JP2004339001A - Manufacturing method of glass having color pattern therein - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing glass capable of forming a color pattern of an arbitrary shape. <P>SOLUTION: In this method, a glass having a color pattern of an arbitrary shape therein and the trace of the condensed point being colored at least in two colors is manufactured by irradiating and condensing a pulse laser light of a specified wave length inside the glass containing an Au ion with not less than two specified peak power densities while moving the condensed point, then heating the glass. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing glass having a color pattern therein.
[0002]
[Prior art]
A transparent colored glass is conventionally produced by dispersing metal fine particles in glass using a thermal reduction method or a photoreduction method.
[0003]
In the thermal reduction method, glass containing metal ions such as Au ⁺ , Ag ⁺ , and Cu ⁺ and multivalent valence ions such as Sn ²⁺ and Sb ^{3+ is} used as a raw material, and at a temperature much lower than the melting temperature of the glass. The raw material is heat-treated. Thereby, metal ions such as Au ⁺ , Ag ⁺ , and Cu ⁺ are reduced to generate metal fine particles, and a metal fine particle-dispersed glass, that is, a glass having a transparent color is generated.
[0004]
In the photoreduction method, glass obtained by adding a photosensitizer (or photochemical reducing agent) such as Ce ³⁺ together with metal ions such as Au ⁺ , Ag ⁺ , and Cu ^{+ is} used as a raw material. Etc. are irradiated and exposed, or ultraviolet rays, X-rays, etc. are heated after exposure. As a result, metal fine particles are generated in the portion irradiated with ultraviolet rays or the like, and a metal fine particle-dispersed glass is obtained.
[0005]
Recently, a method of condensing and irradiating pulsed laser light inside a glass containing Ce metal and other metal ions has been proposed (see Patent Document 1). As a result, only the portion where the laser beam is focused and irradiated is turned into fine metal particles, and a colored glass is obtained.
[0006]
[Patent Document 1]
Japanese Patent Laid-Open No. 11-60271
[Problems to be solved by the invention]
In the glass manufacturing method proposed in Patent Document 1, the glass can only be colored in a single color. For this reason, ornaments, figurines and the like produced using glass produced by such a method are limited in color design.
[0008]
If it is possible to color any part of a glass in various colors, and if the color pattern can be made into a desired shape, it can be produced industrially like ornaments and figurines. It is possible to apply an arbitrary glass design to not only articles that are made, but also art objects such as objects, which expands the possibilities of design.
Further, in addition to items that are important in design, such as decorative items, it is also possible to manufacture industrial products such as optical multicolor filters.
[0009]
The present invention has been made to solve such problems, and the object of the present invention is to be able to color the inside of the glass in various colors, and to make the color pattern a desired shape. It is in providing the manufacturing method of the glass which can be made.
[0010]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, a method for producing a glass having a color pattern inside according to the present invention comprises: condensing and irradiating a pulse laser beam having a predetermined wavelength inside a glass containing Au ions; The glass is heated after the condensing point is moved while changing the output of the laser beam to form a predetermined locus pattern.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
In the method for producing glass according to the present invention, first, Au ions are contained in glass (mother glass). As the mother glass, silicate glass is usually used, but glass having other compositions can also be used. However, the composition of the mother glass is such that the Au fine particles are not deposited in the matrix before the laser beam condensing irradiation, and the Au fine particles are selectively applied only to the condensing irradiation portion by the laser light condensing irradiation or the heat treatment after the condensing irradiation. It must be deposited.
[0012]
Au ions are contained in the mother glass by adding an aqueous solution of chloroauric acid, a hydrochloric acid solution of gold chloride, chloroaurate, or the like. Here, i) When Au ions are less than 0.001% by weight with respect to the total glass raw material, Au ions are not deposited as Au fine particles by laser light irradiation or heat treatment after irradiation, or the color cannot be controlled by laser irradiation conditions. Ii) In an amount exceeding 1% by weight, Au ions may precipitate as Au fine particles in the glass melting stage before laser light irradiation or in the stage of cooling from the molten state to vitrification, and Since the irradiation region other than the condensing point and the laser light non-irradiation region may be colored during the heat treatment, it is desirable to contain Au ions in a range of 0.001 to 1% with respect to the total raw material weight.
[0013]
In order to promote the reduction of Au ions, CeO ₂ acting as a photochemical reducing agent may be added to the mother glass, and Sb ₂ O ₃ and SnO ₂ acting as a thermal reducing agent may be further added. When CeO ₂ is added, Au fine particles are precipitated by irradiation with a laser beam with a lower power, and when Sb ₂ 0 ₃ and SnO ₂ are added, coloring occurs in a shorter heat treatment. However, if these reducing agents are added excessively, Au fine particles will be deposited even in the irradiated part other than the condensing point and the laser light non-irradiated part, so this must be avoided.
[0014]
When laser light is focused and irradiated to a predetermined part inside the glass produced using the above glass raw material and the glass is heated, Au fine particles are precipitated only at the part irradiated with the laser light, and Au fine particle dispersion It becomes glass. Here, the inside of glass includes not only the inside of glass but also the glass surface.
[0015]
Laser light irradiation uses a laser that emits pulse laser light having a predetermined wavelength as a light source. At this time, in the pulsed laser light whose emission wavelength does not reach 250 nm, the reduction reaction of Au ions is likely to occur at portions other than the irradiated portion, and Au fine particles may be deposited at locations other than the focal point, When the emission wavelength exceeds 1.6 μm, the reduction reaction of metal ions does not occur even in the condensing part, and Au fine particles may not be deposited. Therefore, the laser beam in the wavelength region of 250 nm to 1.6 μm is irradiated. preferable.
[0016]
When the laser light emitted from the light source is condensed and irradiated inside the glass by a condensing device such as a lens, Au fine particles are deposited at the condensing point. For this reason, when the condensing point is continuously moved, Au fine particles are deposited on the locus pattern of the condensing point. Further, when the condensing point is continuously moved so as to fill the surface or the solid region, the Au fine particles are deposited so as to fill the surface or the solid region. Here, the surface includes not only a flat surface but also a curved surface, and the three-dimensional region includes not only a simple shape such as a cube but also various complicated three-dimensional shapes.
[0017]
The coloring by the metal fine particles is based on the absorption and scattering of light by the metal fine particles, and the color tone of the glass changes depending on the particle size and concentration of the deposited metal fine particles. Here, in the glass manufacturing method according to the present invention, a crystal is grown by heating the glass after generating crystal nuclei in the irradiated region by condensing and irradiating the inside of the glass with pulsed laser light. For this reason, it is possible to change the amount of crystal nuclei generated by the power of the pulse laser beam, and thereby the particle size of the Au fine particles (crystals) to be deposited can be controlled.
[0018]
For example, when the power of the pulse laser beam to be irradiated is low and the amount of crystal nuclei generated is small, the amount of Au ions that remain without forming crystal nuclei is large, so that crystal growth during heating is promoted. One Au fine particle has a large particle size. As a result, the Au fine particles absorb longer wavelength light.
On the other hand, when the pulse laser beam power is high and the amount of nucleation is large, almost all Au doped in the glass is used for nucleation, so that crystal growth during heating is suppressed. As a result, the particle diameter of each Au fine particle becomes small, and the Au fine particle absorbs light having a shorter wavelength.
Here, the peak power of the pulsed laser beam is expressed in watts (W), which is a value obtained by dividing the output energy (J) per pulse by the pulse width (seconds), and the peak power density is determined by dividing the irradiation spot. Expressed in W / cm ² divided by area.
[0019]
From the above mechanism, when a predetermined locus pattern is formed by moving the condensing point while changing the output of the pulse laser beam, the locus pattern is colored in various colors, and the glass has a color pattern inside. If the output change of the pulse laser beam is continuous, the color pattern changes continuously. If the output change is stepwise, the color pattern also changes stepwise. Here, when the peak power density is less than 1 × 10 ⁸ W / cm ² , there is a case where the Au ion reduction reaction does not occur in the light converging portion and the Au fine particles may not be deposited. The peak exceeding 1 × 10 ¹⁸ W / cm ² With respect to the power density, Au ions may undergo a reduction reaction at a portion other than the focal point, and Au fine particles may be deposited outside the focal point. Therefore, the range of the peak power density is 1 × 10 ⁸ to 1 × 10 ¹⁸ W / Preferably it is cm ² . When the peak power density is increased, purple, magenta, red, orange, and yellow colors are obtained as the peak power density is increased. In addition, when the glass composition is different, the coloring obtained by laser irradiation at a constant peak power density is different.
[0020]
After condensing and irradiating the inside of the glass with pulsed laser light, heat treatment is performed to promote crystal growth of Au fine particles. Here, when heated at less than 450 ° C., the crystal growth is not promoted, so that coloring may not be obtained (or coloring does not enter the visible range). On the other hand, when heated at a temperature exceeding 650 ° C., other than the condensing point Since the Au fine particles may be deposited on the irradiated portion and the non-irradiated portion of the laser and the glass may be colored, it is desirable to heat in the range of 450 to 650 ° C. The heating time is about 3 minutes to 3 hours and is appropriately determined depending on the glass composition.
[0021]
【The invention's effect】
According to the method of the present invention, glass having a color pattern of an arbitrary shape can be produced. Thereby, it is possible to apply an arbitrary glass design not only to industrially produced articles such as ornaments and ornaments but also to art objects such as objects. It is also possible to manufacture industrial products such as optical multicolor filters.
[0022]
【Example】
(Example 1)
To produce a glass having a composition of 70SiO ₂ · 20Na ₂ 0 · 10CaO · 0.5Au (wt%), 21.00 g of SiO _2, 10.25 g of Na ₂ CO ₃ , 5.35 g of CaCO ₃ , and chloroauric acid mixed salt _{(AuHCl 4 · 4H 2 O)} 0.31g, was charged with these glass raw materials in a platinum crucible. These were heated and melted while stirring in an air atmosphere at 1550 ° C. for 3 hours, and then the melted glass raw material was poured into a mold to form a 7 mm thick plate and cooled.
[0023]
The glass plate obtained above was cut and polished to obtain a sample 10 having a thickness of 5 mm, and the sample 10 was irradiated with pulsed laser light.
[0024]
The sample 10 was irradiated with pulsed laser light as shown in FIG. In other words, the pulse laser beam 11 is condensed by the lens 12, adjusted so that the condensing point 13 is located at a specific part inside the sample 10, and then the glass sample 10 so that the condensing point 13 draws a linear locus. The sample 10 was irradiated with the pulsed laser beam 11 while moving in parallel. As the pulse laser beam 11, light having a pulse width of 150 fs, a repetition period of 1 kHz, and a wavelength of 750 nm oscillated from a Ti-sapphire laser is used, and 3 × 10 ¹⁰ , 8 × 10 ¹² , 1 × 10 ¹⁶ W / cm ² . Irradiation was performed stepwise with three conditions of peak power density.
After irradiating the laser beam 11, the glass sample 10 was put into an electric furnace and heated at 600 ° C. for 10 minutes.
[0025]
As a result, as shown in FIG. 2, a blue-violet region irradiated with a peak power density of 3 × 10 ¹⁰ W / cm ² , a red region of 8 × 10 ¹² W / cm ² , 1 × 10 ¹⁶ W / cm ² A glass having a linear color pattern 14 consisting of a yellow region was obtained.
[0026]
(Example 2)
SiO ₂ 21.00 g, Na ₂ CO ₃ 7.69 g, CaCO ₃ so as to have a glass composition of 70SiO ₂ · 15Na ₂ 0 · 10CaO · 5Al ₂ 0 ₃ · 0.1Au · 0.005CeO ₂ (wt%) _5.35g, Al ₂ 0 _{3 1.50g,} a mixture of CeO 2 0.0015 g, and chloroauric acid salt _{(AuHCl 4 · 4H 2 O)} 0.063g, was charged with these glass raw materials in a platinum crucible. These were heated and dissolved with stirring in an air atmosphere at 1550 ° C. for 3 hours, then poured into a mold, formed into a 7 mm thick plate and cooled.
[0027]
The glass plate obtained above is cut and polished to obtain a sample 20 having a thickness of 5 mm, and the glass sample 20 is drawn inside the sample 20 in the same manner as in Example 1 so that the condensing point 13 draws a linear locus. The sample 20 was irradiated with the pulsed laser beam 11 while moving in parallel.
As the pulse laser beam 11, light having a pulse width of 200 fs, a repetition period of 1 kHz, and a wavelength of 800 nm oscillated from a Ti-sapphire laser is used, and 5 × 10 ¹¹ , 3 × 10 ¹⁴ , 1 × 10 ¹⁷ W / cm ² . Irradiation was performed stepwise with three conditions of peak power density.
After irradiating the laser beam 11, the glass sample 20 was put in an electric furnace and heat-treated at 550 ° C. for 20 minutes.
[0028]
As a result, as in Example 1, a blue-violet region irradiated with a peak power density of 5 × 10 ¹¹ W / cm ² , a red-violet region of 3 × 10 ¹⁴ W / cm ² , and 1 × 10 ¹⁷ W / cm ² A glass having a linear color pattern consisting of a yellow region was obtained.
[0029]
(Example 3)
SiO ₂ 22.50 g, Na ₂ CO ₃ 7.69 g, CaCO so as to have a glass composition of 75SiO ₂ · 15Na ₂ 0 · 10CaO · 0.05Au · 0.003Sb ₂ 0 ₃ · 0.003SnO (wt%) _{3 5.35g,} Sb ₂ 0 ₃ were mixed 0.0009g, SnO0.0009g, and chloroauric acid salt _{(AuHCl 4 · 4H 2 O)} 0.031g, he was charged with these glass raw materials in a platinum crucible. After being heated and dissolved while stirring in an air atmosphere at 1550 ° C. for 3 hours, it was poured into a mold, formed into a 7 mm thick plate and cooled.
[0030]
The glass plate obtained above is cut and polished to obtain a sample 30 having a thickness of 5 mm, and the glass sample 30 is drawn inside the sample 30 in the same manner as in Example 1 so that the condensing point 13 draws a linear locus. The sample 30 was irradiated with the pulsed laser beam 11 while moving in parallel.
As the pulse laser beam 11, light having a pulse width of 800 fs, a repetition period of 1 kHz, and a wavelength of 630 nm oscillated from a Ti-sapphire laser is used, and 1 × 10 ¹² , 5 × 10 ¹⁵ , 5 × 10 ¹⁷ W / cm ² . Irradiation was performed stepwise with three conditions of peak power density.
The irradiated glass sample 30 was placed in an electric furnace and heat treated at 500 ° C. for 60 minutes.
[0031]
As a result, as in Example 1 and Example 2, a blue-violet region irradiated with a peak power density of 1 × 10 ¹² W / cm ² , an orange region of 5 × 10 ¹⁵ W / cm ² , and 5 × 10 ¹⁷ W / cm ^2. A glass having a linear color pattern consisting of a yellow area of cm ² was obtained.
[0032]
(Comparative Example 1)
SiO ₂ 21.00 g, Na ₂ CO ₃ 10.25 g, CaCO ₃ 5.35 g, CeO so as to have a glass composition of 70SiO ₂ · 20Na ₂ 0 · 10CaO · 0.0005Au · 0.003CeO ₂ (% by weight). ₂ 0.0009 g, and then mixed with chloroauric acid salt _{(AuHCl 4 · 4H 2 O)} 0.0003g, was charged with these glass raw materials in a platinum crucible. After being heated and dissolved while stirring in an air atmosphere at 1550 ° C. for 3 hours, it was poured into a mold, formed into a 7 mm thick plate and cooled.
[0033]
The glass plate obtained above is cut and polished to obtain a sample 40 having a thickness of 5 mm, and the glass sample 40 is drawn inside the sample 40 in the same manner as in Example 1 so that the focal point 13 draws a linear locus. The sample 40 was irradiated with the pulsed laser light 11 while moving in parallel.
As the pulse laser beam 11, light having a pulse width of 1.50 fs oscillated from a Ti-sapphire laser, a repetition period of 1 kHz, and a wavelength of 750 nm is used, and 3 × 10 ¹⁰ , 5 × 10 ¹⁴ , 5 × 10 ¹⁷ W / cm. was stepwise irradiation the peak power density of ² three conditions.
The glass sample 40 after irradiation was put into an electric furnace and heat-treated at 600 ° C. for 10 minutes.
[0034]
As a result, in the sample 40, both of the regions irradiated with the peak power densities of 5 × 10 ¹⁴ W / cm ² and 5 × 10 ¹⁷ W / cm ² are colored purple, and the peak power density is 3 × 10 ¹⁰ W / cm. ^The area irradiated with ² was not colored at all. Thus, in a glass containing only 0.001% by weight or less of Au ions, the color of the pulse laser beam irradiation region cannot be controlled or the glass is not colored (Au fine particles do not precipitate) due to a change in peak power density. confirmed.
[0035]
(Comparative Example 2)
SiO ₂ 21.00 g, Na ₂ CO ₃ 10.25 g, CaCO ₃ 5.35 g, and chloroaurate (so that the glass composition of 70SiO ₂ · 20Na ₂ 0 · 10CaO · 1.2Au (wt%) AuHCl ₄ · _4H 2 O) were mixed 0.75 g, was charged these glass raw materials in a platinum crucible. After being heated and dissolved while stirring in an air atmosphere at 1550 ° C. for 3 hours, it was poured into a mold, formed into a 7 mm thick plate and cooled.
[0036]
The glass plate obtained above is cut and polished to obtain a sample 50 having a thickness of 5 mm, and the glass sample 50 is drawn inside the sample 50 in the same manner as in Example 1 so that the focal point 13 draws a linear locus. The sample 50 was irradiated with the pulsed laser beam 11 while moving in parallel.
As the pulse laser beam 11, light having a pulse width of 150 fs, a repetition period of 1 kHz, and a wavelength of 800 nm oscillated from a Ti-sapphire laser is used, and 5 × 10 ⁸ , 3 × 10 ¹⁴ , 5 × 10 ¹⁷ W / cm ² . Irradiation was performed stepwise with three conditions of peak power density.
The glass sample 50 after irradiation was put into an electric furnace and heat-treated at 550 ° C. for 20 minutes.
[0037]
As a result, in the sample 50, the region irradiated with the peak power density of 5 × 10 ⁸ W / cm ² is bluish purple, the region of 3 × 10 ¹⁴ W / cm ² is red purple, and the region of 5 × 10 ¹⁷ W / cm ² . Was colored yellow, but the non-irradiated areas were also colored. Thus, in the case of glass containing 1.2% by weight of Au ions, it was confirmed that the region other than the portion where the laser beam 11 was condensed and irradiated was also colored.
[Brief description of the drawings]
FIG. 1 is a diagram in which pulsed laser light is focused and irradiated inside glass.
FIG. 2 is a diagram of glass in which only a region irradiated with focused laser light is colored.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 10 ... Sample 11 ... Pulse laser beam 12 ... Lens 13 ... Condensing point 14 ... Color pattern

Claims (6)

After condensing and irradiating a pulse laser beam having a predetermined wavelength inside the glass containing Au ions, and changing the output of the pulse laser beam to form a predetermined locus pattern, A method for producing a glass having a color pattern therein, wherein the glass is heated. The method for producing a glass having a color pattern therein according to claim 1, wherein 0.001 to 1 wt% of Au ions are contained in the glass raw material. 2. The method for producing glass having a color pattern therein according to claim 1, wherein the wavelength of the pulsed laser light for focused irradiation is 250 nm to 1.6 μm. ^{2. The} method for producing a glass having a color pattern therein according to claim 1, wherein the peak power density of the pulsed laser beam to be focused and irradiated is 1 × 10 ⁸ to 1 × 10 ¹⁸ W / cm ² . The method for producing a glass having a color pattern therein, according to claim 1, wherein the heating temperature of the glass is 450 to 650 ° C. The color pattern of any shape is formed inside the glass by continuously moving the condensing point of the pulsed laser light so as to fill a surface or a three-dimensional region. The manufacturing method of the glass which has a color pattern in the inside of description.

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