CN102421718A

CN102421718A - Glass ceramic, sintered glass ceramic material, glass ceramic complex, glass micropowder, slurry-like mixture, and photocatalyst

Info

Publication number: CN102421718A
Application number: CN201080020832XA
Authority: CN
Inventors: 傅杰
Original assignee: Ohara Inc
Current assignee: Ohara Inc
Priority date: 2009-07-31
Filing date: 2010-07-30
Publication date: 2012-04-18
Anticipated expiration: 2030-07-30
Also published as: CN102421718B; WO2011013797A1

Abstract

Disclosed are a glass ceramic, a sintered glass ceramic material, a glass ceramic complex, a glass ceramic micropowder, a slurry-like mixture, and a photocatalyst, each of which comprises a crystalline phase comprising tungsten oxide and/or a solid solution thereof and has a photocatalytic activity. The glass ceramic may contain 10 to 95 mol% of a WO3 component and may additionally contain 0 to 60 mol% of a P2O5 component, 0 to 60 mol% of a B2O3 component, 0 to 60 mol% of an SiO2 component, and/or 0 to 60 mol% of a GeO2 component relative to the total amount of all components in terms of oxide contents.

Description

Glass-ceramic, glass-ceramic sintered compact, glass-ceramic complex body, glass powder plastochondria, pulp-like mixture and photocatalyst

Technical field

The present invention relates to glass-ceramic and utilization thereof.

Background technology

Known titanium and Tungsten oxide 99.999 have highlight catalytic active.These compounds (following brief note sometimes is " photocatalyst ") with photocatalytic activity are in case the light of the energy more than the illuminated band-gap energy; Will generate electronics or hole; Therefore at the near surface of the molding that contains photocatalyst, redox reaction obtains strong promotion.Therefore known in addition, the surface of containing the molding of photocatalyst demonstrates the wetting ability that is easy to by water infiltration, has the so-called automatic cleaning action that can be cleaned by the water droplet of rainwater etc.

As photocatalyst, mainly research is titanium oxide, yet because the band gap of titanium oxide is 3～3.2eV, therefore needs the ultraviolet ray below the illumination wavelength 400nm, has the shortcoming that can't utilize the enough photocatalytic activities of visible light acquisition.On the other hand, Tungsten oxide 99.999 (WO for example ₃) band gap be about 2.5eV, possess the photocatalytic activity of visible light-responded property, therefore lacking ultraviolet indoor also utilizable strong point even have.

But, as making base material support the method for photocatalyst, studied the technology that forms the film that contains photocatalyst on the surface of base material, made the technology that contains photocatalyst in the base material etc.As the method that forms the film that contains photocatalyst on the surface of base material, form the coating method of coated film except utilizing coating, also known have sputter, vapor deposition, collosol and gel, CVD methods such as (chemical vapour depositions).For example, in TOHKEMY 2009-56398 communique, proposing to contain average particle diameter is the Tungsten oxide 99.999 particulate of 0.01～0.05 μ m and the visible-light-responsive photocatalyst coating that contains tackiness agent.In addition, in TOHKEMY 2001-152130 communique, proposed in oxygen atmosphere at the surface sputtering tungsten of base material and formed the method for oxidation tungsten film.

On the other hand, as making the technology that contains photocatalyst in the base material, though relate to the technology of titanium oxide, for example in japanese kokai publication hei 9-315837 communique, disclose the SiO that contains specified amount ₂, Al ₂O ₃, CaO, MgO, B ₂O ₃, ZrO ₂And TiO ₂Glass is used in the photochemical catalysis of each composition.

As stated, in numerous technology in the past, adopted through surface and formed the idea that the film that contains photocatalyst supports photocatalyst at base material.But,, can enumerate the aspect of the weather resistance of the adaptation that is difficult to guarantee base material and the film that contains photocatalyst and film self as the common problem of method that with this kind idea is basis.That is to say that the photocatalysis functional product that produces with these methods might make the film that contains photocatalyst and base material is peeled off or film generation deterioration and damage photo-catalysis function.For example as TOHKEMY 2009-56398 communique, using coating to form under the situation of coated film; The resin or the organic binder bond that residue in the coated film are decomposed because of ultraviolet ray etc.; Or because of the oxidized reduction of the katalysis of photocatalyst; Consequently, coated film is easy to pass and deterioration in time, has the insufficient problem of weather resistance.In addition; In order to bring into play the activity that supports the photocatalyst in film fully, need photocatalyst be processed into the ultramicron of nano-scale, yet the ultramicron cost of manufacture of nano-scale uprises; And, exist to be difficult to disposal concerns because of the increase of surface energy is easy to cohesion.

As TOHKEMY 2001-152130 communique, utilizing sputter to form under the situation of photocatalyst film; Do not need micronize; The adaptation of base material and photocatalyst film also improves slightly, yet has that film forming speed is slow, a problem such as the material that needs large-scale equipment such as sputter equipment, adaptable base material or shape are limited.

On the other hand, disclosed photochemical catalysis contains titanium oxide with glass in the japanese kokai publication hei 9-315837 communique in glass, and technical idea was different in the past with other in this.But, in the technology of japanese kokai publication hei 9-315837 communique, do not have crystalline structure as the titanium oxide of photocatalyst, be present in the glass with unbodied form, so a little less than its photocatalytic activity, abundant inadequately.

Summary of the invention

The present invention accomplishes in view of above-mentioned truth, and its purpose is, a kind of also very excellent photocatalysis functional starting material of excellent photocatalysis activity and visible light-responded property and weather resistance that have are provided.

The inventor etc. further investigate in order to address the above problem repeatedly, and the result finds, through in glass, producing the crystalline phase that comprises Tungsten oxide 99.999 and/or its sosoloid, blank and product with excellent photo-catalysis function just can be provided, thereby accomplish the present invention.That is, the invention reside in following (1)～(21).

(1) a kind of glass-ceramic, it contains the crystalline phase that comprises Tungsten oxide 99.999 and/or its sosoloid.

(2) according to above-mentioned (1) described glass-ceramic, wherein, as said Tungsten oxide 99.999, total amount of convert forming with respect to oxide compound contains 10～95% WO in mole % ₃Composition.

(3) according to above-mentioned (1) or (2) described glass-ceramic, wherein, the total amount with respect to oxide compound converts and forms, in mole %, also contain:

0～60% P ₂O ₅Composition and/or

0～60% B ₂O ₃Composition and/or

0～60% SiO ₂Composition and/or

0～60% GeO ₂Each composition of composition.

(4) according to any described glass-ceramic in above-mentioned (1) to (3), wherein, also contain 0～60% TiO ₂Composition.

(5) according to any described glass-ceramic in above-mentioned (1) to (4), wherein, the total amount with respect to oxide compound converts and forms, in mole %, also contain:

0～40% Li ₂The O composition and/or

0～40% Na ₂The O composition and/or

0～40% K ₂The O composition and/or

0～10% Rb ₂The O composition and/or

0～10% Cs ₂Each composition of O composition.

(6) according to any described glass-ceramic in above-mentioned (1) to (5), wherein, the total amount with respect to oxide compound converts and forms, in mole %, also contain:

0～40% MgO composition and/or

0～40% CaO composition and/or

0～40% SrO composition and/or

Each composition of BaO composition of 0～40%.

(7) according to any described glass-ceramic in above-mentioned (1) to (6), wherein, the total amount with respect to oxide compound converts and forms, in mole %, also contain:

0～30% Al ₂O ₃Composition and/or

0～30% Ga ₂O ₃Composition and/or

0～10% In ₂O ₃Each composition of composition.

(8) according to any described glass-ceramic in above-mentioned (1) to (7), wherein, the total amount with respect to oxide compound converts and forms, in mole %, also contain:

0～20% ZrO ₂Composition and/or

Each composition of SnO composition of 0～10%.

(9) according to any described glass-ceramic in above-mentioned (1) to (8), wherein, the total amount with respect to oxide compound converts and forms, in mole %, also contain:

0～50% Nb ₂O ₅Composition and/or

0～50% Ta ₂O ₅Composition and/or

0～50% MoO ₃Each composition of composition.

(10) according to any described glass-ceramic in above-mentioned (1) to (9), wherein, the total amount with respect to oxide compound converts and forms, in mole %, also contain:

0～50% ZnO composition and/or

0～20% Bi ₂O ₃Composition and/or

0～20% TeO ₂Composition and/or

Add up to 0～30% Ln ₂O ₃Composition (in the formula, Ln be selected among Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and the Lu more than a kind) and/or

Add up to 0～5% M _xO _yComposition (in the formula, M be selected among V, Cr, Mn, Fe, Co and the Ni more than a kind, x and y are respectively and satisfy x: the natural number of valent minimum of y=2: M.Here, the valency of V is 5, and the valency of Cr is 3, and the valency of Mn is 2, and the valency of Fe is 3, and the valency of Co is 2, and the valency of Ni is 2.) and/or add up to 0～5% As ₂O ₃Composition and/or Sb ₂O ₃Each composition of composition.

(11) according to any described glass-ceramic in (1) to (10), wherein, also contain the composition more than at least a kind among F, Cl, Br, S, N and the C that is selected from below 15% in external ratio mass ratio with respect to the glass total mass.

(12), wherein, also contain at least a kind of metallics among Cu, Ag, Au, Pd, Ru, Rh, Re and the Pt that is selected from below 10% in external ratio mass ratio with respect to the glass total mass according to any described glass-ceramic in above-mentioned (1) to (11).

(13) according to any described glass-ceramic in above-mentioned (1) to (12), wherein, also contain TiO ₂, TiP ₂O ₇, (TiO) ₂P ₂O ₇, RnTi ₂(PO ₄) ₃, RTi ₄(PO ₄) ₆(in the formula, Rn be selected among Li, Na, K, Rb, the Cs more than a kind, R be selected among Mg, Ca, Sr, the Ba more than a kind) and their sosoloid in the crystal more than a kind.

(14) according to any described glass-ceramic in above-mentioned (1) to (13), it utilizes the light of the wavelength from the ultraviolet region to the visibility region to embody catalytic activity.

(15) according to any described glass-ceramic in above-mentioned (1) to (14), wherein, the surface and the contact angle of water droplet that have shone the light of the wavelength from the ultraviolet region to the visibility region are below 30 °.

(16) a kind of photocatalyst, it comprises any described glass-ceramic in above-mentioned (1) to (15).

(17) a kind of glass-ceramic sintered compact is with pulverizing the glass-ceramic sintered compact that glass sintering forms, it is characterized in that, in said glass-ceramic sintered compact, containing any described glass-ceramic in above-mentioned (1) to (15).

(18) a kind of glass-ceramic complex body is the glass-ceramic complex body that has base material and be located at the glass-ceramic layer on this base material, it is characterized in that, said glass-ceramic layer contains any described glass-ceramic in above-mentioned (1) to (15).

(19) a kind of glass powder plastochondria, it contains any described glass-ceramic in above-mentioned (1) to (15).

(20) a kind of glass powder plastochondria, it generates any described glass-ceramic in above-mentioned (1) to (15) through being heated.

(21) a kind of pulp-like mixture, it contains above-mentioned (19) or (20) described glass powder plastochondria and solvent.

Description of drawings

Fig. 1 is the XRD spectra of the glass-ceramic of relevant embodiments of the invention A1.

Fig. 2 is the result's that estimates of the wetting ability of the glass-ceramic of expression relevant embodiments of the invention A1, A4 a graphic representation.

Fig. 3 is the result's that estimates of the other wetting ability of the glass-ceramic of expression relevant embodiments of the invention A1, A4 a graphic representation.

Fig. 4 is the result's that estimates of the Socryl Blue BRL degrading activity of the glass-ceramic of expression relevant embodiments of the invention A44, A48, A54 a graphic representation.

Fig. 5 is the XRD spectra of the glass-ceramic sintered compact of relevant embodiments of the invention B1, B4, B18, B20.

Fig. 6 is the result's that estimates of the Socryl Blue BRL degrading activity of the glass-ceramic sintered compact of the relevant embodiments of the invention B1 of expression a graphic representation.

Fig. 7 be changed about the composition identical with embodiments of the invention C1 burn till, the XRD spectra of the glass-ceramic layer of crystallization condition.

Fig. 8 is the result's that estimates of the Socryl Blue BRL degrading activity of the glass-ceramic layer of the relevant embodiments of the invention C1 of expression a graphic representation.

Fig. 9 is the XRD spectra of the glass powder plastochondria (behind the crystallization) of relevant embodiments of the invention D1.

Figure 10 is the XRD spectra of the glass powder plastochondria (behind the crystallization) of relevant embodiments of the invention D11.

Figure 11 is the result's that estimates of the Socryl Blue BRL degrading activity of the glass powder plastochondria (behind the crystallization) of the relevant embodiments of the invention D1b of expression a graphic representation.

Figure 12 is the result's that estimates of the Socryl Blue BRL degrading activity of the glass powder plastochondria (behind the crystallization) of the relevant embodiments of the invention D14 of expression a graphic representation.

Embodiment

Below, embodiment of the present invention is elaborated.First embodiment of the present invention relates to glass-ceramic and method of manufacture thereof.Second embodiment relates to glass-ceramic sintered compact and method of manufacture thereof.The 3rd embodiment relates to the method for manufacture of glass-ceramic complex body.The 4th embodiment relates to the glass powder plastochondria and contains its slip shape mixture.

First embodiment: glass-ceramic

The glass-ceramic of this embodiment contains the crystalline phase that comprises Tungsten oxide 99.999 and/or its sosoloid, and (following note is sometimes made " WO ₃Crystalline phase ").Glass-ceramic is through glass heat being handled and in glassy phase, separated out the material that crystalline phase gets, also being known as " sintered glass ceramics ".Glass-ceramic can not only comprise the material with glassy phase and crystalline phase, but also comprises that glassy phase all becomes the material of crystalline phase, and promptly the crystallization content in the material (percent crystallinity) is the material of 100 quality %.The glass-ceramic of this embodiment can be utilized the control of crystallization step to control the crystalline particle diameter, separate out crystalline kind, percent crystallinity.

[composition]

Below, the composition of the glass-ceramic of this embodiment is described.And, in this manual, under the situation of the content that does not particularly point out each composition that constitutes glass or glass-ceramic, the amount of all representing for the mole % of total amount of forming to convert with respect to oxide compound.Here; So-called " oxide compound converts and forms "; Be that the oxide compound that uses as the raw material of glass constituent in supposition, composite salt, metal fluoride etc. all decompose during in fusion and become under the situation of oxide compound, be expressed in the composition of each contained in glass or glass-ceramic composition with total amount of this generation oxide compound as 100 moles of %.

Tungsten oxide 99.999 is the composition that brings photocatalysis characteristic to glass-ceramic.There is WO in Tungsten oxide 99.999 according to the oxide compound that raw material or preparation method become 2～6 valencys ₃, WO, W ₂O ₃, W ₄O ₁₁, WO ₂, W ₂O ₅, W ₃O ₈And W ₅O ₁₄In the glass-ceramic of this embodiment, as long as have photocatalytic activity, no matter the kind of Tungsten oxide 99.999 why can, yet preferably comprise WO with strong especially photocatalytic activity ₃So the typical example as Tungsten oxide 99.999 in the following explanation is enumerated WO ₃Describe.WO ₃Owing to absorbing wavelength plays photocatalytic activity up to the visible light of 480nm, therefore give the photocatalysis characteristic of visible light-responded property to glass-ceramic.Known WO ₃Have isometric system, tetragonal spheroidal, rhombic system, oblique system and triclinic crystalline structure, yet, no matter be that which kind of crystalline structure can as long as have photocatalytic activity.

WO ₃Crystal also can exist with the state with the sosoloid of other elements.Here, as said sosoloid, for example can enumerate and be selected from Mo _qW _1-qO ₃, Rn _qTaW _1-qO ₃, Rn _qNb _qW _1-qO ₃, R _qZr _qW _1-qO ₃(in the formula, Rn be selected among Li, Na, K, Rb, the Cs more than a kind, R be selected among Mg, Ca, Sr, the Ba more than a kind, q is meant the number that on stoichiometry, can obtain) etc.And sosoloid both can be substitutional solid solution, also can be calking type sosoloid.

Total amount that the glass-ceramic of this embodiment preferably converts and forms with respect to oxide compound contains WO in the preferred scope 10～95% of mole % ₃Composition.If WO ₃The content of composition then can't obtain enough photocatalytic activities less than 10%.On the other hand, if WO ₃The content of composition surpasses 95%, and then the stability of glass just suffers damage.So, with respect to total amount that oxide compound converts and forms, WO ₃The content of composition preferably with 10%, more preferably with 15%, most preferably be lower limit with 20%, preferably with 95%, more preferably with 80%, most preferably be the upper limit with 75%.WO ₃Composition can be through for example using WO as raw material ₃Wait and import in the glass.

P ₂O ₅Composition is the composition that constitutes the eyed structure of glass, is the composition that can at random add.Through the glass-ceramic with this embodiment is P ₂O ₅Composition is the phosphate-based glass of the principal constituent of eyed structure, just can be with more WO ₃Composition is introduced glass.In addition, through cooperating P ₂O ₅Composition can be separated out WO under lower thermal treatment temp ₃Crystal, and containing TiO ₂Under the situation of composition, can also expect to reduce from the high anatase titanium dioxide TiO of photocatalytic activity ₂Crystal is to the effect of the phase transformation of the low rutile-type of photocatalytic activity.But, if P ₂O ₅Content surpass 60%, then be difficult to separate out WO ₃Crystalline phase.So, adding P ₂O ₅Under the situation of composition, with respect to total amount that oxide compound converts and forms, P ₂O ₅The content of composition preferably with 1%, more preferably with 5%, most preferably be lower limit with 15%, preferably with 60%, more preferably with 50%, most preferably be the upper limit with 40%.P ₂O ₅Composition can be through for example using Al (PO as raw material ₃) ₃, Ca (PO ₃) ₂, Ba (PO ₃) ₂, NaPO ₃, BPO ₄, H ₃PO ₄Wait and import in the glass.

B ₂O ₃Composition is the eyed structure that constitutes glass, the composition that improves the stability of glass, is the composition that can at random add.But,, then be difficult to separate out WO if its content surpasses 60% ₃The tendency of crystalline phase will strengthen.So, with respect to total amount that oxide compound converts and forms, B ₂O ₃The content of composition preferably with 60%, more preferably with 50%, most preferably be the upper limit with 40%.B ₂O ₃Composition can be through for example using H as raw material ₃BO ₃, Na ₂B ₄O ₇, Na ₂B ₄O ₇10H ₂O, BPO ₄Wait and import in the glass.

SiO ₂Composition is the composition of the eyed structure that constitutes glass, the stability that improves glass and chemical weather resistance, and is present in and separates out Si ⁴⁺Ionic WO ₃Near the crystalline phase, being the composition that helps to improve photocatalytic activity, is the composition that can at random add.But, if SiO ₂The content of composition surpasses 60%, and then glass melting property variation is difficult to separate out WO ₃Crystalline phase.So, adding SiO ₂Under the situation of composition, with respect to total amount that oxide compound converts and forms, SiO ₂The content of composition preferably with 0.1%, more preferably be lower limit with 0.5%, preferably with 60%, more preferably with 50%, most preferably be the upper limit with 40%.SiO ₂Composition can be through for example using SiO as raw material ₂, K ₂SiF ₆, Na ₂SiF ₆Wait and import in the glass.

GeO ₂Composition is to have and above-mentioned SiO ₂The composition of similar action is the composition that can in the glass of this embodiment, at random add.Particularly, owing to pass through with GeO ₂The content of composition is below 60%, can compress the GeO to costliness ₂Use, therefore can reduce the material cost of glass-ceramic.So, with respect to total amount that oxide compound converts and forms, GeO ₂The content of composition preferably with 60%, more preferably with 45%, most preferably be the upper limit with 30%.GeO ₂Composition can be through for example using GeO as raw material ₂Wait and import in the glass.

The glass-ceramic of this embodiment preferably contains in the scope below 60% more than 5 and is selected from P ₂O ₅Composition, B ₂O ₃Composition, SiO ₂Composition and GeO ₂Composition more than at least a kind in the composition.Particularly, through with P ₂O ₅Composition, B ₂O ₃Composition, SiO ₂Composition and GeO ₂The total amount of composition is below 60%, and glass melting property, stability and chemical durability improve, and are difficult to crack in the glass-ceramic after thermal treatment, therefore can obtain the more glass-ceramic of high mechanical strength very simply.So, with respect to total amount that oxide compound converts and forms, total amount (P ₂O ₅+ B ₂O ₃+ SiO ₂+ GeO ₂) preferably with 60%, more preferably with 55%, most preferably be the upper limit with 45%.And, if the total amount of these compositions then is difficult to obtain glass less than 5%, therefore preferably add more than 5%, more preferably more than 10%, most preferably more than 20%.

TiO ₂Composition is through with the glass crystallization, and as TiO ₂Crystal or separate out from glass with the crystal of the compound of phosphorus, particularly demonstrate the composition of strong photocatalytic activity in the ultra-violet region, be any composition.Through with WO ₃Crystal contains TiO in combination ₂Crystal just can be given the photocatalytic activity that the wavelength to broad range from the ultraviolet ray to the visible light has responsiveness to the glass-ceramic of this embodiment.As the crystal formation of titanium oxide, known have sharp titanium (Anatase) type, rutile (Rutile) type and brookite (Brookite) type, however preferred anatase titanium dioxide and brookite type, the special titanium oxide that preferably contains the anatase titanium dioxide that possesses high photocatalysis characteristic.In addition, through with above-mentioned P ₂O ₅Composition contains TiO in combination ₂Composition can be separated out TiO under lower thermal treatment temp ₂Crystal, thus can reduce from the high anatase titanium dioxide TiO of photocatalytic activity ₂Crystal is to the phase transformation of the low rutile-type of photocatalytic activity.In addition, because TiO ₂Composition also has the WO of playing ₃The nucleus of crystalline phase generates the effect of the effect of agent, therefore helps WO ₃Separating out of crystalline phase.But, if TiO ₂The content of composition surpasses 60%, and then vitrifying becomes very difficult.So, adding TiO ₂Under the situation of composition, with respect to total amount that oxide compound converts and forms, TiO ₂The content of composition preferably with 1%, more preferably with 5%, most preferably be lower limit with 10%, preferably with 60%, more preferably with 50%, most preferably be the upper limit with 45%.TiO ₂Composition can be through for example using TiO as raw material ₂Wait and import in the glass.

Li ₂The O composition is to improve glass melting property and stability, make the composition that is difficult to crack in the glass-ceramic after thermal treatment, is the composition that can at random add.In addition, be to reduce second-order transition temperature and be easy to generate WO ₃Crystal and the composition of suppressing thermal treatment temp lower.In addition, through reducing thermal treatment temp, containing TiO ₂Can also expect under the situation of composition to reduce from the high anatase titanium dioxide TiO of photocatalytic activity ₂Crystal is to the effect of the phase transformation of the low rutile-type of photocatalytic activity.But, if Li ₂The content of O composition surpasses 40%, and the stability of glass is variation on the contrary, WO ₃Separating out of crystalline phase also can become difficult.So, with respect to total amount that oxide compound converts and forms, Li ₂The content of O composition preferably with 40%, more preferably with 30%, most preferably be the upper limit with 25%.Li ₂The O composition can be through for example using Li as raw material ₂CO ₃, LiNO ₃, LiF waits and imports in the glass.

Na ₂The O composition is to improve glass melting property and stability, make the composition that is difficult to crack in the glass-ceramic after thermal treatment, is the composition that can at random add.In addition, be to reduce second-order transition temperature and be easy to generate WO ₃Crystal and the composition of suppressing thermal treatment temp lower.In addition, through reducing thermal treatment temp, containing TiO ₂Can also expect under the situation of composition to reduce from the high anatase titanium dioxide TiO of photocatalytic activity ₂Crystal is to the effect of the phase transformation of the low rutile-type of photocatalytic activity.But, if Na ₂The content of O composition surpasses 40%, and the stability of glass is variation on the contrary, WO ₃Separating out of crystalline phase also can become difficult.So, with respect to total amount that oxide compound converts and forms, Na ₂The content of O composition preferably with 40%, more preferably with 30%, most preferably be the upper limit with 25%.Na ₂The O composition can be through for example using Na as raw material ₂O, Na ₂CO ₃, NaNO ₃, NaF, Na ₂S, Na ₂SiF ₆Wait and import in the glass.

K ₂The O composition is to improve glass melting property and stability, make the composition that is difficult to crack in the glass-ceramic after thermal treatment, is the composition that can at random add.In addition, be to reduce second-order transition temperature and be easy to generate WO ₃Crystal and the composition of suppressing thermal treatment temp lower.In addition, through reducing thermal treatment temp, containing TiO ₂Can also expect under the situation of composition to reduce from the high anatase titanium dioxide TiO of photocatalytic activity ₂Crystal is to the effect of the phase transformation of the low rutile-type of photocatalytic activity.But, if K ₂The content of O composition surpasses 40%, and the stability of glass is variation on the contrary, WO ₃Separating out of crystalline phase also can become difficult.So, with respect to total amount that oxide compound converts and forms, K ₂The content of O composition preferably with 40%, more preferably with 30%, most preferably be the upper limit with 25%.K ₂The O composition can be through for example using K as raw material ₂CO ₃, KNO ₃, KF, KHF ₂, K ₂SiF ₆Wait and import in the glass.

Rb ₂The O composition is to improve glass melting property and stability, make the composition that is difficult to crack in the glass-ceramic after thermal treatment, is the composition that can at random add.In addition, be to reduce second-order transition temperature and be easy to generate WO ₃Crystal and the composition of suppressing thermal treatment temp lower.In addition, through reducing thermal treatment temp, containing TiO ₂Can also expect under the situation of composition to reduce from the high anatase titanium dioxide TiO of photocatalytic activity ₂Crystal is to the effect of the phase transformation of the low rutile-type of photocatalytic activity.But, if Rb ₂The content of O composition surpasses 10%, and the stability of glass is variation on the contrary, WO ₃Separating out of crystalline phase also can become difficult.So, with respect to total amount that oxide compound converts and forms, Rb ₂The content of O composition preferably with 10%, more preferably with 8%, most preferably be the upper limit with 5%.Rb ₂The O composition can be through for example using Rb as raw material ₂CO ₃, RbNO ₃Wait and import in the glass.

Cs ₂The O composition is to improve glass melting property and stability, make the composition that is difficult to crack in the glass-ceramic after thermal treatment, is the composition that can at random add.In addition, be to reduce second-order transition temperature and be easy to generate WO ₃Crystal and the composition of suppressing thermal treatment temp lower.In addition, through reducing thermal treatment temp, containing TiO ₂Can also expect under the situation of composition to reduce from the high anatase titanium dioxide TiO of photocatalytic activity ₂Crystal is to the effect of the phase transformation of the low rutile-type of photocatalytic activity.But, if Cs ₂The content of O composition surpasses 10%, and the stability of glass is variation on the contrary, WO ₃Separating out of crystalline phase also can become difficult.So, with respect to total amount that oxide compound converts and forms, Cs ₂The content of O composition preferably with 10%, more preferably with 8%, most preferably be the upper limit with 5%.Cs ₂The O composition can be through for example using Cs as raw material ₂CO ₃, CsNO ₃Wait and import in the glass.

The glass-ceramic of this embodiment preferably contains the Rn that is selected from below 40% ₂O (in the formula, Rn be selected among Li, Na, K, Rb and the Cs more than a kind) the composition more than at least a kind in the composition.Particularly, through making Rn ₂The total amount of O composition is below 40%, and the stability of glass improves, and is easy to separate out WO ₃Crystalline phase it is hereby ensured the catalytic activity of glass-ceramic.So, with respect to total amount that oxide compound converts and forms, Rn ₂The total amount of O composition preferably with 40%, more preferably with 30%, most preferably be the upper limit with 25%.In addition, containing Rn ₂Under the situation of O composition, in order to embody its effect, preferably with 0.1%, more preferably with 0.5%, most preferably be lower limit with 1%.

The MgO composition is the composition that improves glass melting property and stability, is the composition that can at random add.In addition, be to reduce second-order transition temperature and be easy to generate WO ₃Crystal and the composition of suppressing thermal treatment temp lower.In addition, through reducing thermal treatment temp, containing TiO ₂Can also expect under the situation of composition to reduce from the high anatase titanium dioxide TiO of photocatalytic activity ₂Crystal is to the effect of the phase transformation of the low rutile-type of photocatalytic activity.But if the content of MgO composition surpasses 40%, the stability of glass is variation on the contrary, WO ₃Separating out of crystalline phase also can become difficult.So, with respect to total amount that oxide compound convert to be formed, the content of MgO composition preferably with 40%, more preferably with 30%, most preferably be the upper limit with 20%.The MgO composition can be through for example using MgCO as raw material ₃, MgF ₂Wait and import in the glass.

The CaO composition is the composition that improves glass melting property and stability, is the composition that can at random add.In addition, be to reduce second-order transition temperature and be easy to generate WO ₃Crystal and the composition of suppressing thermal treatment temp lower.In addition, through reducing thermal treatment temp, containing TiO ₂Can also expect under the situation of composition to reduce from the high anatase titanium dioxide TiO of photocatalytic activity ₂Crystal is to the effect of the phase transformation of the low rutile-type of photocatalytic activity.But if the content of CaO composition surpasses 40%, the stability of glass is variation on the contrary, WO ₃Separating out of crystalline phase also can become difficult.So, with respect to total amount that oxide compound convert to be formed, the content of CaO composition preferably with 40%, more preferably with 30%, most preferably be the upper limit with 25%.The CaO composition can be through for example using CaCO as raw material ₃, CaF ₂Wait and import in the glass.

The SrO composition is the composition that improves glass melting property and stability, is the composition that can at random add.In addition, be to reduce second-order transition temperature and be easy to generate WO ₃Crystal and the composition of suppressing thermal treatment temp lower.In addition, through reducing thermal treatment temp, containing TiO ₂Can also expect under the situation of composition to reduce from the high anatase titanium dioxide TiO of photocatalytic activity ₂Crystal is to the effect of the phase transformation of the low rutile-type of photocatalytic activity.But if the content of SrO composition surpasses 40%, the stability of glass is variation on the contrary, WO ₃Separating out of crystalline phase also can become difficult.So, with respect to total amount that oxide compound convert to be formed, the content of SrO composition preferably with 40%, more preferably with 30%, most preferably be the upper limit with 25%.The SrO composition can be through for example using Sr (NO as raw material ₃) ₂, SrF ₂Wait and import in the glass.

The BaO composition is the composition that improves glass melting property and stability, is the composition that can at random add.In addition, be to reduce second-order transition temperature and be easy to generate WO ₃Crystal and the composition of suppressing thermal treatment temp lower.In addition, through reducing thermal treatment temp, containing TiO ₂Can also expect under the situation of composition to reduce from the high anatase titanium dioxide TiO of photocatalytic activity ₂Crystal is to the effect of the phase transformation of the low rutile-type of photocatalytic activity.But if the content of BaO composition surpasses 40%, the stability of glass is variation on the contrary, WO ₃Separating out of crystalline phase also can become difficult.So, with respect to total amount that oxide compound convert to be formed, the content of BaO composition preferably with 40%, more preferably with 30%, most preferably be the upper limit with 25%.The BaO composition can be through for example using BaCO as raw material ₃, Ba (NO ₃) ₂, BaF ₂Wait and import in the glass.

The glass-ceramic of this embodiment preferably contain below 50% be selected from RO (in the formula, R be selected among Mg, Ca, Sr and the Ba more than a kind) the composition more than at least a kind in the composition.Particularly, be below 50% through the total amount that makes the RO composition, the stability of glass improves, and is easy to separate out WO ₃Crystalline phase it is hereby ensured the catalytic activity of glass-ceramic.So, with respect to total amount that oxide compound convert to be formed, the total amount of RO composition preferably with 50%, more preferably with 40%, most preferably be the upper limit with 30%.In addition, under the situation that contains the RO composition, in order to embody its effect, preferably with 0.1%, more preferably with 0.5%, most preferably be lower limit with 1%.

In addition, the glass-ceramic of this embodiment preferably contain below 50% be selected from RO (in the formula, R be selected among Mg, Ca, Sr and the Ba more than a kind) composition and Rn ₂O (in the formula, Rn be selected among Li, Na, K, Rb, the Cs more than a kind) the composition more than at least a kind in the composition.Particularly, through making RO composition and Rn ₂The total amount of O composition is below 50%, and the stability of glass improves, and second-order transition temperature (Tg) reduces, and is difficult to crack, and can more easily obtain the high glass-ceramic of physical strength.On the other hand, if RO composition and Rn ₂The total amount of O composition is greater than 50%, the bad stability of glass then, WO ₃Separating out of crystalline phase also can become difficult.So, with respect to total amount that oxide compound converts and forms, total amount (RO+Rn ₂O) preferably with 50%, more preferably with 40%, most preferably be the upper limit with 30%.In addition, containing RO composition and Rn ₂Under the situation of O, in order to embody its effect, preferably with 0.1%, more preferably with 0.5%, most preferably be lower limit with 1%.

Here, the glass-ceramic of this embodiment through contain be selected from RO (in the formula, R be selected among Mg, Ca, Sr and the Ba more than a kind) composition and Rn ₂O (in the formula, Rn be selected among Li, Na, K, Rb, the Cs more than a kind) in the middle of the composition in the composition more than 2 kinds, the stability of glass increases substantially, the physical strength of the glass-ceramic after the thermal treatment is higher, and is easier to from glass, separate out WO ₃Crystalline phase.So the glass-ceramic of this embodiment preferably contains and is selected from RO composition and Rn ₂In the middle of the composition in the O composition more than 2 kinds.

Al ₂O ₃Composition be improve glass stability and glass-ceramic chemistry weather resistance, promote WO ₃Crystalline phase from glass separate out and because of Al ³⁺The ion solid solution is in WO ₃The composition that helps the raising of photocatalysis characteristic in the crystalline phase is the composition that can at random add.But if its content surpasses 30%, then melt temperature obviously rises, and is difficult to vitrifying.So, adding Al ₂O ₃Under the situation of composition, with respect to total amount that oxide compound converts and forms, Al ₂O ₃The content of composition preferably with 0.1%, more preferably with 0.5%, most preferably be lower limit with 1%, preferably with 30%, more preferably with 20%, most preferably be the upper limit with 15%.Al ₂O ₃Composition can be through for example using Al as raw material ₂O ₃, Al (OH) ₃, AlF ₃Wait and import in the glass-ceramic.

Ga ₂O ₃Composition is stability, the promotion WO that improves glass ₃Crystalline phase from glass separate out and because of Ga ³⁺The ion solid solution is in WO ₃The composition that helps the raising of photocatalysis characteristic in the crystalline phase is the composition that can at random add.But if its content surpasses 30%, then melt temperature obviously rises, and is difficult to vitrifying.So, with respect to total amount that oxide compound converts and forms, Ga ₂O ₃The content of composition preferably with 30%, more preferably with 20%, most preferably be the upper limit with 10%.Ga ₂O ₃Composition can be through for example using Ga as raw material ₂O ₃, GaF ₃Wait and import in the glass-ceramic.

In ₂O ₃Composition is to have and above-mentioned Al ₂O ₃And Ga ₂O ₃The composition of the effect that composition is similar is the composition that can at random add.Because In ₂O ₃The composition price is high, therefore preferably make its content on be limited to below 10%, more preferably below 8%, most preferably be below 5%.In ₂O ₃Composition can be through for example using In as raw material ₂O ₃, InF ₃Wait and import in the glass-ceramic.

The glass-ceramic of this embodiment preferably contains the Al that is selected from below 50% ₂O ₃Composition, Ga ₂O ₃Composition and In ₂O ₃Composition more than at least a kind in the composition.Particularly, be below 50% through the total amount that makes these compositions, be easier to separate out WO ₃Therefore crystalline phase can help the further raising of the photocatalysis characteristic of glass-ceramic.So, with respect to total amount that oxide compound converts and forms, total amount (Al ₂O ₃+ Ga ₂O ₃+ In ₂O ₃) preferably with 50%, more preferably with 40%, most preferably be the upper limit with 30%.And, though even do not contain Al ₂O ₃Composition, Ga ₂O ₃Composition and In ₂O ₃Composition also can obtain to have the glass-ceramic of high photocatalysis characteristic, yet is more than 0.1% through the total amount that makes these compositions, can further promote WO ₃Therefore separating out of crystalline phase can help the further raising of the photocatalysis characteristic of glass-ceramic.So, with respect to total amount that oxide compound converts and forms, total amount (Al ₂O ₃+ Ga ₂O ₃+ In ₂O ₃) preferably with 0.1%, more preferably with 0.5%, most preferably be lower limit with 1%.

ZrO ₂Composition is chemical durability, the promotion WO that improves glass-ceramic ₃Crystalline phase separate out and because of Zr ⁴⁺The ion solid solution is in WO ₃The composition that helps the raising of photocatalysis characteristic in the crystalline phase is the composition that can at random add.But, if ZrO ₂The content of composition surpasses 20%, then is difficult to vitrifying.So, with respect to total amount that oxide compound converts and forms, ZrO ₂The content of composition preferably with 20%, more preferably with 15%, most preferably be the upper limit with 10%.ZrO ₂Composition can be through for example using ZrO as raw material ₂, ZrF ₄Wait and import in the glass-ceramic.

The SnO composition is to promote WO ₃Crystalline phase separate out, suppress W ⁶⁺Reduction and be easy to obtain WO ₃Crystalline phase and solid solution are in WO ₃In the crystalline phase and to improving the effective composition of photocatalysis characteristic; In addition; And have the effect that improves photocatalytic activity after under the Ag that states or Au or the Pt ion situation of adding; Being the composition that plays the effect of reductive agent, helps the activity of photocatalyst to improve indirectly, is the composition that can at random add.But, if the content of these compositions surpasses 10%, the bad stability of glass then, photocatalysis characteristic also reduces easily.So, with respect to total amount that oxide compound convert to be formed, the content of SnO composition preferably with 10%, more preferably with 8%, most preferably be the upper limit with 5%.In addition, adding under the situation of these compositions, preferably with 0.01%, more preferably with 0.02%, most preferably be lower limit with 0.03%.The SnO composition can be through for example using SnO, SnO as raw material ₂, SnO ₃Wait and import in the glass-ceramic.

The glass-ceramic of this embodiment preferably contains the ZrO that is selected from below 20% ₂Composition more than at least a kind in composition, the SnO composition.Particularly, be below 20% through the total amount that makes these compositions, just can guarantee the stability of glass-ceramic, therefore can form good glass-ceramic.So, with respect to total amount that oxide compound converts and forms, total amount (ZrO ₂+ SnO) preferably with 20%, more preferably with 15%, most preferably be the upper limit with 10%.And, though even do not contain ZrO ₂Composition and SnO composition also can obtain to have the glass-ceramic of high photocatalysis characteristic, yet are more than 0.01% through the total amount that makes these compositions, can further improve the photocatalysis characteristic of glass-ceramic.So, with respect to total amount that oxide compound converts and forms, total amount (ZrO ₂+ SnO) preferably with 0.01%, more preferably with 0.02%, most preferably be lower limit with 0.03%.

Nb ₂O ₅Composition is the composition that improves glass melting property and stability, and is in WO through solid solution ₃In the crystalline phase, or be present near it and improve the composition of photocatalysis characteristic, be the composition that can at random add.But, if Nb ₂O ₅The content of composition surpasses 50%, then the obvious variation of the stability of glass.So, with respect to total amount that oxide compound converts and forms, Nb ₂O ₅The content of composition preferably with 50%, more preferably with 30%, most preferably be the upper limit with 20%.Nb ₂O ₅Composition can be through for example using Nb as raw material ₂O ₅Wait and import in the glass-ceramic.

Ta ₂O ₅Composition is the composition that improves the stability of glass, and is in WO through solid solution ₃In the crystalline phase, or be present near it and improve the composition of photocatalysis characteristic, be the composition that can at random add.But, if Ta ₂O ₅The content of composition surpasses 50%, then the obvious variation of the stability of glass.So, with respect to total amount that oxide compound converts and forms, Ta ₂O ₅The content of composition preferably with 50%, more preferably with 30%, most preferably be the upper limit with 20%.Ta ₂O ₅Composition can be through for example using Ta as raw material ₂O ₅Wait and import in the glass-ceramic.

MoO ₃Composition is the composition that improves glass melting property and stability, and is in WO through solid solution ₃In the crystalline phase, or be present near it and improve the composition of photocatalysis characteristic, be the composition that can at random add.But, if MoO ₃The content of composition surpasses 50%, then the obvious variation of the stability of glass.So, with respect to total amount that oxide compound converts and forms, MoO ₃The content of composition preferably with 50%, more preferably with 30%, most preferably be the upper limit with 20%.MoO ₃Composition can be through for example using MoO as raw material ₃Wait and import in the glass-ceramic.

The glass-ceramic of this embodiment preferably contains the Nb that is selected from below 50% ₂O ₅Composition, Ta ₂O ₅Composition and MoO ₃Composition more than at least a kind in the composition.Particularly, be below 50% through the total amount that makes these compositions, just can guarantee the stability of glass-ceramic, therefore can form good glass-ceramic.So, with respect to total amount that oxide compound converts and forms, total amount (Nb ₂O ₅+ Ta ₂O ₅+ MoO ₃) preferably with 50%, more preferably with 30%, most preferably be the upper limit with 20%.And, though even do not contain Nb ₂O ₅Composition, Ta ₂O ₅Composition and MoO ₃Composition also can obtain to have the glass-ceramic of high photocatalysis characteristic, yet is more than 0.1% through the total amount that makes these compositions, can further improve the photocatalysis characteristic of glass-ceramic.So, with respect to total amount that oxide compound converts and forms, total amount (Nb ₂O ₅+ Ta ₂O ₅+ MoO ₃) preferably with 0.1%, more preferably with 0.5%, most preferably be lower limit with 1%.

The ZnO composition is the composition that improves glass melting property and stability, is the composition that can at random add.In addition, be to reduce second-order transition temperature and be easy to generate WO ₃Crystal and the composition of suppressing thermal treatment temp lower.In addition, through reducing thermal treatment temp, containing TiO ₂Can also expect under the situation of composition to reduce from the high anatase titanium dioxide TiO of photocatalytic activity ₂Crystal is to the effect of the phase transformation of the low rutile-type of photocatalytic activity.But if the content of ZnO composition surpasses 50%, the stability of glass is variation on the contrary, WO ₃Separating out of crystalline phase also can become difficult.So, with respect to total amount that oxide compound convert to be formed, the content of ZnO composition preferably with 50%, more preferably with 40%, most preferably be the upper limit with 30%.The ZnO composition can be through for example using ZnO, ZnF as raw material ₂Wait and import in the glass-ceramic.

Bi ₂O ₃Composition is the composition that improves glass melting property and stability, is the composition that can at random add.In addition, be to reduce second-order transition temperature and be easy to generate WO ₃Crystal and the composition of suppressing thermal treatment temp lower.In addition, through reducing thermal treatment temp, containing TiO ₂Can also expect under the situation of composition to reduce from the high anatase titanium dioxide TiO of photocatalytic activity ₂Crystal is to the effect of the phase transformation of the low rutile-type of photocatalytic activity.But, if Bi ₂O ₃The content of composition surpasses 20%, and the stability of glass will variation, WO ₃Separate out become the difficulty.So, with respect to total amount that oxide compound converts and forms, Bi ₂O ₃The content of composition preferably with 20%, more preferably with 15%, most preferably be the upper limit with 10%.Bi ₂O ₃Composition can be through for example using Bi as raw material ₂O ₃Wait and import in the glass-ceramic.

TeO ₂Composition is the composition that improves glass melting property and stability, is the composition that can at random add.In addition, be to reduce second-order transition temperature and be easy to generate WO ₃Crystal and the composition of suppressing thermal treatment temp lower.In addition, through reducing thermal treatment temp, containing TiO ₂Can also expect under the situation of composition to reduce from the high anatase titanium dioxide TiO of photocatalytic activity ₂Crystal is to the effect of the phase transformation of the low rutile-type of photocatalytic activity.But, if TeO ₂The content of composition surpasses 20%, and the stability of glass will variation, WO ₃Separate out become the difficulty.So, with respect to total amount that oxide compound converts and forms, TeO ₂The content of composition preferably with 20%, more preferably with 15%, most preferably be the upper limit with 10%.TeO ₂Composition can be through for example using TeO as raw material ₂Wait and import in the glass-ceramic.

Ln ₂O ₃Composition (in the formula, Ln be selected among Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and the Lu more than a kind) be the composition that improves the chemical durability of glass, and be in WO through solid solution ₃In the crystalline phase, or be present near it and improve the composition of photocatalysis characteristic, be the composition that can at random add.But, if Ln ₂O ₃The total of the content of composition surpasses 30%, then the obvious variation of the stability of glass.So, with respect to total amount that oxide compound converts and forms, Ln ₂O ₃The total amount of composition preferably with 30%, more preferably with 20%, most preferably be the upper limit with 10%.Ln ₂O ₃In the middle of the composition, Ce particularly ₂O ₃Composition can prevent W ⁶⁺Reduction, promote WO ₃Separate out, therefore have the effect that obviously helps to improve photocatalysis characteristic.Ln ₂O ₃Composition can be through for example using La as raw material ₂O ₃, La (NO ₃) ₃XH ₂O (X be integer) arbitrarily, Gd ₂O ₃, GdF ₃, Y ₂O ₃, YF ₃, CeO ₂, CeF ₃, Nd ₂O ₃, Dy ₂O ₃, Yb ₂O ₃, Lu ₂O ₃Wait and import in the glass-ceramic.

M _xO _yComposition (in the formula, M be selected among V, Cr, Mn, Fe, Co, the Ni more than a kind, x and y are respectively and satisfy x: the natural number of valent minimum of y=2: M.Here, the valency of V is 5, and the valency of Cr is 3, and the valency of Mn is 2, and the valency of Fe is 3, and the valency of Co is 2, and the valency of Ni is 2.) be in WO through solid solution ₃In the crystalline phase, or be present near it and help the raising of photocatalysis characteristic and absorb a part wavelength visible light and give the composition of appearance color to glass-ceramic, be any composition in the glass of this embodiment.Particularly, through making M _xO _yThe total amount of composition is below 10%, can improve the stability of glass-ceramic, regulates the color of the outward appearance of glass-ceramic at an easy rate.So, with respect to total amount that oxide compound converts and forms, M _xO _yThe total amount of composition preferably with 10%, more preferably with 8%, most preferably be the upper limit with 5%.In addition, adding under the situation of these compositions, preferably with 0.0001%, more preferably with 0.002%, most preferably be lower limit with 0.005%.

As ₂O ₃Composition and/or Sb ₂O ₃Composition is to make that glass is limpid, the composition of deaeration; In addition; And have the effect that improves photocatalytic activity after under the Ag that states or Au or the Pt ion situation of adding; Owing to have the effect of reductive agent, be the composition that helps to improve photocatalytic activity indirectly therefore, be the composition that can at random add.But if the content of these compositions add up to surpass 5%, then the stability of glass will variation, and photocatalysis characteristic also reduces easily.So, with respect to total amount that oxide compound converts and forms, As ₂O ₃Composition and/or Sb ₂O ₃The total of the content of composition preferably with 5%, more preferably with 3%, most preferably be the upper limit with 1%.In addition, adding under the situation of these compositions, preferably with 0.001%, more preferably with 0.002%, most preferably be lower limit with 0.005%.As ₂O ₃Composition and Sb ₂O ₃Composition can be through for example using As as raw material ₂O ₃, As ₂O ₅, Sb ₂O ₃, Sb ₂O ₅, Na ₂H ₂Sb ₂O ₇5H ₂O waits and imports in the glass-ceramic.

And, make that glass is limpid, the composition of deaeration is not limited to above-mentioned As ₂O ₃Composition and Sb ₂O ₃Composition for example can use CeO ₂Composition or TeO ₂Become known limpid dose or deaerating agent or their combination in the field that glass is made grade and so on.

In the glass-ceramic of this embodiment, also can contain the non-metallic element composition more than at least a kind that is selected from F composition, Cl composition, Br composition, S composition, N composition and the C composition.These compositions are in WO through solid solution ₃In the crystalline phase, or be present near it and improve the composition of photocatalysis characteristic, be the composition that can at random add.But, if the content of these compositions add up to surpass 15%, the obvious variation of the stability of glass then, photocatalysis characteristic also reduces easily.So, in order to ensure good characteristic, with respect to the glass-ceramic total mass that oxide compound convert to be formed, the total of the external ratio mass ratio of the content of non-metallic element composition preferably with 15%, more preferably with 10%, most preferably be the upper limit with 5%.These non-metallic element compositions preferably import in the glass with forms such as the fluorochemical of basic metal or alkaline-earth metal, muriate, bromide, sulfide, nitride, carbide.And; The content of the non-metallic element composition in this specification sheets is the value that obtains as follows; Promptly; Suppose constitute glass-ceramic cation constituent all with electric charge just in time equilibrated oxygen combines and oxide compound occur, will be 100% with the quality of the bulk glass of these oxide compounds appearance, represent the quality (with respect to the external ratio quality % of the quality of oxide compound benchmark) of the composition of non-metallic element with quality %.The raw material of non-metallic element composition is not special to be limited, yet for example can use ZrF through the raw material as the F composition ₄, AlF ₃, NaF, CaF ₂Deng, use NaCl, AgCl etc., use NaBr etc., use NaS, Fe as the raw material of Cl composition as the raw material of S composition as the raw material of Br composition ₂S ₃, CaS ₂Deng, use AlN as the raw material of N composition ₃, SiN ₄Deng, use TiC, SiC or ZrC to wait as the raw material of C composition to import in the glass.And these raw materials both can make up and add more than 2 kinds, also can add separately.

In the glass-ceramic of this embodiment, also can contain at least a kind of metallic element composition that is selected from Cu composition, Ag composition, Au composition, Pd composition, Ru composition, Rh composition, Re composition and the Pt composition.These metallic element compositions are through being present in WO ₃Near crystalline phase and improve the composition of photocatalytic activity is the composition that can at random add.Particularly Cu composition and Ag composition be owing to also have antibacterial effect even without the irradiation of light, therefore preferably contains wherein one or both.But, if the total of the content of these metallic element compositions surpasses 10%, the obvious variation of the stability of glass then, photocatalysis characteristic reduces on the contrary easily.So with respect to the glass-ceramic total mass that oxide compound convert to be formed, the external ratio mass ratio of the content of above-mentioned metallic element composition adds up to preferably with 10%, more preferably with 5%, most preferably be the upper limit with 1%.These metallic element compositions can be through for example using CuO, Cu as raw material ₂O, Ag ₂O, AuCl ₃, PtCl ₂, PtCl ₄, H ₂PtCl ₆, RuO ₂, RhCl ₃, ReCl ₃, PdCl ₂Wait and import in the glass-ceramic.And; The content of the metallic element composition in this specification sheets is the value that obtains as follows; Promptly; Suppose constitute glass-ceramic cation constituent all with electric charge just in time equilibrated oxygen combines and oxide compound occur, will be 100% with the quality of the bulk glass of these oxide compounds appearance, represent the quality (with respect to the external ratio quality % of the quality of oxide compound benchmark) of metallic element composition with quality %.In addition, adding under the situation of these compositions, preferably with 0.0001%, more preferably with 0.002%, most preferably be lower limit with 0.005%.

In the glass-ceramic of this embodiment, can in the scope of the characteristic of not damaging glass-ceramic, add the composition beyond the mentioned component as required.But; The trend that lead compounds such as PbO, Th, Cd, Tl, Os, Se, each composition of Hg have control to use as deleterious chemical goods and materials in recent years; Be not only the manufacturing process of glass-ceramic, even the disposal after manufacturing procedure and the commercialization all needs the measure on the environmental cure.So, under the situation of paying attention to the influence on the environment, except inevitably sneaking into, in fact preferably do not contain them.Like this, the material that in glass-ceramic, does not in fact just contain contaminate environment.Thus, even do not take the measure on the special environmental cure, also can make, process and discard this glass-ceramic.

The glass-ceramic of this embodiment is owing to represent its mole % that forms total amount of forming to convert with respect to oxide compound; Therefore be not the record that directly is expressed as quality %, take following value haply yet the composition of representing based on quality % that is present in each composition in the compsn that satisfies desired various characteristics in this embodiment converts to form in oxide compound.

WO ₃ Composition 10～90 quality %

And:

P ₂O ₅Composition 0～50 quality % and/or

B ₂O ₃Composition 0～50 quality % and/or

SiO ₂Composition 0～50 quality % and/or

GeO ₂Composition 0～40 quality % and/or

TiO ₂Composition 0～80 quality % and/or

Li ₂O composition 0～15 quality % and/or

Na ₂O composition 0～30 quality % and/or

K ₂O composition 0～30 quality % and/or

Rb ₂O composition 0～25 quality % and/or

Cs ₂O composition 0～30 quality % and/or

MgO composition 0～20 quality % and/or

CaO composition 0～25 quality % and/or

SrO composition 0～45 quality % and/or

BaO composition 0～45 quality % and/or

Al ₂O ₃Composition 0～35 quality % and/or

Ga ₂O ₃Composition 0～35 quality % and/or

In ₂O ₃Composition 0～10 quality % and/or

ZrO ₂Composition 0～30 quality % and/or

SnO composition 0～15 quality % and/or

Nb ₂O ₅Composition 0～60 quality % and/or

Ta ₂O ₅Composition 0～70 quality % and/or

MoO ₃Composition 0～60 quality % and/or

ZnO composition 0～45 quality % and/or

Bi ₂O ₃Composition 0～60 quality % and/or

TeO ₂Composition 0～20 quality % and/or

Ln ₂O ₃Become subtotaling 0～50 quality % and/or

M _xO _yBecome subtotaling 0～20 quality % and/or

As ₂O ₃Composition and Sb ₂O ₃Become subtotaling 0～10 quality %

In addition,

The external ratio mass ratio of the glass-ceramic total mass of forming to convert 100% with respect to said oxide compound,

Be selected from F composition, Cl composition, Br composition, S composition, N composition and the C composition 0～15 quality % of the non-metallic element composition more than at least a kind and/or

Be selected from least a kind of metallic element composition 0～10 quality % in Cu composition, Ag composition, Au composition, Pd composition, Ru composition, Rh composition, Re composition and the Pt composition.

The glass-ceramic of this embodiment also can contain in crystalline phase and comprise TiO ₂, TiP ₂O ₇And (TiO) ₂P ₂O ₇And the crystal more than a kind in the middle of their sosoloid, under this situation, more preferably contain the TiO that comprises sharp titanium (Anatase) type or brookite (Brookite) type ₂Crystal.Through containing these crystal, glass-ceramic just can have high photo-catalysis function.Wherein, the titanium oxide (TiO of anatase titanium dioxide particularly ₂) even to compare photo-catalysis function also very high with rutile (Rutile) type, therefore can give higher photo-catalysis function to glass-ceramic.

In addition, the glass-ceramic of this embodiment also can contain the titanium phosphate cpd, particularly contains RnTi ₂(PO ₄) ₃Crystal or its sosoloid or RTi ₄(PO ₄) ₆Crystal or its sosoloid (in the formula, Rn be selected among Li, Na, K, Rb, the Cs more than a kind, R be selected among Mg, Ca, Sr, the Ba more than a kind).Through from glass, separating out these crystal, just can embody higher photochemical catalysis effect.As this kind titanium phosphate cpd, can illustration go out LiTi ₂(PO ₄) ₃, NaTi ₂(PO ₄) ₃, KTi ₂(PO ₄) ₃, MgTi ₄(PO ₄) ₆, CaTi ₄(PO ₄) ₆, SrTi ₄(PO ₄) ₆, B aTi ₄(PO ₄) ₆Deng.

[rerum natura]

The glass-ceramic of this embodiment preferably contains in the scope below 95% more than 1% in the volume ratio with respect to the glass TV and comprises WO ₃, and TiO ₂, TiP ₂O ₇, (TiO) ₂P ₂O ₇, RnTi ₂(PO ₄) ₃, RTi ₄(PO ₄) ₆, and their sosoloid in the middle of the crystal more than a kind (in the formula, Rn be selected among Li, Na, K, Rb, the Cs more than a kind, R be selected among Mg, Ca, Sr, the Ba more than a kind).Through the containing ratio that makes above-mentioned crystalline phase is more than 1%, and glass-ceramic just can have good photocatalysis characteristic.On the other hand, be below 95% through the containing ratio that makes above-mentioned crystalline phase, glass-ceramic just can obtain excellent mechanical intensity.

In addition, the crystallization rate of the glass-ceramic of this embodiment in volume ratio preferably with 1%, more preferably with 5%, most preferably be lower limit with 10%, preferably with 98%, more preferably with 95%, most preferably be the upper limit with 90%.For said crystalline size, the mean diameter of preferably carrying out after the spheric approximation is 5nm～3 μ m.Through the control heat-treat condition, can control the crystalline size of separating out, yet, preferably crystalline is of a size of the scope of 5nm～3 μ m in order to bring into play effective photocatalysis characteristic, the scope of 10nm～1 μ m more preferably most preferably is the scope of 10nm～300nm.The half breadth of the diffraction peak of XRD be can utilize, crystal particle diameter and MV thereof estimated based on the Sherrer formula.Under the more weak or synergetic situation of diffraction peak, can it be assumed to circle according to the crystal particles area that uses scanning electron microscope (SEM) or infiltration type electron microscope (TEM) to determine, obtain its diameter and measure.When using microscope to calculate MV, preferably measure the crystal diameter more than 100 randomly.

The glass ceramics of present embodiment preferably utilizes the light of the wavelength from the ultraviolet region to the visibility region to embody catalytic activity.Here, the hertzian wave of the obscue rays that the only wavelength ratio visible rays of the wavelength of ultraviolet region is short and longer than soft X-ray, its wavelength approximately is in the scope of 10～400nm.In addition, the hertzian wave of the wavelength that can be seen by human eye in the middle of the only hertzian wave of the wavelength of visibility region, its wavelength approximately is in the scope of 400nm～700nm.Through to the light of these any wavelength from the ultraviolet region to the visibility region of surface irradiation of glass-ceramic, or the light time of wavelength that they are composited embody catalytic activity; Dirt material or the bacteriums etc. that are attached to the surface of glass-ceramic just are utilized oxidation or reduction reaction is decomposed, and therefore can glass-ceramic be used for antifouling purposes or antibacterial application etc.And, though TiO ₂Crystal demonstrates high catalytic effect for ultraviolet irradiation, yet it is low to compare ultraviolet responsiveness for the responsiveness of visible light, and in this embodiment WO ₃Crystal demonstrates excellent responsiveness for visible light, is therefore containing WO ₃Crystal and TiO ₂Under the two the situation of crystal, can obtain the light of the broad wavelength from the ultraviolet ray to the visible rays is had the glass-ceramic of excellent especially responsiveness.

In addition, the irradiation of the glass-ceramic of this embodiment surface and the contact angle of water droplet of light of the wavelength from the ultraviolet region to the visibility region be preferably below 30 °.Like this, the surface of glass-ceramic demonstrates wetting ability, has automatic cleaning action, therefore can water the surface of glass cleaning pottery at an easy rate, the reduction of the photocatalysis characteristic that can suppress to cause by dirt.Shone the glass-ceramic surface of light and the contact angle of water droplet and be preferably below 30 °, more preferably below 25 °, most preferably be below 20 °.

[method of manufacture of glass-ceramic]

Below, go out the first following method and second method through illustration, come the method for manufacture of the glass-ceramic of this embodiment is described.But the method for manufacture of the glass-ceramic of this embodiment is not limited to the method shown in first method and second method.

< first method >

The method of manufacture of the glass-ceramic of first method of this embodiment can remain temperature and the fusion more than 1250 ℃ through the mixture with raw material, thereafter with its cooling, solidify and carry out.Here, fused solution can be formed generation by the raw material more than at least a kind, it is also conceivable that the reduction of the generation temperature of the fused solution that causes because of the compound that adds more than 2 kinds.So, the temperature that will keep preferably according to the kind and the suitably change of amount of want raw materials mixed, yet in general be preferably more than 1250 ℃, more preferably more than 1300 ℃, most preferably be more than 1350 ℃.

More particularly, the starting raw material of regulation is put into the container that comprises platinum or refractory body etc. after mixing equably, with electric furnace with the heating of the specified temperature more than 1250 ℃ and keep the making fused solution., fused solution flowed into mould and make it curing, obtain required glass-ceramic thereafter.Like this, through not via crystallisation procedure does, but in controlled chilling speed, solution is cooled off, in the refrigerative process, make it to pass the crystallized temperature zone, just can from liquid, directly separate out WO with specific time by vitrifying and reheat ₃Crystalline phase and make required glass-ceramic.Here, in fused solution refrigerative process, cause the generation and the growth of nucleus.This method for example enrichment separate out required crystalline phase and the state of glass melting liquid is effective under the situation such as instability relatively.

[etching work procedure]

Glass-ceramic behind the generation crystal can directly be used, and perhaps under the state of the processing of having implemented machineries such as grinding, brings into play high photocatalysis characteristic, yet also can carry out etching to this glass-ceramic.Owing to utilize etching, remove crystalline phase glassy phase on every side, the specific surface area of the crystalline phase of exposing on the surface increases, and therefore can further improve the photocatalysis characteristic of glass-ceramic.In addition, through solutions employed or etching period in the control etching work procedure, can obtain residual WO ₃The porous insert of crystalline phase.Here, Wet-type etching that as etching method, for example can enumerate dry-etching, is undertaken by the dipping in solution and their methods such as combination.The surface that as long as used acid or alkaline solution can the etching glass pottery in the dipping, just not special the qualification for example also can be the acid (hydrofluoric acid, hydrochloric acid) that contains fluorine or chlorine.And this etching work procedure for example can carry out through hydrogen fluoride gas, hydrogen chloride gas, hydrofluoric acid, hydrochloric acid etc. are blowed to the surface of glass-ceramic.

< second method >

The method of manufacture of the glass-ceramic of second method of this embodiment can have: mixing raw material and obtain the fusion operation, the said liquation of cooling of its liquation and obtain glass refrigerating work procedure, with the temperature of said glass be elevated to the crystallized temperature zone the reheat operation, in said crystallized temperature zone, keep said temperature and produce the crystalline crystallization step, said temperature is reduced to outside the said crystallized temperature zone and obtains the refrigerating work procedure again of crystalline dispersion glass.And, suitably omit explanation for the operation identical with first method.

[fusion operation]

The fusion operation is the operation that the raw materials mix with above-mentioned composition is obtained its liquation.More particularly; So that being in the interior mode of scope of the content of regulation, each composition of glass-ceramic concocts raw material; Mix equably, the mixture of producing dropped into platinum crucible, quartz crucible or alumina crucible, with electric furnace with 1200～1600 ℃ TR fusion 1～24 hour; Stirring produced liquation.And the fused condition of raw material is not limited to the said temperature scope, can suitably set according to the composition of feedstock composition and use level etc.

[refrigerating work procedure]

Refrigerating work procedure is that the operation of glass is made in vitrifying through utilizing the liquation cooling that the fusion operation obtains.Specifically, the suitably cooling through flowing out liquation, form vitrifying vitreum.Here, vitrified condition is not special to be limited, and can suitably set according to the composition of raw material and amount etc.In addition, the Vitrea shape of utilizing this operation to obtain is not particularly limited, and can be tabular, granular etc., yet from can be rapidly and make Vitrea aspect in large quantities and consider, is preferably tabular.

[reheat operation]

The reheat operation is the operation that the temperature of the glass that utilizes refrigerating work procedure to obtain is elevated to the crystallized temperature zone.In this operation,, control critically therefore that their are very important because heat-up rate and temperature can cause very big influence to the formation or the crystalline size of crystalline phase.

[crystallization step]

Crystallization step is through in the crystallized temperature zone, keeping specific time to generate WO ₃Deng the crystalline operation.Through in this crystallization step, keeping the specified time in the crystallized temperature zone, just can be with WO with required size from nanometer to micron unit ₃Be scattered in Vitrea internally formation equably in crystal.The crystallized temperature zone is for example for surpassing the temperature province of second-order transition temperature.Different because second-order transition temperature is formed along with glass, therefore preferably set crystallized temperature according to second-order transition temperature.In addition, the crystallized temperature zone is preferably than the high temperature province more than 10 ℃ of second-order transition temperature, and is more preferably high more than 20 ℃, most preferably high more than 30 ℃.The following of preferred crystallized temperature zone is limited to 450 ℃, more preferably 500 ℃, most preferably is 550 ℃.On the other hand, if crystallized temperature is too high, the tendency of then separating out the unknown phase beyond the target strengthens, the photocatalysis characteristic easily dissolved, so the upper limit in crystallized temperature zone is preferably 1200 ℃, more preferably 1100 ℃, most preferably is 1050 ℃.In this operation,, therefore suitably control very important according to composition or thermal treatment temp because heat-up rate and temperature can make a big impact to the crystalline size.In addition, the heat treatment time that is used for crystallization need be according to the composition of glass or thermal treatment temp etc., makes crystal growth to a certain degree and can separate out under the crystalline condition of q.s and set.Heat treatment time can be set in various scopes according to crystallized temperature.If the reduction heat-up rate, if the situation that also has the thermal treatment temp of being heated to get final product, however being under the situation of comparatively high temps as target, be preferably set to the short period of time, under the situation of lesser temps, be preferably set to long-time.Crystallisation procedure does both can be through the heat treatment process in 1 stage, also can be through 2 heat treatment processes more than the stage.

(refrigerating work procedure again)

Refrigerating work procedure is after crystallization finishes again, temperature is reduced to outside the crystallized temperature zone and obtains having WO ₃The operation of the crystalline dispersion glass of crystalline phase.

(etching work procedure)

In this second method, also preferably implement etching work procedure.Etching can be carried out with first method identically.

In above-mentioned first method and second method, can as required forming process be set and glass or glass-ceramic are processed as shape arbitrarily.

[photocatalyst]

The glass-ceramic of making as described above can directly be used, and perhaps is processed as arbitrarily and uses as photocatalyst after the shape.Here " photocatalyst " for example is the state, Powdered etc. of bulk, and no matter its shape can why.In addition, photocatalyst so long as the active material that has the organic effects of photolysis such as the ultraviolet ray of utilizing and reduce to give any side of hydrophilic effect with the contact angle of water get final product, yet be preferably active material with the two.This photocatalyst for example can be used as photocatalyst material, photocatalytic elements (for example water purification material, material for air purification etc.), hydrophilic material, hydrophilic member utilizations such as (for example window, mirror, panel, ceramic tiles etc.).

[glass-ceramic molding]

Be shaped with shape arbitrarily through the glass-ceramic that will make as described above, the glass-ceramic molding and/or the hydrophilic glass-ceramic molding that just can be used as photocatalysis functional are used for purposes such as various machineries, device, utensil class.Particularly, be preferred in the purposes such as ceramic tile, window frame, building materials.Like this, just can kill the mould on the surface that is attached to the glass-ceramic molding, therefore when being used for these purposes, can the surface be kept health at the surface of glass-ceramic molding performance photo-catalysis function.In addition, because the surperficial possess hydrophilic property of glass-ceramic molding, therefore when being used for these purposes, can utilize raindrop etc. to wash the dirt on the surface that is attached to the glass-ceramic molding at an easy rate off.

In addition, the glass-ceramic molding of this embodiment can be processed as various forms according to purposes.Particularly, for example, can increase WO through adopting the form of granulated glass sphere or spun glass (glassfiber) ₃Crystalline phase expose area, therefore can further improve the photocatalytic activity of glass-ceramic molding.Below, the representational processing form as glass-ceramic describes for giving an example out with granulated glass sphere and spun glass.

[granulated glass sphere]

The granulated glass sphere of this embodiment is not the pearl that decoration is used, handicraft is used, and relates to industrial pearl.For industrial pearl, consider from advantages such as weather resistance, mainly use glass to make, in general, the small ball (diameter is counted μ m to several mm) of glass is called granulated glass sphere.As representative purposes, coating used in the marking plate, road surface display line of road, reflective cloth, filtering material, shot-peening abrasive substance etc. are for example arranged.If in road markings coating, reflective cloth etc., sneak into, disperse granulated glass sphere, the light that then penetrates from car light etc. at night will be via pearl to the old place reflection (circulation reflection), and visibility improves.This of granulated glass sphere kind of function can also be used for jogging with clothes, construction with vest, cyclist with vest etc.If in coating, sneak into the glass ceramics pearl of present embodiment, the dirt that then can utilize photo-catalysis function will be attached in marking plate or the line decomposes, and therefore can keep clean state always, thereby can reduce the work of maintenance significantly.In addition, the glass-ceramic pearl of this embodiment can also be formed, separate out the amount of crystalline size and crystalline phase through adjustment, and has circulation reflection function and photo-catalysis function simultaneously.And, in order to obtain the higher glass-ceramic pearl of reflectivity of circulating, the glass matrix that constitutes this pearl mutually and/or the specific refractory power of crystalline phase be preferably in 1.8～2.1 the scope particularly more preferably about 1.9.

As other purposes, industrial granulated glass sphere can be used as filtering material and uses.Granulated glass sphere is different with sand or stone etc., all is sphere, so filling ratio is high, and therefore all right calculated gap rate can be used separately, and perhaps the filtering material with other makes up and use widely.The glass-ceramic pearl of this embodiment also has photo-catalysis function concurrently except the original function of this kind granulated glass sphere.Particularly, do not have film or coat etc., demonstrate photocatalysis characteristic individually,, save the work of changing or safeguarding, for example go in strainer and the refining plant therefore not by peeling off the catalytic activity deterioration that causes.In addition, utilized the filter member of photo-catalysis function and purified member to be mostly in device and the adjacent formation of member that becomes light source, and the pearl of glass-ceramic can be accommodated in the container in the device etc. very simply, so can utilize rightly.

In addition, granulated glass sphere is because chemicalstability is excellent, and be spherical, therefore not too can damage machined object, can be used for the shot-peening grinding and use material.So-called shot-peening is meant,, cleans, decoration, shot peening strengthening etc. with the machined surface collision through spraying the grain material.The glass-ceramic pearl of this embodiment except this advantage, also have photo-catalysis function concurrently, processing when having used light-catalyzed reaction when therefore can be implemented in shot-peening.

The particle diameter of the granulated glass sphere of this embodiment can suitably determine according to its purposes.Under the situation in being coupled to coating, for example can be 100～2500 μ m, be preferably the particle diameter of 100～2000 μ m.Be used under the situation of reflective cloth, for example can be 20～100 μ m, be preferably the particle diameter of 20～50 μ m.Be used under the situation of filtering material, for example can be 30～8000 μ m, be preferably the particle diameter of 50～5000 μ m.

Below, the method for manufacture of the glass-ceramic pearl of this embodiment is described.The method of manufacture of the glass-ceramic pearl of this embodiment can comprise: mixing raw material and obtain its liquation the fusion operation, use liquation or the glass that obtains by liquation and be configured as the pearl body forming process, the temperature of pearl body is elevated to above the crystallized temperature zone of second-order transition temperature and with this temperature keep specific time and separate out required crystalline crystallization step.And, because the prior manufacturing method of the glass-ceramic explain also can be applied in reconcilable scope in this concrete example in above-mentioned first and second method, so suitably quote these methods and omit multiple and put down in writing.

(fusion operation)

Can implement with above-mentioned second method identically.

(forming process)

By the liquation that in fusion operation obtain be configured as particulate pearl body thereafter.In the manufacturing process of pearl body, the whole bag of tricks is arranged,, yet in general, can make via the process of glass melt or glass → pulverizing → granularity adjustment → balling as long as suitably select.Just like inferior method, that is, in pulverizing process, through with cooling curing glass pulverize, or with carrying out granulation in the glass flows entry of liquation shape, pulverize etc. with ball mill then, obtain beaded glass., use sieve wait adjusts granularity, heat once more and utilize surface tension, or add in the drum, when making it to rotate, utilize physical force with spherical shaping with powdered materials such as graphite with spherical shaping thereafter.Perhaps, also can take without pulverizing process and by the method for the direct balling of melten glass.Following method etc. is for example arranged; Promptly; Melten glass is sprayed in air and utilizes the surface tension balling, cut the melten glass that flies from mass flowing nozzle, to come out finely and balling, in fluid, drip and in the whereabouts, make it balling with the member of cutter of rotation and so on.As a rule, the pearl after the shaping forms product after adjusting granularity once more.As long as the viscosity of the glass under the consideration forming temperature or devitrification easness etc. select best method to get final product from these methods.

(crystallization step)

The pearl body that utilizes said process to obtain is heated once more the crystallization step that required crystal is separated out.In the crystallization step, need form based on glass transition temperature every kind of glass and set crystallized temperature, yet specifically, preferably heat-treat in the high temperature province more than 10 ℃ than glass transition temperature.Be under the situation more than 500 ℃ at second-order transition temperature for example, preferred the following of thermal treatment temp is limited to 510 ℃, more preferably 600 ℃, most preferably is 650 ℃.On the other hand, if thermal treatment temp is too high, then comprise WO ₃The TiO of crystal and even any composition ₂Crystal, TiP ₂O ₇Crystal, (TiO) ₂P ₂O ₇Crystal, RnTi ₂(PO ₄) ₃Crystal and RTi ₄(PO ₄) ₆The tendency that the crystalline phase of crystal etc. reduces will be strengthened the photocatalysis characteristic easily dissolved.So the upper limit of thermal treatment temp is preferably 1200 ℃, more preferably 1100 ℃, most preferably be 1050 ℃.If be higher than 1200 ℃, then WO ₃Crystalline is separated out and is tailed off, and the TiO of any composition of conduct ₂Crystal be easy to become the rutile-type that activity degree is lower than anatase titanium dioxide.Particularly from separating out RnTi ₂(PO ₄) ₃Crystal and RTi ₄(PO ₄) ₆The crystalline aspect is considered, is preferably below 1000 ℃.Because the temperature and time of crystallization causes very big influence to the formation or the crystalline size of crystalline phase, it is very important therefore critically controlling them.After obtaining required crystal, be cooled to outside the crystallized temperature zone, obtain being dispersed with crystalline glass-ceramic pearl.

And,, the method for pearl body shaping post crystallizationization, also can utilize by the direct balling of liquation, refrigerative process and separate out crystalline phase except foregoing.

Produce even carry out crystallization step under the state that the glass-ceramic pearl behind the crystal directly uses and also can bring into play very high photocatalysis characteristic, yet can carry out etching work procedure this glass-ceramic pearl.Owing to utilize etching, remove crystalline phase glassy phase on every side, it is big that the specific surface area of the crystalline phase of exposing on the surface becomes, and therefore can further improve the photocatalysis characteristic of glass-ceramic pearl.In addition, through solutions employed or etching period in the control etching work procedure, can obtain the only porous insert pearl of residual light catalysis crystalline phase.Etching work procedure can be implemented with above-mentioned first and second method identically.

[glass-ceramic fibre]

The glass-ceramic fibre of this embodiment has the general character of spun glass.That is, compare with common fiber, have that the tensile strength specific tenacity is big, the modular ratio Young's modulus is big, dimensional stability good, thermotolerance greatly, the advantage on not flammable, the rerum natura such as chemical resistant properties is good, can be used for effectively utilizing their various uses.In addition,, therefore except described advantage, also have photocatalysis characteristic, can be used in the more fiber construct of extensive fields thereby can provide owing to have the photochemical catalysis crystal on the inside and the surface of fiber.Here said fiber construct is meant the three-dimensional structure that fiber is for example formed as fabric, fabric, sandwich or their complex body, for example can enumerate non-woven fabrics.

Purposes as the thermotolerance of effectively utilizing spun glass, non-inflammability; Curtain, sheet, wallpaper, fly net, clothes class or lagging material etc. are for example arranged; If yet use the glass-ceramic fibre of this embodiment; Then also can give the deodorization functions that brings by photocatalysis, dirt decomposition function etc., the work that can reduce cleaning significantly or safeguard to the article of said purposes.

In addition; Though spun glass is used as filtering material more and uses owing to its chemical resistant properties; Yet the glass-ceramic fibre of this embodiment does not merely filter; Also utilize light-catalyzed reaction to decompose repugnant substance in the object being treated, dirt, bacterium etc., therefore refining plant and the strainer with more positive purification function can be provided.In addition, owing to can not produce the deterioration that breaks away from the characteristic that causes of peeling off basically, therefore help the long lifetime of these products by photocatalysis layer.

Below, the method for manufacture of the glass-ceramic fibre of this embodiment is described.The method of manufacture of the glass-ceramic fibre of this embodiment can comprise: mixing raw material and obtain its liquation the fusion operation, use liquation or the glass that obtains by liquation and with the spinning process of fibrous shaping, the temperature of this fiber is elevated to above the temperature province of second-order transition temperature and with this temperature keep specific time and separate out required crystalline crystallization step.And, because the prior manufacturing method of the glass-ceramic explain also can be applied in reconcilable scope in this concrete example in above-mentioned first and second method, so suitably quote these methods and omit multiple and put down in writing.

(fusion operation)

Can implement with above-mentioned second method identically.

(spinning process)

Then, be configured as spun glass by the liquation that in the fusion operation, obtains.The manufacturing process of corpus fibrosum is not particularly limited, as long as use known method to be shaped.For example; Under situation about being shaped with the fiber (macrofiber) that is wound on the type on the up-coiler continuously; As long as with known DM method (directly molten fiber elongation method) or MM method (crucible fiber elongation method) spinning; Under the situation that the staple fibre about tens of cm is shaped with staple length, also can use centrifuging or cut said macrofiber.Fibre diameter is as long as suitably select based on purposes.But, detailed rules and regulations can form the fabric of flexibility height, good hand touch more more, however the production efficiency variation, cost of spinning raise, if cross slightly that though the spinning productivity improves on the contrary, yet processibility or the property disposed variation.Under the situation of processing fiber products such as fabric, preferably be the scope of 3～24 μ m with Fibre diameter, under the situation of laminate structure of processing purposes such as being suitable for refining plant, strainer etc., be more than the 9 μ m preferably with Fibre diameter.Can according to purposes process cotton shape or make fiber constructs such as rove, cloth thereafter.

(crystallization step)

Then, fiber that utilizes said process to obtain or fiber construct are heated once more, carry out in fiber, reaching the surface and separate out required crystalline crystallization step.This crystallization step can be implemented with the crystallization step of granulated glass sphere identically.After obtaining required crystal, be cooled to obtain being dispersed with photochemical catalysis crystalline glass-ceramic fibre or fiber construct outside the crystallized temperature zone.

And, the method for corpus fibrosum shaping post crystallizationization, also can control the temperature of the spun glass in the spinning process except foregoing, side by side carry out crystallization step.

Produce even carry out crystallization step under the state that the glass-ceramic fibre behind the crystal directly uses and also can bring into play very high photocatalysis characteristic, yet can carry out etching work procedure this glass-ceramic fibre.Owing to utilize etching, remove crystalline phase glassy phase on every side, it is big that the specific surface area of the crystalline phase of exposing on the surface becomes, and therefore can further improve the photocatalysis characteristic of glass-ceramic fibre.In addition, through solutions employed or etching period in the control etching work procedure, can obtain the only porous insert fiber of residual light catalysis crystalline phase.Etching work procedure can be implemented with above-mentioned first and second method identically.

As stated, the glass-ceramic of this embodiment since within it portion and surface separate out the Tungsten oxide 99.999 with photocatalytic activity and/or the crystalline phase of its sosoloid equably, therefore have excellent photocatalysis activity and visible light-responded property, and weather resistance is also very excellent.So, do not have as only being provided with and peel off the situation of losing photocatalytic activity because of photocatalysis layer the photocatalysis functional member of technology in the past of photocatalysis layer on the surface of base material.In addition, if the surface is cut and exposed the crystalline phase that is present in interior oxidation tungsten and/or its sosoloid, also can keep photocatalytic activity.In addition, therefore the glass-ceramic of this embodiment can process the isochronous degree of freedom height of size or shape by the form manufacturing of melten glass, can be processed into the various article that require photo-catalysis function.

In addition; Method of manufacture according to the glass-ceramic of this embodiment; Generate the crystalline phase of Tungsten oxide 99.999 and/or its sosoloid owing to the control of cooperation composition that can utilize raw material and thermal treatment temp; Therefore can make glass-ceramic at an easy rate with regard to not needing always with industrialized scale as required work in the miniaturization of the crystal particles of the big problem in the photocatalysis technology with excellent photocatalysis activity and visible light-responded property.

Second embodiment: glass-ceramic sintered compact and method of manufacture thereof

Below, the glass-ceramic sintered compact and the method for manufacture thereof of second embodiment of the present invention described.The glass-ceramic sintered compact of this embodiment is with pulverizing the glass-ceramic sintered compact that glass sintering forms, containing the crystalline phase (WO that comprises Tungsten oxide 99.999 and/or its sosoloid at least ₃Crystalline phase).That is to say that the glass-ceramic sintered compact of this embodiment comprises the glass-ceramic of first embodiment.

The method of manufacture of the glass-ceramic sintered compact of this embodiment has vitrifying operation, pulverizing process, forming process and sintering circuit as main operation.Below the details of each operation is described.And, so-called " glass-ceramic sintered compact " be meant the powdered material cured sintering that comprises glass powder and material.The glass-ceramic sintered compact of this embodiment contains WO at least ₃Crystalline phase, this crystalline phase are evenly dispersed in the inside and the surface of glass-ceramic sintered compact.

[vitrifying operation]

In the vitrifying operation,, make vitreum through feedstock composition fusion and vitrifying with regulation.Specifically, in the container that comprises platinum or refractory body, drop into feedstock composition, through feedstock composition is heated to high temperature and fusion.The melten glass that obtains is thus flowed out, through suitably cooling off, form vitrifying vitreum.Fusion and vitrified condition are not special to be limited, and can suitably set according to the composition of feedstock composition and amount etc.In addition, Vitrea shape is not special to be limited, and for example also can be tabular, granular etc.The fused temperature and time is different along with the composition of glass, yet for example is preferably 1200～1650 ℃, 1～24 hour scope respectively.

(feedstock composition)

Feedstock composition is prepared to, and the vitreum of gained for example contains 10～95% Tungsten oxide 99.999 composition in the mole % that oxide compound converts and forms, and also contains 5～60% P ₂O ₅Composition, B ₂O ₃Composition, SiO ₂Composition and GeO ₂The composition more than at least a kind in the composition.

In addition, feedstock composition preferably uses the material for preparing as followsly, that is, and and except above-mentioned WO ₃Composition and P ₂O ₅Composition, B ₂O ₃Composition, SiO ₂Composition and GeO ₂Beyond the composition more than at least a kind in the composition, the vitreum of gained also contains in the mole % that oxide compound converts and forms:

0～60% TiO ₂Composition,

0～50% alkalimetal oxide composition and/or alkaline-earth metals oxide composition and/or

0～50% M _aO _b(in the formula, M be selected among Nb, Ta and the Mo more than a kind.A and b satisfy a: b=2: the natural number of valent minimum of M.Here, the valency of Nb is 5, and the valency of Ta is 5, and the valency of Mo is 6.) composition and/or

0～20% M ¹ _cO _d(in the formula, M ¹Be be selected among Zr and the Sn more than a kind.C and d satisfy c: d=2: M ¹The natural number of valent minimum.Here, the valency of Zr is 4, and the valency of Sn is 2.) composition and/or

0～50% M ² ₂O ₃(in the formula, M ²Be be selected among Al, Ga and the In more than a kind.) composition and/or

0～30% Ln ₂O ₃(in the formula, Ln be selected among Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and the Lu more than a kind.) composition and/or

0～10% M ³ _eO _f(in the formula, M ³Be be selected among V, Cr, Mn, Fe, Co and the Ni more than a kind.E and f satisfy e: f=2: M ³The natural number of valent minimum.Here, the valency of V is 5, and the valency of Cr is 3, and the valency of Mn is 2, and the valency of Fe is 3, and the valency of Co is 2, and the valency of Ni is 2.) and/or

0～20% Bi ₂O ₃Composition+TeO ₂Composition and/or

0～5% As ₂O ₃Composition+Sb ₂O ₃Each composition of composition,

The external ratio quality % of the total mass of forming to convert with respect to said Vitrea oxide compound, contain:

Below 15% be selected from N composition, S composition, F composition, Cl composition, Br composition and the C composition the non-metallic element composition more than at least a kind and/or

Be selected from least a kind of metallic element composition among Cu, Ag, Au, Pd, Ru, Rh, Re and the Pt below 10%.

In this embodiment, content beyond the above-mentioned aspect, that constitute Vitrea each composition, compositing range and cooperate purpose identical with first embodiment, so quote the content of explaining in [composition] hurdle of first embodiment here and omit explanation.

[pulverizing process]

In the pulverizing process, vitreum is pulverized and made and pulverize glass.Pulverizing the particle dia or the shape of glass can come suitably to set according to the shape of the molding of making in the forming process and the essential precision that is regarded as of size.For example, under the situation of the shape that need not manage the glass-ceramic sintered compact or form, the average particle diameter of pulverizing glass also can be the unit of tens of mm.On the other hand, the glass-ceramic sintered compact is shaped with required shape or with other crystal compound tendency, if it is excessive to pulverize the average particle diameter of glass, the difficulty that will become that then is shaped, so average particle diameter is more little good more.So the upper limit of pulverizing the average particle diameter of glass is preferably 100 μ m, more preferably 50 μ m most preferably are 10 μ m.And the average particle diameter of pulverizing glass for example can use the value of utilizing the laser diffraction and scattering method to survey periodic D50 (accumulative total 50% diameter).Specifically, can use the value of particle size distribution device MICROTRAC (MT3300EXII) mensuration of utilizing Nikkiso Company Limited.

And Vitrea breaking method is not special to be limited, and carries out yet for example can use ball mill, jet mill to wait.

[forming process]

Forming process is with pulverizing the operation that the molding of glass with desired shape is shaped.Under the situation of processing required shape, preferred use will be pulverized the drawing that glass is put into mould and pressurize.In addition, also can be deposited on the refractory body and be shaped pulverizing glass.Under this situation, also can use tackiness agent.

[sintering circuit]

In the sintering circuit, be heated into body and make sintered compact.Like this, bonded generates WO simultaneously between the Vitrea particle that constitutes molding ₃Crystalline phase forms the glass-ceramic sintered compact.In addition, for example by in pulverizing glass, having added WO ₃And/or anatase titanium dioxide TiO ₂Deng the crystalline mixture manufacture under the situation of body, will in the glass-ceramic sintered compact, generate more WO ₃And/or anatase titanium dioxide TiO ₂Thus, just can obtain higher photocatalytic activity.

The concrete step of sintering circuit is not special to be limited, yet also can comprise: to molding in addition preheating operation, with molding be warmed up at leisure design temperature operation, with molding with design temperature keep the operation of certain hour, with the molding operation of cool to room temperature at leisure.

The condition of sintering can suitably set based on the Vitrea composition that constitutes formed body.In the sintering circuit,, need make conditions such as thermal treatment temp meet the crystallization condition of the glass that constitutes molding in order from glass, to generate crystal.If sintering temperature is low excessively, then can't obtain to have the sintered compact of required crystalline phase, therefore need be higher than the sintering under the temperature of Vitrea second-order transition temperature (Tg) at least.Specifically, in this embodiment, the lower limit of sintering temperature is more than the Vitrea second-order transition temperature (Tg), is preferably more than Tg+50 ℃, more preferably more than Tg+100 ℃, most preferably is more than Tg+150 ℃.On the other hand, if sintering temperature is too high, WO then ₃Crystalline is separated out and is tailed off, and the TiO of any composition of conduct ₂The crystal inversion of phases be the rutile that activity degree is lower than anatase titanium dioxide, because of separating out the tendency grow that crystal beyond the target etc. reduces photocatalytic activity significantly.So, for the upper limit of sintering temperature, in this embodiment, be preferably below Vitrea Tg+600 ℃, more preferably below Tg+500 ℃, most preferably be below Tg+450 ℃.

In addition, the WO that comprises crystal state at molding ₃And/or TiO ₂Deng situation under, need to consider WO ₃And/or TiO ₂Amount, crystalline size and crystal formation wait and set sintering condition.

In addition, the lower limit of sintering time need be set according to sintering temperature, yet under the situation of comparatively high temps, is preferably set to the short period of time, under the situation of lesser temps, is preferably set to long-time.Specifically, in this embodiment, consider from carrying out the agglomerating aspect fully, preferably with 3 minutes, more preferably with 20 minutes, most preferably to be with 30 minutes be lower limit.On the other hand, if sintering time surpasses 24 hours, then the crystal of target will become excessive or generate other crystal and might can't obtain enough photocatalysis characteristics.So, for the upper limit of sintering time, in this embodiment, be preferably 24 hours, more preferably 19 hours, most preferably being was 18 hours.And said here sintering time is meant that the central firing temperature of sintering circuit is held necessarily (for example above-mentioned design temperature) length of above time.

Sintering circuit is for example preferably more ventilated on one side in gas furnace, microwave oven, electric furnace etc. and is carried out on one side.But, being not limited to this condition, for example also can in inert gas atmosphere, reducing gas atmosphere, oxidizing gas atmosphere etc., carry out.

In this embodiment; Owing to constitute content, the compositing range of each composition utilize the glass-ceramic sintered compact that sintering circuit forms and cooperate purpose identical, so quote the content of explaining in [composition] hurdle of first embodiment here and omit explanation with first embodiment.

[mixed processes]

The manufacture method of present embodiment can comprise by in pulverizing glass, mixing the mixed processes that composition arbitrarily increases this composition.The operation arbitrarily that this operation is can be after pulverizing process, carry out before the forming process.As the composition that in mixed processes, in pulverizing glass, adds; Be not particularly limited, however yet the composition of preferred mixing can be by strengthening this composition in the stage of pulverizing glass function or can only be engaged in slightly owing to make vitrifying become difficult in the feedstock composition of melten glass and can promote the one-tenth of photocatalysis to grade.And in this embodiment, the state that sometimes will be in this operation in pulverizing glass, mixes behind other compositions is generically and collectively referred to as " mixture ".Under the situation of carrying out mixed processes, in each operation that mixed processes carries out later on, " pulverizing glass " when will not carry out mixed processes replaces with " mixture ", can likewise implement.

(WO ₃And/or TiO ₂Interpolation)

The method of manufacture of this embodiment also can have the WO of mixed crystal state in pulverizing glass ₃And/or TiO ₂And the operation of making mixture.In the method for this embodiment, even the WO of mixed crystal state not ₃And/or TiO ₂, also can generate WO by vitreum ₃Crystalline phase.But, through will being the WO of crystal state ₃And/or TiO ₂Add to and pulverize in the glass, can increase the crystalline amount, contain galore and comprise WO ₃Crystal and even TiO ₂The crystalline crystalline phase, thus the glass-ceramic sintered compact that has strengthened photo-catalysis function can be made reliably.

The WO of crystal state ₃And/or TiO ₂Combined amount can be according to the temperature of Vitrea composition, manufacturing process etc., in the glass-ceramic sintered compact, to generate the WO of required amount ₃Crystal and/or TiO ₂The crystalline mode is suitably set.The WO of crystal state ₃And/or TiO ₂Mixing be arbitrarily, yet if the WO of crystal state ₃And/or TiO ₂Addition too small, then be difficult to make the WO in the glass-ceramic sintered compact ₃Crystal and/or TiO ₂The crystalline amount is abundant, if addition is too much, then is easy to generate the sintering obstacles such as difficulty that become.So, the WO of institute's blended crystal state ₃And/or TiO ₂The lower limit of amount be preferably 0.5% in mass ratio with respect to mixture, more preferably 1%, most preferably be 3%.On the other hand, the WO of institute's blended crystal state ₃And/or TiO ₂The upper limit of amount be preferably 95% in mass ratio with respect to mixture, more preferably 80%, most preferably be 60%.And, mixing WO ₃Crystal and TiO ₂Under the two the situation of crystal, WO ₃Crystal and TiO ₂Crystalline total amount is preferably in the scope of above-mentioned higher limit and lower value.

The WO that adds in known operation ₃Crystal has isometric system, tetragonal spheroidal, rhombic system, oblique system and triclinic crystalline structure, however as long as have photocatalytic activity, no matter be which kind of crystalline structure can.In addition, in general, at TiO ₂In the crystalline crystal formation, these 3 kinds of sharp titaniums, rutile, brookite are arranged.Wherein, the TiO of used crystal state in this operation ₂Can be in the middle of these 3 kinds more than a kind or 2 kinds, yet consider from the excellent aspect of photo-catalysis function, be preferably the combination of sharp titanium and brookite, more preferably sharp titanium.

For adding the WO that pulverizes in the glass to ₃Crystal and/or TiO ₂Crystalline raw material size of particles is considered from the viewpoint that improves photocatalytic activity, and is more little good more.But if the raw material size of particles is too small, then meeting and glass reaction in sintering might can't keep crystal state and disappear.In addition, if the raw material particle is too tiny, then also have the problem that the disposal in the manufacturing process becomes difficult.On the other hand, if the raw material size of particles is excessive, then easy form with the raw material particle residues in the finished product, is difficult to obtain the tendency grow of required photocatalysis characteristic.So the raw material particle is preferably dimensioned to be in the scope of 11～500nm, more preferably in the scope of 15～100nm, most preferably be in the scope of 20～50nm.

(interpolation of non-metallic element composition)

The method of manufacture of this embodiment also can have containing the additives mixed more than a kind that is selected from N composition, S composition, F composition, Cl composition, Br composition and the C composition operation in described pulverizing glass or the mixture.These non-metallic element compositions also can the part as the composition of feedstock composition cooperate in stage of making admixtion before making vitreum as previously mentioned or glass cullet.But, after making vitreum, these non-metallic element compositions are mixed into the way of pulverizing in the glass and import more easily, and can more effectively bring into play its function, therefore can obtain to have the glass-ceramic sintered compact of higher photocatalysis characteristic at an easy rate.

Under the situation of adding the non-metallic element composition, its combined amount can be according to suitably settings such as Vitrea compositions.Consider from the viewpoint of the photo-catalysis function that improves the glass-ceramic sintered compact fully; Effectively way is; Total as nonmetal composition; More than 0.01%, more preferably to add more than 0.05%, most preferably add more than 0.1% with respect to the preferred interpolation of the mass ratio of chippy vitreum or its mixture.On the other hand, if too much add, then photocatalysis characteristic reduces easily; Therefore for the upper limit of combined amount,, be preferably 20% in mass ratio with respect to chippy glass or its mixture as the total of nonmetal composition; More preferably 10%, most preferably be 5%.

Raw material during as interpolation non-metallic element composition, not special the qualification, however the N composition can use AlN ₃, SiN ₄Deng, the S composition can use NaS, Fe ₂S ₃, CaS ₂Deng, the F composition can use ZrF ₄, AlF ₃, NaF, CaF ₂Deng, the Cl composition can use NaCl, AgCl etc., and the Br composition can use NaBr etc., and the C composition can use TiC, SiC or ZrC etc.And the raw material of these non-metallic element compositions both can make up ground interpolation more than 2 kinds, also can add individually.

(interpolation of metallic element composition)

The method of manufacture of this embodiment also can have in pulverizing glass or mixture, to mix and comprises the operation that is selected from the metallic element composition more than a kind among Cu, Ag, Au, Pd, Ru, Rh, Re and the Pt.These metallic element compositions also can the part as the composition of feedstock composition cooperate in the stage of making making admixtion or glass cullet before the vitreum as previously mentioned.But, after making vitreum, these non-metallic element compositions are mixed into the way of pulverizing in the glass and import more easily, and can more effectively bring into play its function, therefore can obtain to have the glass-ceramic sintered compact of higher photocatalysis characteristic at an easy rate.

Under the situation of adding the metallic element composition, its combined amount can be according to suitably settings such as Vitrea compositions.Consider from the viewpoint of the photo-catalysis function that improves the glass-ceramic sintered compact fully; Effectively way is; Total as metal ingredient; More than 0.001%, more preferably to add more than 0.005%, most preferably add more than 0.01% with respect to the preferred interpolation of the mass ratio of chippy vitreum or its mixture.On the other hand, if too much add, then photocatalysis characteristic reduces easily; Therefore for the upper limit of combined amount,, be preferably 10% in mass ratio with respect to chippy glass or its mixture as the total of nonmetal composition; More preferably 5%, most preferably be 3%.And, the raw material during as interpolation metallic element composition, not special the qualification, however for example can use CuO, Cu ₂O, Ag ₂O, AuCl ₃, PtCl ₄, H ₂PtCl ₆, RuO ₂, RhCl ₃, ReCl ₃, PdCl ₂Deng.And the raw material of these metallic element compositions both can make up ground interpolation more than 2 kinds, also can add individually.

The particle dia of metallic element composition or shape can be according to Vitrea composition, WO ₃Amount, crystal formation etc. suitably set, yet in order to bring into play the photo-catalysis function of glass-ceramic sintered compact to greatest extent, the average particle diameter of metallic element composition is more little good more.So the upper limit of the average particle diameter of metallic element composition is preferably 5.0 μ m, more preferably 1.0 μ μ m most preferably are 0.1 μ m.

[slurry chemical industry preface]

The method of manufacture of this embodiment combines owing to Vitrea particle fusion in sintering circuit securely; Therefore glass particle self is undertaken the effect as the tackiness agent of glass-ceramic sintered compact, yet also can have pulverizing that glass or mixture are distributed in the fluid arbitrarily and the operation (slurry chemical industry preface) of processing slurry form.Like this, the shaping in the forming process will become easy.This operation be after pulverizing process or mixed processes before the forming process, or the operation arbitrarily that can side by side carry out with pulverizing process.Specifically, can prepare slurry through preferred organic inorganic adhesive of interpolation and/or solvent in pulverizing glass or mixture.

As organic binder bond, for example can use the habitual commercially available tackiness agent of using as drawing or rubber punching press, extrusion molding, injection forming of shaping additive.Specifically, for example can enumerate the multipolymer etc. of vinyl resin, TKK 021, polyvinyl butyral, methacrylic resin, urethane resin, NSC 20956, ethene base system.As inorganic adhesive, for example can enumerate metal alkoxide, water glass, aluminum oxide (Al ₂O ₃NH ₂O) etc., consider preferred inorganic adhesive from weather resistance aspect to photocatalysis.For the lower value of the containing ratio of the tackiness agent with respect to slurry, consider that from the aspect that can make the shaping facilitation fully be preferably 40 quality %, more preferably 30 quality % most preferably are 20 quality %.

As solvent, for example can use known solvents such as Z 150PH (PVA), Virahol (IPA), butanols, water, yet consider alcohols or water from the aspect that can alleviate environmental pressure.In addition, in order to obtain more uniform molding, also can and with an amount of dispersion agent, the de-bubble efficient when improving drying also can be also with an amount of tensio-active agent.As dispersion agent; Not special the qualification; For example can enumerate hydro carbons such as toluene, YLENE, benzene, hexane, hexanaphthene, cellosolve, Trivalin SF, THF (ester classes such as ketones such as ethers, acetone, methylethylketone, MIBK, pimelinketone, methyl acetate, ETHYLE ACETATE, n-butyl acetate, pentyl acetate such as THF) 、 diox etc.; They can use separately, perhaps make up ground use more than 2 kinds.

[degreasing process]

In the method for manufacture of this embodiment, pulverizing glass (or mixture) when containing organic binder bond, preferably before sintering circuit,, comprising the degreasing process that molding is heated to the temperature more than 350 ℃ as operation arbitrarily.Like this, be decomposed, gasify and discharge, therefore can from the glass-ceramic sintered compact, remove organism owing to pulverizing organic binder bond contained in the glass (or mixture) etc.For the lower limit of the Heating temperature in the degreasing process, consider from removing organic aspect fully, be preferably 350 ℃, more preferably 400 ℃, most preferably be 450 ℃.Though according to the kind of organic binder bond and difference, yet for example preferably carry out degreasing process with about 2 hours time.

Degreasing process is preferably identical with sintering circuit, Yi Bian Yi Bian for example in gas furnace, microwave oven, electric furnace etc., more ventilate and carry out.But, being not limited to this condition, for example also can in inert gas atmosphere, reducing gas atmosphere, oxidizing gas atmosphere etc., carry out.

[surface treatment procedure]

The glass-ceramic sintered compact that the method for manufacture of this embodiment also can also have sintering carries out surface-treated operations (surface treatment procedure) such as etching.That is to say that this surface treatment procedure is any operation that can after sintering circuit, carry out.Etching for example can be implemented through dipping glass-ceramic sintered compact in the solution of oxytropism or alkalescence.If so operation just can make the glassy phase dissolving and the surface of glass-ceramic sintered compact is made as concavo-convex state or is the porous state.Consequently, WO ₃The area that exposes of crystalline phase increases, and therefore can obtain higher photocatalytic activity.Used acid or alkaline solution in the dipping is so long as WO that can the etching glass ceramic sintered bodies ₃Glass beyond the crystalline phase equates that just not special the qualification for example can be used the acid (hydrofluoric acid, hydrochloric acid etc.) that contains fluorine or chlorine.

In addition, as etched other method, for example also can blow hydrogen fluoride gas, hydrogen chloride gas, hydrofluoric acid, hydrochloric acid through surface and wait and carry out etching to the glass-ceramic sintered compact.

The glass-ceramic sintered compact that utilizes above method manufacturing is owing to the WO with photocatalytic activity is separated out on portion and surface equably within it ₃Therefore crystalline phase has excellent photocatalysis activity and visible light-responded property, and weather resistance is also very excellent.So, do not have as only being provided with and peel off the situation of losing photocatalytic activity because of photocatalysis layer the photocatalysis functional member of technology in the past of photocatalysis layer on the surface of base material.In addition,, the surface exposes the WO that is present in inside if being cut ₃Crystalline phase also can be kept photocatalytic activity.In addition, the glass-ceramic sintered compact of this embodiment is via the form manufacturing of pulverizing glass, therefore processes the isochronous degree of freedom height of size or shape, can be processed into the various article that require photo-catalysis function.

[composition of glass-ceramic sintered compact]

The content that constitutes each composition of glass-ceramic sintered compact is preferably, even in the glass powder of raw material, adding various additives behind the sintering, also is in the scope identical with the Vitrea composition of above-mentioned raw material.Like this, just can give excellent photocatalysis characteristic and weather resistance to the glass-ceramic sintered compact.Specifically, the mole % that the glass-ceramic sintered compact converts and forms in oxide compound, the scope with 10～95% contains the Tungsten oxide 99.999 composition, and the scope with 5～60% contains P ₂O ₅Composition, B ₂O ₃Composition, SiO ₂Composition and GeO ₂The composition more than at least a kind in the composition.

In addition, the glass-ceramic sintered compact also contains in the mole % that oxide compound converts and forms:

0～60% TiO ₂Composition and/or

0～50% M _aO _b(in the formula, M be selected among Nb, Ta and the Mo more than a kind.A and b satisfy a: b=2: the natural number of the minimum of (valency of M).Here, the valency of Nb is 5, and the valency of Ta is 5, and the valency of Mo is 6.) composition and/or

0～20% M ¹ _cO _d(in the formula, M ¹Be be selected among Zr and the Sn more than a kind.C and d satisfy c: d=2: (M ¹Valency) the natural number of minimum.Here, the valency of Zr is 4, and the valency of Sn is 2.) composition and/or

0～30% Ln ₂O ₃(in the formula, Ln be selected among Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and the Lu more than a kind.) and/or

0～10% M ³ _eO _f(in the formula, M ³Be be selected among V, Cr, Mn, Fe, Co and the Ni more than a kind.E and f satisfy e: f=2: (M ³Valency) the natural number of minimum.Here, the valency of V is 5, and the valency of Cr is 3, and the valency of Mn is 2, and the valency of Fe is 3, and the valency of Co is 2, and the valency of Ni is 2.) and/or

0～20% Bi ₂O ₃Composition+TeO ₂Composition and/or

0～5% As ₂O ₃Composition+Sb ₂O ₃Each composition of composition,

The external ratio quality % of the total mass of forming to convert with respect to oxide compound, contain:

< photocatalysis functional member >

Utilize glass-ceramic sintered compact that above method makes as the photocatalysis functional member, because of be exposed in the outside atmosphere and adhere to organism etc. receive pollute or the atmosphere of the mould that is being easy to suspend etc. in the middle ten minutes such as machinery, device, utensil that use useful.For example, through with the glass-ceramic sintered compact of this embodiment as the member of formation of photocatalysis functional member as ceramic tile, window frame, lamp, building materials etc., just can make these members have photo-catalysis function.

< hydrophilic member >

In addition, the glass-ceramic sintered compact that utilizes aforesaid method to make is also very useful as hydrophilic member.For example, through the glass-ceramic sintered compact of this embodiment is used for the member of formation of panel for building, ceramic tile, window etc. as hydrophilic member, just can make these members have self-cleaning function.

As stated, according to the method for this embodiment, can make the WO that contains the photocatalytic activity that possesses visible light-responded property ₃Crystalline phase and glass-ceramic sintered compact with enough weather resistance.Owing to, have WO equably on the inside and the surface of glass-ceramic sintered compact ₃Therefore crystalline phase has excellent photocatalysis activity and visible light-responded property.In addition, in the method for present embodiment, can the mixed processes that mix any composition be set in the stage of pulverizing glass, under this situation, can increase with the photocatalysis composition at an easy rate is master's specific composition and strengthen photocatalytic activity significantly.In addition, because therefore the glass ceramics sintered body can design its shape based on purposes high-freedom degree ground via pulverizing glass manufacturing.

In addition; In the method for this embodiment; Owing to utilize the cooperation composition of raw material and the control of thermal treatment temp to generate the crystal that demonstrates photocatalytic activity by glassy phase; The crystalline material of the photocatalyst of the nano-scale that therefore not necessarily need be easy to condense and be difficult to dispose need not use special devices yet.So; According to the method for this embodiment, can make at an easy rate with industrialized scale possess excellent photocatalysis activity and visible light-responded property, for example as very useful glass-ceramic sintered compact in various uses such as photocatalysis functional member or hydrophilic member.

The 3rd embodiment: glass-ceramic complex body and method of manufacture thereof

Below, the glass-ceramic complex body and the method for manufacture thereof of the 3rd embodiment of this embodiment described.In this embodiment, so-called glass-ceramic complex body (following note do " complex body ") sometimes is to possess through glass heat is handled to make it to generate the glass-ceramic layer that crystalline phase gets and the material of base material.The glass-ceramic layer of complex body contains the crystalline phase (WO that comprises Tungsten oxide 99.999 and/or its sosoloid at least ₃Crystalline phase).That is to say that the glass-ceramic complex body of this embodiment comprises the glass-ceramic of first embodiment.

< method of manufacture of glass-ceramic complex body >

The method of manufacture of the glass-ceramic complex body of this embodiment has the pulverizing glass that is obtained by feedstock composition burnt till on base material and form and contains WO at least ₃The operation of the glass-ceramic layer of crystalline phase (firing process).In the preferred mode of the method for this embodiment, can comprise: process Vitrea vitrifying operation, pulverize vitreum and make the pulverizing process of pulverizing glass and on base material, burn till the firing process that forms glass-ceramic layer through pulverizing glass through fused raw material compsn and vitrifying.

And; Said in this embodiment " pulverizing glass " is to pulverize the material that get through the vitreum that will be obtained by feedstock composition, comprises i) crushed material of the glass of non-crystal state, the glass-ceramic that ii) will have a crystalline phase is pulverized and must crushed material, iii) in the crushed material of glass, separate out these three meanings of material of crystalline phase.That is, " pulverizing glass " has situation with crystalline phase and the situation that does not have crystalline phase.Have under the situation of crystalline phase pulverizing glass, both can make, also can separate out crystalline phase manufacturing through after pulverizing vitreum, heat-treating to make to pulverize in the glass through after separating out crystalline phase at the heat-treated glass body it being pulverized.And, do not contain under the situation of crystalline phase at " pulverizing glass ", can be through pulverizing configurations of glass on base material, the control firing temperature is separated out crystalline phase.With making the thermal treatment of separating out crystalline phase in the glass be called " crystallization processing " as described above.

Here, crystallization for example handle can be before (a) vitrifying operation subsequent pulverization step, behind (b) pulverizing process before the firing process, (c) implement with simultaneously each of firing process constantly.Wherein, from the sintering of glass-ceramic layer need tackiness agent easily and not, improve throughput by the simplification of process, viewpoint such as energy-conservation considers, preferably above-mentioned (c) side by side carries out crystallization with firing process and handles in burning till.But, using as the base material that constitutes complex body under the situation of the low material of thermotolerance, preferably before above-mentioned (a) vitrifying operation subsequent pulverization step or (b) behind the pulverizing process moment before the firing process carry out crystallization.

Below, the details of each operation is described.And, for the content identical, suitably omit explanation with first and second embodiment.

[vitrifying operation]

The vitrifying operation can likewise be implemented with the vitrifying operation of second embodiment.Here, be used to make Vitrea feedstock composition and be prepared to, the vitreum of gained for example contains 10～95% Tungsten oxide 99.999 composition in the mole % that oxide compound converts and forms, and also contains 5～60% P ₂O ₅Composition, B ₂O ₃Composition, SiO ₂Composition and GeO ₂The composition more than at least a kind in the composition.

0～60% TiO ₂Composition,

0～20% Bi ₂O ₃Composition+TeO ₂Composition and/or

0～5% As ₂O ₃Composition+Sb ₂O ₃Each composition of composition,

The quality % of the total mass of forming to convert with respect to said Vitrea oxide compound, contain:

[pulverizing process]

In the pulverizing process, vitreum is pulverized and made and pulverize glass.Pulverize glass through making, and Vitrea particle diameter is become smaller, therefore be easy to be applied on the base material.In addition, through processing pulverizing glass, just be easy to mix other composition.The particle dia of pulverizing glass or shape can wait suitably and set according to the kind of base material and to the surface property that complex body requires.Specifically, if it is excessive to pulverize the average particle diameter of glass, then be difficult in the glass-ceramic layer that forms desired shape on the base material, so average particle diameter is more little good more.So the upper limit of pulverizing the average particle diameter of glass is preferably 100 μ m, more preferably 50 μ m most preferably are 10 μ m.And the average particle diameter of pulverizing glass for example can use the value of utilizing the laser diffraction and scattering method to survey periodic D50 (accumulative total 50% diameter).Specifically, can use the value of particle size distribution device MICROTRAC (MT3300EXII) mensuration of utilizing Nikkiso Company Limited.

[firing process]

In the firing process, burn till, make complex body through pulverizing configurations of glass post-heating on base material.Like this, just on base material, form and contain WO ₃The glass-ceramic layer of crystalline phase.Here; The concrete step of firing process is not special to be limited, yet can comprise: will pulverize configurations of glass in the operation on the base material, will be disposed at pulverizing glass on the base material be warmed up at leisure design temperature operation, will pulverize glass with the operation of design temperature maintenance certain hour, will pulverize the glass operation of cool to room temperature at leisure.

(configuration on base material)

In the method for manufacture of this embodiment, will pulverize configurations of glass on base material.Like this, just can give photocatalysis characteristic and wetting ability to the wideer base material of kind scope.The material of used here base material is not special to be limited, however from easily with contain WO ₃The aspect of compoundization of crystalline glass-ceramic considers, for example preferably uses inorganic materials such as glass, pottery or metal etc.

To pulverize configurations of glass on base material the time, preferably will contain the slurry of pulverizing glass and be disposed on the base material with the gauge of regulation.Like this, just can on base material, form at an easy rate and have the glass-ceramic layer of photocatalysis characteristic.Here, the thickness of formed glass-ceramic layer can suitably be set according to the purposes of complex body.The thickness of can wide region ground setting glass-ceramic layer also is one of the speciality of the method for this embodiment.The viewpoint that has enough weather resistance from glass-ceramic layer is not peeled off considers that its thickness for example is preferably below the 500 μ m, more preferably below the 200 μ m, most preferably is below the 100 μ m.As the method that slurry is disposed on the base material, for example can enumerate and scrape print process, mould cladding process, spray method, injection molding method, extrusion molding method, rolling process, punching formation, roll formings etc. such as the skill in using a kitchen knife in cookery or coating methods such as calendering method, spin-coating method or dip coating, ink-jet, Bubblejet (registered trademark), hectograph.

And, as pulverizing the method for configurations of glass on base material, being not limited to the method for above-mentioned use slurry, also can powder that pulverize glass directly be positioned on the base material.In addition, contained because of heat treatment under the situation of crystal at the pulverizing glass that is disposed on the base material, also can mix with the organic or inorganic adhesive ingredients based on its degree of crystallinity, perhaps folder is established adhesive phase ground and is disposed between itself and base material.Under this situation, consider from aspect, as the preferred inorganic adhesive of tackiness agent for the weather resistance of photocatalysis.

(burning till)

The condition of burning till in the firing process can suitably be set based on the kind of Vitrea composition that constitute to pulverize glass, the additive that mixed and amount etc.Specifically, the atmosphere temperature when burning till, two kinds of controls stating after can carrying out according to the state that is disposed at the pulverizing glass on the base material.

First process for calcining is to have generated required WO in the pulverizing glass on being disposed at base material ₃The situation of crystalline phase for example can be enumerated vitreum or pulverizing glass have been implemented the situation that crystallization is handled.Firing temperature under this situation can suitably be selected in the TR below 1100 ℃ in the stable on heating while of considering base material, yet if firing temperature surpasses 1100 ℃, the WO that is generated ₃Crystalline phase is converted into other crystalline phase easily.So the upper limit of firing temperature is preferably 1100 ℃, more preferably 1050 ℃, most preferably be 1000 ℃.

Second process for calcining is that the pulverizing glass that is disposed on the base material is not handled by crystallization as yet, thereby does not have WO ₃The situation of crystalline phase.Under this situation need with burn till the crystallization that side by side carries out glass and handle.If firing temperature is low excessively, then can't obtain to have the sintered compact of required crystalline phase, therefore need at least than burning till under the high temperature of Vitrea second-order transition temperature (Tg).Specifically, the following Vitrea second-order transition temperature (Tg) that is limited to of firing temperature is preferably Tg+50 ℃, more preferably Tg+100 ℃, most preferably is Tg+150 ℃.On the other hand, if firing temperature is too high, WO then ₃Crystalline phase reduces, thus the tendency that has photocatalysis characteristic to disappear, so the upper limit of firing temperature is preferably Vitrea Tg+600 ℃, more preferably Tg+500 ℃, most preferably is Tg+450 ℃.

In addition, firing time need wait according to the composition of glass or firing temperature and set.If the reduction heat-up rate, if the situation that also has the thermal treatment temp of being heated to get final product, however being under the situation of comparatively high temps as target, be preferably set to the short period of time, under the situation of lesser temps, be preferably set to long-time.Specifically, from make crystal growth to a certain degree and the crystalline aspect of separating out q.s consider, preferably with 3 minutes, more preferably with 5 minutes, most preferably be lower limit with 10 minutes.On the other hand, if heat treatment time surpasses 24 hours, then the crystal of target becomes excessive or generates other crystal and might can't obtain enough photocatalysis characteristics.So the upper limit of firing time is preferably 24 hours, more preferably 19 hours, most preferably being was 18 hours.And, said here firing time, be meant firing temperature in the middle of the firing process be held necessarily more than (for example above-mentioned design temperature) during length.

Firing process for example preferably more ventilates on one side in gas furnace, microwave oven, electric furnace etc. and carries out on one side.But, being not limited to this condition, for example also can in inert gas atmosphere, reducing gas atmosphere, oxidizing gas atmosphere etc., carry out.

In this embodiment; Owing to constitute content, the compositing range of each composition utilize the glass-ceramic layer that firing process forms and cooperate purpose identical, so quote the content of explaining in [composition] hurdle of first embodiment here and omit explanation with first embodiment.In addition, because the rerum natura of the glass-ceramic layer of this embodiment is identical with first embodiment, so quotes the content of explaining in [rerum natura] hurdle of first embodiment here and omit explanation.

[crystallization step]

In the method for manufacture of this embodiment, the moment before the firing process carries out under the situation that crystallization handles before vitrifying operation subsequent pulverization step or behind the pulverizing process, can be respectively implements as operation (crystallization step) independently.As stated, the purpose of crystallization processing is to vitreum or pulverizes glass and implement thermal treatment and make inside separate out crystal.Owing to utilize crystallization to handle, separate out WO on the inside and the surface of vitreum or pulverizing glass ₃Therefore crystalline phase can make and contain WO in the glass-ceramic layer reliably ₃Crystalline phase.Heat treated condition (temperature, time) can be according to the suitably settings such as degree of Vitrea composition, necessary crystallization.

Specifically, the following Vitrea second-order transition temperature (Tg) that is limited to of thermal treatment temp is preferably Tg+10 ℃, more preferably Tg+20 ℃, most preferably is Tg+30 ℃.On the other hand, if temperature is too high, WO then ₃The tendency that crystalline phase reduces will grow, so the photocatalysis characteristic easily dissolved.So the upper limit of the temperature in the thermal treatment is preferably Vitrea Tg+600 ℃, more preferably Tg+500 ℃, most preferably be Tg+450 ℃.The heat treatment period that is used for crystallization is identical with above-mentioned firing process.

And; Side by side carrying out under the situation that crystallization handles with firing process, through as stated, using in inside and the surface is not separated out crystalline and pulverized glass; And with the firing temperature in the firing process be controlled to be can crystallization temperature, just can from glassy phase, separate out required crystal.

[mixed processes]

The manufacture method of present embodiment can comprise by in pulverizing glass, mixing the mixed processes that becomes to assign to increase this composition arbitrarily.This operation can be after pulverizing process, carry out before the firing process.Because this mixed processes can likewise implement with the mixed processes of second embodiment, therefore quote the content of explaining in [mixed processes] hurdle of second embodiment here and omit explanation.

[slurry chemical industry preface]

The method of manufacture of this embodiment also can have pulverizing that glass or mixture are scattered in the fluid arbitrarily and the operation (slurry chemical industry preface) of processing slurry form.Like this, just can make the operation facilitation that is disposed on the base material.Specifically, can preferably prepare slip through in pulverizing glass or mixture, adding solvent.In addition; The method of manufacture of this embodiment combines owing to Vitrea particle fusion in firing process securely; Therefore glass particle self is undertaken the effect as the tackiness agent of glass-ceramic; Yet under the high situation of the percent crystallinity of the pulverizing glass in the time of on being disposed at base material,, therefore also can add organic or inorganic adhesive because the function as tackiness agent of glass self has the tendency that dies down.

As organic binder bond, for example can use the habitual commercially available tackiness agent of using as drawing or rubber punching press, extrusion molding, injection forming of shaping additive.Specifically, for example can enumerate the multipolymer etc. of vinyl resin, TKK 021, polyvinyl butyral, methacrylic resin, urethane resin, NSC 20956, ethene base system.As inorganic adhesive, for example can enumerate metal alkoxide, water glass, aluminum oxide (Al ₂O ₃NH ₂O) etc.They can separately use under the situation about being heating and curing and under near the solidified situation normal temperature.For the lower value of the containing ratio of the tackiness agent with respect to slurry, consider that from the aspect that can make the shaping facilitation fully be preferably 40 quality %, more preferably 30 quality % most preferably are 20 quality %.

As solvent, for example can use known solvents such as Z 150PH (PVA), Virahol (IPA), butanols, water, yet consider alcohols or water from the aspect that can alleviate environmental pressure.In addition, in order to obtain more uniform molding, also can and with an amount of dispersion agent, the de-bubble efficient when improving drying also can be also with an amount of tensio-active agent.As dispersion agent; Not special the qualification; Yet for example can enumerate hydro carbons such as toluene, YLENE, benzene, hexane, hexanaphthene, cellosolve, Trivalin SF, THF (ester classes such as ketones such as ethers, acetone, methylethylketone, MIBK, pimelinketone, methyl acetate, ETHYLE ACETATE, n-butyl acetate, pentyl acetate such as THF) 、 diox etc.; They can use separately, perhaps make up ground use more than 2 kinds.

[degreasing process]

In the method for manufacture of this embodiment, pulverizing glass (or mixture) when containing organic binder bond, preferably before firing process,, comprising the degreasing process that molding is heated to the temperature more than 350 ℃ as operation arbitrarily.Like this, be decomposed, gasify and discharge, therefore can from glass-ceramic layer, remove organism owing to pulverizing organic binder bond contained in the glass (or mixture) etc.For the lower limit of the Heating temperature in the degreasing process, consider from removing organic aspect fully, be preferably 350 ℃, more preferably 400 ℃, most preferably be 450 ℃.Though according to the kind of organic binder bond and difference, yet for example preferably carry out degreasing process with about 2 hours time.

Degreasing process is preferably identical with firing process, Yi Bian Yi Bian for example in gas furnace, microwave oven, electric furnace etc., more ventilate and carry out.But, being not limited to this condition, for example also can in inert gas atmosphere, reducing gas atmosphere, oxidizing gas atmosphere etc., carry out.

[surface treatment procedure]

The method of manufacture of this embodiment also can also have carries out surface-treated operations (surface treatment procedure) such as etching to the glass-ceramic layer of complex body, the particularly complex body that has burnt till.Therefore the surface treatment procedure of this embodiment can be implemented with the surface treatment procedure of second embodiment identically, quotes the content of explaining in [surface treatment procedure] hurdle of second embodiment here and omits explanation.

Utilize the glass-ceramic complex body of above method manufacturing owing to separate out WO equably with photocatalytic activity on the inside and the surface of glass-ceramic layer ₃Therefore crystalline phase has excellent photocatalysis activity and visible light-responded property, and weather resistance is also very excellent.In addition,, therefore process size or the isochronous degree of freedom height of shape, can be processed into the various article that require photo-catalysis function according to the shape of base material because the glass-ceramic layer of the glass-ceramic complex body of this embodiment is to make via the form of pulverizing glass.

[composition of glass-ceramic layer]

In the glass-ceramic complex body of this embodiment, the content that constitutes each composition of glass-ceramic layer is preferably, even in the glass powder of raw material, adding various additives behind the sintering, also is in the scope identical with the Vitrea composition of above-mentioned raw material.Like this, just can to glass-ceramic layer give excellent photocatalysis characteristic, with the adaptation and the weather resistance of base material.Specifically, the mole % that glass-ceramic layer converts and forms in oxide compound, the scope with 10～95% contains the Tungsten oxide 99.999 composition, and the scope with 5～60% contains P ₂O ₅Composition, B ₂O ₃Composition, SiO ₂Composition and GeO ₂The composition more than at least a kind in the composition.

In addition, the glass-ceramic complex body also contains in the mole % that oxide compound converts and forms:

0～60% TiO ₂Composition and/or

0～20% Bi ₂O ₃Composition+TeO ₂Composition and/or

0～5% As ₂O ₃Composition+Sb ₂O ₃Each composition of composition,

< photocatalysis functional member >

The glass-ceramic complex body is for example as the photocatalysis functional member, because of be exposed in the outside atmosphere and adhere to organism etc. receive pollute or the atmosphere of the mould that is being easy to suspend etc. in the machinery, device, utensil etc. that use ten minutes useful.For example, through the glass-ceramic complex body of this embodiment is used for the member of formation of ceramic tile, window frame, lamp, building materials etc. as the photocatalysis functional member, just can make it to have photo-catalysis function.

< hydrophilic member >

In addition, the glass-ceramic complex body is also very useful as hydrophilic member.For example, through the glass-ceramic complex body of this embodiment is used for the member of formation of panel for example for building, ceramic tile, window etc. as hydrophilic member, just can make these members have self-cleaning function.

As stated,, can make following glass-ceramic complex body, that is, on base material, form the crystal of the Tungsten oxide 99.999 that contains the photocatalytic activity that possesses visible light-responded property and had the glass-ceramic layer of enough weather resistance according to the method for this embodiment.This glass-ceramic layer is high with the adaptation of base material because of the tackiness agent effect of glass self.In addition, owing to, have WO equably on the inside and the surface of glass-ceramic layer ₃Therefore crystalline phase has excellent photocatalysis activity and visible light-responded property.In addition, in the method for this embodiment, can the mixed processes that mix any composition be set in the stage of pulverizing glass, under this situation, can make with the photochemical catalysis composition at an easy rate is master's specific abundantization of composition and strengthen photocatalytic activity significantly.In addition, the thickness of the glass-ceramic complex body of manufacturing or shape can be according to the shape high freedom ground designs of purposes or base material.

In addition; In the method for this embodiment; Owing to utilize the cooperation composition of raw material and the control of thermal treatment temp to generate the crystalline phase that demonstrates photocatalytic activity by glassy phase; The crystalline material of the photocatalyst of the nano-scale that therefore not necessarily need be easy to condense and be difficult to dispose need not use special devices yet.So; According to the method for this embodiment, can make at an easy rate with industrialized scale possess excellent photocatalysis activity and visible light-responded property, for example as very useful glass-ceramic complex body in various uses such as photocatalysis functional member or hydrophilic member.

The 4th embodiment: glass powder plastochondria

The glass powder plastochondria of this embodiment contains the crystal with photocatalysis characteristic at glass, or can in glass, generate said crystalline material through being heated.This uniform crystal dispersion reaches in the inside of the non-crystal glass that constitutes the glass powder plastochondria and exists outwardly or generation.

Contain under the crystalline situation at " glass powder plastochondria ", the glass powder plastochondria has photocatalysis characteristic.This kind glass powder plastochondria can obtain through following operation,, after the vitreum that will be obtained by feedstock composition is pulverized, makes it crystallization that is, perhaps pulverizes after making it crystallization in the vitreum thermal treatment that will be obtained by feedstock composition.In this embodiment, will contain crystalline glass powder plastochondria note sometimes like this and make " glass-ceramic powder body ".On the other hand, do not contain under the crystalline situation at " glass powder plastochondria ", the glass powder plastochondria does not have photocatalysis characteristic, can make it to separate out crystal through heating glass powder body.In this embodiment, will can utilize thermal treatment to generate crystalline glass powder plastochondria note sometimes like this and make " not sintered glass ceramics powder body " with photocatalysis characteristic.When abbreviating the glass powder plastochondria as, be to comprise " glass-ceramic powder body " and " not sintered glass ceramics powder body " the two meaning.

[glass-ceramic powder body]

Below, the composition of the glass-ceramic powder body of this embodiment is described.

The feedstock composition that is used to make glass-ceramic powder body preferably uses the material for preparing as followsly, that is, and and the mole % of the total mass that the vitreum of gained is formed to convert with respect to oxide compound, contain:

10～95% WO ₃Composition and TiO ₂In the composition more than at least a kind and/or

5～60% P ₂O ₅Composition, B ₂O ₃Composition, SiO ₂Composition and GeO ₂The composition more than at least a kind in the composition and/or

0～30% Al ₂O ₃Composition and/or

0～30% Ga ₂O ₃Composition and/or

0～10% In ₂O ₃Composition and/or

0～20% ZrO ₂Composition and/or

0～10% SnO composition and/or

0～40% Li ₂The O composition and/or

0～40% Na ₂The O composition and/or

0～40% K ₂The O composition and/or

0～10% Rb ₂The O composition and/or

0～10% Cs ₂The O composition and/or

0～40% MgO composition and/or

0～40% CaO composition and/or

0～40% SrO composition and/or

0～40% BaO composition and/or

0～50% Nb ₂O ₅Composition and/or

0～50% Ta ₂O ₅Composition and/or

0～50% MoO ₃Composition and/or

0～50% ZnO composition and/or

0～20% Bi ₂O ₃Composition and/or

0～20% TeO ₂Composition and/or

Add up to 0～30% Ln ₂O ₃Composition (in the formula, Ln be selected among Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and the Lu more than a kind.) and/or

Add up to 0～10% M ³ _eO _fComposition (in the formula, M ³Be be selected among V, Cr, Mn, Fe, Co and the Ni more than a kind.E and f satisfy e: f=2: M respectively ³The natural number of valent minimum.Here, the valency of V is 5, and the valency of Cr is 3, and the valency of Mn is 2, and the valency of Fe is 3, and the valency of Co is 2, and the valency of Ni is 2.) and/or

Add up to 0～5% As ₂O ₃Composition and/or Sb ₂O ₃Composition and/or

With count with respect to the mass ratio of the glass total mass of oxide compound benchmark 0～15% be selected among F, Cl, Br, S, N and the C the composition more than at least a kind and/or

Mass ratio with respect to the glass total mass of oxide compound benchmark is counted 0～10% at least a kind of metallics among Cu, Ag, Au, Pd, Ru, Rh, Re and the Pt that is selected from.

Total amount that the glass-ceramic powder body of this embodiment preferably convert to be formed with respect to oxide compound contains WO in mole % in 10～95% scope ₃Composition and TiO ₂In the composition more than at least a kind.Particularly, through with WO ₃Composition and TiO ₂The total amount of composition is more than 10%, just can obtain enough photocatalytic activities, and through being below 95%, just can obtain the stability of glass.So, the total amount (WO with respect to total amount that the oxide compound conversion is formed ₃+ TiO ₂) in mole % preferably with 10%, more preferably with 15%, most preferably be lower limit with 20%, preferably with 95%, more preferably with 80%, most preferably be the upper limit with 75%.In addition, contain WO individually ₃Composition or TiO ₂WO during composition ₃Composition or TiO ₂The content of composition is in the mole % of total amount of convert forming with respect to oxide compound, preferably with 10%, more preferably with 15%, most preferably be lower limit with 20%, preferably with 95%, more preferably with 80%, most preferably be the upper limit with 75%.

The glass-ceramic powder body of this embodiment preferably contains in crystalline phase and comprises WO ₃, TiO ₂, the crystal more than a kind in their sosoloid.In addition, more preferably in crystalline phase, also contain and comprise TiP ₂O ₇, and (TiO) ₂P ₂O ₇In the crystal more than a kind.In addition, TiO ₂The crystal of more preferably sharp titanium (Anatase) type of crystal or brookite (Brookite) type.Through containing these crystal, glass-ceramic powder body just can have very high photo-catalysis function.

In this embodiment, content beyond the above-mentioned aspect, that constitute each composition of glass powder plastochondria, compositing range and cooperate purpose identical with first embodiment, so quote the content of explaining in [composition] hurdle of first embodiment here and omit explanation.

Therefore in addition, in this embodiment, the rerum natura of glass-ceramic powder body is identical with first embodiment, quotes the content of explaining in [rerum natura] hurdle of first embodiment here and omits explanation.

[not sintered glass ceramics powder body]

Therefore the not sintered glass ceramics powder body of this embodiment has and the identical in fact compositing range of above-mentioned glass-ceramic powder body owing to utilize heating (thermal treatment) to generate crystalline phase.This not sintered glass ceramics powder body be the photocatalysis functional blank of following potentiality; Promptly; For example through process the pulp-like mixture to coating on the base material arbitrarily etc. wait use after; Or (just in the stage of filming and forming thing or solidifying to form thing) enforcement thermal treatment in the back that is shaped as the cured formation thing, be easy to separate out crystal with photocatalysis characteristic.Because it is sintered glass ceramics powder body does not also possess photocatalytic activity, therefore excellent aspect the convenience of keeping or disposal.Specifically, even for example contact, or preserving down with organism blended state with organism arbitrarily, do not worry yet because of photocatalytic activity with this organism decomposition.In addition, owing to also do not possess photocatalytic activity, therefore do not worry in preservation losing or reducing photocatalytic activity because of changes in crystal structure etc. yet.In addition, through before being applied on the base material etc. soon, or heat-treat and the crystal of photocatalyst separated out in the stage (stage of commercialization just) that forms thing or cured formation thing of filming, just can give always stable photo-catalysis function to product.

(glass powder plastochondria particle)

The particle diameter or the shape of the glass powder plastochondria of this embodiment (glass-ceramic powder body reaches not sintered glass ceramics powder body) can be according to suitably settings such as its purposes.In order to bring into play enough photocatalytic activities, median size is more little good more, and shape subglobular more is good more.Not being that intention limits especially, if enumerate the scope of preferred median size, for example is in the scope of 0.05 μ m～5000 μ m.

For example, process under the situation of photocatalysis functional coating the glass powder plastochondria being coupled in the coating, for obtain in coating dispersiveness with have enough photocatalysis characteristics, for example be preferably the median size of 0.05～80 μ m.In addition, the glass powder plastochondria being mixed with fluids such as appropriate solvent and processing under the situation of pulp-like mixture, for example be preferably the median size of 0.05～300 μ m.In addition, the glass powder plastochondria is being utilized method cured formations such as sintering and processing under the situation of photocatalysis functional member, for example be preferably the median size of 0.1～2000 μ m.

There is big particle if the size-grade distribution of glass powder plastochondria is wide, just can't obtains homogeneity or compactness, might difference occur in the structure in material.Thus, preferably reduce extreme particle contained in the glass-ceramic powder body greater than median size.So in having the glass powder plastochondria of above-mentioned each median size, the maximum particle diameter of glass powder plastochondria is preferably below 10 times of median size, more preferably below 5 times, most preferably is below 3 times.And median size is bigger, more little good more with the difference of maximum particle diameter.

According to the purposes of glass powder plastochondria, also might use the glass powder plastochondria of the big particle diameter of mm unit.Through making sintered compact, for example can also be applied in building materials used in filtering material (strainer) or the fountain etc. etc. with through hole by big particle.

And the median size of glass powder plastochondria for example can be used the value of utilizing the laser diffraction and scattering method to survey periodic D50 (accumulative total 50% diameter).Specifically, can use the value of particle size distribution device MICROTRAC (MT3300EXII) mensuration of utilizing Nikkiso Company Limited.

And, surpass under the situation of 2000 μ m at the minimum diameter of glass powder plastochondria, can obtain median size with the sieve analysis of stipulating among the JIS A120.

< method of manufacture of glass powder plastochondria >

Below, to the method for manufacture of the glass powder plastochondria of this embodiment, be divided into glass-ceramic powder body and not sintered glass ceramics powder body describe.And the method for manufacture of the glass powder plastochondria of this embodiment can comprise the operation operation arbitrarily in addition of following explanation.

(1) method of manufacture of glass-ceramic powder body

Though not special the qualification, yet glass-ceramic powder body can utilize 2 kinds of following methods to make.

Method of manufacture A1:

This method of manufacture A1 can have: through feedstock composition fusion and vitrifying are made Vitrea vitrifying operation, vitreum is implemented the pulverizing process that thermal treatment is made the crystallization step of glass-ceramic, the glass-ceramic pulverizing made glass-ceramic powder body.

[vitrifying operation]

[crystallization step]

In the crystallization step, vitreum is implemented thermal treatment, make glass-ceramic.Owing to utilize crystallization step, in Vitrea inside and the surface separate out and comprise WO ₃Therefore crystal and/or TiO crystalline crystalline phase can contain reliably in making the glass powder plastochondria thereafter and comprise WO ₃Crystal and/or TiO crystalline crystalline phase.Heat treated condition (temperature, time) can be according to the suitably settings such as degree of Vitrea composition, necessary crystallization.Specifically, the following Vitrea second-order transition temperature (Tg) that is limited to of thermal treatment temp is preferably Tg+10 ℃, more preferably Tg+20 ℃, most preferably is Tg+30 ℃.On the other hand, if temperature is too high, the tendency of then separating out the unknown phase beyond the target will grow, so the photocatalysis characteristic easily dissolved.So the upper limit of the temperature in the thermal treatment is preferably Vitrea Tg+600 ℃, more preferably Tg+500 ℃, most preferably be Tg+450 ℃.In addition, in this operation,, therefore control very important rightly according to composition or thermal treatment temp because heat-up rate causes very big influence to crystalline size.

In addition, the heat treatment time that is used for crystallization need wait according to the shape of glass or thermal treatment temp to be set.If the reduction heat-up rate, if the situation that also has the thermal treatment temp of being heated to get final product, however being under the situation of comparatively high temps as target, be preferably set to the short period of time, under the situation of lesser temps, be preferably set to long-time.Specifically, from make crystal growth to a certain degree and the crystalline aspect of separating out q.s consider, preferably with 3 minutes, more preferably with 5 minutes, most preferably be lower limit with 10 minutes.On the other hand, if heat treatment time surpasses 24 hours, then the crystal of target becomes excessive or generates other crystal and might can't obtain enough photocatalysis characteristics.So the upper limit of firing time is preferably 24 hours, more preferably 19 hours, most preferably being was 18 hours.

[pulverizing process]

In the pulverizing process, glass-ceramic is pulverized and making glass-ceramic powder body.And the breaking method of glass is not special to be limited, and carries out yet for example can use ball mill, jet mill to wait.In addition, also can in the kind that changes kibbler, carry out pulverizing process, till the particle diameter that reaches target.

Method of manufacture A2:

Method of manufacture A2 can have: through feedstock composition fusion and vitrifying being made Vitrea vitrifying operation, vitreum being pulverized the pulverizing process of making sintered glass ceramics powder body not, sintered glass ceramics powder body is not implemented the crystallization step that glass-ceramic powder body is made in thermal treatment.

[vitrifying operation]

The vitrifying operation is made vitreum through with feedstock composition fusion and vitrifying.This vitrifying operation can be implemented with the vitrifying operation of method of manufacture A1 identically.

[pulverizing process]

In the pulverizing process, not sintered glass ceramics powder body is made in the vitreum pulverizing.This pulverizing process except will be not crystallized vitreum pulverize and make not the sintered glass ceramics powder body, can implement with the pulverizing process of method of manufacture A1 identically.

[crystallization step]

In the crystallization step,, make glass-ceramic powder body to not sintered glass ceramics powder body enforcement thermal treatment.Utilize crystallization step, in the inside of glass-ceramic and the surface separate out and comprise WO ₃Crystal and/or TiO ₂The crystalline crystalline phase.Heat treated condition in this crystallization step (temperature, time) is heat-treated this point sintered glass ceramics powder body not except replacing vitreum, can implement with the crystallization step of method of manufacture A1 identically.

(2) method of manufacture of sintered glass ceramics powder body not

Method of manufacture A3:

The method of manufacture of sintered glass ceramics powder body is not special limits, yet can have: through feedstock composition fusion and vitrifying are made Vitrea vitrifying operation, vitreum pulverized made the not pulverizing process of sintered glass ceramics powder body.That is to say, except the crystallization step of the method for manufacture A2 of glass-ceramic powder body, can implement identically with above-mentioned method of manufacture A2.Like this, though yet just can make and not contain crystal and can utilize heating thereafter to generate not sintered glass ceramics powder body of this crystalline with photocatalysis characteristic.

And, heat sintered glass ceramics powder body not and heat-treating methods when generating crystal can be implemented with the above-mentioned crystallization step explained in the method for manufacture of glass-ceramic powder body identically.But, waiting under the situation about supporting through on base material arbitrarily, being coated with, the heat resisting temperature that is preferably based on base material is regulated heat treatment temperature.

[interpolation operation]

The method of manufacture A1 of this embodiment～A3 can comprise through in the glass powder plastochondria, mixing the interpolation operation that becomes to assign to increase this composition arbitrarily.This operation is preferably carried out after pulverizing process in method of manufacture A1～A3, most preferably after pulverizing process, heat-treats among the method for manufacture A2 of (crystallization step) and carries out before in thermal treatment (crystallization step).Add the composition in the glass powder plastochondria to as adding in the operation; Not special restriction, however preferred mixing can increase the composition of the function that strengthens this composition through the stage at the glass powder plastochondria or the one-tenth that can only be coupled to slightly owing to be difficult to vitrifying in the feedstock composition of melten glass grades.And in this specification sheets, the state that sometimes will be in this operation in the glass powder plastochondria, mixes behind other compositions is generically and collectively referred to as " powder/particle mixture ".Carrying out adding under the situation of operation, in adding each operation that operation carries out later on,, can implement identically except " glass powder plastochondria " when adding operation replaces with " powder/particle mixture ".

(WO ₃And/or TiO ₂Interpolation)

The method of manufacture A1 of this embodiment～A3 also can have the WO that in the glass powder plastochondria, adds crystal state ₃And/or TiO ₂And the interpolation operation of making powder/particle mixture.In the method for this embodiment, even the WO of mixed crystal state not ₃And/or TiO ₂, also can generate and contain WO by vitreum ₃Crystal and/or TiO ₂The crystalline crystalline phase.But, through will being the WO of crystal state ₃And/or TiO ₂Add in the glass powder plastochondria, just can increase the amount of crystalline phase, contain WO galore ₃Crystal and TiO ₂The crystalline crystalline phase, thus the glass powder plastochondria that has strengthened photo-catalysis function can be made.

The WO of crystal state ₃And/or TiO ₂Combined amount can be according to temperature in Vitrea composition, the manufacturing process etc., in the material that has used the glass powder plastochondria, there to be the WO of required amount ₃Crystal and/or TiO ₂The crystalline mode is suitably set.Consider the WO of institute's blended crystal state from the viewpoint of the photo-catalysis function that improves the glass powder plastochondria ₃And/or TiO ₂The lower limit of amount in mass ratio with respect to powder/particle mixture, be preferably 1%, more preferably 5%, most preferably be 10%.On the other hand, the WO of institute's blended crystal state ₃And/or TiO ₂The upper limit of amount in mass ratio with respect to powder/particle mixture, be preferably 95%, more preferably 80%, most preferably be 60%.And, with WO ₃And TiO ₂Under the two blended situation, WO ₃And TiO ₂The total amount be preferably in the scope of above-mentioned higher limit and lower value.

For the WO that adds in the glass powder plastochondria ₃And/or TiO ₂Crystalline raw material size of particles is considered from the viewpoint that improves photocatalytic activity, and is more little good more.But if the raw material size of particles is too small, then meeting and glass reaction in thermal treatment might can't keep crystal state and disappear.In addition, if the raw material particle is too tiny, then also have the problem that the disposal in the manufacturing process becomes difficult.On the other hand, if the raw material size of particles is excessive, then easy form with the raw material particle residues in the finished product, is difficult to obtain the tendency grow of required photocatalysis characteristic.So the raw material particle is preferably dimensioned to be in the scope of 11～500nm, more preferably in the scope of 21～200nm, most preferably be in the scope of 31～100nm.

(interpolation of non-metallic element composition)

The method of manufacture A1 of this embodiment～A3 also can have and adds the interpolation operation in described glass powder plastochondria or the powder/particle mixture to containing the additive more than a kind that is selected from N composition, S composition, F composition, Cl composition, Br composition and the C composition.These non-metallic element compositions also can the part as the composition of feedstock composition cooperate in stage of making admixtion before making vitreum as previously mentioned or glass cullet.But the way that after making vitreum, these non-metallic element compositions is mixed in the glass powder plastochondria imports more easily, and can more effectively bring into play its function, therefore can obtain to have the glass powder plastochondria of higher photocatalysis characteristic at an easy rate.

Under the situation of adding the non-metallic element composition, its combined amount can be according to suitably settings such as Vitrea compositions.Consider from the viewpoint of the photo-catalysis function that improves the glass powder plastochondria fully; Effectively way is; Total as nonmetal composition; More than 0.01%, more preferably to add more than 0.05%, most preferably add more than 0.1% with respect to the preferred interpolation of the mass ratio of chippy vitreum or its powder/particle mixture.On the other hand, if too much add, then photocatalysis characteristic reduces easily; Therefore for the upper limit of combined amount,, be preferably 20% in mass ratio with respect to chippy glass or its mixture as the total of nonmetal composition; More preferably 10%, most preferably be 5%.

(interpolation of metallic element composition)

The method of manufacture A1 of this embodiment～A3 also can have in glass powder plastochondria or powder/particle mixture to mix and comprises the interpolation operation that is selected from the metallic element composition more than a kind among Cu, Ag, Au, Pd, Ru, Rh, Re and the Pt.These metallic element compositions also can the part as the composition of feedstock composition cooperate in the stage of making making admixtion or glass cullet before the vitreum as previously mentioned.But the way that after making vitreum, these non-metallic element compositions is mixed in the glass powder plastochondria imports more easily, and can more effectively bring into play its function, therefore can obtain to have the glass powder plastochondria of higher photocatalysis characteristic at an easy rate.Under the situation of adding the metallic element composition, its combined amount can be according to suitably settings such as Vitrea compositions.Consider from the viewpoint of the photo-catalysis function that improves the glass powder plastochondria fully; Effectively way is; Total as metal ingredient; More than 0.001%, more preferably to add more than 0.005%, most preferably add more than 0.01% with respect to the preferred interpolation of the mass ratio of chippy vitreum or its powder/particle mixture.On the other hand, if too much add, then photocatalysis characteristic reduces easily; Therefore for the upper limit of combined amount,, be preferably 10% in mass ratio with respect to chippy glass or its powder/particle mixture as the total of nonmetal composition; More preferably 5%, most preferably be 3%.And, the raw material during as interpolation metallic element composition, not special the qualification, however for example can use CuO, Cu ₂O, Ag ₂O, AuCl ₃, PtCl ₄, H ₂PtCl ₆, RuO ₂, RhCl ₃, ReCl ₃, PdCl ₂Deng.And the raw material of these metallic element compositions both can make up ground interpolation more than 2 kinds, also can add individually.

Particle dia or shape as the metallic element composition of additive can be according to Vitrea composition, WO ₃And/or TiO ₂Amount, crystal formation etc. suitably set, yet in order to bring into play the photo-catalysis function of glass powder plastochondria to greatest extent, the average particle diameter of metallic element composition is more little good more.So the upper limit of the average particle diameter of metallic element composition is preferably 5.0 μ m, more preferably 1.0 μ m most preferably are 0.1 μ m.

[surface treatment procedure]

The glass powder plastochondria that the method for manufacture A1 of this embodiment～A3 also can also have obtaining as described above carries out surface-treated operations (surface treatment procedure) such as etching.This operation is especially preferably carried out the glass-ceramic powder body that utilizes method of manufacture A1 and A2 to obtain.Therefore the surface treatment procedure of this embodiment can be implemented with the surface treatment procedure of second embodiment identically, quotes the content of explaining in [surface treatment procedure] hurdle of second embodiment here and omits explanation.

< pulp-like mixture >

Glass powder plastochondria through this embodiment that will obtain as described above (glass-ceramic powder body and not sintered glass ceramics powder body) and solvent arbitrarily etc. mix, and can prepare the pulp-like mixture.Like this, for example coating on base material etc. will become easy.Specifically, can add inorganic or organic binder bond and/or solvent prepare slip through preferred in the glass powder plastochondria.

As inorganic be adhesive; Be not particularly limited; Yet preferably see through the material of the character of ultraviolet ray or luminous ray, for example can enumerate silicate and be the particulate of adhesive, phosphate-based adhesive, inorganic glue system adhesive, aluminium oxide, silica, zirconia etc. etc.

As organic binder bond, for example can use the habitual commercially available tackiness agent of using as drawing or rubber punching press, extrusion molding, injection forming of shaping additive.Specifically, for example can enumerate the multipolymer etc. of vinyl resin, TKK 021, polyvinyl butyral, methacrylic resin, urethane resin, NSC 20956, ethene base system.

As solvent; For example can make water, methyl alcohol, ethanol, propyl alcohol, butanols, Virahol (IPA), acetate, DIMETHYL FORMAMIDE, acetonitrile, acetone, Z 150PH known solvents such as (PVA); Yet consider alcohols or water from the aspect that can alleviate environmental pressure.

In addition, in order to realize the homogenizing of slurry, also can be also with an amount of dispersion agent.As dispersion agent; Not special the qualification; For example can enumerate hydro carbons such as toluene, YLENE, benzene, hexane, hexanaphthene, cellosolve, Trivalin SF, THF (ester classes such as ketones such as ethers, acetone, methylethylketone, MIBK, pimelinketone, methyl acetate, ETHYLE ACETATE, n-butyl acetate, pentyl acetate such as THF) 、 diox etc.; They can use separately, perhaps make up ground use more than 2 kinds.

In the pulp-like mixture of this embodiment, can be according to its purposes, except mentioned component, also cooperate the additive component that for example is used to regulate curing speed, proportion etc.

The content of the glass powder plastochondria in the pulp-like mixture of this embodiment can suitably be set according to its purposes.So; The content of the glass powder plastochondria in the pulp-like mixture is not special to be limited; Yet if enumerate an example, consider from the viewpoint of bringing into play photocatalysis characteristic fully, preferably with 2 quality %, more preferably with 3 quality %, most preferably be lower limit with 5 quality %; Consider as the flowability of slurry and functional viewpoint from guaranteeing, preferably with 80 quality %, more preferably with 70 quality %, most preferably be the upper limit with 65 quality %.

[method of manufacture of pulp-like mixture]

The pulp-like mixture of this embodiment can be made through the glass powder plastochondria is scattered in the solvent.That is, the method for manufacture of the pulp-like mixture of this embodiment can utilize following method of manufacture B1～B3 any one carry out.And the method for manufacture of the pulp-like mixture of this embodiment can comprise the operation operation arbitrarily in addition of following explanation.

Method of manufacture B1:

Method of manufacture B1 is a method of making the pulp-like mixture contain glass-ceramic powder body and solvent, can have: through feedstock composition fusion and vitrifying are made Vitrea vitrifying operation, to vitreum implement thermal treatment make the crystallization step of glass-ceramic, with the glass-ceramic pulverizing make said glass-ceramic powder body pulverizing process, glass-ceramic powder body is scattered in the mixed processes in the solvent.

Method of manufacture B2:

Method of manufacture B2 is an other method of making the pulp-like mixture contain glass-ceramic powder body and solvent, can have: through feedstock composition fusion and vitrifying are made Vitrea vitrifying operation, with vitreum pulverize the pulverizing process of making sintered glass ceramics powder body not, to sintered glass ceramics powder body enforcement thermal treatment not make glass-ceramic powder body crystallization step, glass-ceramic powder body is scattered in the mixed processes in the solvent.

Method of manufacture B3:

Method of manufacture B3 makes to contain the not method of the pulp-like mixture of sintered glass ceramics powder body and solvent, can have: through feedstock composition fusion and vitrifying are made Vitrea vitrifying operation, with vitreum pulverize the pulverizing process of making sintered glass ceramics powder body not, general sintered glass ceramics powder body be not scattered in the mixed processes in the solvent.

Among above method of manufacture B1～B3, owing to except mixed processes, can implement with above-mentioned method of manufacture A1～A3 identically, therefore the details to each operation omits explanation.Mixed processes can through with glass-ceramic powder body or not sintered glass ceramics powder body be scattered in the above-mentioned solvent and carry out.In addition, also can comprise above-mentioned interpolation operation or surface treatment procedure.

Method of manufacture B1～the B3 of the pulp-like mixture of this embodiment can also have the operation of the aggregate of removing the glass powder plastochondria.The glass powder plastochondria is along with its particle diameter diminishes, and the surface energy quantitative change is big, thereby the tendency that is easy to condense is arranged.In case the cohesion of glass powder plastochondria then can't disperse equably in the pulp-like mixture, thereby have the situation that can't obtain required photocatalytic activity.Thus, the preferred operation that the aggregate of removing the glass powder plastochondria is set.For example removing of aggregate can be implemented through filtering the pulp-like mixture.The filtration of pulp-like mixture for example can use the filtering materials such as screen cloth of the mesh of regulation to carry out.

The pulp-like mixture that utilizes the glass powder plastochondria of this embodiment that above method obtains and contain it can be used as the photocatalysis functional blank, for example be coupled to coating, can be shaped/the mixing thing of solidified etc. in and use.

< solidifying to form thing >

The glass powder plastochondria of this embodiment can be through preparing its curing the cured formation thing of shape arbitrarily.The glass powder plastochondria is owing to be the powder shape, and the degree of freedom that the shape when therefore being shaped is selected is high, can form the photocatalysis functional member of different shape.The cured formation thing both can only be made up of the glass powder plastochondria, also can for example comprise base material, also can also contain tackiness agent etc. arbitrarily.

[method of manufacture of cured formation thing]

The method of manufacture of cured formation thing is not special to be limited, and comprises glass powder plastochondria sintering, the heat-treating methods that adds hot stamping are made yet for example can utilize.Under this situation, being used for the thermal treatment of cured formation, constituting between the particle of glass powder plastochondria of cured formation thing and combine, is being under the situation of raw material with sintered glass ceramics powder body not simultaneously, can generate to comprise WO ₃Crystal and/or TiO ₂The crystalline crystalline phase.And, also can not apply thermal treatment, the bounding force of tackiness agent comes cured formation and for example only utilize.But,, preferably be accompanied by heat treated process based on following reason; That is and since the glass powder plastochondria be originally with glass as parent, therefore comprise the heat treated cured formation method under the specified temperature through employing; Even do not use tackiness agent, also can be with combining between the glass particle; Under the situation of sintered glass ceramics powder body not, the thermal treatment when utilizing cured formation can also be separated out crystal.And, also can, the glass powder plastochondria be shaped and preparation cured formation thing after temporarily being processed the form of above-mentioned pulp-like mixture with required shape.

Sintering or add in the hot stamping heat treated condition can according to the composition of the glass that constitutes the glass powder plastochondria, kind and the amount etc. of mixed additive suitably set.Specifically, heat treatment temperature can for example be carried out two kinds of following controls based on the state of glass dust plastochondria.

First heat treating method is to comprise required WO by having ₃Crystal and/or TiO ₂The situation that the glass-ceramic powder body of crystalline crystalline phase is shaped, the thermal treatment temp under this situation can suitably be selected in 1200 ℃ TR.If thermal treatment temp surpasses 1200 ℃, then comprise WO ₃Crystal and/or TiO ₂The crystalline crystalline phase is converted into easily and comprises other crystalline crystalline phases.So the upper limit of thermal treatment temp is preferably 1200 ℃, more preferably 1100 ℃, most preferably be 1050 ℃.

Second heat treating method is a situation about being shaped by sintered glass ceramics powder body not, can handle with the crystallization that cured formation side by side carry out glass under this situation.If thermal treatment temp is low excessively, then can't separate out required crystalline phase, therefore need be higher than the heating under the temperature of second-order transition temperature (Tg) of the glass that constitutes the glass powder plastochondria at least.Specifically, the following second-order transition temperature (Tg) that is limited to glass of thermal treatment temp is preferably Tg+10 ℃, more preferably Tg+20 ℃, most preferably is Tg+30 ℃.On the other hand, if thermal treatment temp is too high, then crystalline phase reduces, thus the tendency that has photocatalysis characteristic to disappear, so the upper limit of thermal treatment temp is preferably Tg+600 ℃ of the glass that constitutes the glass powder plastochondria, more preferably Tg+500 ℃, most preferably is Tg+400 ℃.

In addition, the heat treatment time that is used for sintering or pressurization punching press need be set according to thermal treatment temp, under the situation of comparatively high temps, is preferably set to the short period of time, under the situation of lesser temps, is preferably set to long-time.Specifically, consider from the crystalline aspect that can be cured the aspect of shaping fully and carry out can separating out under the situation that crystallization handles q.s at the same time, preferably with 3 minutes, more preferably with 5 minutes, most preferably be lower limit with 10 minutes.On the other hand, if heat treatment time surpasses 24 hours, WO then ₃, TiO ₂Reaction in crystal and glass will advance, might can't obtain to be enough to performance photo-catalysis function in glass size comprise WO ₃And/or TiO ₂Crystal.So the upper limit of heat treatment time is preferably 24 hours, more preferably 19 hours, most preferably being was 18 hours.

As stated; The glass powder plastochondria of this embodiment contains the crystal with photocatalysis characteristic; Perhaps can be through being heated at the said crystal of the inner generation of powder body; Therefore as photocatalysis functional blank, perhaps very useful as the blank that has photo-catalysis function potentially with excellent photocatalysis activity.In addition, therefore the glass powder plastochondria of this embodiment mixes other compositions easily owing to process the powder shape, and the application on base material etc. also is easy to, and in addition, for example also is easy to be processed as form arbitrarily such as pulp-like, solid-like.In addition, can be directly be filled in the container-like member, for example be used for filtration applications etc. with the state of powder body.So, can provide according to the kind of its purposes, base material of being employed etc. or shape form with the best, go in various photocatalysis functional members or the hydrophilic member.

In addition; With regard to the glass powder plastochondria of this embodiment; Owing to can utilize the control of cooperation composition and thermal treatment temp, temperature and the heat-up rate of raw material; Generate the crystal that demonstrates photocatalytic activity by glassy phase, therefore not necessarily need use the photocatalyst crystals material of the nano-scale that is easy to condense and is difficult to dispose, also need not use special devices.

Below, utilize embodiment that the present invention is further elaborated, yet the present invention is not restricted by following embodiment.And, in following embodiment, short of particularly pointing out, the evaluation of various mensuration just is based on following method.

[separating out crystalline species structure size]

Use X-ray diffraction device (Philips corporate system, trade(brand)name: X ' Pert-MPD), identify and separate out crystalline phase.In addition, according to the half breadth of the diffraction peak of X-ray diffraction analysis (XRD), rein in (Scherrer) formula based on thanking: D=0.9 λ/(β cos θ) estimates and separates out the crystalline size.Here, D is the crystalline size, and λ is the wavelength of X ray, and θ is Bragg angle (diffraction angle 2 θ's is half the).

[having or not of photocatalysis characteristic]

Utilize the gas-phase decomposition of acetaldehyde to confirm having or not of photocatalysis characteristic.

[wetting ability]

Estimate with the contact angle of water droplet through utilizing θ/2 method working samples surface.Promptly; Before uviolizing and the water that drips respectively of the surface of postradiation glass-ceramic; Use the contact angle appearance (DM501) of consonance interface science corporate system to measure from the surface of glass-ceramic the radius r of the face that contacts with test film of the height h on the summit of water droplet, water droplet, according to θ=2tan ^-1(h/r) relational expression is obtained the contact angle θ with water.And uviolizing is short of to particularly point out, and just is to use mercuryvapour lamp, with 10mW/cm ²Illumination, 30 minutes irradiation time carry out.

Embodiment A 1～A56:

In table 1～5, express glass composition, the crystallized temperature of the raw material of the glass-ceramic that becomes embodiments of the invention A1～A56 and the kind of the principal crystalline phase of in these glass-ceramic, separating out.The glass-ceramic of embodiment A 1～A56 all is to have used used highly purified raw material in the common glass such as each self-corresponding oxide compound, oxyhydroxide, carbonate, nitrate salt, fluorochemical, muriate, metaphosphoric acid compound as the material choice of each composition.After these raw materials are mixed with the mode weighing of the ratio of the composition that reaches each embodiment shown in table 1～5 equably; Drop into quartz crucible; The fusion difficulty of forming according to glass melted 1～24 hour in 1200 ℃～1600 ℃ TR with electric furnace, stirring and carry out the froth breaking etc. of glass melt., for embodiment A 1～A43, the temperature of glass melt be reduced to 1500 ℃ below and stir after be poured in mould, cool off at leisure and produce glass thereafter.To the glass of gained, be heated to the crystallized temperature of putting down in writing among the embodiment A 1～A43 in table 1～table 4, carry out crystallization with the time maintenance of being put down in writing.From crystallized temperature cooling obtain have the glass-ceramic of the crystalline phase of target thereafter.On the other hand, for the embodiment A 44～A56 in table 4 and the table 5, the glass melt of having changed through stirring is cast in flowing water, and obtains granular or flaky vitreum.With crystallization under the crystallization condition shown in the embodiment A 44～A56 of this vitreum in table 4 and table 5.

Shown in table 1～5,, all contain the high WO of photocatalytic activity as principal crystalline phase separating out in the crystalline phase of the glass-ceramic of embodiment A 1～A56 ₃Crystal.In addition, utilize XRD to distinguish, WO ₃Crystalline is of a size of below the 200nm.

Then, change the crystallization condition to be grouped into and carry out crystallization (temperature, time), studied WO with embodiment A 1 identical one-tenth ₃The crystalline structure.Crystallized temperature is 750 ℃ in embodiment A 1a, A1b is 900 ℃, and A1d is 1000 ℃, and the heat treatment time of crystallization all is 4 hours.The result of XRD is shown among Fig. 1.In the XRD spectra of embodiment A 1a, A1b,, can confirm WO to be the peak of main product life near input angle 2 θ=23.6 ° with " zero " expression ₃The existence of cube crystalline substance.In addition, in the XRD spectra of embodiment A 1c, A1d,, can confirm WO to be the peak of main product life near input angle 2 θ=23.1 °, 23.7 ° with " " expression ₃Oblique crystal or triclinic existence.So can think, the glass-ceramic of embodiment A 1a～A1d has the photocatalytic activity of visible light-responded property.

In addition, among embodiment A 1b～A1d, in XRD spectra, near input angle 2 θ=25.3 °, observe TiO with the anatase titanium dioxide of " △ " expression ₂The crystalline peak.So the glass-ceramic of embodiment A 1b～A1d has the TiO that has the anatase titanium dioxide of excellent photocatalysis at ultraviolet region with the blended state ₂Crystal and have the WO of strong photocatalysis in the visible region ₃Crystal can be inferred, from the ultraviolet region to the visible region, utilizes the light performance photocatalytic activity of wide wavelength range.

In addition, can also be clear that,, can control WO through changing crystallized temperature according to the result of Fig. 1 ₃Crystalline structure.

Use these embodiment to utilize the gas-phase decomposition of acetaldehyde to confirm having or not of photocatalysis characteristic, consequently, utilize the irradiation of high pressure mercury vapour lamp, confirming has the CO by due to the acetaldehyde decomposition ₂Generation, show to have photocatalysis characteristic.

In addition, to the wetting ability of a part of glass-ceramic of embodiment A 1～A56, estimate with the contact angle of water droplet through utilizing θ/2 method working samples surface.That is, the glass-ceramic of embodiment A 1, A2, A4, A7, A11, A32, A35 has been estimated wetting ability, consequently as shown in table 6, utilize 30 minutes ultraviolet irradiation, can confirm, reach below 20 ° with the contact angle of water.Obvious thus, the glass-ceramic of embodiments of the invention has high-hydrophilic.

Then, with embodiment A 1 and the identical composition of A4 and produce the sample of glass-ceramic with only changing the crystallization condition.The crystallization condition in embodiment A 1e be 750 ℃ following 4 hours, embodiment A 1f be 850 ℃ following 8 hours, embodiment A 4a be 850 ℃ following 4 hours.To each sample of gained, working concentration is the hydrofluoric acid of 4.6 quality %, carries out 10 seconds etching.To each sample after the etching, the xenon lamp that uses 300W is as light source, at 10mW/cm ²The condition of ultraviolet illumination under carry out uviolizing.Utilizing θ/2 methods to obtain the contact angle θ of glass-ceramic and water after the etching and estimate hydrophilic result ultraviolet irradiation time and same as described above is shown among Fig. 2.To all samples of embodiment A 1e, A1f and A4a, just utilize 30 minutes uviolizing, just reach below 10 ° with the contact angle of water, thereby have high-hydrophilic.Obviously, through the glass-ceramic of etching embodiments of the invention like this, can improve photocatalytic activity.

In addition, to each sample after the etching of the glass-ceramic of the foregoing description A1e, A1f, A4a, use Blacklight Blue luminescent lamp FL10BLB (Toshiba's system), at 1mW/cm ²The condition of illumination under carry out uviolizing.For the contact angle θ of glass-ceramic after ultraviolet irradiation time and the etching and water, utilize θ/2 methods to obtain same as described abovely, estimate wetting ability.Its result is shown among Fig. 3.According to Fig. 3, even all samples of embodiment A 1e, A1f and A4a is reduced to 1mW/cm with ultraviolet illumination ², also can utilize 300 minutes uviolizing that the contact angle with water is reached below 20 °, thereby have sufficient wetting ability.In addition, crystallized temperature is among 850 ℃ the embodiment A 1f, A4a, even ultraviolet illumination is 1mW/cm ², only also can utilizing, 60 minutes uviolizing will be reduced to 20 ° with the contact angle of water.Thereby show, under the situation of identical composition,, can improve wetting ability through improving crystallized temperature.

Then, the sample to each glass-ceramic of obtaining among embodiment A 44, A48 and the A54 has carried out the evaluation of Socryl Blue BRL (MB) degrading activity.At first, in the container of PS system, add Socryl Blue BRL (MB) aqueous solution of the concentration 0.01mmol/L of 5ml, each sample was in the dark flooded 24 hours.With the pre-treatment that is treated to hereto.Then, be replaced by the solution of same concentrations, having or not the variation that determines MB concentration under the condition of radiation of visible light.That is, each sample in the dark or on the basis of radiation of visible light impregnated in respectively in the MB aqueous solution.Here, using the xenon lamp of 300W as light source, remove the light below the wavelength 400nm, is that the visible light of 10,000 luxs is to sample irradiation with illumination.Consequently, as shown in Figure 4, can confirm that compare with the dark place, the minimizing of a side MB concentration of irradiation visible light is bigger.Obvious thus, the glass-ceramic of embodiments of the invention has the excellent photocatalysis activity by visible light.

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

Embodiment B 1～B16:

With the Vitrea composition of embodiments of the invention B1～B16, when using these vitreums to make glass-ceramic sintered compacies sintering (crystallization) temperature and time and use the kind of separating out crystalline phase of the glass-ceramic sintered compact that these vitreums make to be shown in table 7 and the table 8.Among Embodiment B 1～B16; It all is used highly purified raw material in the common glass such as each self-corresponding oxide compound of material choice, oxyhydroxide, carbonate, nitrate salt, fluorochemical, muriate, metaphosphoric acid compound etc. as each composition; With the mode weighing of the ratio of the composition that reaches each embodiment after mixing equably; Drop into quartz crucible; Form according to glass and to melt 2～6 hours in 1250 ℃～1500 ℃ TR with electric furnace, stirring be afterwards through dropping into glass melt in the flowing water, and obtain granular or flaky vitreum.Through this vitreum is pulverized with jet mill, obtaining size of particles is the pulverizing glass below the 10 μ m.This powder glass is filled in the mould, carry out single shaft pressurization after, carry out cold isostatic compaction, process graininess., add in electric furnace, carry out sintering with the temperature and time of the regulation shown in table 7 and table 8 thereafter.

Shown in table 7 and table 8,, all comprise the WO of photocatalytic activity with visible light-responded property separating out in the crystalline phase of the Vitrea glass-ceramic sintered compact that has used Embodiment B 1～B16 ₃Crystal.

Embodiment B 17～B20:

To the pulverizing glass A (Tg=685 ℃) that obtains in the Embodiment B 1, the additive shown in the mixture table 9 carries out sintering and produces the glass-ceramic sintered compact.Specifically, be pulverizing glass A and additive (WO below the 10 μ m with size of particles ₃Crystal or anatase titanium dioxide TiO ₂Crystal) mixes equably, this mixture is filled in the mould, carry out carrying out cold isostatic compaction after the single shaft pressurization, form the particulate state., add in electric furnace, burn till, produce the glass-ceramic molding with the temperature and time shown in the table 9 thereafter.

As shown in table 9, separating out in the crystalline phase of the Vitrea glass-ceramic sintered compact that has used Embodiment B 17～B20, all comprise the WO of photocatalytic activity with visible light-responded property ₃Crystal.

Then, the result with the XRD of the glass-ceramic sintered compact of Embodiment B 1, B4, B18, B20 is shown among Fig. 5.In the XRD spectra of Fig. 5, in the Embodiment B 4,, can confirm WO to be the peak of main product life near input angle 2 θ=23.4 ° with " zero " expression ₃The existence of cube crystalline substance.In addition, in the XRD spectra of Embodiment B 1, B18, B20,, can confirm WO to be the peak of main product life near input angle 2 θ=23.8 ° with " zero " expression ₃Oblique crystal or triclinic existence.Can think that thus the glass-ceramic sintered compact of Embodiment B 1, B4, B18, B20 has the photocatalytic activity of visible light-responded property.

In addition, among Embodiment B 1, B18, the B20, in XRD spectra, near input angle 2 θ=25.1 °, observe TiO with the anatase titanium dioxide of " △ " expression ₂The crystalline peak.So the glass-ceramic sintered compact of Embodiment B 1, B18, B20 has the TiO that has the anatase titanium dioxide of excellent photocatalysis at ultraviolet region with the blended state ₂Crystal and have the WO of strong photocatalysis in the visible region ₃Crystal can be inferred, from the ultraviolet region to the visible region, utilizes the light performance photocatalytic activity of wide wavelength range.

In addition, use the sintered compact of these embodiment to utilize the gas-phase decomposition of acetaldehyde to confirm having or not of photocatalysis characteristic, consequently, utilize the irradiation of high pressure mercury vapour lamp, confirming has the CO by due to the acetaldehyde decomposition ₂Generation, show to have photocatalysis characteristic.

Then, the sample to the glass-ceramic sintered compact that obtains in the Embodiment B 1 has carried out the evaluation of Socryl Blue BRL (MB) degrading activity.At first, in the container of PS system, add Socryl Blue BRL (MB) aqueous solution of the concentration 0.01mmol/L of 5ml, each sample was in the dark flooded 24 hours.Processing hereto is made as pre-treatment.Then, be replaced by the solution of same concentrations, having or not the variation that determines MB concentration under the condition of radiation of visible light.That is, each sample in the dark or on the basis of radiation of visible light impregnated in respectively in the MB aqueous solution.Here, using the xenon lamp of 300W as light source, remove the light below the wavelength 400nm, is that the visible light of 10,000 luxs is to sample irradiation with illumination.Consequently, as shown in Figure 6, can confirm that compare with the dark place, the minimizing of a side MB concentration of irradiation visible light is bigger.Obvious thus, the glass-ceramic sintered compact of embodiments of the invention has the excellent photocatalysis activity by visible light.

[table 7]

[table 8]

[table 9]

Embodiment C 1～C16:

With the Vitrea composition of embodiments of the invention C1～C16, burning till (crystallization) temperature and time and using the kind of separating out crystalline phase of the glass-ceramic layer of the glass-ceramic complex body that these vitreums make to be shown in table 10 and the table 11 when using these vitreums to make glass-ceramic.Among Embodiment C 1～C16; It all is used highly purified raw material in the common glass such as each self-corresponding oxide compound of material choice, oxyhydroxide, carbonate, nitrate salt, fluorochemical, muriate, metaphosphoric acid compound etc. as each composition; With the mode weighing of the ratio of the composition that reaches each embodiment after mixing equably; Drop into quartz crucible; Form according to glass and to melt 2～6 hours in 1250 ℃～1500 ℃ TR with electric furnace, stirring be afterwards through dropping into glass melt in the flowing water, and obtain granular or flaky vitreum.Through this vitreum is pulverized with jet mill, obtaining size of particles is the pulverizing glass below the 10 μ m.

Should pulverize glass and be scattered in the methyl alcohol, form slurry.This slurry is coated on the aluminum oxide base material, obtained pulp layer.To this pulp layer, be warmed up in table 10 and the table 11 temperature of record, time of record and side by side carry out the processing of firing process and crystallization in maintenance table 10 and the table 11 under this temperature.After the firing process, cool to room temperature and obtain having the glass-ceramic layer of 50 μ m thickness.

Shown in table 10 and table 11,, all comprise the WO of photocatalytic activity with visible light-responded property separating out in the crystalline phase of the Vitrea glass-ceramic layer of having used Embodiment C 1～C16 ₃Crystal.Can think to have the photocatalytic activity of visible light-responded property thus.

Then, in order to study WO ₃The crystalline structure changes the crystallization condition to be grouped into Embodiment C 1 identical one-tenth and carries out crystallization (temperature, time), has carried out X-ray diffraction analysis (XRD).The crystallization condition be 850 ℃ following 1 hour, or following 0.5 hour at 900 ℃.The result of XRD is shown among Fig. 7.In the XRD spectra of Fig. 7,, thereby can confirm WO with input angle 2 θ=23.8 ° of peaks that are the main product life with " zero " expression ₃Crystalline exist.

In addition, utilize the gas-phase decomposition of acetaldehyde to confirm having or not of photocatalysis characteristic to these embodiment, consequently, utilize the irradiation of high pressure mercury vapour lamp, confirming has the CO by due to the acetaldehyde decomposition ₂Generation, show to have photocatalysis characteristic.

Then, the sample to the glass-ceramic layer of the complex body that obtains in the Embodiment C 1 has carried out the evaluation of Socryl Blue BRL (MB) degrading activity.At first, in the container of PS system, add Socryl Blue BRL (MB) aqueous solution of the concentration 0.01mmol/L of 5ml, each sample was in the dark flooded 24 hours.Processing hereto is made as pre-treatment.Then, be replaced by the solution of same concentrations, having or not the variation that determines MB concentration under the condition of radiation of visible light.That is, each sample in the dark or on the basis of radiation of visible light impregnated in respectively in the MB aqueous solution.Here, using the xenon lamp of 300W as light source, remove the light below the wavelength 400nm, is that the visible light of 10,000 luxs is to sample irradiation with illumination.Consequently, as shown in Figure 8, can confirm that compare with the dark place, the minimizing of a side MB concentration of irradiation visible light is bigger.Obvious thus, the glass-ceramic layer of the complex body of embodiments of the invention has the excellent photocatalysis activity by visible light.

[table 10]

[table 11]

Embodiment D1～D35:

The arrival temperature before the composition of the glass powder plastochondria of embodiments of the invention D1～D35, the termination heating when using these glass powder plastochondrias to make sintered glass ceramics powder bodies and the kind of separating out crystalline phase of heat-up rate or crystallized temperature and time and these glass powder plastochondrias are shown in table 12～table 16.Among embodiment D1～D35; It all is used highly purified raw material in the common glass such as each self-corresponding oxide compound of material choice, oxyhydroxide, carbonate, nitrate salt, fluorochemical, oxyhydroxide, metaphosphoric acid compound etc. as each composition; With the mode weighing of the ratio of the composition that reaches each embodiment after mixing equably; Drop into quartz crucible; Form according to glass and to melt 2～6 hours in 1250 ℃～1500 ℃ TR with electric furnace, stirring be afterwards through dropping into glass melt in the flowing water, and obtain granular or flaky vitreum.Through this vitreum is pulverized with jet mill, obtain the glass powder plastochondria that size of particles (median size) is 10 μ m.And, for embodiment D1～D10, be warmed up to the arrival temperature shown in the identical table with the heat-up rate shown in the table 12.

Shown in table 12 and table 14～16,, all comprise the WO of photocatalytic activity with visible light-responded property separating out in the crystalline phase of the glass powder plastochondria of embodiment D1～D10 and D17～D35 ₃Crystal.In addition, as shown in table 13, separating out in the crystalline phase of the glass powder plastochondria of embodiment D11～D16, all contain and comprise the TiO that has the anatase titanium dioxide of intensive photocatalytic activity for ultraviolet ray ₂Crystal and NaTi ₂(PO ₄) ₃The crystalline crystalline phase.

Then, in order to study WO ₃The crystalline structure is grouped into and changes the crystallization condition with the one-tenth identical with embodiment D1 and carries out crystallization (temperature, time), has carried out X-ray diffraction analysis (XRD).The crystallization condition is that embodiment D1a is 800 ℃, and embodiment D1b is 900 ℃, and embodiment D1c is 1000 ℃.The result of XRD is shown among Fig. 9.In the XRD spectra of Fig. 9, among the embodiment D1a,, thereby can confirm WO with input angle 2 θ=23.8 ° of peaks that are the main product life with " zero " expression ₃Crystalline exist.Can think that thus the glass powder plastochondria of embodiment D1a has the photocatalytic activity of visible light-responded property.In addition, in the XRD spectra of embodiment D1b, D1c, being the peak of main product life near input angle 2 θ=23.1 °, 23.9 °, thereby can confirm WO with " zero " expression ₃Oblique crystal or triclinic existence.Can think that thus the glass powder plastochondria of embodiment D1b, D1c has the photocatalytic activity of visible light-responded property.

In addition, among embodiment D1b, the D1c, in the XRD spectra of Fig. 9, near input angle 2 θ=25.1 °, observe TiO with the anatase titanium dioxide of " △ " expression ₂The crystalline peak.So the glass powder plastochondria of embodiment D1b, D1c has the TiO that has the anatase titanium dioxide of excellent photocatalysis at ultraviolet region with the blended state ₂Crystal and have the WO of strong photocatalysis in the visible region ₃Crystal can be inferred, from the ultraviolet region to the visible region, utilizes the light performance photocatalytic activity of wide wavelength range.

In addition, can also be clear that,, can control WO through changing crystallized temperature according to the result of Fig. 9 ₃Crystalline structure.

In addition, will be shown among Figure 10 to the XRD spectra of the glass powder plastochondria that obtains among the embodiment D11.In the XRD spectra of Figure 10, observe respectively to be TiO near input angle 2 θ=25.1 ° with the anatase titanium dioxide of " zero " expression ₂The crystalline peak, near input angle 2 θ=24.3 ° to be NaTi with " zero " expression ₂(PO ₄) ₃Near crystalline peak and input angle 2 θ=22.4 ° to be NaTi with " △ " expression ₂(PO ₄) ₃The crystalline peak.

In addition, use the glass powder plastochondria of these embodiment to utilize the gas-phase decomposition of acetaldehyde to confirm having or not of photocatalysis characteristic, consequently, utilize the irradiation of high pressure mercury vapour lamp, confirming has the CO by due to the acetaldehyde decomposition ₂Generation, show to have photocatalysis characteristic.

Then, the sample to the glass powder plastochondria that obtains among the embodiment D1b has carried out the evaluation of Socryl Blue BRL (MB) degrading activity.At first, in the container of PS system, add Socryl Blue BRL (MB) aqueous solution of the concentration 0.01mmol/L of 5ml, sample was in the dark flooded 24 hours.Processing hereto is made as pre-treatment.Then, be replaced by the solution of same concentrations, having or not the variation that determines MB concentration under the condition of radiation of visible light.That is, each sample in the dark or on the basis of radiation of visible light impregnated in respectively in the MB aqueous solution.Here, using the xenon lamp of 300W as light source, remove the light below the wavelength 400nm, is that the visible light of 10,000 luxs is to sample irradiation with illumination.Consequently, shown in figure 11, can confirm that compare with the dark place, the minimizing of a side MB concentration of irradiation visible light is bigger.Obvious thus, the glass powder plastochondria of embodiments of the invention has the excellent photocatalysis activity by visible light.

Then,, impregnated in the MB aqueous solution, have or not the variation of the MB concentration of uviolizing, estimated photocatalysis characteristic through mensuration for the sample of the glass powder plastochondria that obtains among the embodiment D14.As light source, use Blacklight Blue luminescent lamp FL10BLB (Toshiba's system), with 1mW/cm ²The illumination irradiation ultraviolet radiation.Its result is shown among Figure 12.Shown in figure 12, can know the ultraviolet irradiation of utilization to sample, MB concentration reduces widely.Can confirm that thus the glass-ceramic that obtains among the embodiment D14 has excellent MB degrading activity.

[table 12]

[table 13]

[table 14]

[table 15]

[table 16]

Though more than for illustrative purposes embodiment of the present invention is specified, yet the present invention is not restricted by above-mentioned embodiment.Those skilled in the art can not break away from thought of the present invention and scope ground much changes, and they also are contained in the scope of the present invention.This world application advocates to quote its full content here based on Japanese patent application 2009-180188 number of application on July 31st, 2009, identical 2009-180189 number, identical 2009-180190 number and 2009-180191 number identical right of priority.

Claims

1. glass-ceramic, it contains the crystalline phase that comprises Tungsten oxide 99.999 and/or its sosoloid.

2. glass-ceramic according to claim 1, wherein, as said Tungsten oxide 99.999, total amount of convert forming with respect to oxide compound contains 10～95% WO in mole % ₃Composition.

3. glass-ceramic according to claim 1 and 2, wherein, the total amount with respect to oxide compound converts and forms, in mole %, also contain:

0～60% P ₂O ₅Composition and/or

0～60% B ₂O ₃Composition and/or

0～60% SiO ₂Composition and/or

0～60% GeO ₂Each composition of composition.

4. according to any described glass-ceramic in the claim 1 to 3, wherein, also contain 0～60% TiO ₂Composition.

5. according to any described glass-ceramic in the claim 1 to 4, wherein, the total amount with respect to oxide compound converts and forms, in mole %, also contain:

0～40% Li ₂The O composition and/or

0～40% Na ₂The O composition and/or

0～40% K ₂The O composition and/or

0～10% Rb ₂The O composition and/or

0～10% Cs ₂Each composition of O composition.

6. according to any described glass-ceramic in the claim 1 to 5, wherein, the total amount with respect to oxide compound converts and forms, in mole %, also contain:

0～40% MgO composition and/or

0～40% CaO composition and/or

0～40% SrO composition and/or

Each composition of BaO composition of 0～40%.

7. according to any described glass-ceramic in the claim 1 to 6, wherein, the total amount with respect to oxide compound converts and forms, in mole %, also contain:

0～30% Al ₂O ₃Composition and/or

0～30% Ga ₂O ₃Composition and/or

0～10% In ₂O ₃Each composition of composition.

8. according to any described glass-ceramic in the claim 1 to 7, wherein, the total amount with respect to oxide compound converts and forms, in mole %, also contain:

0～20% ZrO ₂Composition and/or

Each composition of SnO composition of 0～10%.

9. according to any described glass-ceramic in the claim 1 to 8, wherein, the total amount with respect to oxide compound converts and forms, in mole %, also contain:

0～50% Nb ₂O ₅Composition and/or

0～50% Ta ₂O ₅Composition and/or

0～50% MoO ₃Each composition of composition.

10. according to any described glass-ceramic in the claim 1 to 9, wherein, the total amount with respect to oxide compound converts and forms, in mole %, also contain:

0～50% ZnO composition and/or

0～20% Bi ₂O ₃Composition and/or

0～20% TeO ₂Composition and/or

11., wherein, also contain the composition more than at least a kind among F, Cl, Br, S, N and the C that is selected from below 15% in external ratio mass ratio with respect to the glass total mass according to any described glass-ceramic in the claim 1 to 10.

12., wherein, also contain at least a kind of metallics among Cu, Ag, Au, Pd, Ru, Rh, Re and the Pt that is selected from below 10% in external ratio mass ratio with respect to the glass total mass according to any described glass-ceramic in the claim 1 to 11.

13., wherein, also contain TiO according to any described glass-ceramic in the claim 1 to 12 ₂, TiP ₂O ₇, (TiO) ₂P ₂O ₇, RnTi ₂(PO ₄) ₃, RTi ₄(PO ₄) ₆(in the formula, Rn be selected among Li, Na, K, Rb, the Cs more than a kind, R be selected among Mg, Ca, Sr, the Ba more than a kind) and their sosoloid in the crystal more than a kind.

14. according to any described glass-ceramic in the claim 1 to 13, it utilizes the light of the wavelength from the ultraviolet region to the visibility region to embody catalytic activity.

15. according to any described glass-ceramic in the claim 1 to 14, wherein, the surface and the contact angle of water droplet that have shone the light of the wavelength from the ultraviolet region to the visibility region are below 30 °.

16. a photocatalyst, it comprises any described glass-ceramic in the claim 1 to 15.

17. a glass-ceramic sintered compact is with pulverizing the glass-ceramic sintered compact that glass sintering forms, it is characterized in that, in said glass-ceramic sintered compact, containing any described glass-ceramic in the claim 1 to 15.

18. a glass-ceramic complex body is the glass-ceramic complex body that has base material and be located at the glass-ceramic layer on this base material, it is characterized in that, said glass-ceramic layer contains any described glass-ceramic in the claim 1 to 15.

19. a glass powder plastochondria, it contains any described glass-ceramic in the claim 1 to 15.

20. a glass powder plastochondria, it generates any described glass-ceramic in the claim 1 to 15 through being heated.

21. a pulp-like mixture, it contains claim 19 or 20 described glass powder plastochondria and solvents.