CN107555989A - A kind of black zirconia ceramics and preparation method thereof - Google Patents
A kind of black zirconia ceramics and preparation method thereof Download PDFInfo
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- CN107555989A CN107555989A CN201710824838.6A CN201710824838A CN107555989A CN 107555989 A CN107555989 A CN 107555989A CN 201710824838 A CN201710824838 A CN 201710824838A CN 107555989 A CN107555989 A CN 107555989A
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Abstract
The invention discloses a kind of black zirconia ceramics material compositions, the composition of following weight/mass percentage composition is included：Iron oxide 0.01 4%, cobalt oxide 0.01 3.5%, chromium oxide 0.01 3.5%, aluminum oxide 0.01 15%, nickel oxide 0.01 4%, manganese oxide 0.01 3.5%, zinc oxide 0 3.5%, yittrium oxide 2 7%, titanium oxide 0 4%, silica 0 3%, cerium oxide 0 5%, surplus are the zirconium oxide containing hafnium oxide.Black zirconia ceramics material compositions of the present invention, powder granularity is small, is uniformly dispersed, and has higher intensity and hardness, higher covering power and relatively low light transmittance containing its black zirconia ceramics.Meanwhile the invention also discloses the preparation method of the black zirconia ceramics being prepared using the black zirconia ceramics material compositions and the black zirconia ceramics.
Description
Technical field
The present invention relates to a kind of ceramic material and preparation method thereof, especially a kind of zirconia ceramics material and its preparation side
Method.
Background technology
Zirconium dioxide is due to excellent mechanics, calorifics, electric property, in structural material, optical element, oxygen sensitive element
Had a wide range of applications with fuel cell etc..In recent years, as people are to the high speed development of ornament demand, black oxidation
Zircon ceramic turns into high-grade decoration with its excellent mechanical performance, chromatic colour, metallic luster and the features such as acted on without allergy
New lover's material, there are wide market prospects in high-grade watch chain, bangle, phone housing etc..
The preparation of black zirconia ceramics at present mainly uses following two methods：1st, zirconia ceramics is carried out true
Black in empty, reducing atmosphere or inert atmosphere, form Lacking oxygen, so as to form the point defect of colour center, produce the absorption effect to light
Should；2nd, the colorant oxide such as doping iron, cobalt, nickel in zirconium oxide, by adding absorption of the colorant raising to light, so as to improve oxygen
Change the covering power and blackness of zirconia material.Using vacuum drying oven, reducing atmosphere stove or inert atmosphere stove, it is necessary to by zirconium oxide in atmosphere
Sinter porcelain into, then black in above-mentioned sintering furnace, the cost of production technology has so been significantly greatly increased, to special shape and thickness
The product to differ, easily because colour center inhomogeneities causes aberration occur, causes product blackness deficiency to wait a system during nigrescence
Row problem.And the colorant oxide such as doping iron, cobalt, nickel in zirconium oxide, because each oxide is inconsistent to the absorbing wavelength of light,
It is not black to easily cause black, situations such as partially red, partially blue, partially green occurs in product colour；And institute's oxygenates easily rise with yttrium, zirconium
Reaction, destroys the stability of zirconium oxide, easily causes product Transformation Cracking, reduce the intensity and hardness of product, therefore existing oxygen
It is generally relatively low to change zircon ceramic intensity hardness；And because the bad control of Yttrium oxide doping amount, sintering temperature are too high, easily cause oxygen
Change zircon ceramic Tetragonal to coexist with monoclinic phase, this also result in terms of the intensity and hardness of zirconia ceramics is improved in the presence of very big
Problem.
From the foregoing, existing black zirconia ceramics are present, Color uniformity is poor, blackness deficiency, intensity and hardness are low etc.
Bad shortcoming, the requirement of the elements such as high blackness mobile phone board can not be met.
The content of the invention
There is provided it is an object of the invention to overcome in place of above-mentioned the deficiencies in the prior art it is a kind of with higher intensity and
The black zirconia ceramics material compositions of hardness, higher covering power and blackness and the black zirconia containing the composition
Ceramics.Meanwhile present invention also offers the preparation method of the black zirconia ceramics.
To achieve the above object, the technical scheme taken of the present invention is：A kind of black zirconia ceramics material compositions, bag
Composition containing following weight/mass percentage composition：Iron oxide 0.01-4%, cobalt oxide 0.01-3.5%, chromium oxide 0.01-3.5%, oxygen
Change aluminium 0.01-15%, nickel oxide 0.01-4%, manganese oxide 0.01-3.5%, zinc oxide 0-3.5%, yittrium oxide 2-7%, oxidation
Titanium 0-4%, silica 0-3%, cerium oxide 0-5%, surplus are the zirconium oxide containing hafnium oxide.
Preferably, the black zirconia ceramics material compositions, the composition of following weight/mass percentage composition is included：Iron oxide
0.5-3%, cobalt oxide 0.1-1.5%, chromium oxide 1-3%, aluminum oxide 0.01-8%, nickel oxide 0.1-2%, manganese oxide 0.1-
2%th, zinc oxide 0-3%, yittrium oxide 2-5.8%, titanium oxide 0-2%, silica 0-3%, cerium oxide 0-2%, strontium oxide strontia 0-
3%th, calcium oxide 0-3%, magnesia 0-5%, surplus are the zirconium oxide containing hafnium oxide.
In the black zirconia ceramics material compositions of the present invention, the addition of different colorant oxides can not only be notable
The covering power and black by its black zirconia ceramics being prepared are improved, reduces light transmittance；And it can improve by its system
The intensity and hardness of standby obtained black zirconia ceramics.
It is described containing hafnium oxide as the preferred embodiment of black zirconia ceramics material compositions of the present invention
In zirconium oxide, the weight/mass percentage composition of the hafnium oxide is less than 50%.
As the preferred embodiment of black zirconia ceramics material compositions of the present invention, the quality of the aluminum oxide
Percentage composition is 0.5-3%, and the weight/mass percentage composition of the yittrium oxide is 3-5.8%, and other are except zirconium oxide, hafnium oxide, oxidation
The weight/mass percentage composition of oxide outside aluminium, yittrium oxide is 3-20%.
Inventor passes through a large amount of exploration discoveries, the aluminum oxide and yittrium oxide and other combination of oxides of above-mentioned content, can be with
The hardness of the ceramic material is preferably improved, the present invention also limits why while aluminum oxide and yttria levels are limited
The content of other fixed oxides in addition to zirconium oxide, hafnium oxide, aluminum oxide, yittrium oxide, is because inventor has found, when it
When the content of his oxide in addition to zirconium oxide, hafnium oxide, aluminum oxide, yittrium oxide is less than 3%, can not play acceleration of sintering,
Reduce sintering temperature, control the effect of crystal grain, be unfavorable for the raising of the ceramic material hardness；When other are except zirconium oxide, oxidation
When the content of oxide outside hafnium, aluminum oxide, yittrium oxide is higher than 20%, because aluminum oxide, zirconium oxide, yittrium oxide are main body materials
Material, material have the performance of high intensity and high rigidity in itself, and their ratio reduces, and it is hard to be also unfavorable for the ceramic material intensity
The raising of degree.
As the further preferred embodiment of black zirconia ceramics material compositions of the present invention, the aluminum oxide
Weight/mass percentage composition be 0.5-2%, the weight/mass percentage composition of the yittrium oxide is 5-5.5%.
Inventor passes through a large amount of exploration discoveries, the aluminum oxide and yittrium oxide and other combination of oxides of above-mentioned content, can be with
Further improve the hardness of the ceramic material.
As the more preferably embodiment of black zirconia ceramics material compositions of the present invention, the matter of the aluminum oxide
It is 1% to measure percentage composition, and the weight/mass percentage composition of the yittrium oxide is 5%.
Inventor passes through a large amount of exploration discoveries, the aluminum oxide and yittrium oxide and other combination of oxides of above-mentioned content, can be with
Further improve the hardness of the ceramic material.
As the preferred embodiment of black zirconia ceramics material compositions of the present invention, the quality of the aluminum oxide
Percentage composition is 0.5-3%, and the weight/mass percentage composition of the yittrium oxide is 3-5.8%, the weight/mass percentage composition of the strontium oxide strontia
For 1.5-3%, the weight/mass percentage composition of the calcium oxide is 1.5-3%, and the weight/mass percentage composition of the magnesia is 1.5-
5%.
Inventor had found by repetition test, aluminum oxide, yittrium oxide, strontium oxide strontia, calcium oxide, the magnesia of above-mentioned content,
The intensity and hardness by its black zirconia ceramics being prepared can be effectively improved.
As the more preferably embodiment of black zirconia ceramics material compositions of the present invention, the matter of the aluminum oxide
Amount percentage composition is 0.5-3%, and the weight/mass percentage composition of the yittrium oxide is 3-5.8%, and the quality percentage of the strontium oxide strontia contains
Measure as 2-3%, the weight/mass percentage composition of the calcium oxide is 2-3%, and the weight/mass percentage composition of the magnesia is 1.5-5%.
Inventor had found by repetition test, aluminum oxide, yittrium oxide, strontium oxide strontia, calcium oxide, the magnesia of above-mentioned content,
The intensity and hardness by its black zirconia ceramics being prepared can further be improved.
As the more preferably embodiment of black zirconia ceramics material compositions of the present invention, the matter of the aluminum oxide
It is 1% to measure percentage composition, and the weight/mass percentage composition of the yittrium oxide is 5%, and the weight/mass percentage composition of the strontium oxide strontia is 3%,
The weight/mass percentage composition of the calcium oxide is 2%, and the weight/mass percentage composition of the magnesia is 4%.
Inventor has found, aluminum oxide, yittrium oxide, strontium oxide strontia, calcium oxide, the magnesia of above-mentioned content, can further carry
The intensity and hardness for the black zirconia ceramics that Gao Youqi is prepared.
As the more preferably embodiment of black zirconia ceramics material compositions of the present invention, following quality hundred is included
Divide the composition of content：Iron oxide 1-3%, cobalt oxide 0.3-1%, chromium oxide 1-3%, aluminum oxide 0.5-3%, nickel oxide 0.3-
1%th, manganese oxide 0.2-1%, zinc oxide 0-2%, yittrium oxide 3-5.5%, titanium oxide 0-1%, silica 0.01-1%, oxidation
Cerium 0-1%, strontium oxide strontia 2-3%, calcium oxide 2-3%, magnesia 1.5-5%, surplus are the zirconium oxide containing hafnium oxide.
As the preferred embodiment of black zirconia ceramics material compositions of the present invention, the black zirconia pottery
Ceramic material composition is powder, and powder D50 granularities are 0.1-1.5 μm, specific surface area 5-18m2/g。
In addition, another object of the present invention is to provide it is a kind of with high rigidity and intensity, high blackness, high light-proofness it is black
Color zirconia ceramics, in order to achieve this, the technical scheme that the present invention takes is：A kind of black zirconia ceramics, the black
Zirconia ceramics includes black zirconia ceramics material compositions as described above.
The black zirconia ceramics of the present invention contain black zirconia ceramics material compositions as described above, have higher
Intensity and hardness, be provided simultaneously with higher covering power and blackness and relatively low light transmittance.
After the black zirconia ceramics of the present invention are prepared by black zirconia ceramics material compositions described above, lead to
Cross the atoms such as iron, cobalt, chromium, aluminium, nickel, manganese, zinc and form Surface coating to the zirconia grains containing hafnium oxide, contain oxidation
The zirconia grains surface of hafnium forms one layer of oxide skin(coating), due to being doped using surface coating technology, neither influences oxidation
The stable system solid solution of yttrium-zirconium oxide, while suppress zirconia grains and grow up, the ageing resistance of zirconia ceramics can be effectively improved
Energy and heat endurance.
Inventor had found by repetition test, is contained by adjusting aluminum oxide, yittrium oxide, strontium oxide strontia, calcium oxide, magnesia
Amount, the hardness and intensity of zirconia ceramics can be effectively improved.
After the black zirconia ceramics of the present invention are prepared by black zirconia ceramics material compositions described above, oxygen
Change the addition of iron, cobalt oxide, chromium oxide, nickel oxide, manganese oxide, equivalent to the effect of sintering aid, it is possible to achieve low-temperature sintering
(1300 or so), obtained crystal grain are small and fine and close；Alumina material mechanical property itself is good, and control certain proportion can improve oxygen
Change the intensity hardness of zircon ceramic, the content of yittrium oxide is mainly to suppress the monoclinic phase of zirconia ceramics so that zirconia ceramics is
Single Tetragonal；Strontium oxide strontia, calcium oxide, magnesia can reduce sintering temperature with acceleration of sintering, and control crystal grain is small and fine and close,
Intensity hardness improves.Therefore, by adjusting the content of aluminum oxide, yittrium oxide, strontium oxide strontia, calcium oxide, magnesia, can effectively improve
The hardness and intensity of zirconia ceramics.
As the preferred embodiment of black zirconia ceramics of the present invention, the black zirconia ceramics are thick for polishing
Spend light transmittance ＜ 0.4, OD values ＞ 5.0, the potsherd of chromatic value L≤30 under 0.1-1.0mm, 550nm wavelength.
Finally, it is still another object of the present invention to provide a kind of technique is simple, the black oxidation described above that is easy to implement
The preparation method of zircon ceramic, in order to achieve this, the technical scheme that the present invention takes is：A kind of black zirconia pottery as described above
The preparation method of porcelain, comprises the following steps：
(1) each composition contained by black zirconia ceramics material compositions is mixed, obtains black zirconia ceramics material
Composition；
(2) the black zirconia ceramics material compositions that step (1) obtains are molded, roasting obtains black zirconia
Ceramics；
Flow casting molding, dry-pressing formed, injection moulding, hot-forming or gel casting are shaped in the step (2).
The preparation method of black zirconia ceramics of the present invention, the Zirconium powder granularity of preparation is small, is uniformly dispersed, mixes
Miscellaneous oxide is evenly coated at Zirconium powder surface, can effectively improve powder active, and processability is excellent, can meet dry
The different ceramics such as pressure, curtain coating, injection use the demands of technique, and the ceramic section sintered is fine and close, the defects of pore-free, crackle.
It is easy to operate and the technique is prepared simply, do not increase production process and workload, volume production can be achieved, have preferably stable
Property, homogenizing for product can be realized.
The black zirconia ceramics being prepared using the method for the invention, into porcelain density >=5.5g/cm3, 3 points resist
Roll over intensity >=1500Mpa, Vickers hardness >=1350.
As the preferred embodiment of the preparation method of black zirconia ceramics of the present invention, in the step (2)
It is shaped to flow casting molding, dry-pressing formed or injection moulding；
The flow casting molding comprises the following steps：
(1a) ball milling：The black zirconia ceramics material compositions are mixed with dispersant and binding agent in ball mill
Uniformly；
(2a) flow casting molding：Slurry after ball milling is uniformly dispersed carries out flow casting molding, regulation curtain coating work in casting machine
Skill parameter, the curtain coating base substrate that thickness is 0.2-1.1mm is made；
(3a) punch forming：Obtained curtain coating base substrate is put in designed mould and carries out punch forming, punching press is made
Base；
(4a) dumping sinters：Punching press base substrate is subjected to dumping sintering, the wherein dumping time is 60-100h, and sintering time is
40-60h, produce the black zirconia ceramics；
It is described dry-pressing formed to comprise the following steps：
(1b) ball milling is granulated：By the black zirconia ceramics material compositions and dispersant, binding agent in ball mill
It is well mixed, and drying-granulating is carried out on sponging granulator；
(2b) dry-pressing：The powder being granulated is laid in designed dry pressing die set and carries out dry-pressing formed, obtained dry-pressing
Base；
(3b) dumping sinters：Punching press base substrate is subjected to dumping sintering, the wherein dumping time is 60-100h, and sintering time is
40-60h, produce the black zirconia ceramics；
The injection moulding comprises the following steps：
(1c) internally mix：The black zirconia ceramics material compositions are carried out in internal mixer mixing with binding agent
It is even, make injection molding raw material；
(2c) is granulated：The pockets of raw material of internally mix is carried out extruding pelletization in comminutor, produces particle of uniform size
Material, particle length is in 2-3mm；
(3c) is injection moulded：The particulate material being granulated is molded using injection (mo(u)lding) machine, produces base substrate, injection temperature
Degree is 160-175 DEG C, and injection pressure is 30-60Mpa；
(4c) degreasing：First the base substrate being injection moulded is put in solvent and carries out extraction dewaxing, then the base substrate for taking off good wax
Put into and thermal debinding is carried out in draft glue discharging furnace, solvent degreasing temperature is 45-55 DEG C, degreasing time 15-20h, and thermal debinding temperature is
400-500 DEG C, degreasing time 45-55h；
(5c) is sintered：The base substrate for having taken off fat is put into sintering furnace and is sintered, makes base substrate into porcelain, sintering temperature 1300-
1600 DEG C, sintering time 25-35h, produce the black zirconia ceramics.
As the preferred embodiment of the preparation method of black zirconia ceramics of the present invention, in the flow casting molding,
Dispersant in step (1a) is at least one of polyacrylic acid, polyethylene glycol and glycerine, the bonding in the step (1a)
Agent is at least one of PVB, DOP, BBP, DBP；It is described it is dry-pressing formed in, dispersant in step (1b) for PEG, DBS and
At least one of polyacrylic, the binding agent in step (1b) are at least one of PVA, PMMA；The injection moulding
In, the binding agent in step (1c) is the mixture of polypropylene, polyethylene and paraffin.
In the flow casting molding, dispersing uniformity of the powder in casting slurry directly affects the quality of base film, so as to shadow
Ring the series of characteristics such as compactness, the porosity and the mechanical property of material.In tape-casting commonly use dispersant have nonionic,
Anion, cation and the type of amphion 4.Dispersant prioritizing selection polyacrylic acid；During flow casting molding, in order to base
Plate material separates and taking and placing are convenient, and casting films must possess certain intensity, toughness and ductility.Therefore, need to add in the slurry
Enter binding agent.Binding agent is divided into nonionic, anion and the class of cation 3, binding agent preferred PVB, DOP, BBP, DBP by functional group
One or more.It is described it is dry-pressing formed in, the dispersiveness of powder directly affects the mobility and apparent density of powder in dry-pressing,
And then influence compactness, the porosity and the mechanical property of material.Conventional dispersant is one kind of PEG, DBS and polyacrylic
It is or several.And binding agent then influences the intensity of dry-pressing base, it is generally preferable to the one or more such as PVA, PMMA.
Black zirconia ceramics material compositions of the present invention, powder granularity is small, is uniformly dispersed, and contains its black oxygen
Changing zircon ceramic has higher intensity and hardness, higher covering power and blackness, relatively low light transmittance.Black oxygen of the present invention
Change zircon ceramic, by adjusting the content of aluminum oxide, yittrium oxide, strontium oxide strontia, calcium oxide, magnesia, zirconium oxide pottery can be effectively improved
The hardness and intensity of porcelain.The preparation method of black zirconia ceramics material of the present invention, technique is prepared simply, easy to operate, no
Increase production process and workload, volume production can be achieved, there is preferable stability, homogenizing for product can be realized.
Embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
Embodiment 1
A kind of embodiment of black zirconia ceramics material compositions of the present invention, black zirconia ceramics described in the present embodiment
Material compositions contain the component of following weight/mass percentage composition：
Iron oxide 1%, cobalt oxide 0.3%, chromium oxide 2.5%, aluminum oxide 2%, nickel oxide 0.1%, manganese oxide 1%, oxygen
Change zinc 1%, yittrium oxide 5%, titanium oxide 0.15%, silica 0.01%, cerium oxide 0.5%, strontium oxide strontia 1.5%, calcium oxide
1.5%th, magnesia 3%, surplus are the zirconium oxide containing hafnium oxide；In the zirconium oxide containing hafnium oxide, hafnium oxide is in institute
It is 30% to state the weight/mass percentage composition in the zirconium oxide containing hafnium oxide.
The black zirconia ceramics material compositions of the present embodiment are powder, and the powder D50 granularities are 0.8 μm, compare table
Area is 5m2/g。
Embodiment 2
A kind of embodiment of black zirconia ceramics material compositions of the present invention, black zirconia ceramics described in the present embodiment
Material compositions contain the component of following weight/mass percentage composition：
Iron oxide 2%, cobalt oxide 1%, chromium oxide 1%, aluminum oxide 2%, nickel oxide 1%, manganese oxide 0.1%, zinc oxide
1%th, yittrium oxide 5.5%, titanium oxide 1%, silica 1 %, cerium oxide 1%, strontium oxide strontia 2%, calcium oxide 2.5%, magnesia
1.5%, surplus is the zirconium oxide containing hafnium oxide；In the zirconium oxide containing hafnium oxide, hafnium oxide contains oxidation described
Weight/mass percentage composition in the zirconium oxide of hafnium is 15%.
The black zirconia ceramics material compositions of the present embodiment are powder, and the powder D50 granularities are 1 μm, compare surface
Product is 8m2/g。
Embodiment 3
A kind of embodiment of black zirconia ceramics material compositions of the present invention, black zirconia ceramics described in the present embodiment
Material compositions contain the component of following weight/mass percentage composition：
Iron oxide 2%, cobalt oxide 0.8%, chromium oxide 2%, aluminum oxide 1%, nickel oxide 0.5%, manganese oxide 0.5%, oxygen
Change zinc 2%, yittrium oxide 5%, titanium oxide 0.5%, silica 0.5%, cerium oxide 1%, strontium oxide strontia 3%, calcium oxide 2%, oxygen
Change magnesium 4%, surplus is the zirconium oxide containing hafnium oxide；In the zirconium oxide containing hafnium oxide, hafnium oxide is described containing aerobic
It is 10% to change the weight/mass percentage composition in the zirconium oxide of hafnium.
The black zirconia ceramics material compositions of the present embodiment are powder, and the powder D50 granularities are 1.2 μm, compare table
Area is 9m2/g。
Embodiment 4
A kind of embodiment of black zirconia ceramics material compositions of the present invention, black zirconia ceramics described in the present embodiment
Material compositions contain the component of following weight/mass percentage composition：
Iron oxide 1%, cobalt oxide 0.3%, chromium oxide 1%, aluminum oxide 0.5%, nickel oxide 0.3%, manganese oxide 0.2%,
Yittrium oxide 5%, surplus are the zirconium oxide containing hafnium oxide；In the zirconium oxide containing hafnium oxide, hafnium oxide contains described
Weight/mass percentage composition in the zirconium oxide of hafnium oxide is 20%.
The black zirconia ceramics material compositions of the present embodiment are powder, and the powder D50 granularities are 0.3 μm, compare table
Area is 13m2/g。
Embodiment 5
A kind of embodiment of black zirconia ceramics material compositions of the present invention, black zirconia ceramics described in the present embodiment
Material compositions contain the component of following weight/mass percentage composition：
Iron oxide 3%, cobalt oxide 1.5%, chromium oxide 3%, aluminum oxide 3%, nickel oxide 1%, manganese oxide 1%, zinc oxide
3%th, yittrium oxide 5.8%, titanium oxide 1%, silica 3%, cerium oxide 2%, surplus are the zirconium oxide containing hafnium oxide；It is described
In zirconium oxide containing hafnium oxide, weight/mass percentage composition of the hafnium oxide in the zirconium oxide containing hafnium oxide is 5%.
The black zirconia ceramics material compositions of the present embodiment are powder, and the powder D50 granularities are 1.5 μm, compare table
Area is 15m2/g。
Embodiment 6
A kind of embodiment of black zirconia ceramics material compositions of the present invention, black zirconia ceramics described in the present embodiment
Material compositions contain the component of following weight/mass percentage composition：
Iron oxide 0.5%, cobalt oxide 0.1%, chromium oxide 2%, aluminum oxide 8%, nickel oxide 2%, manganese oxide 2%, oxidation
Zinc 1%, yittrium oxide 3%, titanium oxide 2%, silica 0%, cerium oxide 0%, surplus are the zirconium oxide containing hafnium oxide；It is described
In zirconium oxide containing hafnium oxide, weight/mass percentage composition of the hafnium oxide in the zirconium oxide containing hafnium oxide is 20%.
The black zirconia ceramics material compositions of the present embodiment are powder, and the powder D50 granularities are 1.5 μm, compare table
Area is 12m2/g。
Embodiment 7
A kind of embodiment of black zirconia ceramics material compositions of the present invention, black zirconia ceramics described in the present embodiment
Material compositions contain the component of following weight/mass percentage composition：
Iron oxide 4%, cobalt oxide 3.5%, chromium oxide 3.5%, aluminum oxide 0.01%, nickel oxide 4%, manganese oxide 3.5%,
Zinc oxide 3.5%, yittrium oxide 2%, titanium oxide 4%, silica 2.5%, cerium oxide 5%, magnesia 5%, surplus be containing
The zirconium oxide of hafnium oxide；In the zirconium oxide containing hafnium oxide, matter of the hafnium oxide in the zirconium oxide containing hafnium oxide
It is 20% to measure percentage composition.
The black zirconia ceramics material compositions of the present embodiment are powder, and the powder D50 granularities are 0.5 μm, compare table
Area is 15m2/g。
Embodiment 8
A kind of embodiment of black zirconia ceramics material compositions of the present invention, black zirconia ceramics described in the present embodiment
Material compositions contain the component of following weight/mass percentage composition：
Iron oxide 0.01%, cobalt oxide 0.01%, chromium oxide 0.01%, aluminum oxide 15%, nickel oxide 0.01%, manganese oxide
0.01%th, zinc oxide 0.01%, silica 0.01%, yittrium oxide 7%, surplus are the zirconium oxide containing hafnium oxide；It is described to contain
Have in the zirconium oxide of hafnium oxide, weight/mass percentage composition of the hafnium oxide in the zirconium oxide containing hafnium oxide is 20%.
The black zirconia ceramics material compositions of the present embodiment are powder, and the powder D50 granularities are 0.5 μm, compare table
Area is 18m2/g。
The performance test of the black zirconia ceramics of embodiment 9
The present embodiment sets test group 1~8 and control group, the black zirconia ceramics material difference of the test group 1~8
It is prepared using the black zirconia ceramics material compositions of embodiment 1~8, the black oxidation of test group 1~8 and control group
Zircon ceramic is prepared using same preparation method, and the preparation method comprises the following steps：
(1) each composition contained by black zirconia ceramics material compositions is mixed, obtains black zirconia ceramics material
Composition；
(2) the black zirconia ceramics material compositions that step (1) obtains are molded, roasting obtains black zirconia
Ceramics；
Flow casting molding, dry-pressing formed, injection moulding, hot-forming or gel casting are shaped in the step (2).
Wherein, the flow casting molding comprises the following steps：
(1a) ball milling：By the black zirconia ceramics material compositions and dispersant and binding agent, (dispersant is excellent
Select at least one of polyacrylic acid, polyethylene glycol and glycerine, at least one in described binding agent preferred PVB, DOP, BBP, DBP
Kind) be well mixed in ball mill；
(2a) flow casting molding：Slurry after ball milling is uniformly dispersed carries out flow casting molding, regulation curtain coating work in casting machine
Skill parameter, the curtain coating base substrate that thickness is 0.2-1.1mm is made；
(3a) punch forming：Obtained curtain coating base substrate is put in designed mould and carries out punch forming, punching press is made
Base；
(4a) dumping sinters：Punching press base substrate is subjected to dumping sintering, the wherein dumping time is 60-100h, and sintering time is
40-60h, produce the black zirconia ceramics；
It is described dry-pressing formed to comprise the following steps：
(1b) ball milling is granulated：By the black zirconia ceramics material compositions and dispersant, the binding agent (dispersant
It is preferred that at least one of at least one of PEG, DBS and polyacrylic, described binding agent preferred PVA, PMMA) in ball milling
It is well mixed in machine, and drying-granulating is carried out on sponging granulator；
(2b) dry-pressing：The powder being granulated is laid in designed dry pressing die set and carries out dry-pressing formed, obtained dry-pressing
Base；
(3b) dumping sinters：Punching press base substrate is subjected to dumping sintering, the wherein dumping time is 60-100h, and sintering time is
40-60h, produce the black zirconia ceramics；
The injection moulding comprises the following steps：
(1c) internally mix：By the black zirconia ceramics material compositions and binding agent (the preferred polypropylene of the binding agent,
The mixture of polyethylene and paraffin) it is well mixed in internal mixer, make injection molding raw material；
(2c) is granulated：The pockets of raw material of internally mix is carried out extruding pelletization in comminutor, produces particle of uniform size
Material, particle length is in 2-3mm；
(3c) is injection moulded：The particulate material being granulated is molded using injection (mo(u)lding) machine, produces base substrate, injection temperature
Degree is 160-175 DEG C, and injection pressure is 30-60Mpa；
(4c) degreasing：First the base substrate being injection moulded is put in solvent and carries out extraction dewaxing, then the base substrate for taking off good wax
Put into and thermal debinding is carried out in draft glue discharging furnace, solvent degreasing temperature is 45-55 DEG C, degreasing time 15-20h, and thermal debinding temperature is
400-500 DEG C, degreasing time 45-55h；
(5c) is sintered：The base substrate for having taken off fat is put into sintering furnace and is sintered, makes base substrate into porcelain, sintering temperature 1300-
1600 DEG C, sintering time 25-35h, produce the black zirconia ceramics.
Control group is existing relatively common black zirconia ceramics, and the black zirconia ceramics material compositions contain
The component of following weight/mass percentage composition：
Iron oxide 5%, cobalt oxide 5%, chromium oxide 5%, aluminum oxide 17%, nickel oxide 5%, manganese oxide 5%, yittrium oxide
1%th, surplus is the zirconium oxide containing hafnium oxide；In the zirconium oxide containing hafnium oxide, hafnium oxide contains hafnium oxide described
Zirconium oxide in weight/mass percentage composition be 10%.The black zirconia ceramics material compositions are powder, the powder D50
Granularity is 2 μm, specific surface area 15m2/g。
Test group 1~8 is identical with the molding mode that control group uses, the black zirconia pottery of test group 1~8 and control group
The polishing thickness of porcelain also all same (being 0.5mm).The black zirconia ceramics of test group 1~8 and control group are surveyed respectively
Light transmittance under 550nm wavelength, OD values, chromatic value, into porcelain density, 3 rupture strengths and Vickers hardness, the test result such as institute of table 1
Show.
The performance test results of the black zirconia ceramics of table 1
As seen from the results in Table 1, black zirconia ceramics of the invention have higher intensity and hardness, higher covering power
With the black zirconia ceramics of blackness, relatively low light transmittance, especially test group 1,2 and 3, effect is more preferable, especially in intensity
In terms of hardness；Wherein, the black zirconia ceramics of test group 3, effect are best.
Embodiment 10
According to the method in embodiment 9, by the ceramics obtained in embodiment 3 as a control group 1, and set test group 1~
10, alumina and the content of yittrium oxide are Bu Tong outer in test group 1~10, other compositions with embodiment 3 it is ceramic into
Split-phase is same, aluminum oxide, the content of yittrium oxide and its 3 rupture strength, Vickers hardness such as tables in test group 1~10 and control group 1
Shown in 2：
The content and its 3 rupture strengths, Vickers hardnesses of aluminum oxide, yittrium oxide in the test group of table 2 and control group
From table 2 it can be seen that under conditions of other conditions are the same, in ceramic material of the present invention, when the aluminum oxide
Weight/mass percentage composition is 0.5-3%, and when the weight/mass percentage composition of the yittrium oxide is 3-5.8%, hardness is preferable；When the oxidation
The weight/mass percentage composition of aluminium is 0.5-2%, and when the weight/mass percentage composition of the yittrium oxide is 5-5.5%, hardness is more preferable；When described
The weight/mass percentage composition of aluminum oxide is 1%, and when the weight/mass percentage composition of the yittrium oxide is 5%, hardness is best.
Embodiment 11
According to the method in embodiment 9, by the ceramics obtained in embodiment 3 as a control group 1, and set test group 1~
9, zirconium oxide in test group 1~9, hafnium oxide, the content of aluminum oxide and yittrium oxide are in the same manner as in Example 3, other except zirconium oxide,
The content of oxide outside hafnium oxide, aluminum oxide, yittrium oxide is different, specific as shown in table 3：
The test group of table 3 and control group 3 rupture strengths, Vickers hardnesses
From table 3 it can be seen that in the case where other conditions are the same, other in the application ceramic material are except zirconium oxide, oxygen
When the weight/mass percentage composition for changing the oxide outside hafnium, aluminum oxide, yittrium oxide is 3-20%, the hardness of ceramic material is preferable.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of scope is protected, although being explained in detail with reference to preferred embodiment to the present invention, one of ordinary skill in the art should
Understand, technical scheme can be modified or equivalent substitution, without departing from the essence of technical solution of the present invention
And scope.
Claims (10)
1. a kind of black zirconia ceramics material compositions, it is characterised in that include the composition of following weight/mass percentage composition：Oxidation
Iron 0.01-4%, cobalt oxide 0.01-3.5%, chromium oxide 0.01-3.5%, aluminum oxide 0.01-15%, nickel oxide 0.01-4%,
Manganese oxide 0.01-3.5%, zinc oxide 0-3.5%, yittrium oxide 2-7%, titanium oxide 0-4%, silica 0-3%, cerium oxide 0-
5%, surplus is the zirconium oxide containing hafnium oxide.
2. black zirconia ceramics material compositions as claimed in claim 1, it is characterised in that contain comprising following quality percentage
The composition of amount：Iron oxide 0.5-3%, cobalt oxide 0.1-1.5%, chromium oxide 1-3%, aluminum oxide 0.01-8%, nickel oxide 0.1-
2%th, manganese oxide 0.1-2%, zinc oxide 0-3%, yittrium oxide 2-5.8%, titanium oxide 0-2%, silica 0-3%, cerium oxide
0-2%, strontium oxide strontia 0-3%, calcium oxide 0-3%, magnesia 0-5%, surplus are the zirconium oxide containing hafnium oxide.
3. black zirconia ceramics material compositions as claimed in claim 2, it is characterised in that the quality hundred of the aluminum oxide
Point content be 0.5-3%, and the weight/mass percentage composition of the yittrium oxide is 3-5.8%, other remove zirconium oxide, hafnium oxide, aluminum oxide,
The weight/mass percentage composition of oxide outside yittrium oxide is 3-20%.
4. black zirconia ceramics material compositions as claimed in claim 3, it is characterised in that the quality hundred of the aluminum oxide
It is 0.5-2% to divide content, and the weight/mass percentage composition of the yittrium oxide is 5-5.5%.
5. black zirconia ceramics material compositions as claimed in claim 4, it is characterised in that the quality hundred of the aluminum oxide
It is 1% to divide content, and the weight/mass percentage composition of the yittrium oxide is 5%.
6. black zirconia ceramics material compositions as claimed in claim 2, it is characterised in that contain comprising following quality percentage
The composition of amount：Iron oxide 1-3%, cobalt oxide 0.3-1%, chromium oxide 1-3%, aluminum oxide 0.5-3%, nickel oxide 0.3-1%, oxygen
Change manganese 0.2-1%, zinc oxide 0-2%, yittrium oxide 3-5.5%, titanium oxide 0-1%, silica 0.01-1%, cerium oxide 0-
1%th, strontium oxide strontia 0-1.5%, calcium oxide 0-1.5%, magnesia 0-1.5%, surplus are the zirconium oxide containing hafnium oxide.
7. the black zirconia ceramics material compositions as described in any one of claim 1~6, it is characterised in that the black
Zirconia ceramics material composition is powder, and powder D50 granularities are 0.1-1.5 μm, specific surface area 5-18m2/g。
8. a kind of black zirconia ceramics, it is characterised in that the black zirconia ceramics are included as claim 1~7 is any
Black zirconia ceramics material compositions described in.
9. black zirconia ceramics as claimed in claim 8, it is characterised in that the black zirconia ceramics are polishing thickness
Light transmittance ＜ 0.4, OD values ＞ 5.0, the potsherd of chromatic value L≤30 under 0.1-1.0mm, 550nm wavelength.
10. a kind of preparation method of the black zirconia ceramics as described in claim 8 or 9, it is characterised in that including following step
Suddenly：
(1) each composition contained by black zirconia ceramics material compositions is mixed, obtains black zirconia ceramics combination of materials
Thing；
(2) the black zirconia ceramics material compositions that step (1) obtains are molded, roasting obtains black zirconia pottery
Porcelain；
Flow casting molding, dry-pressing formed, injection moulding, hot-forming or gel casting are shaped in the step (2).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104446457A (en) * | 2014-11-18 | 2015-03-25 | 潮州三环（集团）股份有限公司 | Modified zirconium oxide ceramic material and application thereof |
| CN105669191A (en) * | 2016-04-22 | 2016-06-15 | 潮州三环（集团）股份有限公司 | Black zirconia ceramic and preparation method thereof |
| CN105777113A (en) * | 2016-02-04 | 2016-07-20 | 潮州三环（集团）股份有限公司 | Black ceramic and preparing method thereof |
| CN106995308A (en) * | 2017-04-21 | 2017-08-01 | 潮州三环（集团）股份有限公司 | A kind of ceramic chopper material and preparation method thereof |
-
2017
- 2017-09-12 CN CN201710824838.6A patent/CN107555989A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104446457A (en) * | 2014-11-18 | 2015-03-25 | 潮州三环（集团）股份有限公司 | Modified zirconium oxide ceramic material and application thereof |
| CN105777113A (en) * | 2016-02-04 | 2016-07-20 | 潮州三环（集团）股份有限公司 | Black ceramic and preparing method thereof |
| CN105669191A (en) * | 2016-04-22 | 2016-06-15 | 潮州三环（集团）股份有限公司 | Black zirconia ceramic and preparation method thereof |
| CN106995308A (en) * | 2017-04-21 | 2017-08-01 | 潮州三环（集团）股份有限公司 | A kind of ceramic chopper material and preparation method thereof |
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