CN101622206A - Phosphate-based inorganic material - Google Patents

Phosphate-based inorganic material Download PDF

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CN101622206A
CN101622206A CN200880001205A CN200880001205A CN101622206A CN 101622206 A CN101622206 A CN 101622206A CN 200880001205 A CN200880001205 A CN 200880001205A CN 200880001205 A CN200880001205 A CN 200880001205A CN 101622206 A CN101622206 A CN 101622206A
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scope
mole
phosphate
inorganic material
based inorganic
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CN101622206B (en
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中谷寿文
道又融
沼田大志
花田成
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Alps Alpine Co Ltd
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Alps Electric Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/20—Compositions for glass with special properties for chemical resistant glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The object of the present invention is to provide a kind of phosphate-based inorganic material of particularly chemical proofing excellence.The phosphate-based inorganic material of present embodiment is characterised in that, contains at least P 2O 5, CeO 2And Cr 2O 3, and with 30～75 the scope of (mole %) contains P 2O 5, the scope of (mole %) contains CeO with 8～60 2, the scope of (mole %) contains Cr with 1.5～15 2O 3Thus, compare with phosphate-based inorganic material in the past, can improve chemical proofing.Particularly can obtain the chemical proofing also more excellent than silica glass.

Description

Phosphate-based inorganic material
Technical field
The present invention be more particularly directed to a kind of phosphate-based inorganic material of chemical proofing excellence.
Background technology
Disclose with P in the following patent documentation 2O 5Phosphate-based glass for principal component.
All the time, glass contains lead in forming, but from the consideration to environment, has and do not use plumbous tendency as far as possible, shown in following patent documentation, is developing energetically lead-free glass.
Patent documentation 1: TOHKEMY 2007-8777 communique
Patent documentation 2: TOHKEMY 2003-252648 communique
Patent documentation 3: Japanese kokai publication hei 7-267673 communique
Patent documentation 4: Japanese Patent Publication 63-54658 communique
Patent documentation 5: Japanese kokai publication sho 64-87531 communique
Summary of the invention
But, above-mentioned quartz glass for example namely is used in the coating material of product surface, shown in the test, because quartz glass does not have excellent chemical proofing, therefore can not suitably prolong the life-span of goods as described later.
All the time, for example by being that the resin-coated chemical proofing that makes on the surface improves with polytetrafluoroethylene (PTFE), but being resin costliness and processability, described polytetrafluoroethylene (PTFE) also has problems.In addition, for for the coating process of surperficial evaporation inorganic insulation material, the surface of coating layer forms the defect parts such as pin hole, poor reliability easily.
On the other hand, though phosphate-based glass cheapness and the excellent in workability shown in the above-mentioned patent documentation do not considered chemical proofing fully.
Therefore, the present invention implements in order to solve above-mentioned existing problem, and its purpose is, a kind of phosphate-based inorganic material of particularly chemical proofing excellence is provided.
Phosphate-based inorganic material of the present invention is characterised in that, contains at least P 2O 5, CeO 2And Cr 2O 3, and to add up to 50～90 the scope of (mole %) contains P 2O 5And CeO 2, the scope of (mole %) contains Cr with 0.7～15 2O 3
By being set at above-mentioned composition, compare with phosphate-based inorganic material in the past, can improve chemical proofing.Here, so-called " phosphate-based inorganic material " be meant except integral body is the inorganics of vitreousness, also contain some or whole crystallization inorganics.
Among the present invention, preferably contain P with the scope that adds up to 60.5～81 (mole %) 2O 5And CeO 2, the scope of (mole %) contains Cr with 0.7～10 2O 3
In addition, among the present invention, more preferably contain P with the scope that adds up to 60.5～75 (mole %) 2O 5And CeO 2, the scope of (mole %) contains Cr with 1.5～10 2O 3Among the present invention, specifically can obtain the chemical proofing more excellent than quartz glass.
In addition, phosphate-based inorganic material of the present invention is characterised in that, contains at least P 2O 5, CeO 2And Cr 2O 3, and with 45～65 the scope of (mole %) contains P 2O 5, the scope of (mole %) contains CeO, contains Cr with the scope of 0.7～15 (mole %) with 5～40 2O 3At this moment, preferably contain P with the scope that adds up to 50～90 (mole %) 2O 5And CeO 2By being set at above-mentioned composition, compare with phosphate-based inorganic material in the past, can improve chemical proofing.
In addition, among the present invention, preferably the scope with 50～60 (mole %) contains P 2O 5, the scope of (mole %) contains CeO, contains Cr with the scope of 0.7～10 (mole %) with 8.5～25 2O 3At this moment, preferably contain P with the scope that adds up to 60.5～81 (mole %) 2O 5And CeO.
In addition, among the present invention, more preferably the scope with 50～60 (mole %) contains P 2O 5, the scope of (mole %) contains CeO, contains Cr with the scope of 1.5～10 (mole %) with 8.5～18 2O 3At this moment, more preferably contain P with the scope that adds up to 60.5～75 (mole %) 2O 5And CeO 2Among the present invention, particularly can obtain the chemical proofing also more excellent than silica glass.
Among the present invention, the scope of (mole %) contains and is selected from B preferably with 5～30 2O 3, ZnO, BaO, Al 2O 3, Nb 2O 5, La 2O 3, Ta 2O 5In at least any the 1st auxiliary element.
In addition, among the present invention, the scope of (mole %) contains and is selected from B more preferably with 9.5～27.5 2O 3, ZnO, BaO, Al 2O 3, Nb 2O 5, La 2O 3, Ta 2O 5In at least any the 1st auxiliary element.Thus, can suitably obtain stable vitreousness.
In addition, among the present invention, the scope of (mole %) contains and is selected from SnO preferably with 0.0～30 2, TiO 2, Al 2O 3, Nb 2O 5, La 2O 3, Ta 2O 5In at least any the 2nd auxiliary element.
In addition, among the present invention, the scope of (mole %) contains and is selected from SnO more preferably with 0.0～12 2, TiO 2, Al 2O 3, Nb 2O 5, La 2O 3, Ta 2O 5In at least any the 2nd auxiliary element.Thus, can effectively improve chemical proofing.
Phosphate-based inorganic material of the present invention is compared with phosphate-based inorganic material in the past, can improve chemical proofing.Among the present invention, particularly can obtain the chemical proofing also more excellent than silica glass.
Description of drawings
Fig. 1 will contain 0.5,1.5,2.5,3.8,7.0 and 10.0 (mole %) Cr 2O 3Each phosphate-based inorganic material and the result of the test of the mass change of quartz glass when impregnated among the 50%HF.
Fig. 2 will contain 0.5,1.5,2.5,3.8,7.0 and 10.0 (mole %) Cr 2O 3Each phosphate-based inorganic material and quartz glass impregnated in 60%HNO 3The result of the test of the mass change when middle.
Fig. 3 will contain 0.5,1.5,2.5,3.8,7.0 and 10.0 (mole %) Cr 2O 3Each phosphate-based inorganic material and quartz glass impregnated in 98%H 2SO 4The result of the test of the mass change when middle.
Fig. 4 will contain 0.5,1.5,2.5,3.8,7.0 and 10.0 (mole %) Cr 2O 3Each phosphate-based inorganic material and the result of the test of the mass change of quartz glass when impregnated among the 36%HCl.
Embodiment
The phosphate-based inorganic material of present embodiment contains P at least 2O 5, CeO 2And Cr 2O 3
In the 1st embodiment, contain P with the scope that adds up to 50～90 (mole %) 2O 5And CeO 2, the scope of (mole %) contains Cr with 0.7～15 2O 3In each embodiment, the summation that consists of all the components of phosphate-based inorganic material is made as 100 moles of %.
Here, content is the content with respect to phosphate-based inorganic material integral body, and as described later, when the preparation phosphate-based inorganic material, the mole % based on described content is scaled quality %, carries out weighing, allotment.
Here, " phosphate-based inorganic material " in the present embodiment not only integral body is the structure of vitreousness, and a part or integral body also can crystallizations.Be the mixing phase time of vitreousness and crystalline state, the part of crystallization is preferably below 50% of integral body.Wherein, from the considerations such as viewpoint of chemical proofing, processibility, weathering resistance, preferred integral body is the solid (glass) of vitreousness.
Contain P as neccessary composition with add up to 50～90 scope of (mole %) 2O 5And CeO 2The time, can suppress crystallization, can promote vitreousness.
Except P 2O 5And CeO 2In addition, Cr 2O 3It also is the neccessary composition of the phosphate-based inorganic material of present embodiment.Like this, Cr 2O 3Content be in 0.7～15 scope of (mole %) in.Make Cr 2O 3Content be less than 0.7 when (mole %), can not suitably improve chemical proofing.In addition, make Cr 2O 3Content more than 15 when (mole %), the vitreousness instabilityization promotes crystallization easily.Because crystallization, cause for example can not obtaining to improve the effect of chemical proofing.Therefore, in the present embodiment, with Cr 2O 3Content be made as 15 below (mole %).
Utilize the phosphate-based inorganic material of the 1st embodiment, water tolerance is more excellent, and weathering resistance is also excellent.
In the 2nd embodiment, contain P with the scope that adds up to 60.5～81 (mole %) 2O 5And CeO 2, the scope of (mole %) contains Cr with 0.7～10 2O 3Compare P with above-mentioned the 1st embodiment 2O 5And CeO 2Total content and Cr 2O 3Compositing range narrow down, not only can keep well chemical proofing, and can seek the further stabilisation of vitreousness.
In the 3rd embodiment, contain P with the scope that adds up to 60.5～75 (mole %) 2O 5And CeO 2, the scope of (mole %) contains Cr with 1.5～10 2O 3Compare P with above-mentioned the 2nd embodiment 2O 5And CeO 2Total content and Cr 2O 3Scope further narrow down, not only can seek the further stabilisation of vitreousness, and can seek the raising of chemical proofing.Particularly according to test described later, compare with quartz glass, can improve widely chemical proofing.
Then, in the 4th embodiment, the scope of (mole %) contains P with 45～65 2O 5, the scope of (mole %) contains CeO, contains Cr with the scope of 0.7～15 (mole %) with 5～40 2O 3
From above-mentioned the 1st embodiment to the 3 embodiments, stipulated P 2O 5And CeO 2Total content, in the 4th embodiment, stipulated P 2O 5And CeO 2Component content separately.Here, Cr 2O 3Content identical with the 1st embodiment.
Thus, can suppress crystallization, promote vitreousness, and, compare with phosphate-based inorganic material in the past, can improve chemical proofing.In addition, can also suitably improve water tolerance, weathering resistance.
In above-mentioned the 4th embodiment, identical with the 1st embodiment, contain P with the scope that adds up to 50～90 (mole %) 2O 5And CeO 2, this is being preferred aspect stabilisation of effectively seeking vitreousness.
Then, in the 5th embodiment, the scope of (mole %) contains P with 50～60 2O 5, the scope of (mole %) contains CeO, contains Cr with the scope of 0.7～10 (mole %) with 8.5～25 2O 3Compare P with above-mentioned the 4th embodiment 2O 5, CeO 2And Cr 2O 3The scope of content narrow down, thus, can keep good chemical proofing, and can seek the further stabilisation of vitreousness.
In described the 5th embodiment, identical with the 2nd embodiment, contain P with the scope that adds up to 60.5～81 (mole %) 2O 5And CeO 2, this is preferred seeking aspect the stabilisation of vitreousness.
Then, in the 6th embodiment, the scope of (mole %) contains P with 50～60 2O 5, the scope of (mole %) contains CeO, contains Cr with the scope of 1.5～10 (mole %) with 8.5～18 2O 3Compare P with above-mentioned the 5th embodiment 2O 5, CeO 2And Cr 2O 3Scope further narrow down, thus, not only can more effectively seek the stabilisation of vitreousness, and can effectively improve chemical proofing.Particularly compare with quartz glass, can improve widely chemical proofing.
In the 6th embodiment, identical with the 3rd embodiment, contain P with the scope that adds up to 60.5～75 (mole %) 2O 5And CeO 2, this is preferred seeking aspect the stabilisation of vitreousness.
In above-mentioned the 1st embodiment, the 4th embodiment, except the P as neccessary composition 2O 5, CeO 2And Cr 2O 3In addition, the scope of (mole %) contains and is selected from B preferably with 5～30 2O 3, ZnO, BaO, Al 2O 3, Nb 2O 5, La 2O 3, Ta 2O 5In at least any the 1st auxiliary element.Described the 1st ancillary component is the composition (stablizer) that is used to promote the stabilization of vitreousness.
In the present embodiment, as mentioned above, Cr 2O 3Neccessary composition, by containing Cr 2O 3, vitreousness is instabilityization easily.Increase Cr 2O 3Content the time, as described later the test shown in, can more effectively seek the raising of chemical proofing, on the other hand, promote easily crystallization.Therefore, in the present embodiment, by containing for example B of described the 1st auxiliary element 2O 3Even contain a large amount of Cr 2O 3, also can keep and mainly utilize P 2O 5The skeleton of the vitreousness that produces, seek the stabilisation of vitreousness.
In addition, in the 2nd embodiment, the 3rd embodiment, the 5th embodiment and the 6th embodiment, except the P as neccessary composition 2O 5, CeO 2And Cr 2O 3In addition, the scope of (mole %) contains and is selected from B preferably with 9.5～27 2O 3, ZnO, BaO, Al 2O 3, Nb 2O 5, La 2O 3, Ta 2O 5In at least any the 1st auxiliary element.Thus, in the 2nd embodiment, the 3rd embodiment, the 5th embodiment and the 6th embodiment, can seek the further stabilization of vitreousness.
Then, in above-mentioned the 1st embodiment, the 4th embodiment, except the P as neccessary composition 2O 5, CeO 2And Cr 2O 3In addition, the scope of (mole %) contains and is selected from SnO preferably with 0.0～30 2, TiO 2, Al 2O 3, Nb 2O 5, La 2O 3, Ta 2O 5In at least any the 2nd auxiliary element.Described the 2nd ancillary component is the composition that promotes the raising of chemical proofing.
Cr 2O 3Be the composition that helps chemical proofing to improve, still, for example, can not increasing Cr in order stably to keep vitreousness 2O 3Content the time, can be by an amount of SnO that adds as described the 2nd auxiliary element 2And TiO 2Effectively seek the raising of chemical proofing.
In addition, in the 2nd embodiment, the 3rd embodiment, the 5th embodiment and the 6th embodiment, except the P as neccessary composition 2O 5, CeO 2And Cr 2O 3In addition, the scope of (mole %) contains and is selected from SnO preferably with 0.0～12 2, TiO 2, Al 2O 3, Nb 2O 5, La 2O 3, Ta 2O 5In at least any the 2nd auxiliary element.Thus, in the 2nd embodiment, the 3rd embodiment, the 5th embodiment and the 6th embodiment, can improve chemical proofing effectively.
Here, described the 2nd ancillary component is preferably more than 3.3 (the mole %).
In the present embodiment, because P 2O 5, CeO 2And Cr 2O 3Be neccessary composition, therefore, can only consist of phosphate-based inorganic material with these 3 kinds of compositions.Wherein, by suitably containing above-mentioned the 1st ancillary component and the 2nd ancillary component as required, can seek the stabilization of vitreousness effectively or seek the raising of chemical proofing.
Can also further contain Pr in the phosphate-based inorganic material 6O 11Preferably in the phosphate-based inorganic material of above-mentioned the 1st embodiment, the 4th embodiment, contain 0.02～3 (mole %) Pr 6O 11P 2O 5When being reduced, becoming gasiform metal phosphorus (P) and evaporate Pr 6O 11Has the P of preventing 2O 5The effect of reduction.Therefore, phosphate-based inorganic material contains Pr 6O 11The time, having the above-mentioned effect that prevents the phosphorus evaporation, water tolerance improves.
In addition, preferably in the phosphate-based inorganic material of the 2nd embodiment, the 3rd embodiment, the 5th embodiment and the 6th embodiment, contain 0.4～2.2 (mole %) Pr 6O 11
In addition, the phosphate-based inorganic material of present embodiment can suitably add for example SrO, Fe 2O 3, SiO 2, Li 2O, CaO, Na 2O is as other micro constitutent.
After the composition as previously discussed of weighing specified amount and the mixing, prepare phosphate-based inorganic material by heating.For example, phosphoric acid uses dehydration phosphoric acid, and the mole % of weighing ormal weight uses mortar with the CeO of same weighing 2, Cr 2O 3, other composition pulverizes, and mix fully, so that it is even.Mixed uniformly powdered material composition is packed in the crucible of platinum system for example, use electric furnace in atmosphere, under about 1300～1600 ℃ temperature, to heat specific time, carry out fusion.At this moment, heat-up rate is not particularly limited, and heats sharp with 10 ℃/minute heat-up rates to get final product.
Then, the limit is configured as the quenching of tabular or bar-shaped limit, obtains phosphate-based inorganic material.Perhaps, also tabular the or bar-shaped phosphate-based inorganic material that obtains can be pulverized, obtain pulverous phosphate-based inorganic material.
The phosphate-based inorganic material of present embodiment can keep stable vitreousness, for example, even the glass of heating glass state and cooling once more also can return to vitreousness once more under the situation of non-crystallizableization.
The thermal expansivity of the phosphate-based inorganic material of present embodiment (α) can be 60～90 (* 10 -7/ ℃) scope in.In addition, second-order transition temperature (Tg) can be in 500～700 ℃ scope.Thus, the thermotolerance of the phosphate-based inorganic material of present embodiment is also excellent.
The chemical proofing excellence of the phosphate-based inorganic material of present embodiment.Described phosphate-based inorganic material is to strong acid and alkaline excellent corrosion resistance.Therefore, the phosphate-based inorganic material of present embodiment can be used for for example grinding stone or ceramic tackiness agent effectively, perhaps in the various lining materials (coating material) such as turbine vane or etching bath, pipeline, valve.In addition, for example, also can form substrate self with described phosphate-based inorganic material.
By the phosphate-based inorganic material of present embodiment is used for above-mentioned for example lining material (coating material), compare with the situation of using quartz glass etc., can effectively prolong the life-span of parts and device.In addition, because phosphate-based inorganic material cheapness and processability are also excellent, so economy and operability are also excellent.
Embodiment
Preparation has the phosphate-based inorganic material of the ratio of components shown in the table 1 (mole %).
According to the raw material of each regulation of the composition weighing shown in the table 1, and mix, join then in the platinum crucible, heating is about 30 minutes in about 1300～1600 ℃ electric furnace, with its melting, and carries out quenching, obtains each phosphate-based inorganic material of regulation shape.
Each phosphate-based inorganic material of table 1 listed examples becomes glass.
Then, each phosphate-based inorganic material of the comparative example that table 1 is cited, embodiment 16,28,42,45,47 impregnated in the following aqueous solution, the described aqueous solution be respectively contain be in mass 50% HF hydrofluoric acid aqueous solution (50%HF), to contain be 60% HNO in mass 3Aqueous nitric acid (60%HNO 3), to contain be 98% H in mass 2SO 4Aqueous sulfuric acid (98%H 2SO 4), to contain be the aqueous hydrochloric acid (36%HCl) of 36% HCl in mass.Then, measure each phosphate-based inorganic material and impregnated in each aqueous solution quality, quality, dipping the quality 27 hour after of dipping after 6 hours before, obtain qualitative change.
In addition, as example in the past, quartz glass is immersed in above-mentioned each aqueous solution, obtains qualitative change.The results are shown among following table 2～table 5 and Fig. 1～Fig. 4.
Table 2
《50％HF》
Cr 2O 3 Before the test (g) After 6 hours (g) After 27 hours (g)
0.5% 2.3569 2.3292 2.2590
1.5% 3.1429 3.1198 3.0667
2.5% 2.0983 2.0853 2.0546
3.8% 2.6089 2.6054 2.5971
7.0% 1.6350 1.6343 1.6334
10.0% 1.4643 1.4642 1.4637
Quartzy 0.2703 0.0347 -
" velocity of variation "
Cr 2O 3 Initial stage After 6 hours After 27 hours
0.5% 0.000% -1.175% -4.154%
1.5% 0.000% -0.735% -2.425%
2.5% 0.000% -0.620% -2.083%
3.8% 0.000% -0.134% -0.452%
7.0% 0.000% -0.043% -0.098%
10.0% 0.000% -0.007% -0.041%
Quartzy 0.000% -87.162%
Table 3
《60％HNO 3》
Cr 2O 3 Before the test (g) After 6 hours (g) After 27 hours (g)
0.5% 2.3396 2.3366 2.3366
1.5% 2.7572 2.7564 2.7564
2.5% 2.7858 2.7849 2.7849
3.8% 2.7486 2.7477 2.7474
7.0% 1.5080 1.5077 1.5075
10.0% 1.6621 1.6620 1.6619
Quartzy 0.2699 0.2696 0.2696
" velocity of variation "
Cr 2O 3 Initial stage After 6 hours After 27 hours
0.5% 0.000% -0.128% -0.128%
1.5% 0.000% -0.029% -0.029%
2.5% 0.000% -0.032% -0.032%
3.8% 0.000% -0.033% -0.044%
7.0% 0.000% -0.020% -0.033%
10.0% 0.000% -0.006% -0.012%
Quartzy 0.000% -0.111% -0.111%
Table 4
《98％H 2SO 4》
Cr 2O 3 Before the test (g) After 6 hours (g) After 27 hours (g)
0.5% 2.5206 2.5195 2.5192
1.5% 2.6071 2.6066 2.6065
2.5% 2.4077 2.4072 2.4071
3.8% 2.3964 2.3959 2.3958
7.0% 1.5507 1.5502 1.5503
10.0% 1.6173 1.6172 1.6171
Quartzy 0.2708 0.2708 0.2707
" velocity of variation "
Cr 2O 3 Initial stage After 6 hours After 27 hours
0.5% 0.000% -0.044% -0.056%
1.5% 0.000% -0.019% -0.023%
2.5% 0.000% -0.021% -0.025%
3.8% 0.000% -0.021% -0.025%
7.0% 0.000% -0.032% -0.026%
10.0% 0.000% -0.006% -0.012%
Quartzy 0.000% -0.074% -0.037%
Table 5
《36％HCl》
Cr 2O 3 Before the test (g) After 6 hours (g) After 27 hours (g)
0.5% 2.5193 2.5167 2.5150
1.5% 2.6064 2.6065 2.6061
2.5% 2.4072 2.4072 2.4068
3.8% 2.3958 2.3960 2.3956
7.0% 1.5503 1.5505 1.5501
10.0% 1.6173 1.6172 1.6171
Quartzy 0.2709 0.2709 0.2707
" velocity of variation "
Cr 2O 3 Initial stage After 6 hours After 27 hours
0.5% 0.000% -0.103% -0.171%
1.5% 0.000% 0.004% -0.012%
2.5% 0.000% 0.000% -0.017%
3.8% 0.000% 0.008% -0.008%
7.0% 0.000% 0.013% -0.013%
10.0% 0.000% -0.006% -0.012%
Quartzy 0.000% 0.000% -0.074%
Table 2 and Fig. 1 are the result of the tests when impregnated in each phosphate-based inorganic material and quartz glass among the 50%HF, and table 3 and Fig. 2 impregnated in 60%HNO with each phosphate-based inorganic material and quartz glass 3Result of the test when middle, table 4 and Fig. 3 impregnated in 98%H with each phosphate-based inorganic material and quartz glass 2SO 4In the time result of the test, table 5 and Fig. 4 are the result of the tests when impregnated in each phosphate-based inorganic material and quartz glass among the 36%HCl.
Mass change shown in each table is obtained by { (quality (g)-6 hour before the test or the quality (g) after 27 hours)/preceding quality (g) of test } * 100 (%).Mass change is more little, illustrates that elching resistant in undissolved situation (chemical proofing) is more excellent.
Shown in each table and figure, as can be known for the phosphate inorganic thing, Cr 2O 3Contain quantitative change when big, mass change diminishes.
In the test in impregnated in 50%HF, for the quartz glass of comparative example, later on all dissolvings in 27 hours.In addition, impregnated in 60%HNO 3, 98%H 2SO 4, 36%HCl test in, by making the Cr of phosphate-based inorganic material 2O 3Content all greater than 0.5 (mole %), after dipping 27 hours, compare with quartz glass, mass change diminishes.
At first draw P in the phosphate-based inorganic material by above test 2O 5And CeO 2Total content and Cr 2O 3Content.
As the widest scope, be defined as: contain P with the scope that adds up to 50～90 (mole %) 2O 5And CeO 2, contain Cr with the scope of 0.7～15 (mole %) 2O 3(the 1st embodiment).
Then, based on the embodiment shown in the table 1, as preferred scope, be defined as: contain P with the scope that adds up to 60.5～81 (mole %) 2O 5And CeO 2, contain Cr with the scope of 0.7～10 (mole %) 2O 3(the 2nd embodiment).
Then, the embodiment 16～embodiment 47 based on shown in the table 1 as preferred scope, is defined as: contain P with the scope that adds up to 60.5～75 (mole %) 2O 5And CeO 2, contain Cr with the scope of 1.5～10 (mole %) 2O 3(the 3rd embodiment).
Draw then the P in the phosphate-based inorganic material 2O 5, CeO 2And Cr 2O 3Content separately.
As the widest scope, be defined as: the scope with 45～65 (mole %) contains P 2O 5, the scope of (mole %) contains CeO, contains Cr with the scope of 0.7～15 (mole %) with 5～40 2O 3(the 4th embodiment).At this moment, be defined as: preferably as above-mentioned the 1st embodiment, contain P with the scope that adds up to 50～90 (mole %) 2O 5And CeO 2
Then, based on the embodiment shown in the table 1, as preferred scope, be defined as: the scope with 50～60 (mole %) contains P 2O 5, the scope of (mole %) contains CeO, contains Cr with the scope of 0.7～10 (mole %) with 8.5～25 2O 3(the 5th embodiment).At this moment, be defined as: preferably as above-mentioned the 2nd embodiment, contain P with the scope that adds up to 60.5～81 (mole %) 2O 5And CeO 2
Then, the embodiment 16～embodiment 47 based on shown in the table 1 as preferred scope, is defined as: the scope with 50～60 (mole %) contains P 2O 5, the scope of (mole %) contains CeO, contains Cr with the scope of 1.5～10 (mole %) with 8.5～18 2O 3At this moment, be defined as: preferably contain P such as above-mentioned the 3rd embodiment with the scope that adds up to 60.5～75 (mole %) 2O 5And CeO 2
In addition,, will be used to promote that the total content of vitrified the 1st ancillary component (M1) is defined as 5～30 (mole %),,, be defined as 9.5～27.5 (mole %) based on table 1 as preferred range by above-mentioned test.
In addition, by above-mentioned test, the total content that will be used to improve the 2nd ancillary component (M2) of chemical proofing is defined as 0.0～30 (mole %), as preferred range, is defined as 0.0～12 (mole %).

Claims (13)

1, a kind of phosphate-based inorganic material is characterized in that,
At least contain P 2O 5, CeO 2And Cr 2O 3, and contain P with the scope that adds up to 50～90 moles of % 2O 5And CeO 2, contain Cr with the scope of 0.7～15 mole of % 2O 3
2, phosphate-based inorganic material according to claim 1, wherein,
Contain P with the scope that adds up to 60.5～81 moles of % 2O 5And CeO 2, contain Cr with the scope of 0.7～10 mole of % 2O 3
3, phosphate-based inorganic material according to claim 1, wherein,
Contain P with the scope that adds up to 60.5～75 moles of % 2O 5And CeO 2, contain Cr with the scope of 1.5～10 moles of % 2O 3
4, a kind of phosphate-based inorganic material is characterized in that,
At least contain P 2O 5, CeO 2And Cr 2O 3, and contain P with the scope of 45～65 moles of % 2O 5, contain CeO, contain Cr with the scope of 0.7～15 mole of % with the scope of 5～40 moles of % 2O 3
5, phosphate-based inorganic material according to claim 4, wherein,
Contain P with the scope that adds up to 50～90 moles of % 2O 5And CeO 2
6, phosphate-based inorganic material according to claim 4, wherein,
Scope with 50～60 moles of % contains P 2O 5, contain CeO, contain Cr with the scope of 0.7～10 mole of % with the scope of 8.5～25 moles of % 2O 3
7, phosphate-based inorganic material according to claim 6, wherein,
Contain P with the scope that adds up to 60.5～81 moles of % 2O 5And CeO 2
8, phosphate-based inorganic material according to claim 4, wherein,
Scope with 50～60 moles of % contains P 2O 5, contain CeO, contain Cr with the scope of 1.5～10 moles of % with the scope of 8.5～18 moles of % 2O 3
9, phosphate-based inorganic material according to claim 8, wherein,
Contain P with the scope that adds up to 60.5～75 moles of % 2O 5And CeO 2
10, according to claim 1,4 or 5 described phosphate-based inorganic materials, wherein,
Contain with the scope of 5～30 moles of % and to be selected from B 2O 3, ZnO, BaO, Al 2O 3, Nb 2O 5, La 2O 3, Ta 2O 5In at least any the 1st auxiliary element.
11, according to each described phosphate-based inorganic material in the claim 2,3,6,7,8,9, wherein,
Contain with the scope of 9.5～27.5 moles of % and to be selected from B 2O 3, ZnO, BaO, Al 2O 3, Nb 2O 5, La 2O 3, Ta 2O 5In at least any the 1st auxiliary element.
12, according to each described phosphate-based inorganic material in the claim 1,4,5 or 10, wherein,
Contain with the scope of 0.0～30 mole of % and to be selected from SnO 2, TiO 2, Al 2O 3, Nb 2O 5, La 2O 3, Ta 2O 5In at least any the 2nd auxiliary element.
13, according to each described phosphate-based inorganic material in the claim 2,3,6,7,8,9,11, wherein,
Contain with the scope of 0.0～12 mole of % and to be selected from SnO 2, TiO 2, Al 2O 3, Nb 2O 5, La 2O 3, Ta 2O 5In at least any the 2nd auxiliary element.
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