CN107266035A - A kind of ceramic base heat accumulating using copper ashes as raw material and preparation method thereof - Google Patents
A kind of ceramic base heat accumulating using copper ashes as raw material and preparation method thereof Download PDFInfo
- Publication number
- CN107266035A CN107266035A CN201710619325.1A CN201710619325A CN107266035A CN 107266035 A CN107266035 A CN 107266035A CN 201710619325 A CN201710619325 A CN 201710619325A CN 107266035 A CN107266035 A CN 107266035A
- Authority
- CN
- China
- Prior art keywords
- raw material
- copper ashes
- ceramic base
- heat accumulating
- base heat
- 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.)
- Pending
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
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/132—Waste materials; Refuse; Residues
- C04B33/138—Waste materials; Refuse; Residues from metallurgical processes, e.g. slag, furnace dust, galvanic waste
-
- 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
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/1305—Organic additives
-
- 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
- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
- C04B33/131—Inorganic additives
-
- 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
- C04B2235/3201—Alkali metal oxides 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
- C04B2235/30—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
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3227—Lanthanum oxide 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
- C04B2235/30—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
- C04B2235/30—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
- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
-
- 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
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- 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
- C04B2235/40—Metallic constituents or additives not added as binding phase
-
- 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
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/402—Aluminium
-
- 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
- C04B2235/40—Metallic constituents or additives not added as binding phase
- C04B2235/407—Copper
-
- 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
- C04B2235/658—Atmosphere during thermal treatment
-
- 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
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- 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
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Abstract
The present invention relates to a kind of ceramic base heat accumulating using copper ashes as raw material and preparation method thereof.Its technical scheme is：First copper ashes, silicon-containing material, mantoquita, stabilizer and complexing agent are mixed, grinding obtains abrasive；The mantoquita, inorganic salts, aluminium powder, manganese powder and copper powder are mixed again, compressing, are heat-treated under the conditions of neutral atmosphere and 400 ~ 600 DEG C, ball milling, are dried, screening, obtain the screening material B that granularity is less than 0.088mm for 0.088 ~ 1mm screening material A and granularity.Then 20 ~ 50wt% abrasive, 10 ~ 30wt% screening material A, 20 ~ 40wt% screening material B and 5 ~ 10wt% inorganic salts are mixed, it is compressing, it is heat-treated under the conditions of neutral atmosphere and 400 ~ 600 DEG C, the ceramic base heat accumulating using copper ashes as raw material is made.Raw material sources of the present invention are wide, production cost is low and technique is simple, and the storage density of prepared ceramic base heat accumulating is big, thermal conductivity factor is big, compressive resistance is high and thermal shock resistance is high.
Description
Technical field
The invention belongs to ceramic base heat accumulating technical field.Specifically related to a kind of ceramic base heat accumulation using copper ashes as raw material
Material and preparation method thereof.
Background technology
Heat accumulating is the current more extensive new function material of application, be mainly used in industry it is remaining/Waste Heat Recovery utilizes,
The field such as solar energy composite exploitation and high-temperature energy-conservation.Mainly include two kinds of researching of sensible heat storage material and latent heat heat accumulating.Heat accumulation material
Material belongs to researching of sensible heat storage material, using refractory material as the main body for absorbing heat, because the absorption of heat is only by resistance to
The sensible heat of fiery material holds change, and this heat accumulating has that volume is big, cost is high, thermal inertia is big and power output is gradually reduced
Shortcoming.Latent heat formula heat accumulating then utilizes suction exothermic character of the phase change medium in phase transition process, with storage density is big, volume
The advantage such as small and transition temperature range is wide, is one of focus of heat memory technology research.
It is main at present that latent heat heat accumulating is prepared using mixed-sintering method and melting method of impregnation, all come with some shortcomings.
Mixed-sintering method is to mix matrix material, phase-change material and additive etc., is molded, and sintering obtains latent heat heat accumulating.The method
Though it is relatively easy, the drain evaporation of phase-change material can be caused when sintering temperature is too high or phase-change material content is larger, so that
Reduce the heat storage performance of material.For the loss in reduction phase-change material solid, liquid transition process, there is researcher to encapsulate phase-change material
In dedicated container, but the thermal resistance of material, reduction heat transfer efficiency, raising production cost can be increased.Melting infiltration rule needs advance
Porous ceramic film material is prepared, then liquid state phase change material is infiltrated up in porous ceramics hole, is cooled down, latent heat heat accumulation material is made
Material.Though this method can avoid phase-change material drain evaporation, sintering process bulk effect is reduced, previously prepared porous pottery is needed
Porcelain body, the content of phase-change material depends on the pore size and its distribution of porous ceramic preforms, and not only process is more multiple
It is miscellaneous, and cost of manufacture is high.In addition, it is stable also to there is higher mechanical strength, thermal conductivity factor and thermal shock in existing heat accumulating
The problem of performances such as property are low.
Copper ashes is the industrial solid castoff produced during Copper making, with quantity is big, fine size and wide variety etc.
Feature, main mineral constituent be copper in fayalite, magnetic iron ore and amorphous phase, copper ashes it is main with vitreous copper, metallic copper and
The forms such as cupric oxide are present, and the grade of iron is more than 40% in copper ashes, much larger than the average grade of iron ore 29.1%.It is substantial amounts of
Copper ashes is deposited in slag due to being difficult to effectively utilize, and not only land occupation but also environment has been polluted, while being also the huge wasting of resources.
How raising and the increasingly depleted of mineral resources with environmental protection requirement, reclaimed and provided using these valuable copper, iron etc.
Source tool is of great significance and considerable economic benefit.The production technology scheme carried out currently for copper ashes, generally
It is the filler as cement, devitrified glass or other products, the feature such as composition, structure not from copper ashes lacks
It is few that copper ashes resources advantage is made full use of.
The content of the invention
It is contemplated that overcoming the defect that prior art is present, it is therefore an objective to provide that a kind of raw material sources are wide, production cost is low
With the preparation method of the simple ceramic base heat accumulating by raw material of copper ashes of technique, prepared with this method using copper ashes as raw material
Ceramic base heat accumulating storage density it is big, thermal conductivity factor is big, compressive resistance is high and thermal shock resistance is high.
To achieve the above object, the technical solution adopted by the present invention is comprised the concrete steps that：
The first step, by 40 ~ 60wt% copper ashes, 20 ~ 40wt% silicon-containing material, 1 ~ 10wt% mantoquita, 0.1 ~ 10wt% stabilization
Agent and 10 ~ 30wt% complexing agent mixing, grind 0.5 ~ 2 hour, obtain abrasive at ambient temperature.
Second step, by the 20 ~ 40wt% mantoquita, 30 ~ 50wt% inorganic salts, 10 ~ 30wt% aluminium powder, 10 ~ 30wt%
Manganese powder and 10 ~ 30wt% copper powder be well mixed, it is compressing under the conditions of 50 ~ 100MPa, in neutral atmosphere and 400 ~ 600
Be heat-treated 0.5 ~ 3 hour, crush, ball milling under the conditions of DEG C, dry 12 hours under the conditions of 90 DEG C, screening, obtain granularity for 0.088 ~
1mm screening material A and granularity are less than 0.088mm screening material B.
3rd step, by the 20 ~ 50wt% abrasive, the 10 ~ 30wt% screening material A, 20 ~ 40wt% the sieve
Sub-material B and 5 ~ 10wt% inorganic salts are well mixed, compressing under the conditions of 10 ~ 30MPa, in neutral atmosphere and 400 ~
It is heat-treated 0.5 ~ 3 hour under the conditions of 600 DEG C, the ceramic base heat accumulating using copper ashes as raw material is made.
Fe in the copper ashes2O3Content is more than 30wt%, SiO2Content is more than 22wt%；The granularity of the copper ashes is less than
0.088mm。
The silicon-containing material is fused quartz or is konilite, the SiO in the fused quartz2Content is more than 99wt%, the powder
SiO in quartz2Content is more than 98wt%.The granularity of the silicon-containing material is less than 0.088mm.
The mantoquita is cupric sulfate pentahydrate or is nitrate trihydrate copper, and the purity of the mantoquita is more than 99wt%；The mantoquita
Granularity is less than 0.045mm.
The stabilizer is lanthana powder or is titanium dioxide zirconium powder, the La in the lanthana powder2O3Content is more than 99wt%,
ZrO in the titanium dioxide zirconium powder2Content is more than 99wt%；The granularity of the stabilizer is less than 0.01mm.
The complexing agent is anhydrous oxalic acid or is Citric Acid Mono, and the purity of the complexing agent is more than 99wt%.
The inorganic salts are sodium chloride or are potassium chloride, and the purity of the inorganic salts is more than 99wt%；The grain of the inorganic salts
Degree is less than 0.088mm.
Al content in the aluminium powder is more than 99wt%, and the granularity of the aluminium powder is less than 0.045mm.
Mn contents in the manganese powder are more than 99wt%, and the granularity of the manganese powder is less than 0.088mm.
Cu contents in the copper powder are more than 99wt%, and the granularity of the copper powder is less than 0.088mm.
The neutral atmosphere is nitrogen atmosphere or is argon gas atmosphere.
The ball milling is：The mass ratio of An Wu Liao ︰ zirconium oxide Mo Qiu ︰ absolute ethyl alcohols is the dispensings of 1 ︰, 10 ︰ 5, is put into ball grinder
In, ball milling 12 ~ 15 hours under conditions of 200r/min.
Due to using above-mentioned technical proposal, the present invention has following good effect compared with prior art：
(1) the present invention is based on high content phase-change material, composition, formation and the distribution of control structure material, adjustment structure
The high-temperature reactivity of material and phase-change material, the obtained ceramic base heat accumulating using copper ashes as raw material has larger heat accumulation
Density.
(2) the present invention realizes the micro Distribution of phase-change material using the formation feature of structural material, and control crystallite is in phase transformation material
Formation state in material adjusts the heat absorption, accumulation of heat and Heat transfer of material, thus the obtained ceramic base using copper ashes as raw material
Heat accumulating has higher thermal conductivity factor.
(3) the present invention is using the pyroreaction characteristic between different material, and formation refractoriness is high, compressive resistance is big, thermal expansion
Coefficient is low and the high matrix material of corrosion resistance, and the obtained ceramic base heat accumulating using copper ashes as raw material has higher resistance to
Compressive Strength and thermal shock resistance.
(4) the present invention controls preparation process substep, it is to avoid use high temperature according to the structure and performance characteristics of heat accumulating
The processes such as calcining, had both prevented the loss of phase-change material, the ingenious control of material structure and performance are realized again.Therefore, not only
The raw material sources used are extensive, and simple production process, production cost are low.
(5) the present invention solves the problem of accumulation is taken up an area and pollutes environment using copper ashes as raw material, not only, and turns waste into wealth, real
Synthetical recovery and the utilization of resource of tailings are showed；Meanwhile, using the copper contained in copper ashes, iron, silicon and other beneficiating ingredients, and
The part amorphous phase having in copper ashes, it is engaged with other raw materials, in heat treatment process, forms answering for the distribution that interweaves
Miscellaneous oxide grain, thus the obtained ceramic base heat accumulating using copper ashes as raw material has higher compressive resistance.
Ceramic base heat accumulating using copper ashes as raw material prepared by the present invention is after testing：Storage density is more than 800kJ/kg；
Thermal conductivity factor is more than 1.8W/ (mK)；Compressive resistance is more than 20MPa；Thermal shock resistance (1100 DEG C of water coolings)>20 times.
Therefore, the present invention have that raw material sources are wide, low production cost and the characteristics of simple technique, it is prepared using copper ashes as
The storage density of the ceramic base heat accumulating of raw material is big, thermal conductivity factor is big, compressive resistance is high and thermal shock resistance is high.
Embodiment
With reference to embodiment, the invention will be further described, not to the limitation of its protection domain.
It is first that the technical parameter Unify legislation involved by present embodiment is as follows to avoid repeating, in embodiment not
Repeat again：
Fe in the copper ashes2O3Content is more than 30wt%, SiO2Content is more than 22wt%；The granularity of the copper ashes is less than
0.088mm。
The silicon-containing material is fused quartz or is konilite, the SiO in the fused quartz2Content is more than 99wt%, the powder
SiO in quartz2Content is more than 98wt%.The granularity of the silicon-containing material is less than 0.088mm.
The mantoquita is cupric sulfate pentahydrate or is nitrate trihydrate copper, and the purity of the mantoquita is more than 99wt%；The mantoquita
Granularity is less than 0.045mm.
The stabilizer is lanthana powder or is titanium dioxide zirconium powder, the La in the lanthana powder2O3Content is more than 99wt%,
ZrO in the titanium dioxide zirconium powder2Content is more than 99wt%；The granularity of the stabilizer is less than 0.01mm.
The complexing agent is anhydrous oxalic acid or is Citric Acid Mono, and the purity of the complexing agent is more than 99wt%.
The inorganic salts are sodium chloride or are potassium chloride, and the purity of the inorganic salts is more than 99wt%；The grain of the inorganic salts
Degree is less than 0.088mm.
Al content in the aluminium powder is more than 99wt%, and the granularity of the aluminium powder is less than 0.045mm.
Mn contents in the manganese powder are more than 99wt%, and the granularity of the manganese powder is less than 0.088mm.
Cu contents in the copper powder are more than 99wt%, and the granularity of the copper powder is less than 0.088mm.
The ball milling is：The mass ratio of An Wu Liao ︰ zirconium oxide Mo Qiu ︰ absolute ethyl alcohols is the dispensings of 1 ︰, 10 ︰ 5, is put into ball grinder
In, ball milling 12 ~ 15 hours under conditions of 200r/min.
Embodiment 1
A kind of ceramic base heat accumulating using copper ashes as raw material and preparation method thereof.Preparation method is described in the present embodiment：
The first step, by 40 ~ 50wt% copper ashes, 30 ~ 40wt% konilite, 1 ~ 5wt% cupric sulfate pentahydrate, 0.1 ~ 1wt% oxygen
Change lanthanum powder and 10 ~ 20wt% Citric Acid Mono mixing, in being ground 0.5 ~ 2 hour under room temperature condition, produce abrasive.
Second step, by 20 ~ 30wt% nitrate trihydrate copper, 40 ~ 50wt% potassium chloride, 10 ~ 20wt% aluminium powder, 10 ~
20wt% manganese powder and 10 ~ 20wt% copper powder are well mixed, compressing under the conditions of 50 ~ 100MPa, in nitrogen atmosphere and 400
It is heat-treated 0.5 ~ 1.5 hour, crushes, ball milling under the conditions of ~ 600 DEG C, is dried 12 hours under the conditions of 90 DEG C, screening, obtaining granularity is
0.088 ~ 1mm screening material A and granularity are less than 0.088mm screening material B.
3rd step, by the 20 ~ 30wt% abrasive, the 20 ~ 30wt% screening material A, 30 ~ 40wt% the sieve
Sub-material B and 5 ~ 10wt% potassium chloride are well mixed, compressing under the conditions of 10 ~ 30MPa, in nitrogen atmosphere and 400 ~ 600 DEG C
Under the conditions of be heat-treated 0.5 ~ 1.5 hour, ceramic base heat accumulating using copper ashes as raw material is made.
Ceramic base heat accumulating manufactured in the present embodiment using copper ashes as raw material is after testing：Storage density is more than 820kJ/
kg；Thermal conductivity factor is more than 2W/ (mK)；Compressive resistance is more than 22MPa；Thermal shock resistance (1100 DEG C of water coolings)>20 times.
Embodiment 2
A kind of ceramic base heat accumulating using copper ashes as raw material and preparation method thereof.Preparation method is described in the present embodiment：
The first step, by 50 ~ 60wt% copper ashes, 20 ~ 30wt% fused quartz, 5 ~ 10wt% nitrate trihydrate copper, 1 ~ 5wt% dioxy
Change zirconium powder and 10 ~ 20wt% anhydrous oxalic acid mixing, in being ground 0.5 ~ 2 hour under room temperature condition, produce abrasive.
Second step, by 30 ~ 40wt% cupric sulfate pentahydrate, 30 ~ 40wt% sodium chloride, 10 ~ 20wt% aluminium powder, 10 ~
20wt% manganese powder and 10 ~ 20wt% copper powder are well mixed, compressing under the conditions of 50 ~ 100MPa, in argon gas atmosphere and 400
It is heat-treated 1.5 ~ 3 hours, crushes, ball milling under the conditions of ~ 600 DEG C, is dried 12 hours under the conditions of 90 DEG C, screening, obtaining granularity is
0.088 ~ 1mm screening material A and granularity are less than 0.088mm screening material B.
3rd step, by the 30 ~ 40wt% abrasive, the 20 ~ 30wt% screening material A, 20 ~ 30wt% the sieve
Sub-material B and 5 ~ 10wt% sodium chloride are well mixed, compressing under the conditions of 10 ~ 30MPa, in argon gas atmosphere and 400 ~ 600 DEG C
Under the conditions of be heat-treated 1.5 ~ 3 hours, ceramic base heat accumulating using copper ashes as raw material is made.
Ceramic base heat accumulating manufactured in the present embodiment using copper ashes as raw material is after testing：Storage density is more than 900kJ/
kg；Thermal conductivity factor is more than 2W/ (mK)；Compressive resistance is more than 20MPa；Thermal shock resistance (1100 DEG C of water coolings)>20 times.
Embodiment 3
A kind of ceramic base heat accumulating using copper ashes as raw material and preparation method thereof.Preparation method is described in the present embodiment：
The first step, by 40 ~ 50wt% copper ashes, 20 ~ 30wt% fused quartz, 1 ~ 5wt% nitrate trihydrate copper, 5 ~ 10wt% dioxy
Change zirconium powder and 20 ~ 30wt% anhydrous oxalic acid mixing, in being ground 0.5 ~ 2 hour under room temperature condition, produce abrasive.
Second step, by 20 ~ 30wt% cupric sulfate pentahydrate, 30 ~ 40wt% potassium chloride, 20 ~ 30wt% aluminium powder, 10 ~
20wt% manganese powder and 10 ~ 20wt% copper powder are well mixed, compressing under the conditions of 50 ~ 100MPa, in nitrogen atmosphere and 400
It is heat-treated 2 ~ 3 hours, crushes, ball milling under the conditions of ~ 600 DEG C, is dried 12 hours under the conditions of 90 DEG C, screening, it is 0.088 to obtain granularity
~ 1mm screening material A and granularity are less than 0.088mm screening material B.
3rd step, by the 40 ~ 50wt% abrasive, the 10 ~ 20wt% screening material A, 20 ~ 30wt% the sieve
Sub-material B and 5 ~ 10wt% potassium chloride are well mixed, compressing under the conditions of 10 ~ 30MPa, in nitrogen atmosphere and 400 ~ 600 DEG C
Under the conditions of be heat-treated 2 ~ 3 hours, ceramic base heat accumulating using copper ashes as raw material is made.
Ceramic base heat accumulating manufactured in the present embodiment using copper ashes as raw material is after testing：Storage density is more than 800kJ/
kg；Thermal conductivity factor is more than 1.8W/ (mK)；Compressive resistance is more than 20MPa；Thermal shock resistance (1100 DEG C of water coolings)>20 times.
Embodiment 4
A kind of ceramic base heat accumulating using copper ashes as raw material and preparation method thereof.Preparation method is described in the present embodiment：
The first step, by 50 ~ 60wt% copper ashes, 20 ~ 30wt% konilite, 5 ~ 10wt% cupric sulfate pentahydrate, 1 ~ 5wt% oxidation
Lanthanum powder and 10 ~ 20wt% Citric Acid Mono mixing, in being ground 0.5 ~ 2 hour under room temperature condition, produce abrasive.
Second step, by 20 ~ 30wt% cupric sulfate pentahydrate, 30 ~ 40wt% potassium chloride, 10 ~ 20wt% aluminium powder, 20 ~
30wt% manganese powder and 10 ~ 20wt% copper powder are well mixed, compressing under the conditions of 50 ~ 100MPa, in argon gas atmosphere and 400
It is heat-treated 1 ~ 2 hour, crushes, ball milling under the conditions of ~ 600 DEG C, is dried 12 hours under the conditions of 90 DEG C, screening, it is 0.088 to obtain granularity
~ 1mm screening material A and granularity are less than 0.088mm screening material B.
3rd step, by the 40 ~ 50wt% abrasive, the 10 ~ 20wt% screening material A, 20 ~ 30wt% the sieve
Sub-material B and 5 ~ 10wt% potassium chloride are well mixed, compressing under the conditions of 10 ~ 30MPa, in argon gas atmosphere and 400 ~ 600 DEG C
Under the conditions of be heat-treated 1 ~ 2 hour, ceramic base heat accumulating using copper ashes as raw material is made.
Ceramic base heat accumulating manufactured in the present embodiment using copper ashes as raw material is after testing：Storage density is more than 850kJ/
kg；Thermal conductivity factor is more than 1.9W/ (mK)；Compressive resistance is more than 20MPa；Thermal shock resistance (1100 DEG C of water coolings)>20 times.
Embodiment 5
A kind of ceramic base heat accumulating using copper ashes as raw material and preparation method thereof.Preparation method is described in the present embodiment：
The first step, by 50 ~ 60wt% copper ashes, 20 ~ 30wt% konilite, 5 ~ 10wt% cupric sulfate pentahydrate, 1 ~ 5wt% oxidation
Lanthanum powder and 10 ~ 20wt% Citric Acid Mono mixing, in being ground 0.5 ~ 2 hour under room temperature condition, produce abrasive.
Second step, by 20 ~ 30wt% cupric sulfate pentahydrate, 30 ~ 40wt% potassium chloride, 10 ~ 20wt% aluminium powder, 10 ~
20wt% manganese powder and 20 ~ 30wt% copper powder are well mixed, compressing under the conditions of 50 ~ 100MPa, in nitrogen atmosphere and 400
It is heat-treated 1 ~ 2 hour, crushes, ball milling under the conditions of ~ 600 DEG C, is dried 12 hours under the conditions of 90 DEG C, screening, it is 0.088 to obtain granularity
~ 1mm screening material A and granularity are less than 0.088mm screening material B.
3rd step, by the 30 ~ 40wt% abrasive, the 20 ~ 30wt% screening material A, 20 ~ 30wt% the sieve
Sub-material B and 5 ~ 10wt% sodium chloride are well mixed, compressing under the conditions of 10 ~ 30MPa, in nitrogen atmosphere and 400 ~ 600 DEG C
Under the conditions of be heat-treated 1 ~ 2 hour, ceramic base heat accumulating using copper ashes as raw material is made.
Ceramic base heat accumulating manufactured in the present embodiment using copper ashes as raw material is after testing：Storage density is more than 850kJ/
kg；Thermal conductivity factor is more than 2W/ (mK)；Compressive resistance is more than 22MPa；Thermal shock resistance (1100 DEG C of water coolings)>20 times.
Present embodiment has following good effect compared with prior art：
(1) present embodiment is based on high content phase-change material, composition, formation and the distribution of control structure material,
The high-temperature reactivity of adjustment structure material and phase-change material, the obtained ceramic base heat accumulating using copper ashes as raw material have compared with
Big storage density.
(2) present embodiment realizes the micro Distribution of phase-change material using the formation feature of structural material, controls crystallite
Formation state in phase-change material adjusts the heat absorption, accumulation of heat and Heat transfer of material, thus obtained using copper ashes as raw material
Ceramic base heat accumulating have higher thermal conductivity factor.
(3) present embodiment utilizes the pyroreaction characteristic between different material, forms refractoriness height, compressive resistance
Greatly, the matrix material that thermal coefficient of expansion is low and corrosion resistance is high, the obtained ceramic base heat accumulating tool using copper ashes as raw material
There are higher compressive resistance and thermal shock resistance.
(4) present embodiment controls preparation process substep according to the structure and performance characteristics of heat accumulating, it is to avoid
Using processes such as high-temperature calcinations, the loss of phase-change material was both prevented, the ingenious control of material structure and performance is realized again.Cause
This, the raw material sources not only used are extensive, and simple production process, production cost are low.
(5) present embodiment solves the problem of accumulation is taken up an area and pollutes environment, Er Qiebian using copper ashes as raw material, not only
Waste be changed into values, realizes synthetical recovery and the utilization of resource of tailings；Meanwhile, using the copper contained in copper ashes, iron, silicon and other are beneficial
The part amorphous phase having in composition, and copper ashes, it is engaged with other raw materials, in heat treatment process, is formed and handed over
Knit the complex oxide crystal grain of distribution, thus the obtained ceramic base heat accumulating using copper ashes as raw material have it is higher pressure-resistant
Intensity.
Ceramic base heat accumulating using copper ashes as raw material prepared by present embodiment is after testing：Storage density is more than
800kJ/kg；Thermal conductivity factor is more than 1.8W/ (mK)；Compressive resistance is more than 20MPa；Thermal shock resistance (1100 DEG C of water coolings)>20
It is secondary.
Therefore, the characteristics of present embodiment has wide raw material sources, low production cost and simple technique, it is prepared
The storage density of ceramic base heat accumulating by raw material of copper ashes is big, thermal conductivity factor is big, compressive resistance is high and thermal shock resistance is high.
Claims (13)
1. a kind of preparation method of ceramic base heat accumulating using copper ashes as raw material, it is characterised in that the preparation method is：
The first step, by 40 ~ 60wt% copper ashes, 20 ~ 40wt% silicon-containing material, 1 ~ 10wt% mantoquita, 0.1 ~ 10wt% stabilization
Agent and 10 ~ 30wt% complexing agent mixing, grind 0.5 ~ 2 hour, obtain abrasive at ambient temperature；
Second step, by the 20 ~ 40wt% mantoquita, 30 ~ 50wt% inorganic salts, 10 ~ 30wt% aluminium powder, 10 ~ 30wt% manganese
Powder and 10 ~ 30wt% copper powder are well mixed, compressing under the conditions of 50 ~ 100MPa, in neutral atmosphere and 400 ~ 600 DEG C of bars
It is heat-treated 0.5 ~ 3 hour, crushes, ball milling under part, is dried 12 hours under the conditions of 90 DEG C, screening, it is 0.088 ~ 1mm's to obtain granularity
Screening material A and granularity are less than 0.088mm screening material B；
3rd step, by the 20 ~ 50wt% abrasive, the 10 ~ 30wt% screening material A, 20 ~ 40wt% the screening material B
It is well mixed with the 5 ~ 10wt% inorganic salts, it is compressing under the conditions of 10 ~ 30MPa, in neutral atmosphere and 400 ~ 600 DEG C
Under the conditions of be heat-treated 0.5 ~ 3 hour, ceramic base heat accumulating using copper ashes as raw material is made.
2. the preparation method of the ceramic base heat accumulating according to claim 1 using copper ashes as raw material, it is characterised in that institute
State the Fe in copper ashes2O3Content is more than 30wt%, SiO2Content is more than 22wt%；The granularity of the copper ashes is less than 0.088mm.
3. the preparation method of the ceramic base heat accumulating according to claim 1 using copper ashes as raw material, it is characterised in that institute
State silicon-containing material to be fused quartz or be konilite, the SiO in the fused quartz2Content is more than in 99wt%, the konilite
SiO2Content is more than 98wt%；The granularity of the silicon-containing material is less than 0.088mm.
4. the preparation method of the ceramic base heat accumulating according to claim 1 using copper ashes as raw material, it is characterised in that institute
State mantoquita to be cupric sulfate pentahydrate or be nitrate trihydrate copper, the purity of the mantoquita is more than 99wt%；The granularity of the mantoquita is less than
0.045mm。
5. the preparation method of the ceramic base heat accumulating according to claim 1 using copper ashes as raw material, it is characterised in that institute
State stabilizer to be lanthana powder or be titanium dioxide zirconium powder, the La in the lanthana powder2O3Content is more than 99wt%, the titanium dioxide
ZrO in zirconium powder2Content is more than 99wt%；The granularity of the stabilizer is less than 0.01mm.
6. the preparation method of the ceramic base heat accumulating according to claim 1 using copper ashes as raw material, it is characterised in that institute
State complexing agent to be anhydrous oxalic acid or be Citric Acid Mono, the purity of the complexing agent is more than 99wt%.
7. the preparation method of the ceramic base heat accumulating according to claim 1 using copper ashes as raw material, it is characterised in that institute
State inorganic salts to be sodium chloride or be potassium chloride, the purity of the inorganic salts is more than 99wt%；The granularity of the inorganic salts is less than
0.088mm。
8. the preparation method of the ceramic base heat accumulating according to claim 1 using copper ashes as raw material, it is characterised in that institute
State the Al content in aluminium powder and be more than 99wt%, the granularity of the aluminium powder is less than 0.045mm.
9. the preparation method of the ceramic base heat accumulating according to claim 1 using copper ashes as raw material, it is characterised in that institute
State the Mn contents in manganese powder and be more than 99wt%, the granularity of the manganese powder is less than 0.088mm.
10. the preparation method of the ceramic base heat accumulating according to claim 1 using copper ashes as raw material, it is characterised in that institute
State the Cu contents in copper powder and be more than 99wt%, the granularity of the copper powder is less than 0.088mm.
11. the preparation method of the ceramic base heat accumulating according to claim 1 using copper ashes as raw material, it is characterised in that institute
Neutral atmosphere is stated to be nitrogen atmosphere or be argon gas atmosphere.
12. the preparation method of the ceramic base heat accumulating according to claim 1 using copper ashes as raw material, it is characterised in that institute
Stating ball milling is：The mass ratio of An Wu Liao ︰ zirconium oxide Mo Qiu ︰ absolute ethyl alcohols is the dispensings of 1 ︰, 10 ︰ 5, is put into ball grinder, in 200r/
Ball milling 12 ~ 15 hours under conditions of min.
13. a kind of ceramic base heat accumulating using copper ashes as raw material, it is characterised in that the ceramic base using copper ashes as raw material
Heat accumulating is the preparation side of the ceramic base heat accumulating by raw material of copper ashes according to any one of claim 1 ~ 12
The ceramic base heat accumulating using copper ashes as raw material prepared by method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710619325.1A CN107266035A (en) | 2017-07-26 | 2017-07-26 | A kind of ceramic base heat accumulating using copper ashes as raw material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710619325.1A CN107266035A (en) | 2017-07-26 | 2017-07-26 | A kind of ceramic base heat accumulating using copper ashes as raw material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107266035A true CN107266035A (en) | 2017-10-20 |
Family
ID=60079628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710619325.1A Pending CN107266035A (en) | 2017-07-26 | 2017-07-26 | A kind of ceramic base heat accumulating using copper ashes as raw material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107266035A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181655A (en) * | 2018-09-29 | 2019-01-11 | 辽宁中镁高温材料有限公司 | The formula and preparation method of a kind of hot enhanced physical properties of iron ore for high temperature heat accumulation |
| CN109609099A (en) * | 2018-12-24 | 2019-04-12 | 江苏嘉耐高温材料有限公司 | A kind of high-temperature phase-change heat storage material |
| CN113845308A (en) * | 2021-11-12 | 2021-12-28 | 武汉科技大学 | Preparation method of low-cost microcrystalline glass |
| CN115386345A (en) * | 2022-07-18 | 2022-11-25 | 武汉科技大学 | Composite shell phase-change heat storage ball based on copper slag and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585775A (en) * | 2012-01-20 | 2012-07-18 | 中国科学院过程工程研究所 | High-temperature composite phase change heat storage material and preparation method thereof |
-
2017
- 2017-07-26 CN CN201710619325.1A patent/CN107266035A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585775A (en) * | 2012-01-20 | 2012-07-18 | 中国科学院过程工程研究所 | High-temperature composite phase change heat storage material and preparation method thereof |
Non-Patent Citations (9)
| Title |
|---|
| 中华人民共和国国家质量监督检验检疫总局、中国国家标准化管理委员会: "《GB/T 30873-2014中华人民共和国国家标准 耐火材料 抗热震性试验方法》", 31 August 2014, 中国标准出版社 * |
| 中华人民共和国国家质量监督检验检疫总局、中国国家标准化管理委员会: "《GB/T 5072-2008中华人民共和国国家标准 耐火材料 常温耐压强度试验方法》", 30 September 2008, 中国标准出版社 * |
| 中国材料研究学会: "《96中国材料研讨会论文集II 材料设计与加工2 高性能复合材料》", 30 November 1997, 化学工业出版社 * |
| 冷光辉等: "封装PCM 陶瓷储热材料的性能", 《储能科学与技术》 * |
| 王如竹等: "《绿色建筑能源***》", 31 October 2013, 上海交通大学出版社 * |
| 王沛等: "《中药制药工程原理与设备》", 31 August 2016, 中国中医药出版社 * |
| 葛海鹏: "利用工业废渣制备太阳能蓄热材料的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 邵安林: "《鞍钢矿业铁矿资源发展战略的实践与思考》", 30 June 2012, 冶金工业出版社 * |
| 马伟明: "《氧化物陶瓷刀具与仿真切削》", 31 October 2014, 冶金工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181655A (en) * | 2018-09-29 | 2019-01-11 | 辽宁中镁高温材料有限公司 | The formula and preparation method of a kind of hot enhanced physical properties of iron ore for high temperature heat accumulation |
| CN109609099A (en) * | 2018-12-24 | 2019-04-12 | 江苏嘉耐高温材料有限公司 | A kind of high-temperature phase-change heat storage material |
| CN109609099B (en) * | 2018-12-24 | 2020-12-01 | 江苏嘉耐高温材料股份有限公司 | High-temperature phase-change heat storage material |
| CN113845308A (en) * | 2021-11-12 | 2021-12-28 | 武汉科技大学 | Preparation method of low-cost microcrystalline glass |
| CN113845308B (en) * | 2021-11-12 | 2023-08-11 | 武汉科技大学 | Preparation method of low-cost glass ceramic |
| CN115386345A (en) * | 2022-07-18 | 2022-11-25 | 武汉科技大学 | Composite shell phase-change heat storage ball based on copper slag and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Temuujin et al. | Effect of mechanical activation of fly ash on the properties of geopolymer cured at ambient temperature | |
| CN107266035A (en) | A kind of ceramic base heat accumulating using copper ashes as raw material and preparation method thereof | |
| CN107266050A (en) | A kind of ceramic base high-temperature heat-storage material and preparation method thereof | |
| CN110511053A (en) | A kind of foamed ceramic and preparation method thereof using ceramics squeezing mud production | |
| Ren et al. | Recycling of solid wastes ferrochromium slag for preparation of eco-friendly high-strength spinel–corundum ceramics | |
| CN103626510A (en) | Method for preparing magnesium borate whisker porous ceramic by employing in-situ growth | |
| Badiee et al. | Use of Iranian steel slag for production of ceramic floor tiles | |
| CN103553647A (en) | Method for preparation of silicon nitride bonded silicon carbide refractory material by using silicon cutting waste mortar | |
| CN112876214B (en) | Microcrystalline foamed ceramic and preparation method and application thereof | |
| CN106430981A (en) | Cordierite-based glass ceramics containing modified fly ash and preparation process thereof | |
| CN104446363A (en) | Method of preparing ceramsite from manganese carbonate residues | |
| CN109609099B (en) | High-temperature phase-change heat storage material | |
| CN107324798A (en) | A kind of ceramic base heat accumulating and preparation method thereof | |
| CN108083644B (en) | A method of devitrified glass is prepared using molten blast furnace slag | |
| CN110526719A (en) | Low thermally conductive foamed ceramic of one kind and preparation method thereof | |
| CN107286914A (en) | A kind of ceramic base heat accumulating based on iron tailings and preparation method thereof | |
| Bateni et al. | Effect of soda-lime-silica glass addition on the physical properties of ceramic obtained from white rice husk ash | |
| CN113896517B (en) | Method for preparing mullite-corundum complex-phase ceramic by using bauxite clinker waste | |
| CN110143770B (en) | Preparation method of in-situ-discharged slag ternary composite inorganic cementing material | |
| CN109628068B (en) | Phase-change heat storage material | |
| CN110204312A (en) | A kind of preparation method of ferronickel dregs porcelain granule | |
| CN110511052A (en) | A kind of foamed ceramic and preparation method thereof using the production of steel plant's tailings | |
| CN107188534B (en) | Method for preparing integrated wall material by using ceramic slag and monocrystalline silicon grinding and polishing waste materials | |
| CN109437866A (en) | A kind of corundum-mullite matter heat-barrier material and preparation method thereof | |
| CN104692784A (en) | Method for preparing cordierite ceramic from manganese slag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171020 |