WO2011152289A2 - Method of producing glass - Google Patents

Method of producing glass Download PDF

Info

Publication number
WO2011152289A2
WO2011152289A2 PCT/JP2011/062152 JP2011062152W WO2011152289A2 WO 2011152289 A2 WO2011152289 A2 WO 2011152289A2 JP 2011062152 W JP2011062152 W JP 2011062152W WO 2011152289 A2 WO2011152289 A2 WO 2011152289A2
Authority
WO
WIPO (PCT)
Prior art keywords
glass
denatured layer
phase
porous
phase separation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2011/062152
Other languages
French (fr)
Other versions
WO2011152289A3 (en
Inventor
Kenji Takashima
Zuyi Zhang
Yoshinori Kotani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Canon Inc
Original Assignee
Canon Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Canon Inc filed Critical Canon Inc
Priority to US13/699,977 priority Critical patent/US9278882B2/en
Publication of WO2011152289A2 publication Critical patent/WO2011152289A2/en
Publication of WO2011152289A3 publication Critical patent/WO2011152289A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
    • 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
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • 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
    • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
    • C03C11/005—Multi-cellular glass ; Porous or hollow glass or glass particles obtained by leaching after a phase separation step
    • 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
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/008—Other surface treatment of glass not in the form of fibres or filaments comprising a lixiviation step
    • 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
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium

Definitions

  • the present invention relates to a method of producing
  • phase separation A phase separation
  • a skeleton of the porous glass is mainly formed of silicon oxide.
  • borosilicate glass mainly containing silicon oxide, boron oxide, and an alkali metal oxide is generally used.
  • phase separation heating treatment phase separation heating treatment
  • phase separation, boron or the like on the surface of glass is partly lost to cause a composition displacement, and thus, a denatured layer is formed on the surface of the glass.
  • the denatured layer causes a problem of inhibiting etching with an acid solution in a later process. Hence, the denatured layer is required to be removed.
  • PTL 1 discloses a technique of removing at least 10 ⁇ of outermost surface glass by polishing.
  • glass needs to have mechanical strength to some degree, and there may be problems such as roughening of the surface by polishing and the remaining of an abrasive in performing later processes in some cases.
  • PTL 2 also describes that an outermost surface glass layer of borosilicate glass is removed by a chemical method using hydrofluoric acid, ammonium hydrogen difluoride, or an alkaline glass corrosive.
  • PTL 3 describes a method of removing a denatured layer by a chemical procedure involving washing a denatured layer on the surface of glass with an alkaline aqueous solution.
  • PL 1 "New glass and its physical properties", chapter 2, page 51, edited by T. Izumiya, Management System Laboratory, Co., Ltd. 1987
  • the present invention has been achieved in order to solve such problem as described above, and an object of the present invention is to provide a method of producing porous glass having pores with a uniform pore diameter entirely, particularly in the case of phase separation glass, including selectively removing a denatured layer formed on the surface of glass easily.
  • a method of producing glass of the present invention includes: forming a vitreous body containing silicon oxide, boron oxide, and an alkali metal oxide; and bringing an alkaline solution held by a porous supporting member into contact with the surface of the vitreous body to remove a denatured layer.
  • invention includes: forming phase separation glass
  • phase separation glass containing silicon oxide, boron oxide, and an alkali metal oxide; bringing an alkaline solution held by a porous supporting member into contact with the surface of the phase separation glass to remove the denatured layer; and immersing the phase separation glass with the denatured layer removed therefrom in. an acid solution and/or water to form pores in the phase separation glass.
  • the method of producing glass having pores with a uniform pore diameter entirely including selectively removing a
  • Fig. 1 is a schematic view illustrating one
  • Fig. 2 is a scanning electron microscope (SEM) image of the surface of glass produced in Example 1.
  • Fig. 3 is a scanning electron microscope (SEM) image of the surface of glass produced in Comparative
  • Fig. 4 is a scanning electron microscope (SEM) image of the surface of glass produced in Comparative
  • Fig. 1 is a view illustrating one embodiment of a method of producing glass of the present invention, and illustrates a porous supporting member 1, a denatured layer 2, and a vitreous body or phase separation glass 3.
  • invention includes bringing an alkaline solution held by a porous supporting member into contact with the surface of borosilicate glass to remove a denatured layer.
  • phase separation glass containing silicon oxide, boron oxide, and an alkali metal oxide
  • phase separation glass with the denatured layer removed therefrom in an acid solution and/or water to form pores in the phase separation glass.
  • borosilicate glass is obtained by forming a vitreous body by melting a mixture containing silicon oxide, boron oxide, and an alkali metal oxide, followed by surface treatment, if required.
  • phase separation glass a process of forming phase separation glass by heating the vitreous body to effect phase separation is involved. This heating is referred to as phase separation heating in the present specification.
  • phase separation glass may be obtained without phase separation heating.
  • borosilicate glass is expressed by a weight ratio of oxides such as silicon oxide (silica, Si0 2 ) , boron oxide (B2O3) , and an alkali metal oxide.
  • the borosilicate glass contains mainly silicon oxide, boron oxide, and an alkali metal oxide, and may contain, for example, aluminum oxide, calcium oxide, and magnesium oxide as other metal oxides.
  • phase separation glass borosilicate glass having a
  • composition undergoes, in some cases, a phase separation in which glass is separated into a silicon oxide glass phase mainly containing silicon oxide and a
  • Phase separation borosilicate glass phase mainly containing boron oxide and an alkali metal oxide in the course of the application of heat to the vitreous body. Glass that has undergone the phase separation is referred to as phase separation glass in this description.
  • Phase separation borosilicate glass is, for example, Si0 2 (55 to 80% by weight ) -B 2 C>3-Na 2 0- (AI2O3) -based glass, Si0 2 (35 to 55% by weight ) -B 2 0 3 -Na 2 0- based glass, Si0 2 -B 2 0 3 -CaO-Na 2 0-Al 2 0 3 -based glass, 3 ⁇ 0 2 - ⁇ 2 0 3 - Na2 ⁇ 0-R0 (R: alkaline earth metal, Zn) -based glass, and Si02-B 2 03-CaO-MgO-Na20-Al 2 03-Ti02 (Ti0 2 is contained up to 49.2 mol%)-based glass.
  • the content of an alkali metal oxide is generally 2% by weight or more to 20% by weight or less, particularly preferably 3% by weight or more to 15% by weight or less.
  • the content of boron oxide is generally 10% by weight or more to 55% by weight or less, particularly preferably 15% by weight or more to 50% by weight or less.
  • the content of silicon oxide is generally 45% by weight or more to 80% by weight or less, particularly preferably 55% by weight or more to 75% by weight or less.
  • boron oxide, and an alkali metal oxide is generally 15% by weight or less, particularly preferably 10% by weight or less.
  • phase separation glass In the case of phase separation glass, a phase separation appears generally when the glass is held at about 500°C to 700°C for several hours to tens of hours, and the state of expression of phase separation, and further, the pore diameter and pore density in the case where porous glass is obtained, vary depending upon the temperature and retention time . ,
  • denatured layer mainly containing silicon oxide on the surface is formed in many cases.
  • the thickness of the denatured layer is about several hundred nanometers even when the layer is thick.
  • solid silica covers a portion in which a phase separation occurs, which adversely affects the elution and porosity of a soluble layer of phase separation glass with an acid solution, for example.
  • phase-separated borosilicate glass a borosilicate glass phase mainly containing boron oxide and an alkali metal oxide is soluble in an acid solution.
  • the soluble phase reacts by acid treatment, and a silicon oxide glass phase mainly containing silicon oxide remains as a skeleton.
  • porous glass having pores formed therein is formed.
  • a denatured layer can be removed by allowing an alkaline solution to react with the surface of glass where the denatured layer is formed. This is because the alkaline solution and solid silica mainly forming the denatured layer react with each other on the surface of the glass.
  • the alkaline solution circulates to increase a liquid amount to be reacted per unit area of the denatured layer. Therefore, the alkaline solution not only breaks the
  • he present invention is characterized by using a method of etching glass, including a first process of bringing an alkaline solution held by a porous supporting member into contact with a denatured layer formed on the surface of phase separation glass and leaving the resultant to remove the denatured layer, and a second process of immersing the phase-separated glass with the denatured layer removed therefrom in an acid solution and/or water to form pores in the phase-separated glass.
  • Fig. 1 is a schematic view illustrating one embodiment of a method of producing glass of the present invention.
  • Fig. 1 illustrates a method of removing a denatured layer 2 by bringing a porous supporting member 1 containing an
  • a porous supporting member is allowed to hold a limited amount of an alkaline solution and the resultant is brought into contact with the surface of glass with a denatured layer formed thereon, and thus, the liquid amount to be reacted per unit area of the denatured layer is limited, enabling the denatured layer to be removed selectively.
  • the reaction can be controlled merely by allowing the porous supporting member to hold the liquid amount to be reacted with at most hundreds of nanometers of the
  • the treatment temperature of a glass layer can be set in a range of -5°C to 90°C for adjusting the reaction speed and the holding function on the surface.
  • the pore diameter of the porous supporting member to be used in the present invention is preferably 1 mm or less.
  • the porous supporting member includes preferably a metal, a natural fiber, or a synthetic fiber.
  • the kind of the alkaline solution to be used in the present invention is not limited as long as the solution reacts with and breaks solid silica mainly forming a denatured layer.
  • an alkaline solution of sodium hydroxide or potassium hydroxide is preferred. It is desired that the alkali concentration of the alkaline solution be 10% by weight or more to 40% by weight or less, preferably 20% by weight or more to 30% by weight or less.
  • the present invention is characterized by including a first process of allowing an alkaline solution layer to be held on the surface of glass, and a second process of immersing the glass in an acid solution and/or water.
  • the glass in a state in which the denatured layer has been removed from the surface in the first process can be allowed to elute selectively borosilicate glass mainly containing boron oxide and an alkali metal oxide in phase- separated glass, using an ordinary etching method of immersing the phase separated-glass in an acid solution without the inhibition by the denatured layer.
  • an aqueous solution of hydrochloric acid, sulfuric acid, phosphoric acid, or nitric acid is used, and allows the glass to be immersed therein to dissolve a non silica-rich phase.
  • the acid concentration of the acid solution is 0.1 mol/L or more to
  • silica gel may be any suitable silica gel.
  • silica gel may be any suitable silica gel.
  • etching in multi-stages using acid solutions with different acidities or water can be. used.
  • the etching can also be performed at an etching temperature of room temperature to 95 °C. Depending upon the
  • pores may be formed only with etching using water without using an etching solution of an acid. Further, a residual of the denatured layer broken in the first process can be prevented from being deposited on the surface by combining the second
  • porous glass be rinsed with water for the purpose of removing an acid adhering to the porous glass and a soluble layer remaining without being eluted.
  • producing glass of the present invention has a spinodal structure based on silicon oxide.
  • the phase separations are classified into a spinodal type and a binodal type.
  • the pores obtained by a spinodal-type phase separation are penetrating pores linked from the surface to the inside as shown in Fig. 2, for example.
  • the structure in which the skeleton of a silicon oxide main component is continuously formed as shown in Fig. 2 is referred to as a spinodal
  • a binodal-type phase separation provides a structure having closed pores.
  • spinodal structure penetrating pores linked from the surface to the inside, i.e., the so-called spinodal structure is preferred.
  • nm to 1 ⁇ desirably falls within the range of 1 nm to 1 ⁇ , particularly 2 nm to 0.5 ⁇ , further
  • the glass desirably has a porosity of generally 10 to 90%, particularly 20 to 80%.
  • the glass having pores formed therein is expected to find use in applications such as adsorbents, microcarriers , separation films, and optical materials because its porous structure can be uniformly controlled and its pore
  • diameters can each be changed within a certain range.
  • glass was produced as Production Examples 1 to 7 with the composition in terms of oxide as shown in Table 1.
  • material compounds silica powder (Si02) , boron oxide (B 2 0 3 ) , sodium carbonate (Na 2 C0 3 ) , and aluminum oxide ( ⁇ 2 ⁇ 3) were used.
  • the mixed powder of the respective, material compounds was placed in a platinum crucible and melted at 1,500°C for 24 hours. After that, the temperature of the glass was lowered to 1,300°C, and the resultant was poured into a graphite mold. The mold was cooled in air for 20 minutes. After that, a block of the borosilicate glass thus obtained was cut to 40 mmx30 mmxl.l mm, and both surfaces were polished to mirror finish.
  • the glass used in Examples 1 to 6 is glass described in
  • Example 1 Glass etching was performed using the glass of Production Example 1. A sample to be used was obtained by cutting the phase-separated glass to 2 cm>2 cm.
  • the thickness of the denatured layer of the phase-separated glass was about 200 nm. Further, it was confirmed by XPS measurement that the abundance of boron and sodium was smaller on the surface of the phase-separated glass, compared with that on a cross- section thereof, and the surface of the phase-separated glass was almost occupied with silicon and a denatured layer was present.
  • a potassium hydroxide aqueous solution of a concentration of 30% by weight was used as an alkaline solution.
  • the material for the porous supporting member used was rayon, and the rayon had a pore diameter of 300 nm, a density of 60 Kg/m 3 , and a thickness of 80 pm.
  • porous supporting member containing sufficiently potassium hydroxide was brought into contact with the surface of the phase- separated glass with a denatured layer formed thereon as illustrated in Fig. 1. In the atmosphere, the resultant was left to stand at room temperature for 2.5 hours.
  • Fig. 2 is a scanning electron microscope (SEM) image of the surface of the porous glass produced in
  • Example 2 An etching experiment was conducted in the
  • Example 2 The thickness of the denatured layer was 100 nm. It was found by SEM observation of the glass after the experiment that the denatured layer was removed completely, the porous skeleton remained without being eroded, and the entire sample became porous glass.
  • Example 3 An experiment was conducted in the same way as in Example 1 using the glass of Production Example 3. The thickness of the denatured layer was 150 nm. It was found by SEM observation of the glass after the experiment that the denatured layer was removed completely, the porous skeleton remained without being eroded, and the entire sample became porous glass.
  • Example 4 An experiment was conducted in the same way as in Example 1 using the glass of Production Example 3. The thickness of the denatured layer was 100 nm. It was found by SEM observation of the glass after the experiment that the denatured layer was removed completely, the porous skeleton remained without being eroded, and the entire sample became porous glass.
  • Example 5 An experiment was conducted in the same way as in Example 1 using the glass of Production xample 3. The thickness of the denatured layer was 50 nm. It was found by SEM observation of the glass after the experiment that the denatured layer was removed completely, the porous skeleton remained without being eroded, and the entire sample became porous glass.
  • Example 6 The glass of Production Example 7 was used.
  • denatured layer was 50 nm. It was found by SEM observation of the glass after the experiment that the denatured layer was removed completely.
  • Comparative Example 1 The glass of Production Example 1 was cut to a size of lcmxlcm and used.
  • Fig. 3 is a scanning electron microscope (SEM) image of the surface of the porous glass produced in Comparative Example 1.
  • Comparative Example 2 The glass of Production Example 1 was cut to a size of lcmxlcm and used.
  • phase-separated glass in which the denatured layer was present, the phase-separated glass was immersed in an alkaline solution bath without using a porous
  • the alkaline solution to be used herein is a potassium hydroxide aqueous solution of a concentration of 30% by weight. Then, 50 g of alkaline solution was placed in a polypropylene container, and the phase-separated glass was suspended and placed therein so as to be positioned at the center of the solution with a platinum wire under the condition that the solution was heated to 80°C for the purpose of accelerating a reaction. After the phase- separated glass was left to stand for 1 hour, the immersing treatment with an acid solution was performed as the second process.
  • Fig. 4 is a scanning electron " microscope (SEM) ---- image of the surface of the porous glass produced in
  • Comparative Example 3 The glass of Production Example 6 was cut to a size of lcmxlcm and used, and an experiment was performed in the same way as in Comparative Example 1.
  • Comparative Example 4 The glass of Production Example 6 was cut to a size of lcmxlcm and used, and an experiment was performed in the same way as in Comparative Example 2.
  • a denatured layer on the surface of borosilicate glass can be removed selectively, and in the production of porous glass, a denatured layer on the surface of phase separation borosilicate glass can be removed selectively, and thus, porous phase separation silica can be produced without breaking a silica skeleton of a phase separation structure while keeping a strong silica skeleton.
  • the present invention can be utilized for washing/etching of a substrate of ordinary borosilicate glass, and in phase- separated glass, the glass can be made porous while keeping the smoothness of the surface.
  • the present invention can be utilized in a field in which phase-separated glass is used for a separation film or an optical material.

Landscapes

  • 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)
  • Surface Treatment Of Glass (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)

Abstract

Provided is a method of producing porous glass having pores with a uniform pore diameter entirely, particularly in the case of phase-separated glass, including selectively removing a denatured layer formed on the surface of glass easily. The method of producing glass includes: forming phase-separated glass containing silicon oxide, boron oxide, and an alkali metal oxide; bringing an alkaline solution held by a porous supporting member into contact with the denatured layer formed on the surface of the phase-separated glass to remove the denatured layer; and immersing the phase-separated glass with the denatured layer removed therefrom in an acid solution to form pores in the phase-separated glass.

Description

DESCRIPTION
METHOD OF PRODUCING GLASS
Technical Field
[0001]The present invention relates to a method of producing
glass .
Background Art
[0002]A layer having a composition different from that of an
inner part of glass is liable to appear on the surface of multi-component oxide glass due to the influences of water vapor and heat in the atmosphere.
[0003] For example, one of the. productions of a porous glass
material is to utilize a phase separation. A phase
separation is generally induced by heat treatment of holding molded borosilicate glass at high temperature for a long period of time. By etching the glass with an acid solution to elute a silica-poor phase, the porous glass is obtained. A skeleton of the porous glass is mainly formed of silicon oxide. For making the porous glass material utilizing a phase separation, borosilicate glass mainly containing silicon oxide, boron oxide, and an alkali metal oxide is generally used.
[0004] However, for example, as also described in NPL 1, in a
phase separation induced by holding glass at high
temperature for a long period of time (hereinafter, referred to as "phase separation heating treatment") and phase separation, boron or the like on the surface of glass is partly lost to cause a composition displacement, and thus, a denatured layer is formed on the surface of the glass. The denatured layer causes a problem of inhibiting etching with an acid solution in a later process. Hence, the denatured layer is required to be removed.
[0005] For example, PTL 1 discloses a technique of removing at least 10 μιη of outermost surface glass by polishing.
However, with the removal by polishing, glass needs to have mechanical strength to some degree, and there may be problems such as roughening of the surface by polishing and the remaining of an abrasive in performing later processes in some cases.
[0006] PTL 2 also describes that an outermost surface glass layer of borosilicate glass is removed by a chemical method using hydrofluoric acid, ammonium hydrogen difluoride, or an alkaline glass corrosive.
[0007] PTL 3 describes a method of removing a denatured layer by a chemical procedure involving washing a denatured layer on the surface of glass with an alkaline aqueous solution.
However, PTL 2 and PTL 3 do not disclose a method of
selectively removing a denatured layer. Further, in the case where a denatured layer is formed on thin glass or a glass thin film, it is necessary to selectively remove only a denatured layer, which requires a new facility.
Citation List
Patent Literature
[0008] PTL 1: Japanese Patent Application Laid-Open No. S62- 297223
[0009] PTL 2: Japanese Patent Application Laid-Open No. S62- 297223
[0010] PTL 3: Japanese Patent Application Laid-Open No. 2003- 073145
Non Patent Literature
[0011] PL 1 : "New glass and its physical properties", chapter 2, page 51, edited by T. Izumiya, Management System Laboratory, Co., Ltd. 1987
Summary of Invention
Technical Problem
[0012] The present invention has been achieved in order to solve such problem as described above, and an object of the present invention is to provide a method of producing porous glass having pores with a uniform pore diameter entirely, particularly in the case of phase separation glass, including selectively removing a denatured layer formed on the surface of glass easily.
Solution to Problem
[0013] In order to solve the above mentioned problem, a method of producing glass of the present invention includes: forming a vitreous body containing silicon oxide, boron oxide, and an alkali metal oxide; and bringing an alkaline solution held by a porous supporting member into contact with the surface of the vitreous body to remove a denatured layer.
[ 0014 ] Further, the method of producing glass of the present
invention includes: forming phase separation glass
containing silicon oxide, boron oxide, and an alkali metal oxide; bringing an alkaline solution held by a porous supporting member into contact with the surface of the phase separation glass to remove the denatured layer; and immersing the phase separation glass with the denatured layer removed therefrom in. an acid solution and/or water to form pores in the phase separation glass.
Advantageous Effects of Invention
[0015] According to the present invention, there can be provided the method of producing glass having pores with a uniform pore diameter entirely, particularly in the case of phase separation glass, including selectively removing a
denatured layer formed on the surface of glass easily.
[0016] Further, because the method does not use a mechanical
removing method such as polishing, there are no problems in mechanical strength and. shape of glass . Thus-,- -the method " can be used for all purposes.
[0017] Further features of the present invention will become
apparent from the following description of exemplary embodiments with reference to the attached drawings.
Brief Description of Drawings
[0018] [Fig. l]Fig. 1 is a schematic view illustrating one
embodiment of a method of producing glass of the present invention.
[Fig. 2] Fig. 2 is a scanning electron microscope (SEM) image of the surface of glass produced in Example 1. [Fig. 3] Fig. 3 is a scanning electron microscope (SEM) image of the surface of glass produced in Comparative
Example 1.
[Fig. 4] Fig. 4 is a scanning electron microscope (SEM) image of the surface of glass produced in Comparative
Example 2.
Description of Embodiments
[0019] Hereinafter, one embodiment for carrying out the present invention is described.
[0020] Fig. 1 is a view illustrating one embodiment of a method of producing glass of the present invention, and illustrates a porous supporting member 1, a denatured layer 2, and a vitreous body or phase separation glass 3.
[0021] he method of producing glass according to the present
invention includes bringing an alkaline solution held by a porous supporting member into contact with the surface of borosilicate glass to remove a denatured layer.
[ 0022 ] Further, the method of producing glass according to the
present invention includes: forming phase separation glass containing silicon oxide, boron oxide, and an alkali metal oxide; bringing an alkaline solution held by a porous supporting member into contact with a denatured layer formed on the surface of the phase separation glass to remove the denatured layer; and immersing the phase
separation glass with the denatured layer removed therefrom in an acid solution and/or water to form pores in the phase separation glass.
[0023] In the present invention, borosilicate glass is obtained by forming a vitreous body by melting a mixture containing silicon oxide, boron oxide, and an alkali metal oxide, followed by surface treatment, if required. In the case of forming phase separation glass, a process of forming phase separation glass by heating the vitreous body to effect phase separation is involved. This heating is referred to as phase separation heating in the present specification. With a particular composition, phase separation glass may be obtained without phase separation heating. In general, borosilicate glass is expressed by a weight ratio of oxides such as silicon oxide (silica, Si02) , boron oxide (B2O3) , and an alkali metal oxide. The borosilicate glass contains mainly silicon oxide, boron oxide, and an alkali metal oxide, and may contain, for example, aluminum oxide, calcium oxide, and magnesium oxide as other metal oxides.
[0024] In phase separation glass, borosilicate glass having a
particular composition undergoes, in some cases, a phase separation in which glass is separated into a silicon oxide glass phase mainly containing silicon oxide and a
borosilicate glass phase mainly containing boron oxide and an alkali metal oxide in the course of the application of heat to the vitreous body. Glass that has undergone the phase separation is referred to as phase separation glass in this description. Phase separation borosilicate glass is, for example, Si02 (55 to 80% by weight ) -B2C>3-Na20- (AI2O3) -based glass, Si02 (35 to 55% by weight ) -B203-Na20- based glass, Si02-B203-CaO-Na20-Al203-based glass, 3ί02-Β203- Na2<0-R0 (R: alkaline earth metal, Zn) -based glass, and Si02-B203-CaO-MgO-Na20-Al203-Ti02 (Ti02 is contained up to 49.2 mol%)-based glass.
[ 0025 ] Regarding the preferred composition as main components of a vitreous body to be used in the present invention, the content of an alkali metal oxide is generally 2% by weight or more to 20% by weight or less, particularly preferably 3% by weight or more to 15% by weight or less.
[0026] The content of boron oxide is generally 10% by weight or more to 55% by weight or less, particularly preferably 15% by weight or more to 50% by weight or less.
[0027] The content of silicon oxide is generally 45% by weight or more to 80% by weight or less, particularly preferably 55% by weight or more to 75% by weight or less.
[0028 ] Further, the content of metal oxides other than silicon
oxide, boron oxide, and an alkali metal oxide is generally 15% by weight or less, particularly preferably 10% by weight or less.
[0029] In the case of phase separation glass, a phase separation appears generally when the glass is held at about 500°C to 700°C for several hours to tens of hours, and the state of expression of phase separation, and further, the pore diameter and pore density in the case where porous glass is obtained, vary depending upon the temperature and retention time . ,
[0030] It is ideal that the total content of silicon oxide, boron oxide, and an alkali metal oxide to be contained in the entire glass be the same before and after the phase
separation heat treatment. However, a part of boron oxide and an alkali metal oxide in the vicinity of the surface of glass is lost due to the reaction with water vapor in the atmosphere or the sublimation during heat treatment, and apart from uniform phase separation formation in an inner part, a denatured layer mainly containing silicon oxide is formed on the surface.
[ 0031 ] Further, even in the case of general borosilicate glass,
when the glass is subjected to surface polishing, a
denatured layer mainly containing silicon oxide on the surface is formed in many cases.
[0032] The generation of a denatured layer on the surface can be confirmed by an observation procedure by a scanning
electron microscope (SEM) , etc., or an element analysis procedure such as X-ray photoelectron analysis (XPS), and the thickness of the denatured layer is about several hundred nanometers even when the layer is thick.
[0033] When a denatured layer is generated on the surface of glass, solid silica covers a portion in which a phase separation occurs, which adversely affects the elution and porosity of a soluble layer of phase separation glass with an acid solution, for example.
[0034] In phase-separated borosilicate glass,' a borosilicate glass phase mainly containing boron oxide and an alkali metal oxide is soluble in an acid solution. Thus, the soluble phase reacts by acid treatment, and a silicon oxide glass phase mainly containing silicon oxide remains as a skeleton. Thus, porous glass having pores formed therein is formed. When a denatured layer is formed on the surface, the acid solution does not permeate the inner part of the glass in which the phase separation is effected, and even when the acid solution permeates the inner part, the elution of the soluble phase is inhibited. Thus, pores are hardly
obtained.
[0035]As a mechanical method of removing a denatured layer, for example, there is given mechanical surface polishing.
However, a stress is applied to glass when the surface of the glass is polished with an abrasive, and the glass, if it is fragile, may be broken. Further, it is difficult to precisely control the amount to be removed by polishing, and there is a possibility that a phase-separated uniform glass layer portion may be removed. Further, cracks may occur on the surface of glass after polishing, and the abrasive may remain.
[0036] As a chemical procedure, a denatured layer can be removed by allowing an alkaline solution to react with the surface of glass where the denatured layer is formed. This is because the alkaline solution and solid silica mainly forming the denatured layer react with each other on the surface of the glass.
[0037]When the alkaline solution is allowed to react with the
denatured layer, for example, in the case where phase separation glass in which a denatured layer is formed is immersed sufficiently in a bath of an alkaline solution, the alkaline solution circulates to increase a liquid amount to be reacted per unit area of the denatured layer. Therefore, the alkaline solution not only breaks the
denatured layer but also may erode and break a silicon oxide glass phase mainly containing silicon oxide which mainly forms a skeleton in a phase-separated inner part.
In the alkaline solution that reacts with the denatured layer, the reactivity changes greatly depending upon the temperature, and it is very difficult to selectively remove only the denatured layer under immersing conditions.
[0038] he present invention is characterized by using a method of etching glass, including a first process of bringing an alkaline solution held by a porous supporting member into contact with a denatured layer formed on the surface of phase separation glass and leaving the resultant to remove the denatured layer, and a second process of immersing the phase-separated glass with the denatured layer removed therefrom in an acid solution and/or water to form pores in the phase-separated glass.
[0039] Fig. 1 is a schematic view illustrating one embodiment of a method of producing glass of the present invention. Fig. 1 illustrates a method of removing a denatured layer 2 by bringing a porous supporting member 1 containing an
alkaline solution into contact with the denatured layer 2 formed on the surface of a vitreous body or phase-separated glass 3 and leaving the resultant. In the first process, a porous supporting member is allowed to hold a limited amount of an alkaline solution and the resultant is brought into contact with the surface of glass with a denatured layer formed thereon, and thus, the liquid amount to be reacted per unit area of the denatured layer is limited, enabling the denatured layer to be removed selectively. The reaction can be controlled merely by allowing the porous supporting member to hold the liquid amount to be reacted with at most hundreds of nanometers of the
denatured layer. This can also reduce the alkaline
solution to be required. Further, if necessary, the treatment temperature of a glass layer can be set in a range of -5°C to 90°C for adjusting the reaction speed and the holding function on the surface.
[0040] The pore diameter of the porous supporting member to be used in the present invention is preferably 1 mm or less. Further, the porous supporting member includes preferably a metal, a natural fiber, or a synthetic fiber. The kind of the alkaline solution to be used in the present invention is not limited as long as the solution reacts with and breaks solid silica mainly forming a denatured layer. For example, an alkaline solution of sodium hydroxide or potassium hydroxide is preferred. It is desired that the alkali concentration of the alkaline solution be 10% by weight or more to 40% by weight or less, preferably 20% by weight or more to 30% by weight or less.
[0041] The present invention is characterized by including a first process of allowing an alkaline solution layer to be held on the surface of glass, and a second process of immersing the glass in an acid solution and/or water. In the second process, the glass in a state in which the denatured layer has been removed from the surface in the first process can be allowed to elute selectively borosilicate glass mainly containing boron oxide and an alkali metal oxide in phase- separated glass, using an ordinary etching method of immersing the phase separated-glass in an acid solution without the inhibition by the denatured layer. As an etching solution of the acid solution, an aqueous solution of hydrochloric acid, sulfuric acid, phosphoric acid, or nitric acid is used, and allows the glass to be immersed therein to dissolve a non silica-rich phase. The acid concentration of the acid solution is 0.1 mol/L or more to
5 mol/L or less (0.1 to 5 N) , preferably 0.5 mol/L or more to 2 mol/L or less (0.5 to 2 N) .
[0042 ] Depending upon a glass composition, silica gel may be
deposited in pores between skeletons of silicon oxide. If required, a method of etching in multi-stages, using acid solutions with different acidities or water can be. used. The etching can also be performed at an etching temperature of room temperature to 95 °C. Depending upon the
composition of phase separated-glass, pores may be formed only with etching using water without using an etching solution of an acid. Further, a residual of the denatured layer broken in the first process can be prevented from being deposited on the surface by combining the second
process with the first process.
[0043] It is preferred that, after immersing treatment with an
acid solution, porous glass be rinsed with water for the purpose of removing an acid adhering to the porous glass and a soluble layer remaining without being eluted.
[0044] The porous structure of glass obtained after the denatured
layer is removed and the etching is completed can be
confirmed by an observation procedure such as SEM or a pore distribution measurement such as a mercury penetration
method.
[0045] Glass having pores formed therein by the method of
producing glass of the present invention has a spinodal structure based on silicon oxide. The phase separations are classified into a spinodal type and a binodal type.
The pores obtained by a spinodal-type phase separation are penetrating pores linked from the surface to the inside as shown in Fig. 2, for example. The structure in which the skeleton of a silicon oxide main component is continuously formed as shown in Fig. 2 is referred to as a spinodal
structure based on silicon oxide. The penetrating pores linked from the surface to the inside are formed by the spinodal structure based on silicon oxide. A binodal-type phase separation provides a structure having closed pores.
.. Tt has been well known that, pore diameters and their - distribution can be controlled depending on conditions for the heat treatment during the production of the glass. Of the phase separation phenomena, the spinodal-type phase separation that provides a porous structure having
penetrating pores linked from the surface to the inside, i.e., the so-called spinodal structure is preferred.
[0046] The average pore diameter of the pores, which is not
particularly limited, desirably falls within the range of 1 nm to 1 μιτι, particularly 2 nm to 0.5 μπι, further
particularly 10 nm to 0.1 ym. The glass desirably has a porosity of generally 10 to 90%, particularly 20 to 80%.
[0047] The glass having pores formed therein is expected to find use in applications such as adsorbents, microcarriers , separation films, and optical materials because its porous structure can be uniformly controlled and its pore
diameters can each be changed within a certain range.
[0048]Next, examples of the present invention are described.
[0049] Hereinafter, the present invention is described more
specifically by way of examples, but the present invention is not limited to the following examples.
[0050] Production Examples 1 to 7 of glass
For examples and comparative examples of the present invention, glass was produced as Production Examples 1 to 7 with the composition in terms of oxide as shown in Table 1. As material compounds, silica powder (Si02) , boron oxide (B203) , sodium carbonate (Na2C03) , and aluminum oxide (ΑΊ2Ο3) were used. The mixed powder of the respective, material compounds was placed in a platinum crucible and melted at 1,500°C for 24 hours. After that, the temperature of the glass was lowered to 1,300°C, and the resultant was poured into a graphite mold. The mold was cooled in air for 20 minutes. After that, a block of the borosilicate glass thus obtained was cut to 40 mmx30 mmxl.l mm, and both surfaces were polished to mirror finish.
[0051] Next, the vitreous body thus processed was subjected to
phase separation treatment in an electric furnace under each of the conditions shown in Table 2. Thus, each glass of Production Examples 1 to 7 for examples and comparative examples was obtained.
[0052] The glass used in Examples 1 to 6 is glass described in
Production Examples 1 to 5, and 7.
[ 0053 ] Example 1: Glass etching was performed using the glass of Production Example 1. A sample to be used was obtained by cutting the phase-separated glass to 2 cm>2 cm.
[0054] It was found by SEM observation that the thickness of the denatured layer of the phase-separated glass was about 200 nm. Further, it was confirmed by XPS measurement that the abundance of boron and sodium was smaller on the surface of the phase-separated glass, compared with that on a cross- section thereof, and the surface of the phase-separated glass was almost occupied with silicon and a denatured layer was present.
[0055] In the treatment in the first process using an alkali for removing a denatured layer, a potassium hydroxide aqueous solution of a concentration of 30% by weight was used as an alkaline solution. Further, the material for the porous supporting member used was rayon, and the rayon had a pore diameter of 300 nm, a density of 60 Kg/m3, and a thickness of 80 pm.
[0056] First, a potassium hydroxide aqueous solution was immersed in a porous supporting member to allow the potassium hydroxide aqueous solution to permeate the porous
supporting member sufficiently. The porous supporting member containing sufficiently potassium hydroxide was brought into contact with the surface of the phase- separated glass with a denatured layer formed thereon as illustrated in Fig. 1. In the atmosphere, the resultant was left to stand at room temperature for 2.5 hours.
[0057] After that, in the immersing treatment in the acid solution in the second process, 50 g of 1 mol/L (1 N) nitric acid was used as the acid solution. Nitric acid was placed in a container "made- -of"polypropylene, and previously heated ~to 80°C in an oven. A sample subjected to the treatment in the first process was suspended and placed therein so as to be positioned at the center of the solution with a platinum wire. The polypropylene container was covered and left to stand at 80°C for 24 hours. The glass subjected to the treatment with the acid solution was placed in water at 80°C to perform rinse treatment.
[0058] It was found by SEM observation that the denatured layer was removed completely, the porous skeleton remained without being eroded, and the entire sample became porous glass. Fig. 2 is a scanning electron microscope (SEM) image of the surface of the porous glass produced in
Example 1.
[0059] Example 2: An etching experiment was conducted in the
same way as in Example 1 using the glass of Production
Example 2. The thickness of the denatured layer was 100 nm. It was found by SEM observation of the glass after the experiment that the denatured layer was removed completely, the porous skeleton remained without being eroded, and the entire sample became porous glass.
[0060] Example 3: An experiment was conducted in the same way as in Example 1 using the glass of Production Example 3. The thickness of the denatured layer was 150 nm. It was found by SEM observation of the glass after the experiment that the denatured layer was removed completely, the porous skeleton remained without being eroded, and the entire sample became porous glass.
[0061] Example 4: An experiment was conducted in the same way as in Example 1 using the glass of Production Example 3. The thickness of the denatured layer was 100 nm. It was found by SEM observation of the glass after the experiment that the denatured layer was removed completely, the porous skeleton remained without being eroded, and the entire sample became porous glass.
[0062] Example 5: An experiment was conducted in the same way as in Example 1 using the glass of Production xample 3. The thickness of the denatured layer was 50 nm. It was found by SEM observation of the glass after the experiment that the denatured layer was removed completely, the porous skeleton remained without being eroded, and the entire sample became porous glass.
[0063] Example 6 : The glass of Production Example 7 was used.
When the glass was irradiated with laser light, no phase separation was confirmed. An experiment was conducted in the same way as in Example 1. The thickness of the
denatured layer was 50 nm. It was found by SEM observation of the glass after the experiment that the denatured layer was removed completely.
[006 ] Comparative Example 1: The glass of Production Example 1 was cut to a size of lcmxlcm and used.
[0065] Regarding the phase-separated glass in which the denatured layer was present, the second process involving immersing the glass in an acid solution was performed without
performing the first process involving allowing a porous supporting member to contain an alkaline solution. In the immersing treatment in the acid solution, 50 g of 1 mol/L (1 N) nitric acid was used as the acid solution. Nitric acid was placed in a container made of polypropylene and previously heated to 80 °C in an oven. A sample was
suspended and placed therein with a platinum wire so as to be positioned at the center of the solution. The
polypropylene container was covered and left to stand at 80°C for 24 hours. The glass treated with the acid
solution was placed in water at 80°C and then rinse
treatment was performed.
[0066] It was confirmed by SEM observation that the denatured
layer remained on the surface of the glass after the treatment. Further, the glass after the treatment was cut and the cut surface was observed by SEM. Then, it was confirmed that a soluble layer of the phase-separated glass remained in a portion where the denatured layer remained, --which prevented the treatment with an acid "-solution. Fig. 3 is a scanning electron microscope (SEM) image of the surface of the porous glass produced in Comparative Example 1.
[0067] Comparative Example 2: The glass of Production Example 1 was cut to a size of lcmxlcm and used.
[ 0068 ] Regarding the phase-separated glass in which the denatured layer was present, the phase-separated glass was immersed in an alkaline solution bath without using a porous
supporting member in the first process involving bringing the phase-separated glass into contact with the alkaline solution. The alkaline solution to be used herein is a potassium hydroxide aqueous solution of a concentration of 30% by weight. Then, 50 g of alkaline solution was placed in a polypropylene container, and the phase-separated glass was suspended and placed therein so as to be positioned at the center of the solution with a platinum wire under the condition that the solution was heated to 80°C for the purpose of accelerating a reaction. After the phase- separated glass was left to stand for 1 hour, the immersing treatment with an acid solution was performed as the second process.
[0069] In the immersing treatment in the acid solution in the
second process, 50 g of 1 mol/L (1 N) nitric acid was used as the acid solution. Nitric acid was placed in a
container made of polypropylene and previously heated to 80°C in an oven. A sample subjected to the treatment in the first process was suspended and placed therein so as to be positioned at the center of the solution with a platinum wire. The polypropylene container was covered and left to stand at 80°C for 24 hours. The glass subjected to the treatment with the acid solution was placed in water at 80°C to perform rinse treatment.
[0070]After the treatment, it was found by SEM observation of the surface of the glass that the skeleton of a porous portion was also eroded by an alkali while the denatured layer was ■ removed. Fig. 4 is a scanning electron "microscope (SEM) ---- image of the surface of the porous glass produced in
Comparative Example 2.
[0071] Comparative Example 3: The glass of Production Example 6 was cut to a size of lcmxlcm and used, and an experiment was performed in the same way as in Comparative Example 1.
[0072] In the same way as in Comparative Example 1, it was
confirmed by SEM observation that the denatured layer remained on the surface of the glass after the treatment. Further, the glass after the treatment was cut, and the cut surface was observed by SEM. Then, it was confirmed that a soluble layer of the phase-separated glass remained in the portion where the denatured layer remained, which prevented the treatment with an acid solution.
[0073] Comparative Example 4: The glass of Production Example 6 was cut to a size of lcmxlcm and used, and an experiment was performed in the same way as in Comparative Example 2.
[0074]After the treatment, it was found by SEM observation of the surface of the glass that the skeleton of a porous portion was also eroded by an alkali while the denatured layer was removed in the same way as in Comparative Example 2.
[0075]Table 1
Si02 B203 Na20 A1203
Glass name wt% wt% wt% wt%
Production
63 28 9 - Example 1
Production
63 27 7 3
Example 2
Production
59 30.5 9 1.5 Example 3
Production
75 19 4.5 1.5 Example 4
Production
69 25 4.5 1.5 . Example 5
Production
63 28 9 - Example 6
Production
65 24 11 - Example 7 Table 2
Phase separation
Phase separation
Glass name treatment
treatment time H temperature °C
Production
600 50
Example 1
Production
560 50
Example 2
Production
560 50
Example 3
Production
600 50
Example 4
Production
600 25
Example 5 Production
600 25
Example 6
Production
500 24
Example 7
[0077]Table 3
Figure imgf000018_0001
Industrial Applicability
[ 0078 ] According to the method of producing glass of the present invention, a denatured layer on the surface of borosilicate glass can be removed selectively, and in the production of porous glass, a denatured layer on the surface of phase separation borosilicate glass can be removed selectively, and thus, porous phase separation silica can be produced without breaking a silica skeleton of a phase separation structure while keeping a strong silica skeleton. The present invention can be utilized for washing/etching of a substrate of ordinary borosilicate glass, and in phase- separated glass, the glass can be made porous while keeping the smoothness of the surface. Thus, the present invention can be utilized in a field in which phase-separated glass is used for a separation film or an optical material.
[0079] hile the present invention has been described with
reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed
exemplary embodiments.
[0080] his application claims the benefit of Japanese Patent
Application No. 2010-126328, filed June 1, 2010, which is hereby incorporated by reference herein in its entirety.

Claims

[1] A method of producing glass, comprising:
forming a vitreous body containing silicon oxide, boron oxide, and an alkali metal oxide; and
bringing an alkaline solution held by a porous supporting member into contact with a surface of the vitreous body to remove a denatured layer which is compositionally deviated from a vitreous body.
[2] A method of producing glass comprising:
forming phase-separated glass containing silicon oxide, bringing an alkaline solution held by a porous supporting member into contact with a denatured layer formed on a surface of the phase-separated glass to remove the
denatured layer which is compositionally deviated from a vitreous body; and
immersing the phase-separated glass with the denatured layer removed therefrom in an acid solution and/or water to form pores in the phase-separated glass.
[3] The method of producing glass according to claim 1 to 2, wherein the porous supporting member has a pore diameter of 1 mm or less.
[4] The method of producing glass according to any one of
claims 1 to 3, wherein the porous supporting member
comprises a metal, a natural fiber, or a synthetic fiber.
[5] The method of producing glass according to any one of
claims 1 to 4, wherein an alkali concentration of the alkaline solution is 10% by weight or more to 40% by weight or less.
[6] The method of producing glass according to any one of
claims 2 to 5, wherein an acid concentration of the acid solution is 0.1 mol/L or more to 5 mol/L or less.
PCT/JP2011/062152 2010-06-01 2011-05-20 Method of producing glass Ceased WO2011152289A2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/699,977 US9278882B2 (en) 2010-06-01 2011-05-20 Method of producing glass

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010126328A JP5725734B2 (en) 2010-06-01 2010-06-01 Glass manufacturing method
JP2010-126328 2010-06-01

Publications (2)

Publication Number Publication Date
WO2011152289A2 true WO2011152289A2 (en) 2011-12-08
WO2011152289A3 WO2011152289A3 (en) 2012-04-12

Family

ID=44509978

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/062152 Ceased WO2011152289A2 (en) 2010-06-01 2011-05-20 Method of producing glass

Country Status (3)

Country Link
US (1) US9278882B2 (en)
JP (1) JP5725734B2 (en)
WO (1) WO2011152289A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130164521A1 (en) * 2010-08-10 2013-06-27 Jae Min Myoung Glass substrate manufacturing method and glass thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5911240B2 (en) * 2010-10-04 2016-04-27 キヤノン株式会社 Porous glass, manufacturing method thereof, optical member, and imaging apparatus
JP5882690B2 (en) 2010-11-30 2016-03-09 キヤノン株式会社 Porous glass and method for producing the same
JP6395489B2 (en) 2014-07-29 2018-09-26 キヤノン株式会社 Glass composition and method for producing the same, glass member and imaging device
US12378151B2 (en) 2021-05-20 2025-08-05 Corning Incorporated Phase-separated glass compositions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62297223A (en) 1986-05-28 1987-12-24 ア−・ファウ・エル　ア−・ゲ− Manufacture of carrier material for optical sensor
JP2003073145A (en) 2001-09-04 2003-03-12 Nippon Sheet Glass Co Ltd Method for fine processing glass substrate, glass substrate for fine processing and fine processed glass product
JP2010126328A (en) 2008-11-28 2010-06-10 Sharp Corp Sheet ejection device and image forming device provided with the same

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2106744A (en) 1934-03-19 1938-02-01 Corning Glass Works Treated borosilicate glass
NL302162A (en) 1963-01-18
GB1309333A (en) * 1970-01-19 1973-03-07 Glaverbel Process for bending glass
US4220682A (en) 1974-04-22 1980-09-02 Litovitz Theodore A Strengthened glass structural member
US4019884A (en) * 1976-01-22 1977-04-26 Corning Glass Works Method for providing porous broad-band antireflective surface layers on chemically-durable borosilicate glasses
US4086074A (en) 1976-01-22 1978-04-25 Corning Glass Works Antireflective layers on phase separated glass
US4080188A (en) * 1976-11-22 1978-03-21 Corning Glass Works Durable substrates having porous antireflection coatings
JPS59227047A (en) * 1983-06-07 1984-12-20 Canon Inc optical recording medium
JPS6140841A (en) 1984-07-31 1986-02-27 Miyazakiken Porous moulded product of glass and its preparation
US4781792A (en) * 1985-05-07 1988-11-01 Hogan James V Method for permanently marking glass
JPS6479030A (en) * 1987-09-22 1989-03-24 Asahi Glass Co Ltd Production of porous small glass sphere
JPH01145349A (en) * 1987-11-30 1989-06-07 Agency Of Ind Science & Technol Composition for porous glass and porous glass produced therefrom
JPH1129882A (en) 1997-07-08 1999-02-02 Kanto Bussan Kk Etching method for base material and acidic ink to be used for the same
JP3998226B2 (en) 1998-12-21 2007-10-24 Ｓｕｍｃｏ Ｔｅｃｈｘｉｖ株式会社 Wafer etching method and apparatus
US6553788B1 (en) 1999-02-23 2003-04-29 Nippon Sheet Glass Co., Ltd. Glass substrate for magnetic disk and method for manufacturing
US7416680B2 (en) 2001-10-12 2008-08-26 International Business Machines Corporation Self-cleaning colloidal slurry composition and process for finishing a surface of a substrate
JP2003332868A (en) 2002-05-14 2003-11-21 Univ Nihon Method for manufacturing high-frequency crystal resonator and etching apparatus used for same
JP2004063816A (en) * 2002-07-30 2004-02-26 Nec Kansai Ltd Method for marking identification mark on semiconductor substrate and marking jig
DE102006022093B4 (en) 2006-05-11 2010-04-08 Siltronic Ag Method and apparatus for treating a semiconductor wafer by etching
JP4410312B2 (en) 2007-12-20 2010-02-03 株式会社テオス Selective etching method for photovoltaic device substrate for solar cell using thickening etching coating solution
JP2011241130A (en) 2010-05-20 2011-12-01 Canon Inc Phase-separated glass and porous glass
JP5721348B2 (en) 2010-06-01 2015-05-20 キヤノン株式会社 Glass manufacturing method
JP5796936B2 (en) 2010-06-01 2015-10-21 キヤノン株式会社 Method for producing porous glass
JP5882690B2 (en) 2010-11-30 2016-03-09 キヤノン株式会社 Porous glass and method for producing the same
JP2012131695A (en) 2010-11-30 2012-07-12 Canon Inc Method of manufacturing porous glass and method of manufacturing imaging apparatus

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62297223A (en) 1986-05-28 1987-12-24 ア−・ファウ・エル　ア−・ゲ− Manufacture of carrier material for optical sensor
JP2003073145A (en) 2001-09-04 2003-03-12 Nippon Sheet Glass Co Ltd Method for fine processing glass substrate, glass substrate for fine processing and fine processed glass product
JP2010126328A (en) 2008-11-28 2010-06-10 Sharp Corp Sheet ejection device and image forming device provided with the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"New glass and its physical properties", 1987, MANAGEMENT SYSTEM LABORATORY, CO., LTD., pages: 51

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130164521A1 (en) * 2010-08-10 2013-06-27 Jae Min Myoung Glass substrate manufacturing method and glass thereof
US9112076B2 (en) * 2010-08-10 2015-08-18 Industry-Academic Cooperation Foundation Yonsei University Glass substrate manufacturing method and glass thereof

Also Published As

Publication number Publication date
JP2011251871A (en) 2011-12-15
US20130074548A1 (en) 2013-03-28
WO2011152289A3 (en) 2012-04-12
US9278882B2 (en) 2016-03-08
JP5725734B2 (en) 2015-05-27

Similar Documents

Publication Publication Date Title
JP5721348B2 (en) Glass manufacturing method
US20130068725A1 (en) Method of producing porous glass
US20130233018A1 (en) Method of manufacturing porous glass
US20130045853A1 (en) Method of producing porous glass
EP3201149B1 (en) Method for manufacturing patterned ion-exchanged substrates
US9278882B2 (en) Method of producing glass
JP5950587B2 (en) Method for producing porous glass and method for producing optical member
Mellott et al. Evaluation of surface preparation methods for glass
US9359244B2 (en) Alumina-rich glasses and methods for making the same
US20130192306A1 (en) Method for producing porous glass
EP2731919A2 (en) Chemically durable porous glass with enhanced alkaline resistance
JP7280547B2 (en) Method for manufacturing porous glass member
JP7648988B2 (en) Method for manufacturing porous glass member
CN102688702B (en) Preparation method of silicate glass hollow fiber membrane
JP2012193067A (en) Borosilicate glass, porous glass, and method for producing the same
JP2024060430A (en) Method for producing porous glass material, and porous glass material
JP7303480B2 (en) porous glass member
JP2021038109A (en) Method for forming porous deposit, structure having porous membrane and phase-separated mother glass
Mao et al. Fabrication of a nanoporous Na2O–B2O3–SiO2 glass plate with controlled por size
CN115368020A (en) Phase separated glass composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11725540

Country of ref document: EP

Kind code of ref document: A2

WWE Wipo information: entry into national phase

Ref document number: 13699977

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11725540

Country of ref document: EP

Kind code of ref document: A2