are added as a coloring agent to be melted and formed.

[0003]

Conventionally, in the production of a soda-lime glass or a potassium-based glass which has been defoamed and colored blue, aluminum hydroxide, a fining agent and a coloring agent have been added to silica sand, soda ash and limestone. However, the present invention, by effectively utilizing Miyakejima volcanic ash as a glass raw material, aluminum hydroxide,
An object of the present invention is to provide a method for producing a soda-lime-based glass or a potassium-based glass, which has been defoamed and colored blue, without blending a fining agent and a coloring agent.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and is intended to produce soda-lime glass or potassium-based glass in which silica sand, soda ash or potassium carbonate and limestone are blended and melted as raw materials. In the method, the raw material of the silica sand, soda ash or potassium carbonate, limestone is added to 100 parts by weight of anorthite (CaO.Al ₂ O).
₃ · 2SiO _2), anhydrite (CaSO _4), gypsum _{(CaSO 4 · 2H 2 O)} , magnetite _{(Fe 3 O} 4), silica _(SiO 2), includes a cristobalite (SiO _2), its main When the composition is converted as oxide, Si
O _2: 40 to 55 _{wt%, Al} 2 O 3: _{14~19 wt%,} Na 2 O: 1 to 5 _wt%, K 2 O: 0 to 3 wt%,
CaO: 6 to 12% by weight, MgO: 2 to 7% by weight, Fe
₂ O _3: 8 to 13 _wt%, SO 3: Miyakejima ash containing 2-15% by weight by blending 1 to 100 parts by weight, and melted in a reducing atmosphere, superior characterized by forming the heat ray This is a method for producing a blue-colored glass which is absorbent and has been defoamed.

[0005] The method of the present invention for producing a glass having excellent heat-absorbing properties and being defoamed and colored in a bluish color comprises mixing 1 to 5 parts by weight of Miyakejima volcanic ash and coloring it in pale water blue. It is characterized by the following. In addition, the method for producing a blue colored glass having excellent heat absorbing properties and having excellent heat absorbing properties according to the present invention is characterized in that 6 to 15 parts by weight of Miyakejima volcanic ash are blended and colored in blue. Things. In addition, the method for producing a blue colored glass having excellent heat ray absorption and having excellent heat absorbing properties according to the present invention is characterized in that 16 to 40 parts by weight of Miyakejima volcanic ash are blended and colored blue-green. Things. In addition, the method for producing a glass colored with a blue color having excellent heat ray absorbability and having bubbles removed according to the present invention,
It is characterized by mixing 41 to 70 parts by weight of Miyakejima volcanic ash and coloring dark green. In addition, the method for producing glass which has excellent heat ray absorption and is defoamed and colored in a blue color according to the present invention comprises the steps of:
It is characterized by adding 0 parts and coloring it to a dark green color close to black.

[0006]

According to the present invention, in a method for producing soda-lime glass, raw materials such as silica sand, soda ash and limestone are added in a weight of 10%.
0 parts, 1-100 parts by weight of Miyakejima volcanic ash are further blended, melted in a reducing atmosphere, molded, and slowly cooled,
It is possible to obtain a soda-lime glass having excellent heat ray absorption and being defoamed and colored blue. In the method for producing a potassium-based glass, raw materials such as silica sand, potassium carbonate, and limestone are mixed with 100 parts by weight, and 1 to 100 parts by weight of Miyakejima volcanic ash are further blended, melted, formed, and gradually cooled in a reducing atmosphere. By doing so, it is possible to obtain a potassium-based glass which has excellent heat ray absorption properties and is defoamed and colored blue.

The Miyakejima volcanic ash used in the present invention is anorthite (CaO.Al ₂ O ₃ .2SiO ₂ ), anhydrous gypsum (CaSO ₄ ), gypsum dihydrate (CaSO ₄ .2H)
₂ O), magnetite _{(Fe 3 O} 4), silica _(SiO 2), those containing cristobalite (SiO _2), is converted to its main composition as _oxides, SiO 2: 40 to 55 wt%, Al ₂ O ₃ : 14 to 19% by weight, Na ₂ O: 1 to 1
5 _wt%, K 2 O: _0~3 wt%, CaO: 6 to 12 wt%, MgO: 2 to 7 _{wt%, Fe} 2 O 3: _{8~13 wt%,} SO 3: 2 to 15 wt% Including. Specifically, TiO ₂ : 0 to 3 is added to the above main composition.
% By weight, MnO: 0 to 2% by weight, Cl: 0 to 1% by weight,
P ₂ O ₅ : 0 to 2% by weight, V ₂ O ₅ : 0 to 1% by weight, C
r ₂ O ₃ : 0 to 0.05% by weight, Co ₂ O ₃ : 0 to 0.
05% by weight, CuO: 0-1% by weight, ZnO: 0-0.
05 weight%, SrO: 0~1 weight%, _ZrO 2: 0~
It contains 0.05% by weight. In the Miyakejima volcanic ash, iron is contained in the form of magnetite (Fe ₃ O ₄ ), and the amount is shown in terms of Fe ₂ O ₃ . The features of Miyakejima volcanic ash are that iron is present in the form of magnetite (Fe ₃ O ₄ ) and contains a large amount of CaSO _{4 as} compared to volcanic ash in various places.

Attempts have been made to use volcanic ash from various places in the manufacture of glass, but Miyakejima volcanic ash contains Fe ₃
It exists in the form of O ₄ , and is highly reducible by volcanic ash.
By melting this in a reducing atmosphere, iron is in a Fe ²⁺ state in the soda-lime glass or the potassium-based glass, so that 100 parts by weight of silica sand, soda ash, potassium carbonate, and limestone raw materials are used. By mixing 1 to 100 parts by weight of Miyakejima volcanic ash, it is colored blue. The depth of the blue color increases with the amount of Miyakejima volcanic ash. When Miyakejima volcanic ash is blended by 1 to 5 parts by weight, pale blue,
The composition is colored blue in the composition of 6 to 15 parts, bluish green in the composition of 16 to 40 parts, dark green in the composition of 41 to 70 parts, and dark green almost black in the composition of 71 to 100 parts. Especially 6-1
The blue color obtained by blending 5 parts has a clear blue color like marine blue. Miyakejima volcanic ash is 1 by weight
Less than 10 parts hardly causes coloring. On the other hand, if it exceeds 100 parts, blue coloring cannot be obtained.

The Miyakejima volcanic ash contains CaSO ₄ , and the gas generated by the decomposition of the ash during the vitrification is defoamed by taking in small bubbles in the glass. Soda-lime glass and potassium glass are produced. If the Miyakejima volcanic ash is less than 1 part by weight, there is no bubble elimination effect, that is, no effect as a fining agent. In order to achieve a better bubble elimination state, it is preferable that the Miyakejima volcanic ash be 3 parts by weight or more. Mixing Miyakejima volcanic ash by weight to color light blue
In the case where two parts are used, if the bubble-elimination effect of only Miyakejima volcanic ash does not result in a sufficient bubble-elimination state, a normal fining agent may be added. Further, since iron and the like of Miyakejima volcanic ash are present in the soda-lime-based glass and the potassium-based glass thus produced, the glass has infrared absorption characteristics, that is, excellent heat ray absorption. Furthermore, Miyakejima volcanic ash also contains components corresponding to silica sand, soda ash, calcium carbonate, and aluminum hydroxide, which are the raw materials for soda-lime-based glass and potassium-based glass. The use of calcium carbonate can be reduced. As described above, by mixing 1 to 100 parts of Miyakejima volcanic ash, soda lime-based glass or potassium-based glass that has been defoamed and colored blue without using aluminum hydroxide, a fining agent, a coloring agent, or the like. Can be manufactured.

[0010]

DETAILED DESCRIPTION OF THE INVENTION A soda-lime glass according to the present invention is, for example, SiO ₂ : 55 to 75% by weight, Al
₂ O ₃ : 0.5 to 8% by weight, CaO: 5 to 15% by weight,
MgO: 0.5 to 4 _wt%, Na 2 O: 10 to 20 wt%, which in the range of so-called normal soda-lime glass, such glass compositions as the target, silica sand as a raw material, 100 parts of raw material of soda ash and limestone are mixed with 1 to 100 parts of Miyakejima volcanic ash. The potassium-based glass according to the present invention is obtained by replacing all or a part of sodium of the soda-lime glass with potassium. For example, SiO ₂ : 55 to 75% by weight Al ₂ O ₃ : 0.5 to 8% by weight K ₂ O: 5 to 20 wt% CaO: 5 to 15 wt% MgO: 0.5 to 4 _wt%, Na 2 O: 0 to 15 wt%, in a range of potassium-based glass of the so-called normal,
With the goal of such a glass composition, silica sand,
100 parts by weight of potassium carbonate and limestone are mixed with 1 to 100 parts by weight of Miyakejima volcanic ash. Miyakejima volcanic ash is a fine powder, most of which is finer than 0.5 mm, and the one deposited without any special treatment is used as it is. If any substance other than water and volcanic ash is mixed, remove it before use.

Thus, the raw materials of silica sand, soda ash or potassium carbonate, and limestone are mixed with 100 parts by weight and 1 to 100 parts by weight of Miyakejima volcanic ash, and are melted in a reducing atmosphere. For example, the crucible is covered with a lid and melted in a state where oxygen is shut off. The molding can be performed by, for example, air blowing, die blowing, embossing, or a roll method. The raw material of the silica sand, soda ash or potassium carbonate and limestone of the present invention is 10% by weight.
The viscosity and moldability of a mixture of 0 part and 1 to 100 parts by weight of Miyakejima volcanic ash were similar to those of ordinary soda-lime glass and potassium glass. After the molding, it is gradually cooled and processed as required.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the present invention will be described with reference to Table 1 and FIG.

[Table 1]

Table 1 shows the composition of the soda-lime glass of the embodiment. FIG. 1 shows the spectral characteristics. The unit of the compounding amount of the Miyakejima volcanic ash, the silica sand powder of the raw material part, the soda ash, the limestone, and the aluminum hydroxide shown in Table 1 is g. The ratio (parts) of the Miyakejima volcanic ash to 100 parts of the raw material part indicates the ratio (parts) in which the Miyakejima volcanic ash is blended by weight, with the weight of the silica sand powder, soda ash, limestone, and aluminum hydroxide in the raw material part being 100 parts. It is a thing.
Miyakejima volcanic ash is fine, 0.5 mm or less.
The silica sand powder used was 150 to 200 mesh.
No. 1 in Table 1. No. 1 was prepared by blending 1.2 parts of Miyakejima volcanic ash with 100 parts of the raw material part. 2 is the raw material section 10
No. 0 and 2.4 parts of Miyakejima volcanic ash were blended. No. 3 is a mixture of 100 parts of the raw material part and 6.5 parts of Miyakejima volcanic ash, which is blue. 4 is the raw material section 1
The blue color was obtained by mixing 10.1 parts of Miyakejima volcanic ash with 00 parts. No. No. 5 is a mixture of 100 parts of raw material and 23.6 parts of Miyakejima volcanic ash. No. 6 was a mixture of 100 parts of the raw material part and 36.4 parts of Miyakejima volcanic ash, which was blue-green. No. No. 7 was a mixture of 100 parts of the raw material and 55.6 parts of Miyakejima volcanic ash, which was dark green. In addition, these are bubbles that have been cut by CaSO ₄ contained in Miyakejima volcanic ash.
o. 3-No. 7 was completely defoamed.

The physical properties of the soda-lime glass of the embodiment are as follows. In the case where 6.5 parts of Miyakejima volcanic ash was blended with 100 parts of the raw material part of No. 3, the coefficient of linear expansion was 100 × 1
^{0 - 7 / ℃ (40~400 ℃} ), transition point 557 ° C., a deformation point 609 ° C., No. In the case of mixing 10.1 parts of Miyakejima volcanic ash with 100 parts of the raw material part of No. 4, the coefficient of linear expansion is:
101.5 × 10 ⁻⁷ / ° C. (40 to 400 ° C.), transition point 555 ° C., yield point 606 ° C. The physical properties of this soda-lime glass were equivalent to those of ordinary soda-lime glass.

FIG. 1 shows spectral characteristics. The horizontal axis represents wavelength (nm), and the vertical axis represents transmittance (%). Table 1 No. of the present invention example. 3, the spectral characteristics of glass having the composition shown in FIG. 3, the spectral characteristics of commercially available float glass (soda-lime glass) (3), and the heat-absorbing glass (soda-lime glass)
e-ion-containing) (2). As shown in the spectral characteristics (1) to (3) of FIG.
At a wavelength of 320 nm or less, the transmittance is 0% in all cases. However, in a long wavelength region, the spectral characteristics (1) of the glass of the present invention include the spectral characteristics (3) of the float plate glass and the spectral characteristics of the heat absorbing glass ( The transmittance (%) is lower than 2). In the infrared region having a wavelength of 800 nm or more, the spectrum characteristics are superior to the spectral characteristics (3) of the float plate glass and the spectral characteristics (2) of the heat ray absorbing glass. This corresponds to Table 1 No. This indicates that the soda-lime glass having the composition shown in FIG. 3 has excellent absorption characteristics in the infrared region, that is, excellent heat ray absorption, due to the presence of Miyakejima volcanic ash iron and the like.

[0016]

As described above, according to the present invention,
100 parts of raw material such as silica sand, soda ash, limestone, etc., and 1 to 100 parts of Miyakejima volcanic ash are further blended, melted in a reducing atmosphere, molded, and gradually cooled to provide excellent heat ray absorption and to remove bubbles and blue. It has the effect of being able to obtain soda-lime-based glass colored in the system, and by using Miyakejima volcanic ash as a raw material, the amount of silica sand, soda ash, and calcium carbonate can be reduced, and aluminum hydroxide, clarified It is advantageous in that high quality colored glass without bubbles can be produced at low cost without using an agent or a coloring agent.

[Brief description of the drawings]

FIG. 1 is a diagram showing spectral characteristics.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Minoru Tanaka 3-13-10 Nishigaoka, Kita-ku, Tokyo Tokyo Metropolitan Industrial Research Institute (72) Fumiko Rikui 3-13-10 Nishigaoka, Kita-ku, Tokyo Tokyo Metropolitan Sangyo 4G062 AA01 BB03 CC01 DA06 DA07 DB02 DB03 DD01 DD02 DD03 DE01 DE02 DF01 EA01 EB02 EB03 EB04 EC01 EC02 EC03 EC04 ED02 ED03 EE03 EE04 EF01 EF02 EG01 FA01 FA10 FF01 FC01 FF01 FB02 FB01 FB01 FB02 FB01 FJ01 FK01 FL01 GA01 GB03 GB04 GC01 GD01 GE01 HH01 HH03 HH04 HH05 HH07 HH08 HH09 HH10 HH11 HH12 HH13 HH15 HH17 HH20 JJ01 JJ03 JJ05 JJ06 JJ07 JJ10 KK01 KK03 KK05 NN07 NN10

Claims (6)

[Claims] 1. A method for producing a soda-lime glass or a potassium-based glass in which silica sand, soda ash or potassium carbonate and limestone are blended and melted as raw materials, wherein the raw material for the silica sand, soda ash or potassium carbonate and limestone is weighed. To 100 parts with anorthite (CaO.Al ₂ O ₃ .2)
SiO ₂ ), anhydrous gypsum (CaSO ₄ ), gypsum dihydrate (Ca
SO ₄ .2H ₂ O), magnetite (Fe ₃ O ₄ ), quartz (S
iO ₂ ), cristobalite (SiO ₂ ), and when its main composition is converted as an oxide, SiO ₂ : 40 to
55 _{wt%, Al} 2 O 3: _14~19 wt%, Na
₂ O: 1 to 5 _wt%, K 2 O: _0~3 wt%, CaO:
6-12 wt%, MgO: 2 to 7 _wt%, Fe _{2 O} 3:
8-13 _wt%, SO 3: to 1 to 100 parts at a weight of Miyake Island ash containing 2-15% by weight, perforated and melted in a reducing atmosphere, excellent heat ray absorbing property, which comprises forming A method for producing glass that has been defoamed and colored blue. 2. The method according to claim 1, wherein 1 to 5 parts by weight of the Miyakejima volcanic ash is blended and colored in light blue. Manufacturing method of glass. 3. The method according to claim 1, wherein 6 to 15 parts by weight of the Miyakejima volcanic ash is blended and colored in blue. Glass manufacturing method. 4. The method according to claim 1, wherein 16 to 40 parts by weight of the Miyakejima volcanic ash are blended and colored blue-green.
4. The method for producing a glass which has excellent heat ray absorbability and has been defoamed and colored blue. 5. A dark green color, wherein 41 to 70 parts by weight of the Miyakejima volcanic ash are blended.
4. The method for producing a glass which has excellent heat ray absorbability and has been defoamed and colored blue. 6. The Miyakejima volcanic ash is weighted by 71-100.
2. The method of claim 1, wherein the glass is colored in a dark green color close to black.