CN110002867A - A kind of green is zirconia ceramics and preparation method thereof - Google Patents
A kind of green is zirconia ceramics and preparation method thereof Download PDFInfo
- Publication number
- CN110002867A CN110002867A CN201910321422.1A CN201910321422A CN110002867A CN 110002867 A CN110002867 A CN 110002867A CN 201910321422 A CN201910321422 A CN 201910321422A CN 110002867 A CN110002867 A CN 110002867A
- Authority
- CN
- China
- Prior art keywords
- green
- colorant
- zirconium
- zirconia ceramics
- cobalt
- 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
- 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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
-
- 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
-
- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
-
- 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
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
-
- 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
- C04B2235/3239—Vanadium oxides, vanadates or oxide forming salts thereof, e.g. magnesium vanadate
-
- 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
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
-
- 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
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/443—Nitrates or nitrites
-
- 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
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
-
- 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
- C04B2235/9646—Optical properties
- C04B2235/9661—Colour
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
It is zirconia ceramics and preparation method thereof the invention discloses a kind of green, belongs to ceramic material field.The present invention uses coprecipitation technology to prepare zirconium hydroxide presoma first, the metal salt of vanadium, cobalt, aluminium is then added in presoma, it dries and prepares the zirconium oxide pelletizing containing vanadium pentoxide and cobalt aluminate after being sintered, powder prepares the zirconia ceramics of green after forming and sintering.By adjusting the content and ratio of colorant in Zirconium powder (vanadium pentoxide and cobalt aluminate), the coloration of adjustable zirconia ceramics green.The problem of present invention solves the problems, such as the uniform dispersity that the mode of existing physical mixed colorant causes colorant that crystallite dimension is not achieved, and the mode of co-precipitation addition colorant is easy to cause metal salt that cannot precipitate completely.
Description
Technical field
The present invention relates to a kind of easy zirconia ceramics color methods, and being used to prepare a kind of green is zirconium oxide pottery
Porcelain belongs to field of ceramic material preparation.
Background technique
Zirconia material is since with high-melting-point, higher boiling, high intensity, high temperature resistant, wearability be good and corrosion resistance
The advantages such as excellent are widely used in structural ceramics (such as bearing, valve, cutter and grinding-material), (such as oxygen passes function ceramics
Sensor, solid oxide fuel cell, mobile phone dorsal shield and artificial tooth etc.), the fields such as super toughening ceramic and zirconium cerium eutectic.With
The arriving of 5G communication era is limited by 5G communication wavelengths, and use of traditional metal material in 3C appearance member is restricted, and
Application of the zirconia ceramics material of coloring in the field 3C becomes larger.
Traditional zirconia ceramics material coloring is broadly divided into two major classes: first is that being mixed into coloring powder in Zirconium powder
And the mode Jing Guo physical mixed carries out mixing；Second is that introducing colorant salt in the incipient stage of Zirconium powder preparation, passing through
Co-precipitation mode mixes colorant with Zirconium powder.Such as patent CN201810390477, first kind mode is generally deposited
It is inhomogenous in colorant mixing, the problems such as zirconia sintered body is reduced there are color difference and mechanical property.Such as patent
CN201810523722, the second class mode preparation process is complex, furthermore tends not to realize the common heavy of colorant element
It forms sediment, and then causes to propose wastewater treatment containing a large amount of metal ion in waste water and be relatively strict with.Therefore, traditional stains
There are complex process, ceramic performances to be deteriorated for mode, pollutes the problems such as larger.
Traditional zirconium oxide green colourant is nickel oxide or magnesium oxide-nickel series oxide, shows green or emerald green,
Color is more single, is not able to satisfy 3C appearance member and requires the complexity of color.
Summary of the invention
In order to solve existing zirconia ceramics coloring mode and green is the problems such as color is single, the present invention proposes a kind of green
Colour system zirconia ceramics and preparation method.
To achieve the above object, the technical solution adopted by the present invention are as follows:
It is zirconia ceramics that the present invention, which provides a kind of green, and composition includes the colorant of 1-5wt%, the colorant group
As vanadium pentoxide (V2O5) and cobalt aluminate (CoAl2O4)；Vanadium pentoxide mass percentage in the preferably described colorant
For 10-90wt%.
In the present invention, the green is that the SCI chromatic value of zirconia ceramics is 45≤L≤90, -69≤a≤- 13, -9≤b
≤ 58, it may be implemented to match from yellow green to glaucous wide colour gamut green hue.
Green of the present invention is zirconia ceramics, using vanadium cobalt aluminium salt as novel green colorant, with colorant content
It is increased to 5wt% from 1wt%, green is gradually deepened.Colorant content is lower than 1wt%, and coloring effect is unobvious, colorant content
Higher than 5wt%, ceramic mechanical performance reduces obvious.Colorant of the present invention can heatproof to 1500 DEG C, be higher than 1500 DEG C, color meeting
There is slight volatilization.
Green of the present invention is zirconia ceramics, and the ratio by adjusting vanadic salts and cobalt aluminium salt may be implemented from yellow green to indigo plant
The green of green wider range is color adjustment.In colorant, when component vanadium pentoxide and cobalt aluminate ratio are 9:1, oxygen
Change zircon ceramic and yellow green is presented.In colorant, when component vanadium pentoxide and cobalt aluminate ratio are 1:1, zirconia ceramics is in
It is existing emerald green.In colorant, when component vanadium pentoxide and cobalt aluminate ratio are 1:9, blue-green is presented in zirconia ceramics.
The present invention also provides the preparation method that a kind of green is zirconia ceramics, step includes:
1) zirconium hydroxide precursor pulp is prepared using coprecipitation method；
2) water-soluble vanadic salts, cobalt salt and aluminium salt are added in the zirconium hydroxide precursor pulp of step 1), then passes through
Zirconium hydroxide powder is prepared in drying, and wherein vanadic salts, cobalt salt and aluminium salt are uniformly dispersed in zirconium hydroxide powder；
3) by step 2) zirconium hydroxide powder after high temperature sintering, the zirconium oxide containing vanadium pentoxide and cobalt aluminate is obtained
Solid-solution powder, powder add binder after being sanded, and mist projection granulating obtains colored zirconium oxide pelletizing；
4) by the colored zirconium oxide pelletizing compression moulding of step 3), high temperature sintering, obtained green is zirconia ceramics.
As preferred embodiment, step 1) coprecipitation method prepares zirconium hydroxide precursor pulp, specifically: by ammonia
Water is added in the aqueous solution of zirconium oxychloride, yttrium chloride, adjusts pH value, stirring ageing, and filtration washing obtains filter cake, then by filter cake
It is added in water (preferably deionized water), high speed dispersion mashing obtains zirconium hydroxide precursor pulp；
In the step 1) above method of the present invention, the ammonia concn is 1-14mol/L, preferably 7mol/L, system pH
Value is adjusted to 8-10；The zirconium oxychloride, yttrium chloride aqueous solution in, the concentration of zirconium oxychloride is 0.1-1.5mol/L, chlorination
The concentration 0.006-0.24mol/L of yttrium；Ageing is stirred in reaction process, mixing speed is preferably 200rpm, and digestion time is
0.5-6h, preferably 2h；The speed of zirconium hydroxide presoma high speed dispersion mashing is preferably 300rpm.In embodiments of the present invention,
The method that filtration washing uses for, the reaction solution after ageing is poured into Buchner funnel and is filtered, deionized water wash to filtrate with
The reaction of 0.1mol/L silver nitrate solution does not become cloudy.
The mass percent of zirconium hydroxide is 5-10wt% in the zirconium hydroxide precursor pulp.
In the above-mentioned preparation method step 2) of the present invention, the dry preferably spray drying is spray-dried inlet temperature
200-300℃；
The vanadic salts be ammonium metavanadate and/or sodium metavanadate, the aluminium salt be aluminum nitrate and/or aluminium chloride, it is described
Cobalt salt be cobalt nitrate and/or cobalt chloride；
It is respectively 0.58- that the concentration range of vanadic salts, cobalt salt and aluminium salt is added in the zirconium hydroxide precursor pulp
54.9mmol/L, 0.3-28.3mmol/L, 0.6-56.5mmol/L.
In the above-mentioned preparation method step 3) of the present invention, the high temperature sintering temperature is 800-1100 DEG C, and sintering time is
1-4h, preferably 2h；
Described be sanded is handled using horizontal sand mill, it is preferable that by the Zirconium powder containing colorant before sanded treatment
Be configured to slurry (such as water slurry of 50wt% solid content), be sanded to 0.6 μm of D50 < of slurry, the mist projection granulating use from
The D50 of core type sponging granulator, pelletizing is advisable between 50-70 μm.
The binder is polyvinyl alcohol or polymethyl methacrylate, and additive amount is material (i.e. zirconia powder after being sanded
Body prepare slurry) gross mass 1-2wt%.
In the zirconia solid solution powder of step 3) preparation, the colorant for being 1-5wt% comprising mass percentage, coloring
Agent group becomes vanadium pentoxide (V2O5)With cobalt aluminate (CoAl2O4), wherein vanadium pentoxide accounts for the mass percentage of colorant
For 10-90wt%, the mass percentage that cobalt aluminate accounts for colorant is 10-90wt%.By adjusting middle coloring in preparation process
Vanadium pentoxide and cobalt aluminate ratio in the content and colorant of agent, the coloration of adjustable zirconia ceramics green.
In the above-mentioned preparation method step 4) of the present invention, during colored zirconium oxide pelletizing compression moulding, pressure (i.e. embryo
Pressure suffered by body stress surface) it is 100-120MPa (gauge pressure)；
The high temperature sintering temperature is 1350-1500 DEG C, sintering time 1-4h, preferably 2h, in sintering process organically
Binder component volatilizees completely, and colored zirconium oxide pelletizing is converted into ceramics.
Green provided by the invention is zirconia ceramics preparation method, using first preparing zirconium hydroxide presoma, after
The method preparation coloring powder of colorant metal water soluble salt is added in precursor pulp, solves existing physical mixed colorant
The problem of mode causes colorant that the uniform dispersity of crystallite dimension is not achieved, and co-precipitation mode add being easy for colorant
The problem of causing metal salt that cannot precipitate completely.This method can be realized effectively on colorant and zirconia material crystal particle scale
Uniform mixing, while avoiding coloring metal salt and cannot precipitate caused waste water pollution problem completely.
Green system of the present invention zirconia ceramics, due to Y3+With Zr4+Ionic radius it is approximate, Y3+Oxygen element can be replaced
Substitution solid solution is formed, changes internal crystal structure, forms metastable tetragonal phase, play tetragonal phase of zirconia crystal form ambient-temp-stable
Effect.The group of green colourant becomes vanadium pentoxide (V2O5) and cobalt aluminate (CoAl2O4), content 1-5wt% is high
V under conditions of temperature sintering5+With Co3+Formation color development solid solution in the lattice of zirconium oxide is entered, green coloring purpose is reached.Together
When, this green coloring technique is equally applicable in other colour systems or the stable zirconia ceramics of non-oxide yttrium.
Compared with prior art the present invention has the advantage that
1, the present invention in zirconium hydroxide precursor pulp using being added colorant, after mixing evenly, drying and calcining
Mode obtain coloring powder, compared with the mode of traditional colorant physical blending, this method have simple process, Ke Yishi
Existing colorant is mixed with uniform on zirconia material crystal particle scale, and colorant addition manner is simple, and colorant and zirconium oxide mix
Close excellent effect；
2, the colorant addition manner that the present invention uses avoids compared with the salt that colorant is added in initial reaction solution
The metal salt of different colorant causes a large amount of metal ion cannot to precipitate completely since precipitating pH is different, caused by former material
Material waste and brine waste are led to the problem of；
3, the present invention can not only reach using the mixed component of vanadium pentoxide and cobalt aluminate as high temperature green colourant
The coloring effect of conventional oxidation nickel colorant, and by adjusting the ratio and content of vanadium pentoxide and cobalt aluminate, Ke Yishi
Now match from yellow green to glaucous wide colour gamut green hue.
Specific implementation method
Below with reference to specific embodiment, the following further describes the technical solution of the present invention, and embodiment gives specifically
Embodiment and specific operating process, but protection scope of the present invention is not limited to following embodiments.
Embodiment and comparative example raw material is as follows:
Embodiment and comparative example primary raw material source
The color of zirconia ceramics carries out reference using Pantone colour atla after sintering, and ceramic SCI coloration takes color difference meter
It is tested (Japanese Minolta color difference meter, CM2600D), ceramic three-point bending resistance strength test uses universal testing machine
(INSTRON 5969)。
Embodiment 1
1) prepare zirconium hydroxide precursor pulp: the yttrium chloride solution of zirconium oxychloride and 0.006M with 0.1M adds ammonia
Water (concentration 1mol/L) adjusts pH=8, and 200rpm stirring is aged 0.5 hour.Reaction emulsion after ageing is poured into Bu Shi leakage
It is filtered in bucket, deionized water washing, until washing filtrate is reacted with 0.1mol/L silver nitrate solution and do not become cloudy.Filter cake is taken out,
Add water 300rpm to stir, be dispersed into zirconium hydroxide precursor pulp (wherein the content of zirconium hydroxide is 5wt%).
2) ammonium metavanadate (5.22mmol/L), cobalt nitrate (0.3mmol/L), aluminum nitrate (0.6mmol/L) are added to hydrogen
It in zirconium oxide precursor pulp, stirs evenly, slurry spray drying, dry inlet temperature is 200 DEG C, obtains zirconium hydroxide powder.
3) 800 DEG C of zirconium hydroxide powder calcining 1h obtain the Zirconium powder containing colorant, and the group of colorant becomes five
Two alum and cobalt aluminate are aoxidized, the two accounts for the 0.9wt% and 0.1wt% of Zirconium powder respectively.Then, by the oxygen containing colorant
Change the water slurry that zirconium powder body is made into 50% solid content, the polyvinyl alcohol of 1wt% is added, after broken 0.6 μm of D50 < is sanded, uses
Atomizer pelletizer mist projection granulating, pelletizing D50 are 50-70 μm.
4) pelletizing obtained does compression moulding through 100MPa (gauge pressure), and 1350 DEG C of sintering 1h obtain yellow green zirconium oxide
Ceramics, wherein the colorant containing 1wt%, vanadium pentoxide and cobalt aluminate 9:1 in colorant.Ceramic surface is through sanding and polishing
Afterwards, the SCI chromatic value that uniform yellow green color ceramics are presented is L=90, a=-13, b=58, ceramic three-point bending resistance intensity
For 1000MPa.
Embodiment 2
1) yttrium chloride solution of zirconium oxychloride and 0.06M of the zirconium hydroxide precursor pulp with 1M is prepared, addition ammonium hydroxide is (dense
Spend 7mol/L) pH=9 is adjusted, 200rpm stirring is aged 2 hours.Reaction emulsion after ageing is poured into Buchner funnel and is taken out
Filter, deionized water washing, until washing filtrate is reacted with 0.1mol/L silver nitrate solution and do not become cloudy.Filter cake is taken out, water is added
300rpm stirring stirring is dispersed into zirconium hydroxide precursor pulp (wherein the content of zirconium hydroxide is 8wt%).
2) quantitative ammonium metavanadate (11.6mmol/L), cobalt nitrate (6mmol/L), aluminum nitrate (1.2mmol/L) are added
It into zirconium hydroxide precursor pulp, stirs evenly, slurry spray drying, dry 250 DEG C of inlet temperature obtains hydroxide zirconium powder
Body.
3) 900 DEG C of zirconium hydroxide powder calcining 2h obtain the Zirconium powder containing colorant, and the group of colorant becomes five
Two alum and cobalt aluminate are aoxidized, the two accounts for the 1.25wt% and 1.25wt% of Zirconium powder respectively.Then, colorant will be contained
Zirconium powder is made into the water slurry of 50% solid content, and the polyvinyl alcohol of 1.5wt% is added, after broken 0.6 μm of D50 < is sanded,
Mist projection granulating.
4) pelletizing obtained obtains emerald green zirconium oxide pottery through 110MPa (gauge pressure) compression moulding, 1400 DEG C of sintering 2h
Porcelain, wherein the colorant containing 2.5wt%, vanadium pentoxide and cobalt aluminate 1:1 in colorant.Ceramic surface is through sanding and polishing
Afterwards, uniform emerald green color is presented, ceramic SCI chromatic value is L=50, a=-42, b=42, and ceramic three-point bending resistance is strong
Degree is 1000MPa.
Embodiment 3
1) prepare zirconium hydroxide precursor pulp: the yttrium chloride solution of zirconium oxychloride and 0.24M with 1.5M adds ammonium hydroxide
(concentration 14mol/L) adjusts pH=10, and 200rpm stirring is aged 6 hours.Reaction emulsion after ageing is poured into Buchner funnel
Middle suction filtration, deionized water washing, until washing filtrate is reacted with 0.1mol/L silver nitrate solution and do not become cloudy.Filter cake is taken out, is added
Water 300rpm stirring stirring is dispersed into zirconium hydroxide precursor pulp (wherein the content of zirconium hydroxide is 10wt%).
2) sodium metavanadate (6.1mmol/L), cobalt chloride (28.3mmol/L), aluminium chloride (56.5mmol/L) are added to hydrogen
It in zirconium oxide precursor pulp, stirs evenly, slurry spray drying, dry 300 DEG C of inlet temperature obtains zirconium hydroxide powder.
3) 1100 DEG C of zirconium hydroxide powder calcining 4h obtain the Zirconium powder containing colorant, and the group of colorant becomes five
Two alum and cobalt aluminate are aoxidized, the two accounts for the 0.5wt% and 4.5wt% of Zirconium powder respectively.Then, by the oxygen containing colorant
Change the water slurry that zirconium powder body is made into 50% solid content, the polymethyl methacrylate of 2wt% is added, broken 0.6 μm of D50 < is sanded
Afterwards, mist projection granulating.
4) pelletizing obtained obtains blue-green zirconium oxide pottery through 120MPa (gauge pressure) compression moulding, 1500 DEG C of sintering 4h
Porcelain, wherein the colorant containing 5wt%, vanadium pentoxide and cobalt aluminate 1:9 in colorant.Ceramic surface after sanding and polishing,
Uniform blue-green color is presented, ceramic SCI chromatic value is L=45, a=-69, b=-9, and ceramic three-point bending resistance intensity is
1000MPa。
Comparative example 1
1) prepare zirconium hydroxide precursor pulp: method is the same as embodiment 2.
2) by zirconium hydroxide precursor pulp, slurry is spray-dried, and dry 250 DEG C of inlet temperature obtains zirconium hydroxide powder.
3) 900 DEG C of zirconium hydroxide powder calcining 2h obtain the stable Zirconium powder of yttrium, by colorant (vanadium pentoxide and
Cobalt aluminate) it is added in Zirconium powder according to 1.25wt% the and 1.25wt% ratio of Zirconium powder.Then, will contain has
The Zirconium powder of toner is made into the water slurry of 50% solid content, and the polyvinyl alcohol of 1.5wt% is added, and broken D50 < 0.6 is sanded
After μm, mist projection granulating.
4) pelletizing obtained obtains dirty-green zirconia ceramics through 110MPa compression moulding, 1400 DEG C of sintering 2h, dark green
Color is unevenly distributed, and ceramic floor green is partially shallow, and color has volatilization sign.Ceramic surface is after sanding and polishing, ceramic SCI color
Angle value is L=30, a=-30, b=-5, and ceramic three-point bending resistance intensity is 500MPa.
Comparative example 2
1) prepare zirconium hydroxide precursor pulp: method is the same as embodiment 2.
2) by quantitative ammonium metavanadate (9.08mmol/L), cobalt nitrate (0.25mmol/L), aluminum nitrate (0.49mmol/L)
It is added in zirconium precursor somaplasm material, stirs evenly, slurry spray drying, dry 250 DEG C of inlet temperature obtains zirconium hydroxide powder.
3) 900 DEG C of zirconium hydroxide powder calcining 2h obtain the Zirconium powder containing colorant, and the group of colorant becomes five
Two alum and cobalt aluminate are aoxidized, the two accounts for the 0.95wt% and 0.05wt% of Zirconium powder respectively.Then, colorant will be contained
Zirconium powder is made into the water slurry of 50% solid content, and the polyvinyl alcohol of 1.5wt% is added, after broken 0.6 μm of D50 < is sanded,
Mist projection granulating.
4) pelletizing obtained obtains light yellow zirconia ceramics through 110MPa compression moulding, 1400 DEG C of sintering 2h.
Comparative example 3
1) prepare zirconium hydroxide precursor pulp: method is the same as embodiment 3.
2) by quantitative ammonium metavanadate (3.05mmol/L), cobalt nitrate (29.84mmol/L), aluminum nitrate (59.67mmol/
L) it is added in zirconium hydroxide precursor pulp, stirs evenly, slurry spray drying, dry 250 DEG C of inlet temperature obtains hydroxide
Zirconium powder body.
3) 900 DEG C of zirconium hydroxide powder calcining 2h obtain the Zirconium powder containing colorant, and the group of colorant becomes five
Two alum and cobalt aluminate are aoxidized, the two accounts for the 0.25wt% and 4.75wt% of Zirconium powder respectively.Then, colorant will be contained
Zirconium powder is made into the water slurry of 50% solid content, and the polyvinyl alcohol of 1.5wt% is added, after broken 0.6 μm of D50 < is sanded,
Mist projection granulating.
4) pelletizing obtained obtains dark-blue zirconia ceramic through 110MPa compression moulding, 1400 DEG C of sintering 2h.
Claims (10)
1. a kind of green is zirconia ceramics, which is characterized in that composition includes the colorant of 1-5wt%, the colorant composition
For vanadium pentoxide and cobalt aluminate；Vanadium pentoxide mass percentage is 10-90wt% in the preferably described colorant.
2. green according to claim 1 is zirconia ceramics, which is characterized in that SCI chromatic value is 45≤L≤90, -69
≤a≤-13、-9≤b≤58。
3. green according to claim 1 or 2 is zirconia ceramics, which is characterized in that colorant content is improved from 1wt%
To 5wt%, green is gradually deepened.
4. green according to claim 1-3 is zirconia ceramics, which is characterized in that in colorant, component
When vanadium pentoxide and cobalt aluminate ratio are 9:1, yellow green is presented in zirconia ceramics；In colorant, component vanadium pentoxide
With cobalt aluminate ratio be 1:1 when, zirconia ceramics present it is emerald green；In the presence of in agent component, vanadium pentoxide and cobalt aluminate ratio
When example is 1:9, blue-green is presented in zirconia ceramics.
5. the preparation method that a kind of any one of claim 1-4 green is zirconia ceramics, which is characterized in that including following
Step:
1) zirconium hydroxide precursor pulp is prepared using coprecipitation method；
2) water-soluble vanadic salts, cobalt salt and aluminium salt are added in the zirconium hydroxide precursor pulp of step 1), then passes through drying
Prepare zirconium hydroxide powder；
3) it by step 2) zirconium hydroxide powder after high temperature sintering, obtains being dissolved containing the zirconium oxide of vanadium pentoxide and cobalt aluminate
Body powder, powder add binder after being sanded, and mist projection granulating obtains colored zirconium oxide pelletizing；
4) by the colored zirconium oxide pelletizing compression moulding of step 3), high temperature sintering, obtained green is zirconia ceramics.
6. preparation method according to claim 5, which is characterized in that step 1) coprecipitation method prepares zirconium hydroxide forerunner
Somaplasm material, method are as follows: ammonium hydroxide is added in the aqueous solution of zirconium oxychloride, yttrium chloride, adjusts pH value, diafiltration is crossed in stirring ageing
It washs to obtain filter cake, then filter cake is added to the water, high speed dispersion mashing obtains zirconium hydroxide precursor pulp；And/or
The mass percent of zirconium hydroxide is 5-10wt% in the zirconium hydroxide precursor pulp.
7. preparation method according to claim 6, which is characterized in that the ammonia concn range 1-14mol/L, system pH
Value is adjusted to 8-10；And/or
The zirconium oxychloride, yttrium chloride aqueous solution in, the concentration of zirconium oxychloride is 0.1-1.5mol/L, the concentration of yttrium chloride
0.006-0.24mol/L；And/or
The stirring ageing, mixing speed 200rpm, digestion time 2-6h；And/or
The speed of the high speed dispersion mashing is 300rpm.
8. preparation method according to claim 5, which is characterized in that in step 2), the zirconium hydroxide precursor pulp
The interior concentration range that vanadic salts, cobalt salt and aluminium salt is added is respectively 0.58-54.9mmol/L, 0.3-28.3mmol/L, 0.6-
56.5mmol/L；And/or
The vanadic salts is ammonium metavanadate and/or sodium metavanadate, and the aluminium salt is aluminum nitrate and/or aluminium chloride, the cobalt
Salt is cobalt nitrate and/or cobalt chloride；And/or
The drying is spray drying, it is preferable that 200-300 DEG C of inlet temperature of spray drying.
9. preparation method according to claim 5, which is characterized in that in step 3), the high temperature sintering temperature is 800-
1100 DEG C, sintering time 1-4h；And/or
Described be sanded is handled using horizontal sand mill, 0.6 μm of the D50 < of slurry；And/or
The mist projection granulating uses atomizer pelletizer, and pelletizing D50 is 50-70 μm；And/or
The binder is polyvinyl alcohol or polymethyl methacrylate, and additive amount is the 1-2wt% of material gross mass after being sanded.
10. preparation method according to claim 5, which is characterized in that in step 4), the compression moulding, pressure is
100-120MPa (gauge pressure)；And/or
The high temperature sintering temperature is 1350-1500 DEG C, sintering time 1-4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910321422.1A CN110002867A (en) | 2019-04-22 | 2019-04-22 | A kind of green is zirconia ceramics and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910321422.1A CN110002867A (en) | 2019-04-22 | 2019-04-22 | A kind of green is zirconia ceramics and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110002867A true CN110002867A (en) | 2019-07-12 |
Family
ID=67173279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910321422.1A Pending CN110002867A (en) | 2019-04-22 | 2019-04-22 | A kind of green is zirconia ceramics and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110002867A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112441818A (en) * | 2019-08-30 | 2021-03-05 | 比亚迪股份有限公司 | Three-dimensional mosaic ceramic, preparation method thereof and mobile phone cover plate |
| CN113511676A (en) * | 2021-04-27 | 2021-10-19 | 上海交通大学 | Holmium oxide and scandium oxide composite stable zirconia, preparation method thereof and electrolyte material of solid oxide fuel cell |
| CN114195551A (en) * | 2021-11-20 | 2022-03-18 | 赣州科盈结构陶瓷有限公司 | Bill zirconia ceramic and preparation method thereof |
| CN114804861A (en) * | 2022-04-01 | 2022-07-29 | 潮州三环（集团）股份有限公司 | Yellow ceramic powder, yellow ceramic slurry and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1518844A1 (en) * | 2003-09-25 | 2005-03-30 | Sumitomo Metal Industries, Ltd. | Machinable ceramic |
| CN103382112A (en) * | 2013-06-28 | 2013-11-06 | 无锡特科精细陶瓷有限公司 | Preparation method of dark-blue zirconia ceramic |
| CN105121388A (en) * | 2012-12-21 | 2015-12-02 | 劳力士公司 | Coloured technical ceramic bodies and method for obtaining the same |
| CN106927818A (en) * | 2017-03-16 | 2017-07-07 | 陕西科技大学 | A kind of fast and low-cost preparation method of black zirconia ceramics |
| CN107500807A (en) * | 2017-09-30 | 2017-12-22 | 江西金环颜料有限公司 | A kind of preparation method of high temperature resistant green ceramic pigment |
| CN108314451A (en) * | 2018-05-09 | 2018-07-24 | 陕西科技大学 | A kind of preparation method of blue zirconium oxide ceramic |
| CN108484162A (en) * | 2018-05-09 | 2018-09-04 | 陕西科技大学 | The preparation method of yellow zirconium oxide ceramic |
-
2019
- 2019-04-22 CN CN201910321422.1A patent/CN110002867A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1518844A1 (en) * | 2003-09-25 | 2005-03-30 | Sumitomo Metal Industries, Ltd. | Machinable ceramic |
| CN105121388A (en) * | 2012-12-21 | 2015-12-02 | 劳力士公司 | Coloured technical ceramic bodies and method for obtaining the same |
| CN103382112A (en) * | 2013-06-28 | 2013-11-06 | 无锡特科精细陶瓷有限公司 | Preparation method of dark-blue zirconia ceramic |
| CN106927818A (en) * | 2017-03-16 | 2017-07-07 | 陕西科技大学 | A kind of fast and low-cost preparation method of black zirconia ceramics |
| CN107500807A (en) * | 2017-09-30 | 2017-12-22 | 江西金环颜料有限公司 | A kind of preparation method of high temperature resistant green ceramic pigment |
| CN108314451A (en) * | 2018-05-09 | 2018-07-24 | 陕西科技大学 | A kind of preparation method of blue zirconium oxide ceramic |
| CN108484162A (en) * | 2018-05-09 | 2018-09-04 | 陕西科技大学 | The preparation method of yellow zirconium oxide ceramic |
Non-Patent Citations (2)
| Title |
|---|
| 王晓东: "《绘画色彩教学研究》", 31 January 2017, 辽宁美术出版社 * |
| 班孝东: "《汽车维修漆工》", 29 February 2016, 国防工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112441818A (en) * | 2019-08-30 | 2021-03-05 | 比亚迪股份有限公司 | Three-dimensional mosaic ceramic, preparation method thereof and mobile phone cover plate |
| CN112441818B (en) * | 2019-08-30 | 2022-03-15 | 比亚迪股份有限公司 | Three-dimensional mosaic ceramic, preparation method thereof and mobile phone cover plate |
| CN113511676A (en) * | 2021-04-27 | 2021-10-19 | 上海交通大学 | Holmium oxide and scandium oxide composite stable zirconia, preparation method thereof and electrolyte material of solid oxide fuel cell |
| CN114195551A (en) * | 2021-11-20 | 2022-03-18 | 赣州科盈结构陶瓷有限公司 | Bill zirconia ceramic and preparation method thereof |
| CN114804861A (en) * | 2022-04-01 | 2022-07-29 | 潮州三环（集团）股份有限公司 | Yellow ceramic powder, yellow ceramic slurry and preparation method thereof |
| CN114804861B (en) * | 2022-04-01 | 2023-01-06 | 潮州三环（集团）股份有限公司 | Yellow ceramic powder, yellow ceramic slurry and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110002867A (en) | A kind of green is zirconia ceramics and preparation method thereof | |
| CN102260078B (en) | Zirconia ceramic and preparation method thereof | |
| CN108249806B (en) | A kind of preparation method of hydrated calcium silicate early strength agent and a kind of self-compacting concrete | |
| JP7198826B2 (en) | Blended titanium dioxide pigment composition | |
| JPH03115214A (en) | Tooth paste composition containing color pigment | |
| CN104529437A (en) | Method for synthesis of black zirconia ceramic powder by organic network process | |
| CN102557629A (en) | Blue rare earth zirconium ceramic powder as well as manufacture and application thereof | |
| CN108298980A (en) | A kind of preparation method of yellow zirconium oxide ceramic | |
| CN107986337A (en) | A kind of easily scattered high coloring power iron oxide black and preparation method thereof | |
| CN108314451A (en) | A kind of preparation method of blue zirconium oxide ceramic | |
| CN105923651A (en) | New method for preparing dental colored nano zirconium oxide powder | |
| CN108046794A (en) | The method that metatitanic acid yttrium crystalline ceramics is prepared using Co deposited synthesis powder | |
| CN108003658A (en) | A kind of easily scattered high coloring power iron oxide black | |
| CN104445393A (en) | Organic network preparation method of ferrozirconium red zirconia nano-composite ceramic powder | |
| CN108358635A (en) | A kind of preparation method of magneto-optic holimium oxide crystalline ceramics | |
| JPH10231441A (en) | Microparticulate composite oxide black pigment and its production | |
| JP2599638B2 (en) | Fine-particle composite oxide blue-green pigment and method for producing the same | |
| CN108546119A (en) | A kind of preparation method of red oxidization zircon ceramic | |
| TWI498388B (en) | Composite oxide black pigment and its manufacturing method | |
| JP2002309123A (en) | Particulate composite oxide black pigment and method for manufacturing the same | |
| CN113800905B (en) | Preparation method of black pigment for nano zirconia ceramic | |
| CN110372397B (en) | Composite zirconia powder preparation method, preparation method and application thereof | |
| CN108250800A (en) | A kind of high temperature resistant black nano-coloring material and its application | |
| CN101671499A (en) | Method for preparing ferric oxide composite pigment doped with rare earth and silicon oxide | |
| JPH0337272A (en) | Coloring pigment for zirconia fine ceramics and its preparation |
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 | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210115 Address after: Room 304, management committee office building, Jinxiang Chemical Industrial Park, xianger Town, Dongpo District, Meishan City, Sichuan Province Applicant after: Wanhua chemical (Sichuan) Co.,Ltd. Applicant after: Wanhua Chemical Group Co.,Ltd. Address before: 264006 17 Tianshan Road, Yantai economic and Technological Development Zone, Shandong Applicant before: Wanhua Chemical Group Co.,Ltd. |
|
| TA01 | Transfer of patent application right |