CN113321405A - High-purity opaque quartz glass, manufacturing method and application thereof - Google Patents
High-purity opaque quartz glass, manufacturing method and application thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 74
- 238000001035 drying Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000000465 moulding Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000004576 sand Substances 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 17
- 239000003431 cross linking reagent Substances 0.000 claims description 15
- 239000003999 initiator Substances 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 238000002834 transmittance Methods 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000010440 gypsum Substances 0.000 claims description 6
- 229910052602 gypsum Inorganic materials 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 claims description 5
- 238000007569 slipcasting Methods 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- -1 N, N' -methylene acrylamide Chemical compound 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910002567 K2S2O8 Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims 3
- 238000001746 injection moulding Methods 0.000 claims 2
- 235000012431 wafers Nutrition 0.000 claims 1
- 239000011022 opal Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 12
- 238000001237 Raman spectrum Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 8
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- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
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- 239000000203 mixture Substances 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 229910052744 lithium Inorganic materials 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 238000009489 vacuum treatment Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B20/00—Processes specially adapted for the production of quartz or fused silica articles, not otherwise provided for
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
A method for manufacturing high-purity opaque quartz glass comprises the following steps: preparing slurry, ball-milling high-purity quartz glass sand to prepare the slurry, wherein the granularity of the ball-milled slurry is as follows: 3-30 μm, water content: 16-20%, viscosity: 100 and 500cp, density: 1800 grade 1850g/cm3(ii) a Molding, wherein the molding adopts a wet pouring process; demolding, demolding the molded blank, and then standing and drying; sintering at 1350 ℃ and 1550 ℃ for 1-5 h. The quartz glass prepared by the method has high density, can be welded and has excellent light shielding performance of infrared light.
Description
Technical Field
Embodiments of the present disclosure relate generally to the field of quartz glass production, and more particularly, to a method of manufacturing high purity opaque quartz glass.
Background
Quartz is one of the most abundant deposits on the earth, developing in many different geological settings, mainly for the manufacture of various glasses. Different end markets require different grades of silica content, and very few deposits can be classified as High Purity Quartz (HPQ), which is defined as having a silica content of at least 99.995% (Industrial Minerals, 2013).
The high-purity quartz sand is a high-purity non-metallic mineral raw material which is produced by natural quartz minerals through a series of physical and chemical purification technologies and has certain particle size requirements. Internationally recognized high purity silica sand is a high tech product having less than 20ppm of twelve elemental impurities (Al, K, Na, Li, Ca, Mg, Fe, Mn, Cu, Cr, Ni, B) above the ietin (uni min) IOTA-CG standard in the united states, with alkali metals (K, Na, Li) of less than 1ppm each.
The high-purity quartz sand is a main raw material for producing transparent high-purity quartz glass tubes, rods, plates, lumps, ingots, quartz glass crucibles and the like. The quartz glass is glass with silicon dioxide single component, has high hardness reaching model seven level, and has the advantages of high temperature resistance, low expansion coefficient, good thermal shock resistance, corrosion resistance and high light transmittance. The material has excellent physical and chemical properties, and is widely applied to industries such as high-end electric light sources, semiconductors, solar cells, optical fibers, lasers, aerospace, military and the like. Further, opaque silica glass, that is, opal silica glass, has important uses in fields requiring heat blocking, particularly in the semiconductor industry and photovoltaic industry, and is indispensable as a member for semiconductor manufacturing apparatuses.
The heat-blocking property is related to the light-shielding property of infrared light, and the higher the light-shielding property is, the more excellent the heat-blocking property of the opaque silica glass is. Conventionally, as a method for producing an opaque silica glass, there are known: (1) a method of adding a foaming agent such as silicon nitride or silicon carbide to crystalline silica or amorphous silica and melting the mixture (Japanese patent application laid-open No. Hei 4-65328, Japanese patent application laid-open No. Hei 5-254882, Japanese patent application laid-open No. Hei 7-61827). The opaque silica glass produced by such a production method generally has defects such as a large average diameter of pores formed by vaporization of a foaming agent, a low abundance of the pores, a low density of the opaque silica glass, and a low light-shielding property of infrared light. (2) An opaque silica glass (No. CN 106029586B) was produced by mixing and molding an amorphous silica powder and a pore-forming agent powder, and then sintering the mixture at a predetermined temperature. The pore-forming agent used in the method is graphite powder, amorphous carbon powder, phenolic resin powder, acrylic resin powder, polystyrene powder and the like. The former two pore-forming agents often contain higher and more impurity elements, so that the purity of the quartz glass is difficult to ensure; the latter three pore formers are harmful in their gaseous components generated during thermal decomposition and may cause environmental pollution. In addition, secondary contamination may occur when the amorphous silica powder is mixed with the pore-forming agent powder, and it is difficult to mix them uniformly, which may eventually result in non-uniformity of density and light-shielding rate of the opaque quartz glass. (3) A partially porous SiO2 particle sintered body was prepared from synthetic amorphous SiO2 starting particles, and after the SiO2 particle sintered body was dry-molded into a preform, the preform was fused by an arc to produce an opaque silica glass. Is a method for manufacturing synthetic quartz opaque quartz glass. (publication No.: CN 1413175A).
Disclosure of Invention
According to the embodiments of the present disclosure, there are provided a high-density, weldable, opaque quartz glass excellent in light-shielding properties for infrared light and a method for manufacturing the same. The method comprises the following steps:
(1) preparing slurry, ball-milling high-purity quartz glass sand to prepare the slurry, wherein the granularity of the ball-milled slurry is as follows: 3-30 μm, water content: 16-20%, viscosity: 100 and 500cp, density: 1800 grade 1850g/cm3；
(2) Molding, wherein the molding adopts a wet pouring process; the forming adopts slip casting, the slurry is slowly poured into a gypsum mould until the liquid level of the upper opening of the slurry does not drop any more, and the mould is removed after 24 to 48 hours;
(3) demolding, demolding the molded blank, and then standing and drying: standing the demoulded blank for 24-48h at room temperature, and drying for 15h at 100 ℃;
(4) sintering at 1350 ℃ and 1550 ℃ for 1-5 h.
Further, the high-purity silica glass sand in the step (1) has a particle size of 20 to 200 meshes and a purity of 50ppm or less, preferably 20ppm or less, of the sum of the contents of twelve element impurities Al + K + Na + Li + Ca + Mg + Fe + Mn + Cu + Cr + Ni + B.
Further, slurry is prepared in the step (1) through ball milling or vertical stirring milling, the lining of the milling equipment is made of polyurethane, wear-resistant rubber or quartz glass, the milling medium is made of quartz glass balls, zirconia balls, alumina balls, silicon nitride balls or silicon carbide balls, and the diameter of the milling medium is less than 20 mm.
Further, in the step (2), the manufacturing method according to claim 3, wherein in the step (2), the molding is performed by injection-gel molding, and the injection-gel molding includes the steps of: firstly, quantitatively weighing homogenized slurry, adding a monomer and a cross-linking agent into the slurry according to a ratio, uniformly stirring, adding an initiator, then uniformly stirring, pouring the slurry into a stainless steel mold, and curing in a water bath or a drying chamber at a curing temperature: room temperature to 60 ℃, curing time: 1-20 h.
Further, the monomer is acrylamide (C)2H3CONH2) The cross-linking agent is N, N' -methylene acrylamide (C)7H10N2)2The initiator is potassium persulfate K2S2O8Or ammonium persulfate (NH)4)2S2O8。
Further, the adding amount (mass) of the medicament relative to the slurry in the step (2) is as follows: monomer (b): 6.63-9.63 per mill, 0.07-0.17 per mill of cross-linking agent, initiator: 0.08-0.18 per mill.
Further, in the step (4), the green body is calcined in a high-temperature electric furnace, the temperature is raised to 600 ℃ at the heating rate of 50 ℃ per hour, the temperature is kept for 2 hours, then the temperature is raised to 1350 ℃ at the heating rate of 100 ℃ per hour, the temperature is kept for 1-5 hours, and the temperature is lowered at the rate of 100 ℃ per hour. To achieve vitrification of the body without cristobalite.
Further, an opaque quartz glass prepared by the above-mentioned manufacturing method is provided.
Furthermore, the sum of the contents of twelve element impurities Al + K + Na + Li + Ca + Mg + Fe + Mn + Cu + Cr + Ni + B in the opaque quartz glass is less than 50ppm, the light transmittance is less than 0.03, and the density is 2.12-2.20g/cm3The diameter of the air hole is between 2 and 20 mu m.
Further, there is provided an application of the above opaque quartz glass in the field of semiconductor, photovoltaic manufacturing or equipment for silicon wafer processing.
The invention has the advantages and effects that:
the invention utilizes high-purity quartz glass sand as a slurry raw material, ball milling or vertical stirring milling of wear-resistant materials such as lining polyurethane or rubber is used for pulping, and high-purity quartz glass balls, silicon nitride balls, silicon carbide balls, alumina balls, zirconia balls and the like are used as pulping media, so that the purity of the slurry can be ensured, and the introduction of impurity elements in the pulping process is avoided.
The slurry is not added with any foaming agent component, so that the cost can be reduced, the pollution to the environment can be avoided, the product purity can be kept, and the density can be improved. The ceramic process is utilized, the wet casting molding is adopted, the injection-coagulation formula is optimized, and the proper injection-coagulation additive and content are selected, so that the near-equal net-size molding can be carried out, namely the molding close to the shape of a target product can be carried out, the processing is easy, and the waste of raw materials and blanks is reduced.
Compared with slip casting, the advantages of slip casting are that the forming speed is high, the strength of a green body is high, the mold can be opened after curing in a water bath kettle for one hour after pouring is finished by adjusting the using amounts of the monomer, the cross-linking agent and the initiator, the mold has high mechanical strength after drying, mechanical processing can be implemented if needed, and the production efficiency is greatly improved.
It should be understood that the statements herein reciting aspects are not intended to limit the critical or essential features of the embodiments of the present disclosure, nor are they intended to limit the scope of the present disclosure. Other features of the present disclosure will become apparent from the following description.
Drawings
The above and other features, advantages and aspects of various embodiments of the present disclosure will become more apparent by referring to the following detailed description when taken in conjunction with the accompanying drawings. In the drawings, like or similar reference characters designate like or similar elements, and wherein:
FIG. 1 shows a Raman spectrum of a sample of opal quartz glass obtained in example 2;
FIG. 2 shows a Raman spectrum of a sample of opal quartz glass obtained in example 5;
FIG. 3 shows a micrograph of the pore size and the distribution of the opal quartz glass sample obtained in example 2.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present disclosure more clear, the technical solutions of the embodiments of the present disclosure will be described clearly and completely with reference to the drawings in the embodiments of the present disclosure, and it is obvious that the described embodiments are some, but not all embodiments of the present disclosure. All other embodiments, which can be derived by a person skilled in the art from the embodiments disclosed herein without making any creative effort, shall fall within the protection scope of the present disclosure.
In addition, the term "and/or" herein is only one kind of association relationship describing an associated object, and means that there may be three kinds of relationships, for example, a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
The invention uses 20-200 mesh high-purity quartz glass sand with the code of PQ-GF-6 as a raw material, a 100L vertical stirring mill as a ball mill, and high-purity quartz glass balls with the diameter of 10mm as an ore grinding medium.
50kg of quartz glass balls with the diameter of 10mm are added into a 100L mill, 11kg of high-purity water is added, the ball mill is started, 50kg of 20-200 mesh quartz glass sand is added in batches, and the rotating speed of the ball mill is set to 80 r/min. Grinding the slurry to a set D50 value and a water content of about 18%, pouring the slurry into a barrel, and waiting for pouring.
1. Slip casting
Firstly, the gypsum mould is subjected to water supplementing maintenance, and the slurry is subjected to vacuum treatment. Then, the slurry is slowly poured into the mold, and the slurry is replenished irregularly until the upper liquid level of the slurry does not drop any more. And demolding after 24-48h according to the curing condition. And (3) standing for 24-48h at room temperature after demolding, and then drying for 15h at 100 ℃.
2. Injection-coagulation molding
Quantitatively weighing the slurry, adding the monomer and the cross-linking agent into the slurry according to the proportion, uniformly stirring, adding the initiator, and then uniformly stirring. The adding amount of the medicament is (relative to the amount of the slurry): monomer (b): 8.13 plus or minus 1.5 per mill, 0.12 plus or minus 0.5 per mill of cross-linking agent, initiator: 0.13 plus or minus 0.5 per mill. Smearing a release agent on a stainless steel mould, assembling the mould, pouring the uniformly stirred slurry into the mould, and then putting the mould into a drying room at 40 ℃ or a water bath kettle for curing and forming for 1-10 hours. And (4) standing for 24 hours at room temperature after demolding, and then drying for 15 hours at 100 ℃.
3. Sintering
And calcining the dried green body in a high-temperature furnace, raising the temperature to 600 ℃ at the heating rate of 50 ℃ per hour, keeping the temperature for 2 hours, and then raising the temperature to 1500 ℃ at the heating rate of 100 ℃ per hour, and keeping the temperature for 2 hours. The temperature was reduced at a rate of 100 ℃ per hour.
4. Detection of
After sintering, the impurity content, density, transmittance and softening point of the product were measured. Purity of the product was measured using ICP-OES and density was measured using a balance cylinder method. And (3) carrying out transmittance test, namely cutting the sample to be tested into 3 mm-thick slices with the size of about 20-40 mm, cleaning dust and fine particles attached to the surface before testing, and wiping off residual water. The ultraviolet/visible/near-infrared spectrophotometer Lambda950, manufactured by American PE company, is used for testing, and the spectral transmittance of the material in a certain waveband is tested by utilizing the difference of the absorption degree of the material composition and the structure to ultraviolet, visible and near-infrared light. And (3) softening point testing, namely processing a sample to be tested into a phi 6 x 25mm long column, cleaning dust and fine particles attached to the surface before testing, and wiping off residual water. The Dil 402E thermal expansion instrument produced by German Steady Instrument company is used for testing, a sample is connected with a push rod and placed in a furnace body with controllable temperature, and a displacement sensor is used for continuously measuring the displacement change of the push rod, so that the relation between the scale change of the sample and the temperature is obtained.
Example 1
Slurry was prepared by ball milling according to the above embodiment, D50 ═ 12.6 μm. Stirring the slurry in a homogenizing barrel, homogenizing for 72h, and performing vacuum treatment on the slurry after the performance is stable. And (3) pouring the slurry into a gypsum mould by adopting a grouting process, and opening the mould after 25 hours.
And (3) standing the blank after demolding for 30h, and then drying the blank in a drying furnace for 15h, wherein the temperature of the drying furnace is set to be 100 ℃.
And (3) calcining the dried green body at high temperature, raising the temperature to 600 ℃ at the temperature rise rate of 50 ℃ per hour, keeping the temperature for 2 hours, and then raising the temperature to 1400 ℃ at the temperature rise rate of 100 ℃ per hour, and keeping the temperature for 2 hours. The temperature was reduced at a rate of 100 ℃ per hour.
The opal quartz glass sample obtained was subjected to performance analysis, and the transmittance and density were as shown in table 1, and the impurity detection was as shown in table 2.
Example 2
Slurry was prepared by ball milling according to the above embodiment, D50 ═ 9.5 μm. In the homogenizing barrel, the slurry is stirred and homogenized for 48 h. After the performance is stable, the slurry is poured into a gypsum mould by adopting a grouting process, and the slurry is molded after 30 hours.
And (3) standing the blank after demolding for 40h, and then drying for 20h in a drying furnace, wherein the temperature of the drying furnace is set to be 100 ℃.
And (3) calcining the dried green body at high temperature, raising the temperature to 600 ℃ at the temperature rise rate of 50 ℃ per hour, keeping the temperature for 3 hours, and then raising the temperature to 1500 ℃ at the temperature rise rate of 100 ℃ per hour, and keeping the temperature for 1 hour. The temperature was reduced at a rate of 100 ℃ per hour.
The opal quartz glass sample obtained was subjected to performance analysis, the raman spectrum is shown in fig. 1, the transmittance and density are shown in table 1, and the size and distribution of pores are shown in the micrograph shown in fig. 3. The opal silica glass obtained in example 2 had a raman spectrum as shown in fig. 1, the thinner curve is a raman spectrum of a typical high purity silica glass tube, the thicker curve is a raman spectrum of the opal silica glass obtained in example 2, which completely coincided at wave numbers of 485, 605, 805, 1060 and 1200, and the opal silica glass obtained in example 2 had an SEM image as shown in fig. 3, and the pore size was mostly around 5 μm.
Example 3
Slurry was prepared by ball milling according to the above embodiment, D50 ═ 9.5 μm. In the homogenizing barrel, the slurry is stirred and homogenized for 24 h. And (3) adopting a grouting process, vacuumizing the slurry, pouring the slurry into a gypsum mold, and forming the slurry after 20 hours.
And (3) standing the blank for 30h after demolding, and then drying for 10h in a drying furnace, wherein the temperature of the drying furnace is set to be 100 ℃.
And (3) calcining the dried green body at high temperature, raising the temperature to 600 ℃ at the heating rate of 50 ℃ per hour, keeping the temperature for 2 hours, and then raising the temperature to 1450 ℃ at the heating rate of 100 ℃ per hour, and keeping the temperature for 1 hour. The temperature was reduced at a rate of 100 ℃ per hour.
The opal quartz glass samples obtained were subjected to performance analysis, and the transmittances and densities were as shown in table 1.
Example 4
Slurries were prepared by ball milling according to the above embodiment, D50 ═ 9.5 μm. And (4) homogenizing the slurry in a homogenizing barrel for 72 hours, and pouring by adopting a pour-point process after the performance is stable.
Firstly, quantitatively weighing homogenized slurry, adding a monomer and a cross-linking agent into the slurry according to a ratio, uniformly stirring, adding an initiator, and then uniformly stirring. The adding amount of the medicament is as follows: monomer (b): 8.13 per mill, 0.12 per mill of cross-linking agent, initiator: 0.13 per mill. And vacuumizing the slurry, pouring the slurry into a stainless steel mold, curing the slurry in a hot water bath at 60 ℃, and opening the mold after 1 h.
And (3) standing the demoulded blank for 30h at room temperature, and then drying the blank for 15h in a drying furnace, wherein the temperature of the drying furnace is set to be 100 ℃.
And (3) calcining the dried green body at high temperature, raising the temperature to 600 ℃ at the heating rate of 50 ℃ per hour, keeping the temperature for 2 hours, and then raising the temperature to 1500 ℃ at the heating rate of 100 ℃ per hour, and keeping the temperature for 2 hours. The temperature was reduced at a rate of 100 ℃ per hour.
The opal quartz glass sample obtained was subjected to performance analysis, and the transmittance and density were as shown in table 1, and the impurity detection was as shown in table 2.
Example 5
Slurries were prepared by ball milling according to the above embodiment, D50 ═ 9.5 μm. In the homogenization barrel, the slurry was homogenized for 72 h. And after the performance of the slurry is stable, pouring by adopting a pour-point process.
Firstly, quantitatively weighing homogenized slurry, adding a monomer and a cross-linking agent into the slurry according to a ratio, uniformly stirring, adding an initiator, and then uniformly stirring. The adding amount of the medicament is as follows: monomer (b): 9.60 per mill, 0.15 per mill of cross-linking agent, initiator: 0.16 per mill. And vacuumizing the slurry, pouring the slurry into a stainless steel mold, curing the slurry in a hot water bath at 60 ℃, and forming the slurry after 1 hour.
And (3) standing the blank after demolding for 30h, and then drying the blank in a drying furnace for 15h, wherein the temperature of the drying furnace is set to be 100 ℃.
And (3) calcining the dried green body at high temperature, raising the temperature to 600 ℃ at the heating rate of 50 ℃ per hour, keeping the temperature for 2 hours, and then raising the temperature to 1450 ℃ at the heating rate of 100 ℃ per hour, and keeping the temperature for 2 hours. The temperature was reduced at a rate of 100 ℃ per hour.
The opal quartz glass sample obtained was subjected to performance analysis, the raman spectrum is shown in fig. 2, and the transmittance and density are shown in table 1. The raman spectrum of the opal silica glass obtained in example 5 is shown in fig. 2, and the smaller curve is the raman spectrum of a typical high purity silica glass tube, and the larger curve is the raman spectrum of the opal silica glass obtained in example 5, which are completely matched at wavenumbers of 485, 605, 805, 1060 and 1200.
Example 6
Slurries were prepared by ball milling according to the above embodiment, D50 ═ 9.5 μm. And homogenizing the slurry in a homogenizing barrel for 72 hours, and pouring by adopting a pour-point process after the performance of the slurry is stable.
Firstly, quantitatively weighing homogenized slurry, adding a monomer and a cross-linking agent into the slurry according to a ratio, uniformly stirring, adding an initiator, and then uniformly stirring. The adding amount of the medicament is as follows: monomer (b): 9.60 per mill, 0.15 per mill of cross-linking agent, initiator: 0.16 per mill. And vacuumizing the slurry, pouring the slurry into a stainless steel mold, curing the slurry in a constant-temperature oven at 40 ℃, and forming the slurry after 10 hours.
And (3) standing the blank after demolding for 30h, and then drying the blank in a drying furnace for 15h, wherein the temperature of the drying furnace is set to be 100 ℃. And (3) calcining the dried green body at high temperature, raising the temperature to 600 ℃ at the heating rate of 50 ℃ per hour, keeping the temperature for 2 hours, and then raising the temperature to 1400 ℃ at the heating rate of 100 ℃ per hour, and keeping the temperature for 2 hours. The temperature was reduced at a rate of 100 ℃ per hour.
The opal quartz glass samples obtained were subjected to performance analysis, and the transmittances and densities were as shown in table 1.
TABLE 1 transmission and Density analysis of opal silica glass
TABLE 2 analysis result (ppm) of impurity element of opal quartz glass
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A method for manufacturing high-purity opaque quartz glass is characterized by comprising the following steps:
(1) preparing slurry, ball-milling high-purity quartz glass sand to prepare the slurry, wherein the granularity of the ball-milled slurry is as follows: 3-30 μm, water content: 16-20%, viscosity: 100 and 500cp, density: 1800 grade 1850g/cm3；
(2) Molding, wherein the molding adopts a wet pouring process; the forming adopts slip casting, the slurry is slowly poured into a gypsum mould until the liquid level of the upper opening of the slurry does not drop any more, and the mould is removed after 24 to 48 hours;
(3) demolding, demolding the molded blank, and then standing and drying: standing the demoulded blank for 24-48h at room temperature, and drying for 15h at 100 ℃;
(4) sintering at 1350 ℃ and 1550 ℃ for 1-5 h.
2. The production method according to claim 1, wherein the high purity silica glass sand in the step (1) has a particle size of 20 to 200 mesh and a purity of 50ppm or less, preferably 20ppm or less in total of contents of twelve element impurities Al + K + Na + Li + Ca + Mg + Fe + Mn + Cu + Cr + Ni + B.
3. The manufacturing method according to claim 2, wherein the slurry is prepared by ball milling or vertical stirring milling in the step (1), the lining of the refining equipment is polyurethane, wear-resistant rubber or quartz glass, the refining medium is quartz glass balls, zirconia balls, alumina balls, silicon nitride balls or silicon carbide balls, and the diameter of the refining medium is less than 20 mm.
4. The manufacturing method according to claim 3, wherein in the step (2), the molding is performed by injection molding, and the injection molding includes the steps of: firstly, quantitatively weighing homogenized slurry, adding a monomer and a cross-linking agent into the slurry according to a ratio, uniformly stirring, adding an initiator, then uniformly stirring, pouring the slurry into a stainless steel mold, and curing in a water bath or a drying chamber at a curing temperature: room temperature to 60 ℃, curing time: 1-20 h.
5. The method according to claim 4, wherein the monomer is acrylamide (C)2H3CONH2) The cross-linking agent is N, N' -methylene acrylamide (C)7H10N2)2The initiator is potassium persulfate K2S2O8Or ammonium persulfate (NH)4)2S2O8。
6. The manufacturing method according to claim 5, wherein the amount (by mass) of the agent added to the slurry in the step (2) is: monomer (b): 6.63-9.63 per mill, 0.07-0.17 per mill of cross-linking agent, initiator: 0.08-0.18 per mill.
7. The method according to claim 6, wherein in the step (4), the green body is calcined in a high temperature electric furnace, the temperature is raised to 600 ℃ at a temperature raising rate of 50 ℃ per hour, the temperature is maintained for 2 hours, then the temperature is raised to 1350 ℃ at a temperature raising rate of 100 ℃ per hour, the temperature is maintained for 1 to 5 hours, and the temperature is lowered at a rate of 100 ℃ per hour.
8. Opaque quartz glass produced by the production process as claimed in one of claims 1 to 7.
9. As in claimThe opaque quartz glass as claimed in claim 8, characterized in that the opaque quartz glass has a sum of the contents of twelve elemental impurities Al + K + Na + Li + Ca + Mg + Fe + Mn + Cu + Cr + Ni + B of less than 50ppm, a light transmittance of less than 0.03 and a density of 2.12 to 2.20g/cm3The diameter of the air hole is between 2 and 20 mu m.
10. Use of the opaque quartz glass according to claim 9 in the field of semiconductors, photovoltaic manufacture or in equipment for the processing of silicon wafers.
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