CN106518107B - It is layered the preparation method of high-purity aircon refractory - Google Patents

It is layered the preparation method of high-purity aircon refractory Download PDF

Info

Publication number
CN106518107B
CN106518107B CN201610905862.8A CN201610905862A CN106518107B CN 106518107 B CN106518107 B CN 106518107B CN 201610905862 A CN201610905862 A CN 201610905862A CN 106518107 B CN106518107 B CN 106518107B
Authority
CN
China
Prior art keywords
purity
zircon
refractory
raw material
aircon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610905862.8A
Other languages
Chinese (zh)
Other versions
CN106518107A (en
Inventor
胡丽丽
唐景平
蒋亚丝
邹兆松
钱敏
肖子良
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Optics and Fine Mechanics of CAS
Original Assignee
Shanghai Institute of Optics and Fine Mechanics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Optics and Fine Mechanics of CAS filed Critical Shanghai Institute of Optics and Fine Mechanics of CAS
Priority to CN201610905862.8A priority Critical patent/CN106518107B/en
Publication of CN106518107A publication Critical patent/CN106518107A/en
Application granted granted Critical
Publication of CN106518107B publication Critical patent/CN106518107B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/75—Products with a concentration gradient

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Chemistry (AREA)

Abstract

A kind of preparation method being layered high-purity aircon refractory, preparation, layering isostatic pressing and the high temperature solid-state of preparation, common zircon raw material including high-purity zircon raw material are burnt four steps and are made.Experiment shows that the manufactured high-purity aircon refractory of layering of the invention is few in glass melting process introducing transition metal impurity ionic soil, layer forming technique control cost can be used, and have anti-glass attack effect well.

Description

It is layered the preparation method of high-purity aircon refractory
Technical field
The present invention relates to high-purity refractory material, especially a kind of preparation method for being layered high-purity aircon refractory should Refractory material is used for the material of high-grade optical glass smelting furnace, laser glass smelting furnace and metal smelting furnace.
Background technique
Refractory material is the indispensable basic material of high-temperature technology, the industrial production mistake of related to high-temperature chemical reaction Journey, it is necessary to have both high temperature resistants, and resistant to corrosion, and stress can also be resisted in many cases or temperature is jumpy resistance to Fiery material.China be in the world maximum refractory material producing country and consumption state.Meanwhile China is in refractory material research and development field Positive effect increasingly shows.Have with the concern in world wide to low-carbon economy and environmental protection, and in face of natural resources The difficulty utilized is imitated, Chinese refractories industry must reinforce the innovation work of raw material and basic research, to adjust the product mix, The increasingly harsher requirement of high temperature new technology is adapted to, realizes the sustainable development of Chinese refractories industry, is provided with high attached The refractory material of high quality value added, high-temperature behavior is excellent, using effect and economic benefit better meet individual demand is new Product.
High-grade optical glass will meet image quality and high transmittance, it is desirable that its specific wavelength absorption coefficient very little, Especially laser glass will meet high-gain and high-energy density index, it is desirable that it is smaller more in the absorption coefficient of light of optical maser wavelength It is good, using general commercial refractory material because of Fe2O3The impurity content of equal transition metal is invaded generally in thousands of ppmw magnitudes through glass These impurity can enter in glass melt after erosion, it is difficult to meet wanting for high-grade optical glass especially laser glass low impurity content It asks, the indexs such as transmitance and light absorption to glass cause detrimental effects.There is an urgent need to a kind of not only high temperature resistant, resistance to glass attack but also Impurity is not introduced and economic and practical high-purity refractory material suitable for melting top grade optical glass and laser glass.
Summary of the invention
Aiming at the above shortcomings existing in the prior art and defect, the object of the present invention is to provide a kind of layering high purity zirconium English The preparation method of stone refractory material.This method preparation the high-purity aircon refractory of layering have it is structurally reasonable, easy to process, High temperature resistant corrodes does not pollute glass, and the feature that cost is controllable again.
The technology of the present invention solution is as follows:
A kind of preparation method being layered high-purity aircon refractory, it is characterised in that this method includes the following steps:
1. the preparation of high-purity zircon raw material: selecting the ZrO of purity >=99.9%, 66~67.7wt%2, purity >= 99.9%, the SiO of 32~33wt%2, the TiO of purity >=99.5%, 0.3~2wt%2, it is milled to after mixing with zirconia balls After fineness is 0.1~5 μm >=95%, then warp >=1100 DEG C high-temperature calcination 20~48 hours synthesize, and add that 0.1~0.2wt%'s is excellent Grade pure phosphoric acid, using zirconia balls ball milling at muddy, fineness requirement is 0.1~6 μm >=95%, and the muddy is high Pure zircon drying, powder crushes, and crosses 30 mesh vibrating screens, obtains high-purity zircon raw material；
2. the preparation of common zircon raw material: selecting ZrSiO4>=98.5% common zircon raw material, add 0.3~ The TiO of 2wt%2, 0.1~0.2wt% phosphoric acid, using zirconia balls ball milling at muddy, fineness is 0.1~6 μm >=95%, By the common zircon drying of muddy, powder is crushed, and crosses 30 mesh vibrating screens, obtains common zircon raw material；
3. being layered isostatic pressing: isostatic pressing method is used, it is first general with the common zircon raw material molding one Lead to zircon layer, then covered again with high-purity zircon raw material on the common zircon layer and form one and is high-purity Zircon layer, thickness >=20mm of high-purity zircon layer；
4. high temperature solid-phase sintering；Calcining system are as follows:
Temperature-rise period: room temperature~200 DEG C, heating rate≤8 DEG C/h, 200 DEG C of heat preservation >=4h；200~1000 DEG C, heating speed Rate≤8 DEG C/h, 1000 DEG C of heat preservation >=4h；1000~>=1550 DEG C, heating rate≤8 DEG C/h, kept the temperature at >=1550 DEG C >= 12h；
Temperature-fall period: >=1550 DEG C~400 DEG C, rate of temperature fall≤10 DEG C/h, 400 DEG C~room temperature, rate of temperature fall≤6 DEG C/ H is obtained after sintering and is layered high-purity aircon refractory.
The transition metal impurity content requirement of high-purity zircon raw material: CuO content≤5ppmw, CuO+Co2O3+ NiO+Cr2O3≤ 10ppmw, Fe2O3Content≤100ppmw.
The mud drying temperature is 180~350 DEG C, moisture≤0.2wt% of raw material after drying.
High-purity aircon refractory with a thickness of layering refractory material overall thickness 0.9~0.1.
Pressure >=200Mpa of the static pressure such as the molding of the high-purity aircon refractory of layering.
The size of the high-purity aircon refractory of layering, can be made tens of according to smelting furnace design requirement Millimeter is differed to >=1000 millimeters, and the ratio that high-purity zircon thickness accounts for overall thickness is 0.9~0.1, takes into account economic and practical original Then.
The advantages of this reality is invented is:
1, it is layered the high-purity material of high-purity aircon refractory partly because purity is high, structure even compact, both resistance to height Temperature, resistance to glass attack do not introduce impurity suitable for melting top grade optical glass and laser glass again.
2, it is layered high-purity aircon refractory and uses layered structure, take into account economic and practical principle, both may be controlled to This convenient for design and application, has fine resistant to corrosion effect again, and intensity is also no less than general commercial refractory material.
3, using such high-purity aircon refractory of layering in glass melting process, the foreign ions pair such as transition metal The pollution of glass is few, can ensure high-grade optical glass, especially there is the high-quality and low optical of the laser glass of particular/special requirement Loss requires.
Detailed description of the invention
Fig. 1 is that glass melting furnace of the present invention is layered high-purity zircon structure of refractory schematic diagram.
The high-purity zircon refractory material layer of figure label 1,2 general commercial refractory material layers, the high-purity aircon refractory of D Thickness degree, L are layered high-purity aircon refractory overall thickness.
Fig. 2 is trial furnace schematic diagram of the invention；
Fig. 3 is the XRD diffraction pattern of high-purity aircon refractory and general commercial aircon refractory, and 1 is high purity zirconium Diamond stone refractory material layer, 2 be general commercial aircon refractory layer.
Fig. 4 is the micro-structure diagram of high-purity zircon refractory material layer and general commercial aircon refractory layer.
Specific embodiment:
The present invention is further illustrated with reference to the accompanying drawings and examples, but protection model of the invention is not limited with this It encloses.
As shown in Figure 1, glass melting furnace of the present invention is layered high-purity aircon refractory, including high-purity zircon fire resisting Material layer 1, general commercial refractory material layer 2.
The present invention is layered the preparation method of high-purity aircon refractory, and method includes the following steps:
1. the preparation of high-purity zircon raw material: selecting the ZrO of purity >=99.9%, 66~67.7wt%2, purity >= 99.9%, the SiO of 32~33wt%2, the TiO of purity >=99.5%, 0.3~2wt%2, it is milled to after mixing with zirconia balls After fineness is 0.1~5 μm >=95%, then warp >=1100 DEG C high-temperature calcination 20~48 hours synthesize, and add that 0.1~0.2wt%'s is excellent Grade pure phosphoric acid, using zirconia balls ball milling at muddy, fineness requirement is 0.1~6 μm >=95%, and the muddy is high Pure zircon drying, powder crushes, and crosses 30 mesh vibrating screens, obtains high-purity zircon raw material；
2. the preparation of common zircon raw material: selecting ZrSiO4>=98.5% common zircon raw material, add 0.3~ The TiO of 2wt%2, 0.1~0.2wt% phosphoric acid, using zirconia balls ball milling at muddy, fineness is 0.1~6 μm >=95%, By the common zircon drying of muddy, powder is crushed, and crosses 30 mesh vibrating screens, obtains common zircon raw material；
3. being layered isostatic pressing: isostatic pressing method is used, it is first general with the common zircon raw material molding one Lead to zircon layer, then covered again with high-purity zircon raw material on the common zircon layer and form one and is high-purity Zircon layer constitutes and is layered high-purity aircon refractory, thickness >=20mm of high-purity zircon layer；
4. the high-purity aircon refractory high temperature solid-phase sintering of layering；Calcining system are as follows:
Temperature-rise period: room temperature~200 DEG C, heating rate≤8 DEG C/h, 200 DEG C of heat preservation >=4h；200~1000 DEG C, heating speed Rate≤8 DEG C/h, 1000 DEG C of heat preservation >=4h；1000~>=1550 DEG C, heating rate≤8 DEG C/h, kept the temperature at >=1550 DEG C >= 12h；
Temperature-fall period: >=1550 DEG C~400 DEG C, rate of temperature fall≤10 DEG C/h, 400 DEG C~room temperature, rate of temperature fall≤6 DEG C/ H is obtained after sintering and is layered high-purity aircon refractory.
The transition metal impurity content requirement of high-purity zircon raw material: CuO content≤5ppmw, CuO+Co2O3+ NiO+Cr2O3≤ 10ppmw, Fe2O3Content≤100ppmw.
The mud drying temperature is 180~350 DEG C, moisture≤0.2wt% of raw material after drying.
High-purity aircon refractory with a thickness of layering refractory material overall thickness 0.9~0.1.
Pressure >=200Mpa of the static pressure such as the molding of the high-purity aircon refractory of layering.
The present embodiment one: two blocks of refractory materials of production are 500 millimeters long, 400 millimeters wide.L=100 millimeters of its overall thickness, In high-purity zircon refractory material layer thickness be respectively D=90 millimeters (I bricks) and D=50 millimeters (II brick)；The present embodiment Two: two blocks of refractory materials of production are 400 millimeters long, 300 millimeters wide, and L=100 millimeters of overall thickness, wherein high-purity zircon fire resisting D=50 millimeters of layer thickness (III brick)；The present embodiment three: one block of refractory material of production is 300 millimeters long, 300 millimeters wide, L=200 millimeters of its overall thickness, wherein D=200 millimeters of high-purity zircon refractory material layer thickness (IV brick).
Embodiment one:
According to the size of refractory material, the raw material dosage of high-purity zircon and general commercial zircon is estimated.It is high-purity Zircon raw material needs artificial synthesized.
125 kilograms of high-purity zircon raw material is needed, and makes and needs to reserve the remaining of 30wt% with subsequent process Amount, according to following proportion: high-purity ZrO2For 66.2wt%, high-purity Si O2For 33wt%, the high-purity Ti O of 0.8wt%2, configuration 162 Kilogram raw material.All material purity >=99.9%, and CuO content≤5ppmw, CuO+Co2O3+NiO+Cr2O3≤ 10ppmw, Fe2O3Content≤50ppmw.By zirconium oxide and silica mixture ball milling grind within 36 hours to fineness requirement be 0.1~6 μm >= 95%1 μm, it is put into clean mold after 1350 DEG C are calcined 30 hours that through solid phase reaction to generate high-purity zircon raw material stand-by.
54 kilograms of general commercial zircon raw material is needed, production and the machining allowance of 30wt% are also reserved, then is needed common 70 kilograms of commercial zircon raw material adds 0.7 kilogram of TiO2。
0.1~0.2wt% phosphoric acid is added individually to be milled to general commercial zircon raw material and high-purity zircon raw material Fineness requirement is 0.1~6 μm >=95%, drying.The present embodiment I brick uses general commercial zircon raw material through 200MPa etc. in advance 520 × 420 × 15 millimeters of hydrostatic profile3Blank, then one layer of high-purity zircon raw material is being covered above again, then through 300Mpa Isostatic pressing is at 520 × 420 × 110 millimeters3Blank.The present embodiment II brick use in advance general commercial zircon raw material at 520 × 420 × 55 millimeters of type3Blank, through 200MPa isostatic pressing, then again to cover one layer of high-purity zircon above former Material, through 300Mpa isostatic pressing at 520 × 420 × 110 millimeters3Blank；
The blank of forming is heated up in down-draft kiln with 5 DEG C/h, 200 DEG C of heat preservation 4h, and 200~1000 DEG C, heating rate 5 DEG C/h, 1000 DEG C of heat preservation 4h；1000~1600 DEG C, 8 DEG C/h of heating rate, in 1600 DEG C of heat preservation 12h；It is down to 8 DEG C/h 400 DEG C, then it is down to room temperature with 6 DEG C/h, it is machined to the size needed.
Embodiment two:
According to the size of refractory material, the raw material dosage of high-purity zircon and general commercial zircon is estimated.It is high-purity Zircon raw material needs artificial synthesized.
53.5 kilograms of high-purity zircon raw material is needed, and makes and needs to reserve the remaining of 30wt% with subsequent process Amount, according to following proportion: high-purity ZrO2For 66wt%, high-purity Si O2For 32wt%, the high-purity Ti O of 2wt%2, configure 70 kilograms of originals Material.All material purity >=99.9%, and CuO content≤5ppmw, CuO+Co2O3+NiO+Cr2O3≤ 10ppmw, Fe2O3Content ≤50ppmw.It is 0.1~6 μm >=95%1 μm that zirconium oxide and silica mixture ball milling are ground to fineness requirement for 36 hours, is put Enter that through solid phase reaction to generate high-purity zircon raw material after 1100 DEG C are calcined 20 hours in clean mold stand-by.
53.5 kilograms of general commercial zircon raw material is needed, production and the machining allowance of 30wt% is also reserved, need general Trading uses 70 kilograms of zircon raw material, adds 1.4 kilograms of TiO2。
0.1~0.2wt% phosphoric acid is added individually to be milled to general commercial zircon raw material and high-purity zircon raw material Fineness requirement is 0.1~6 μm >=95%, drying.The present embodiment III brick uses general commercial zircon raw material to form 420 in advance × 320 × 55 millimeters3Blank, through 200MPa isostatic pressing, then again above cover one layer of high-purity zircon raw material, then Through 300Mpa isostatic pressing at 420 × 320 × 110 millimeters3Blank；
The blank of forming is heated up in down-draft kiln with 8 DEG C/h, 200 DEG C of heat preservation 4h, and 200~1000 DEG C, heating rate 8 DEG C/h, 1000 DEG C of heat preservation 4h；1000~1550 DEG C, 8 DEG C/h of heating rate, in 1550 DEG C of heat preservation 12h；It is down to 8 DEG C/h 400 DEG C, then it is down to room temperature with 6 DEG C/h, it is machined to the size needed.
Embodiment three:
According to the size of refractory material, the raw material dosage of high-purity zircon and general commercial zircon is estimated.It is high-purity Zircon raw material needs artificial synthesized.
8 kilograms of high-purity zircon raw material is needed, and makes the surplus for needing reserved 30wt% with subsequent process, According to following proportion: high-purity ZrO2For 67.7wt%, high-purity Si O2For 32wt%, the high-purity Ti O of 0.3wt%2, 10.5 public affairs of configuration Jin raw material.Wherein, ZrO2、SiO2Material purity >=99.9%, TiO2Material purity >=99.5%, and CuO content≤5ppmw, CuO+Co2O3+NiO+Cr2O3≤ 10ppmw, Fe2O3Content≤50ppmw.By zirconium oxide and silica mixture ball milling 36 hours Grinding to fineness requirement is 0.1~6 μm >=95%1 μm, is put into clean mold anti-through solid phase after 1350 DEG C are calcined 24 hours It is stand-by that high-purity zircon raw material should be generated.
72 kilograms of general commercial zircon raw material is needed, production and the machining allowance of 30wt% are also reserved, is needed common 94 kilograms of commercial zircon raw material adds 0.3 kilogram of TiO2。
0.1~0.2wt% phosphoric acid is added individually to be milled to general commercial zircon raw material and high-purity zircon raw material Fineness requirement is 0.1~6 μm >=95%, drying.The present embodiment IV brick use in advance general commercial zircon raw material molding 320 × 320 × 190 millimeters3Blank, through 200MPa isostatic pressing, then again above cover one layer of high-purity zircon raw material, warp 300Mpa isostatic pressing is at 320 × 320 × 215 millimeters3Blank；
The blank of forming is heated up in down-draft kiln with 5 DEG C/h, 200 DEG C of heat preservation 4h, and 200~1000 DEG C, heating rate 5 DEG C/h, 1000 DEG C of heat preservation 4h；1000~1620 DEG C, 8 DEG C/h of heating rate, in 1620 DEG C of heat preservation 20h；It is down to 8 DEG C/h 400 DEG C, then it is down to room temperature with 6 DEG C/h, it is machined to the size needed.At 300 × 300 millimeters of IV brick2Big face in The through-hole IX of 20 millimeters of one Φ of heart brill.
The crystal phase of the high-purity aircon refractory of sampling and testing and compared with general commercial aircon refractory such as Fig. 3 institute Show, all zircon phases of crystal phase, microstructure compares such as Fig. 4, and it is good to compare its compactness with commercial aircon refractory Resistant to corrosion is more excellent.
It is 300 × 300 × 200 millimeters that I~IV brick, which is assembled into volume,3Glass melting furnace as shown in Fig. 2, contact The face of glass is high-purity zircon material, around matches light weight alumina the insulating brick V, top Fe of one layer of 115mm thickness2O3Content The mullite of 50ppmw is caping VI, and one 100 × 100mm is opened in side2Feed opening VIII, above feed opening with 10 Φ 25 Elema VII.The glass melting furnace is warming up to 1200 DEG C of heat preservations with 10 DEG C/h, by 30 kilograms of glass batch Material is added to the glass melting furnace with 5 kilograms/20min, and the present embodiment uses Nd3+Ion concentration 3.5 × 1020A/centimetre3's Phosphate laser glass batch；Melting 6 hours or more after the completion of charging, laser glass melting 6 hours described in the present embodiment, 12 Hour, 24 hours, 48 hours after 72 hours, sample and test through inductively coupled plasma atomic emission spectrometer (ICP-AES) Impurity content in glass, the transition metal impurities such as iron, copper total amount all≤20ppmw, comply fully with laser glass melting requirement.
Experiment shows manufactured the characteristics of being layered high-purity aircon refractory of the invention: no transition metal impurity pollution, It is easy to make, convenient for control cost, can be directly applied in high-grade optical glass and laser glass smelting furnace.
Finally, it is noted that described above be only used to explain the preferred embodiments of the invention, it is not intended to the present invention Make any form of restriction, it will be understood by those of skill in the art that can modify to technical solution of the present invention or Person's equivalent replacement should all cover within the protection scope of the present invention without departing from creation spirit of the invention.

Claims (5)

1. a kind of preparation method for being layered high-purity aircon refractory, it is characterised in that this method includes the following steps:
1. the preparation of high-purity zircon raw material: selecting the ZrO of purity >=99.9%, 66~67.7wt%2, purity >=99.9%, 32 The SiO of~33wt%2, the TiO of purity >=99.5%, 0.3~2wt%2, being milled to fineness with zirconia balls after mixing is 0.1 After~5 μm >=95%, then warp >=1100 DEG C high-temperature calcination 20~48 hours synthesize, and add the top grade pure phosphoric acid of 0.1~0.2wt%, Using zirconia balls ball milling at muddy, fineness requirement is 0.1~6 μm >=95%, by the high-purity zircon of muddy Drying, powder crush, and cross 30 mesh vibrating screens, obtain high-purity zircon raw material；
2. the preparation of common zircon raw material: selecting ZrSiO4>=98.5% common zircon raw material, adds 0.3~2wt%'s TiO2, 0.1~0.2wt% phosphoric acid, using zirconia balls ball milling at muddy, fineness is 0.1~6 μm >=95%, will be described Muddy common zircon drying, powder crushes, and crosses 30 mesh vibrating screens, obtains common zircon raw material；
3. being layered isostatic pressing: using isostatic pressing method, first form a common zirconium with the common zircon raw material Then diamond stone layer is covered with high-purity zircon raw material again on the common zircon layer and forms a high purity zirconium English Rock layers, thickness >=20mm of high-purity zircon layer；
4. high temperature solid-phase sintering；Calcining system are as follows:
Temperature-rise period: room temperature~200 DEG C, heating rate≤8 DEG C/h, 200 DEG C of heat preservation >=4h；200~1000 DEG C, heating rate≤ 8 DEG C/h, 1000 DEG C of heat preservation >=4h；1000~>=1550 DEG C, heating rate≤8 DEG C/h, heat preservation >=12h at >=1550 DEG C；
Temperature-fall period: >=1550 DEG C~400 DEG C, rate of temperature fall≤10 DEG C/h, 400 DEG C~room temperature, rate of temperature fall≤6 DEG C/h are burnt It is obtained after knot and is layered high-purity aircon refractory.
2. being layered the preparation method of high-purity aircon refractory as described in claim 1, it is characterised in that: described is high-purity The transition metal impurity content requirement of zircon raw material: CuO content≤5ppmw, CuO+Co2O3+NiO+Cr2O3≤ 10ppmw, Fe2O3Content≤100ppmw.
3. being layered the preparation method of high-purity aircon refractory as described in claim 1, it is characterised in that: the mud Drying temperature is 180~350 DEG C, moisture≤0.2wt% of raw material after drying.
4. being layered the preparation method of high-purity aircon refractory as described in claim 1, it is characterised in that: described is high-purity Zircon layer with a thickness of being layered the 0.9~0.1 of high-purity aircon refractory overall thickness.
5. being layered the preparation method of high-purity aircon refractory as described in claim 1, it is characterised in that: the layering Pressure >=200Mpa of the layering isostatic pressing of high-purity aircon refractory.
CN201610905862.8A 2016-10-18 2016-10-18 It is layered the preparation method of high-purity aircon refractory Active CN106518107B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610905862.8A CN106518107B (en) 2016-10-18 2016-10-18 It is layered the preparation method of high-purity aircon refractory

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610905862.8A CN106518107B (en) 2016-10-18 2016-10-18 It is layered the preparation method of high-purity aircon refractory

Publications (2)

Publication Number Publication Date
CN106518107A CN106518107A (en) 2017-03-22
CN106518107B true CN106518107B (en) 2019-06-21

Family

ID=58332530

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610905862.8A Active CN106518107B (en) 2016-10-18 2016-10-18 It is layered the preparation method of high-purity aircon refractory

Country Status (1)

Country Link
CN (1) CN106518107B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107117963B (en) * 2017-04-25 2020-09-18 山东君道高温材料有限公司 Manufacturing process of large-size and large-span zircon refractory material
CN116621578A (en) * 2023-04-26 2023-08-22 广州市石基耐火材料厂 Chromium-zirconium refractory material, preparation method thereof and chromium-zirconium electrode brick

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851107A (en) * 2010-05-06 2010-10-06 广州市石基耐火材料厂 Compact zircon brick with low alkali content, hole fusion rate and stress and manufacturing method thereof
CN102229500A (en) * 2010-07-27 2011-11-02 广州市石基耐火材料厂 Preparation method for compact zirconite overflow brick with high breaking-resistance and low expansion
CN102603329A (en) * 2012-03-23 2012-07-25 苏州罗卡节能科技有限公司 Double-layered light composite brick and preparation method thereof
CN105174979A (en) * 2015-08-21 2015-12-23 淄博裕民基诺新材料有限公司 Zircon/zirconia multiphase material based on zircon covered zirconium dioxide powder and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851107A (en) * 2010-05-06 2010-10-06 广州市石基耐火材料厂 Compact zircon brick with low alkali content, hole fusion rate and stress and manufacturing method thereof
CN102229500A (en) * 2010-07-27 2011-11-02 广州市石基耐火材料厂 Preparation method for compact zirconite overflow brick with high breaking-resistance and low expansion
CN102603329A (en) * 2012-03-23 2012-07-25 苏州罗卡节能科技有限公司 Double-layered light composite brick and preparation method thereof
CN105174979A (en) * 2015-08-21 2015-12-23 淄博裕民基诺新材料有限公司 Zircon/zirconia multiphase material based on zircon covered zirconium dioxide powder and preparation method thereof

Also Published As

Publication number Publication date
CN106518107A (en) 2017-03-22

Similar Documents

Publication Publication Date Title
KR102018937B1 (en) Pre-sintered blank for dental purposes
KR101524482B1 (en) Glass-ceramics or Lithium silicate glass for Zirconia overlaying materials and preparation method thereof
CN103709830B (en) Colored glaze mixed negative ion ink for ink-jet printing on ceramic and preparation method thereof
CN103242031B (en) Ceramic sanitary ware prepared from waste ceramic and preparation method thereof
CN102757222B (en) Composite stable microcrystal zirconium oxide ceramic mixed powder and manufacturing process
CN102795772B (en) Method for preparing microcrystalline glass from kaolin-type coal gangue or fly ash and carbide slag
CN103910489B (en) A kind of as the glass of dentistry facing porcelain, preparation method and its usage
CN106518107B (en) It is layered the preparation method of high-purity aircon refractory
Ren et al. The effects of pre-sintering temperature and La2O3 addition on sinterability and corrosion resistance of stoichiometric magnesium aluminate spinel
CN113816610A (en) Lithium silicate glass ceramic restoration and preparation method thereof
CN113845361A (en) High-performance alkaline special ceramic and preparation method thereof
CN105884200A (en) Method for producing microcrystalline glass-ceramic composite material from industrial fly ash and vitrification slag
CN107266069A (en) A kind of utilization glass dust permeates the preparation method of regenerating oxidation zirconium porous ceramics
CN113461336A (en) Lithium silicate glass ceramic for dentistry, preparation method thereof and lithium silicate glass ceramic restoration
CN114956566A (en) Overglaze, preparation method thereof and glazed tile
CN101973787A (en) Method for preparing split-phase coloring iron black glaze
US3929498A (en) Sintered zirconia bodies
CN101851107B (en) Compact zircon brick with low alkali content, hole fusion rate and stress and manufacturing method thereof
CN113135754A (en) Method for preparing gelled composite material with piezoelectric property, gelled composite material and application thereof
You et al. Effect of sintering time on crystal and structure of chlorine-containing low-titanium slag glass-ceramics
Chiang et al. High ionic conducting NaSICON enabled by mechanical activation enhanced reaction
Advocat et al. Melted synthetic zirconolite-based matrices: Effect of cooling rate and heat treatment on ceramic microstructure and chemical durability
CN101186489A (en) High antifouling ceramic tile and preparation method thereof
CN107973586A (en) Handle the method and Ceramic Tiles of ferrochrome slag
CN115028364A (en) Glass ceramic, preparation method thereof and tooth restoration material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant