CN107266068A

CN107266068A - A kind of Zirconium powder, its product and preparation method

Info

Publication number: CN107266068A
Application number: CN201710472689.1A
Authority: CN
Inventors: 游志雄
Original assignee: WUHAN TUOBAISHI TECHNOLOGY Co Ltd
Current assignee: WUHAN TUOBAISHI TECHNOLOGY Co Ltd
Priority date: 2015-01-06
Filing date: 2015-01-06
Publication date: 2017-10-20
Also published as: CN104528823B; CN104528823A

Abstract

The invention discloses a kind of Zirconium powder, its product and preparation method.The Zirconium powder, it is characterised in that its key component of the Zirconium powder is ZrO₂+HfO₂+M_xO_y, wherein M_xO_yFor metal oxide, the molar percentage that its content accounts for key component is less than or equal to 15%, one or more of the M in yttrium, calcium, magnesium, cerium, praseodymium, vanadium, molybdenum and titanium elements, the key component accounts for the mass percent of Zirconium powder more than 90%, and the every kind of mass fraction for accounting for the Zirconium powder of other metal oxides outside key component is less than or equal to 0.01%.Methods described, includes the removal step for carrying out separation of solid and liquid under certain ph twice.Press body prepared by the Zirconium powder, purity is high, good mechanical property, and for preparing ceramic material, radioactivity is low, can serve as bioceramic material, such as artificial tooth, artificial bone.

Description

A kind of Zirconium powder, its product and preparation method

Technical field

The invention belongs to technical field of biological material, more particularly, to a kind of Zirconium powder, its product and preparation method.

Background technology

Zirconia ceramics has high tenacity, high-flexural strength and high-wearing feature, and excellent heat-proof quality, thermal coefficient of expansion connects The advantages of being bordering on steel, therefore it is widely used in structural ceramics field.Zirconia ceramics is general to use the body formed system of zirconia powder .

Current Zirconium powder, its preparation method mainly has the methods such as chemical method, electric smelting method, coprecipitation.But it is existing Technology prepares Zirconium powder, and metals content impurity is higher, causes the form and radioactivity of crystal of zirconium oxide and can not obtain effectively Control, influences the mechanical performance and biocompatibility of ceramic structure, it is impossible to meet requirement of the high technology ceramics to purity, especially It cannot function as bioceramic and be used as in terms of artificial tooth, artificial bone.

The content of the invention

For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of Zirconium powder, its product and Preparation method, it is miscellaneous in zirconia powder production procedure its object is to be removed as far as possible by solid-liquid separation means twice Thus matter solve existing Zirconium powder purity not there is provided a kind of new zirconia powder preparation and Zirconium powder Height, radioactivity is higher, it is impossible to meet high technology ceramics requirement, it is impossible to be used as the technical problem in terms of bioceramic.

To achieve the above object, according to one aspect of the present invention, there is provided a kind of Zirconium powder, the zirconia powder Body key component is ZrO₂+HfO₂+M_xO_y, wherein M_xO_yFor metal oxide, the molar percentage that its content accounts for key component is small Oxygen is accounted in or equal to one or more of 15%, the M in yttrium, calcium, magnesium, cerium, praseodymium, vanadium, molybdenum and titanium elements, the key component Change the mass percent of zirconium powder body more than 90%, other metal oxides outside key component are every kind of to account for the zirconia powder The mass fraction of body is less than or equal to 0.01%.

Preferably, the Zirconium powder, its other described metal oxide is silica, iron oxide, aluminum oxide, oxygen Change caesium, cobalt oxide, strontium oxide strontia, oxidation polonium, radium oxide, urania, thorium oxide, plutonium oxide and fracium oxide.

Preferably, the Zirconium powder, wherein chlorine element mass percent are less than or equal to 0.05%.

Preferably, the Zirconium powder, according to ISO 13356：The 2008 ratio radiation activity measured are less than or equal to 100Bq/kg。

Preferably, the content of the Zirconium powder, its four directions and cube crystalline phase is more than or equal to 90%.

It is another aspect of this invention to provide that there is provided a kind of preparation method of the Zirconium powder, comprising the following steps：

(1) by zirconium precursor liquid solution heating chemically react so that zirconium it is cation ic-converted into zirconium oxide, zirconium hydroxide or Its hydrate, reaction to zirconium cationic monomer conversion is more than or equal to 90%, and reactant mixture containing zirconium is made；The zirconium precursor body is molten Liquid, its zirconium cation concn is less than or equal to 5.0mol/L；

(2) by obtained reactant mixture containing zirconium in step (1), regulation pH is less than or equal to 2.0, then carries out solid-liquid point From processing, solid containing zirconium and solution A are obtained；

(3) obtained solid containing zirconium in step (2) is configured to mass concentration with pure water between 5% to 70% and contains zirconium Slurries, and metal oxide M is added into the slurries containing zirconium according to required stoichiometric proportion_xO_yPresoma, M be selected from yttrium, One or more in calcium, magnesium, cerium, praseodymium, vanadium, molybdenum and titanium elements；

(4) by obtained slurries containing zirconium in step (3), regulation pH value is more than or equal to 6.0, then carried out at separation of solid and liquid Reason, obtains key component precursor solid and solution B；

(5) obtained key component precursor solid in step (4) is dried and calcined, the oxygen is made after washing granulation Change zirconium powder body.

Preferably, the preparation method, its described zirconium precursor body of step (1) is basic zirconium chloride, zirconium chloride, zirconium nitrate, sulphur One or more combinations of sour zirconium, zirconium carbonate and basic zirconium phosphate etc..

Preferably, the preparation method, its described step (1) reaction temperature is between 40 DEG C to 400 DEG C, and pressure exists 0.1MPa is between 3.25MPa；Preferable temperature is between 50 DEG C to 250 DEG C, and pressure is in 0.1MPa between 1.2MPa；More preferably Temperature is between 80 DEG C to 150 DEG C, and pressure is in 0.1MPa between 0.5MPa.

Preferably, the preparation method, its described step (5) calcining heat is between 600 DEG C to 1100 DEG C, heating rate Between 200 DEG C/h to 1200 DEG C/h, calcining maximum temperature is maintained 0.5 hour to 5 hours.

It is another aspect of this invention to provide that there is provided a kind of press body, Zirconium powder compacting provided by the present invention Into its key component is ZrO₂+HfO₂+M_xO_y, wherein M_xO_yFor metal oxide, its content is less than or equal to 15 moles of %, M choosings One or more from yttrium, calcium, magnesium, cerium, praseodymium, vanadium, molybdenum and titanium elements, the key component accounts for the quality hundred of Zirconium powder Divide ratio more than 90%, the every kind of mass fraction for accounting for the Zirconium powder of other metal oxides outside key component is less than Or equal to 0.01%.

Preferably, the press body, according to ISO 13356：2008 measure its than radiation activity be less than or equal to 100Bq/kg。

Preferably, the press body, is more than or equal to 6.0g/cm by the density measured of ISO 18754³, according to ASTM The grain size that E112 is measured is between 30 nanometers to 400 nanometers.

It is another aspect of this invention to provide that there is provided a kind of preparation method of the press body, the press body is by described Zirconium powder compacting sintering be made, sintering temperature is between 1100 DEG C to 1600 DEG C, and sintering time is 0.5 hour to 10 small When.

It is another aspect of this invention to provide that there is provided a kind of ceramic material, including described press body.

In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show Beneficial effect：

(1) Zirconium powder that the present invention is provided, its purity is high, and various metal oxide impurities are relative to existing oxidation Zirconium powder body is significantly reduced, therefore its radioactivity is significantly lower than existing zirconia material, for preparing high technology ceramics, such as biological pottery The materials such as porcelain, with obvious mechanical performance advantage, such as density, hardness, and security performance advantage, such as radioactivity.

(2) present invention provides zirconia powder preparation during chemical method synthesis zirconium oxide, can pass through regulation and control PH≤2.0 of solution after zirconium precursor body heating response so that the metal impurities in addition to zirconium are dissolved in instead in the form of cation Answer in liquid, most of metal cation contained in zirconium precursor body is then removed by the method for separation of solid and liquid；Then, it will reclaim Solid containing zirconium be dispersed in pure water and form slurries, the presoma of the additive such as addition yttrium regulates and controls pH >=6.0 of slurries, makes yttrium Be converted into hydroxide precipitation Deng additive, then carry out second of separation of solid and liquid with remove beyond the additives such as zirconium and yttrium it is cloudy from Son and cation.

(3) present invention provides zirconia powder preparation, by removing impurity anions, on the one hand can substantially reduce The release of poisonous and corrosive gas from anion during subsequent calcination, and mitigate corruption of these gases to production equipment Erosion is acted on；On the other hand, its compressing and sintering character can also be improved, be conducive to being made that relative density is higher, intensity and The more preferable ceramic sintered bodies of toughness.

(4) the press body good mechanical property that the present invention is provided, density is high, in addition with higher degree, relatively low radioactivity With preferable sintering character.

(5) ceramic material that the present invention is provided, purity is high, and good mechanical property can apply to high technology ceramics, such as bioceramic Field.

Brief description of the drawings

Fig. 1 is the X-ray diffracting spectrum of Zirconium powder made from embodiment 1；

Fig. 2 is the X-ray diffracting spectrum of the zirconium oxide precursor before embodiment 1 and the obtained calcining of comparative example 11.

Embodiment

In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below Not constituting conflict each other can just be mutually combined.

The Zirconium oxide powder that the present invention is provided, its key component is ZrO₂+HfO₂+M_xO_y, wherein M_xO_yFor metal oxide, Its molar percentage for accounting for key component is less than or equal to 15 moles of %, preferably between 2 moles of % to 8 moles of %, more preferably Between 2.5 moles of % to 3.5 moles of %, one or more of the M in yttrium, calcium, magnesium, cerium, praseodymium, vanadium, molybdenum and titanium elements, institute State key component and account for the mass percent of Zirconium powder more than 90%.Other metal oxides, such as silica, oxidation Iron, aluminum oxide, cesium oxide, cobalt oxide, strontium oxide strontia, oxidation polonium, radium oxide, urania, thorium oxide, plutonium oxide, fracium oxide etc., often The mass fraction for accounting for the Zirconium powder is planted less than or equal to 0.01%, preferably lower than or equal to 0.005%, more preferably less than Or equal to 0.001%；Chlorine element mass percent is less than or equal to 0.05%.

The Zirconium powder, according to ISO 13356：The 2008 ratio radiation activity measured are less than or equal to 100Bq/kg, Preferably lower than or equal to 50Bq/kg.The content of its four directions and cube crystalline phase is more than or equal to 90%, preferably greater than or equal to 95%, more preferably equal to or greater than 99%.

The metal oxide M_xO_y, M is to be selected from yttrium (Y), calcium (Ca), magnesium (Mg), cerium (Ce), praseodymium (Pr), vanadium (V), molybdenum (Mo), the one kind of element such as titanium (Ti) or its combination, x and y are greater than 0 and the integer less than or equal to 10, and it accounts for key component Molar percentage refer to the value being calculated as follows out.

The content of the four directions and cube crystalline phase refers to utilize monoclinic crystal in powder x-ray diffraction (XRD) collection of illustrative plates measured (111) and (11-1) face of phase, (111) face of tetragonal phase, the diffracted intensity in (111) face of cube crystalline phase is calculated as follows Obtained value.

Wherein, I is the diffracted intensity of correspondence lattice, and subscript m, t and c refer to monocline, four directions and cube crystalline phase respectively.It is used as knot The zirconium oxide of structure ceramic material is using tetragonal phase to be most preferable.Its crystalline phase, outward appearance (color and light transmittance) and water resistant heat deterioration Performance depends on the species and amount of the solid solution metal oxide added in building-up process.

Chlorine element mass percent refers to, by the Zirconium powder of certain massWith HNO₃With HF mixed acid with And excessive silver nitrate aqueous solution is cleared up at 150 DEG C, after zirconium powder body to be oxidized is completely dissolved, uses induced plasma emission spectrum Or the method such as Atomic absorption (AS) determines remaining Ag (ICP)⁺Amount, so that the chlorine ions that inverse goes out in Zirconium powder (M_cl-), the value calculated further according to following formula.

In the Zirconium powder, because hafnium and zirconium are difficult to separate, therefore hafnium always exists with certain proportion, does not influence Zirconium powder properties.

If the content of metallic additionses is too low, just it is not enough to prevent Tetragonal the turning to monoclinic phase of zirconium oxide Change, cause the tetragonal content of zirconium oxide product relatively low.On the other hand if the content of metallic additionses is too high, then it can lead Cause metallic additionses in the segregation at zirconia grains edge, influence the sintering character of Zirconium powder.In order to improve zirconium oxide pottery The biocompatibility and security of porcelain powder, should try one's best reduces the metals content impurity beyond above-mentioned metal oxide additive, Particularly on the influential aluminum oxide of the sintering character of ceramics, silica, iron oxide influential on the outward appearance of ceramics, and it is right The content of the influential caesium of ratio radiation activity, cobalt, strontium, radium, uranium and the thorium of ceramics etc..

The Zirconium oxide powder that the present invention is provided, its preparation method comprises the following steps：

(1) by zirconium precursor liquid solution heating chemically react so that zirconium it is cation ic-converted into zirconium oxide, zirconium hydroxide or Its hydrate, reaction to zirconium cationic monomer conversion is more than or equal to 90%, and reactant mixture containing zirconium is made；The zirconium precursor body is molten Liquid, its zirconium cation concn is less than or equal to 5.0mol/L.

The zirconium precursor body be basic zirconium chloride, zirconium chloride, zirconium nitrate, zirconium sulfate, zirconium carbonate and basic zirconium phosphate etc. one kind or A variety of combinations.The concentration of zirconium precursor liquid solution be less than or equal to 5.0 mol/Ls, preferably 0.1 mol/L to 2.0 moles/ Between rising, more preferably in 0.3 mol/L between 1.2 mol/Ls.

Reaction temperature is between 40 DEG C to 400 DEG C, and pressure is in 0.1MPa between 3.25MPa；Preferable temperature at 50 DEG C extremely Between 250 DEG C, pressure is in 0.1MPa between 1.2MPa；More preferably temperature between 80 DEG C to 150 DEG C, pressure in 0.1MPa extremely Between 0.5MPa.

The pH of reaction solution is less than or equal to 12.0, and preferably pH is less than or equal to 10.0, and more preferably pH is less than or equal to 8.0, inorganic acid, inorganic base or urea is commonly used to regulate and control the pH of zirconium precursor liquid solution.

Reaction time conversion ratio of zirconium ion in reaction solution is defined, it is to be ensured that the conversion ratio of zirconium ion is more than or equal to 90%, preferably greater than or equal to 95%, more preferably equal to or greater than 98%.If the conversion ratio of zirconium is less than 90%, then rear The loss of unconverted zirconium ion can be caused in continuous separation of solid and liquid process, so as to reduce the utilization ratio of raw material, increase zirconium oxide The manufacturing cost of powder.

The conversion ratio of so-called zirconium cation refers to the zirconium ion amount that the zirconium precursor body aqueous solution is converted during heating response Divided by the primary quantity before reaction, it is the value calculated according to following formula.

Here C_iRefer to the concentration of zirconium before heating response, C_fRefer to the concentration of zirconium after heating response, V refers to the volume of reaction solution.

(2) by obtained reactant mixture containing zirconium in step (1), regulation pH is less than or equal to 2.0, then carries out solid-liquid point From processing, solid containing zirconium and solution A are obtained.

If the pH of solution is more than 2.0, understands the metal cation formation precipitation beyond some zirconium, cause separation of solid and liquid The metal impurities beyond zirconium can not be fully removed, so as to cause the content overproof of impurity or ratio radiation in product Zirconium powder Activity is higher.

This method selection can be sufficiently separated the technological means of solid containing zirconium and liquid, such as centrifugation, filtering, press filtration, ultrafiltration It can be selected etc. one kind of technology or combination.

(3) obtained solid containing zirconium in step (2) is configured to mass concentration with pure water between 5% to 70% and contains zirconium Slurries, and metal oxide M is added into the slurries containing zirconium according to required stoichiometric proportion_xO_yPresoma, M be selected from yttrium, One or more in calcium, magnesium, cerium, praseodymium, vanadium, molybdenum and titanium elements.The pure water of the River Bank Stability containing zirconium is according to national standard GB One-level pure water as defined in 6682-2000 (suitable with U.S. clinical pathology meeting CAP Type I pure water).

The method of River Bank Stability containing zirconium, is added according to one-level pure water as defined in national standard GB 6682-2000 (with U.S. clinical disease Neo-Confucianism can CAP Type I pure water it is suitable), between mass concentration preferably 20% to 60%, between more preferably 35% to 50%.

Metal oxide M_xO_yPresoma can be selected for oxide, hydroxide, salt etc. of respective metal.It adds Plus form both can be compound in itself or with the compound prepare solution, can also be with colloidal sol or gel The nanometer or the particle of the metal oxide of micron size existed etc. form.

(4) by obtained slurries containing zirconium in step (3), regulation pH value is more than or equal to 6.0, preferably greater than or equal to 7.0, More preferably equal to or greater than 8.0, separation of solid and liquid processing is then carried out, main component precursor solid and solution B is obtained.

Adjust pH value and be more than or equal to 6.0 so that the metal oxide precursor of addition changes into precipitation, it is to avoid follow-up Separation of solid and liquid process in be lost in, so as to influence the structural stability of product zirconium oxide.After being sufficiently stirred for, to foregoing The slurries for regulating and controlling pH carry out separation of solid and liquid.

Except the anion such as dechlorination from solid containing zirconium, it can significantly decrease and come from having for anion during subsequent calcination The discharge of poison and corrosive gas, so as to mitigate the corrosion to process units and the pollution to environment.

(5) obtained main component precursor solid in step (4) is dried and calcined, the oxygen is made after washing granulation Change zirconium powder body.

The drying steps, as long as the form to solids does not bring the dry technology significantly changed, such as air-dried, low temperature Drying, spray drying, vacuum drying, freeze-drying, one kind of supercritical drying or combination can be selected.

The calcining step, the atmosphere of calcining can also can be carried out in atmosphere of inert gases in atmosphere.Heating Mode can use the one or more of electrical heating, chemical combustion heating, microwave heating etc..Highest calcining heat is at 600 DEG C To between 1100 DEG C, preferably between 850 DEG C to 1050 DEG C, more preferably between 900 DEG C to 1000 DEG C, and temperature is calcined in highest Degree holding 0.5 hour to 5.0 hours, preferably 1.0 hours to 3.0 hours, more preferably between 1.5 hours to 2.5 hours.Calcining Heating rate may be set between 200 DEG C/h to 1200 DEG C/h, preferably between 300 DEG C/h to 600 DEG C/h.

The washing step selects one-level as defined in foundation national standard GB 6682-2000, and (U.S. clinical pathology understand CAP's Type I are suitable) pure water eluted, to remove the solvable cation and anion for being attached to Zirconium powder surface.

The granulation step, can be added to Zirconium powder according to the one-level (U.S. as defined in national standard GB 6682-2000 Clinical pathology association CAP Type I are suitable) pure water progress wet type physical crushing, it can also be added during physical crushing including oxidation Toughener including the nano particles such as aluminium and/or including polyvinyl alcohol, polyacrylic acid, polymethylacrylic acid, paraffin, cellulose and The adhesives such as its derivative, until obtaining after desired particle diameter, then are spray-dried.

The press body that the present invention is provided, Zirconium powder sintering provided by the present invention is made, therefore its composition and ratio are put Penetrate activity identical with the Zirconium powder.The press body is more than or equal to 6.0g/cm by the density measured of ISO 18754³, The grain size that foundation ASTM E112 are measured is between 30 nanometers to 400 nanometers.

The press body its preparation method that the present invention is provided is specific as follows：

A, the Zirconium powder that provides of the present invention is pressed, according to circumstances can it is compressing from mould, The one kind of technology such as isostatic cool pressing is compressing, high temperature insostatic pressing (HIP) is compressing or its combination.To oxidation such as under 70MPa pressure Zirconium powder is carried out after compression molding, gives press body to load rubber mold by what is obtained, cold etc. in being carried out under 200MPa pressure Static pressure is suppressed.

B, above-mentioned press body is sintered.Atmosphere is sintered, both can in atmosphere, can also be in inert gas atmosphere Enclose middle progress.Mode of heating, one kind that can be from electrical heating, chemical combustion heating, microwave heating etc. or the heating of its combination Mode.Maximum sintering temperature may be set between 1100 DEG C to 1600 DEG C, preferably between 1100 DEG C to 1500 DEG C, more preferably Kept for 0.5 hour to 10.0 hours between 1200 DEG C to 1450 DEG C, and in maximum sintering temperature, it is preferably 1.0 hours to 5.0 small When, more preferably at 1.5 hours to 2.5 hours.The heating rate of sintering may be set between 200 DEG C/h to 1200 DEG C/h, excellent It is selected between 200 DEG C/h to 800 DEG C/h, more preferably between 300 DEG C/h to 600 DEG C/h.The sintering method can also rise Kept for 0.1 hour to 10.0 hours between 100 DEG C to 1100 DEG C before to maximum sintering temperature.

The ceramic material that the present invention is provided, including the press body that the present invention is provided.It has excellent mechanical performance and life Thing compatibility, its density is more than or equal to 6.0g/cm³, hardness be more than 10GPa, bending strength be more than 900MPa, than radiation activity It is low.The ceramic material, is particularly suitable for use as biological structure ceramic material, with long lifespan, radiates low feature, for example with Make artificial tooth processing grinding blank, specific such as orthodontic bracket, or artificial bone turned blank, specific such as artificial femur joint biology Ceramic material.

It is embodiment below：

Embodiment 1

A kind of Zirconium oxide powder, its key component is ZrO₂+HfO₂+Y₂O₃, Y₂O₃The molar percentage for accounting for main component is 2.8%, the mass percent that the main component accounts for Zirconium powder is 99.9%.Containing other metal oxide contents, specifically 1 is shown in Table, chlorine element mass percent is 0.035%.

Other metal oxide contents (mass fraction) of table 1

Note：Detection is limited to 0.00001%

The Zirconium powder, according to ISO 13356：The 2008 ratio radiation activity 80Bq/kg measured.It is wherein cubic and vertical The content of prismatic crystal phase is 100%.

Described Zirconium oxide powder, its preparation method comprises the following steps：

(1) by 0.5mol/L zirconium oxychloride solution, heating chemically reacts so that zirconium is cation ic-converted into oxidation Zirconium, zirconium hydroxide or its hydrate, react to zirconium cationic monomer conversion 98.8%, and reactant mixture containing zirconium is made.

150 DEG C of heating response temperature, pressure 0.41MPa.

(2) by obtained reactant mixture containing zirconium in step (1), with ammoniacal liquor regulation pH=1.0, then 6000 × g from Centrifuged 30 minutes under mental and physical efforts, carry out separation of solid and liquid processing, obtain solid containing zirconium and solution A.

(3) obtained solid containing zirconium in step (2) is configured to mass concentration with pure water and is 45% slurries containing zirconium, and added Plus relative to key component be 5.6 moles of % yttrium chlorides.

(4) by obtained slurries containing zirconium in step (3), pH=8.5 is adjusted using ammoniacal liquor, then in 4000 × g centrifugal force Lower centrifugation 30 minutes, carries out separation of solid and liquid processing, obtains main component precursor solid and solution B.

(5) obtained main component precursor solid in step (4) is configured to be spray-dried and calcine after slurries with pure water, The Zirconium powder is made after washing granulation.

The calcining step, in air atmosphere, using electrical heating.1000 DEG C of highest calcining heat, temperature is calcined in highest Degree is kept for 2.0 hours.The heating rate of calcining is 300 DEG C/h.

Washing step one-level as defined in foundation national standard GB 6682-2000 be (U.S. clinical pathology meeting CAP's Type I are suitable) pure water carry out elution 3 times.

The granulation step, can to Zirconium powder add pure water carry out, be put into ball grinder, with a diameter of 6mm and 2mm zirconia ball ball milling 5 hours together, toughener aluminum oxide nanoparticle is added during physical crushing, and (particle diameter is 10 to 20nm Between) and adhesive polyacrylic acid, until average grain diameter is less than after 1.0 microns, then it is spray-dried, obtaining average grain diameter is 3.5 microns of powder.

The X-ray diffracting spectrum of the Zirconium powder, as shown in Figure 1.As seen from Figure 1, oxygen made from the inventive method Change zirconium powder body to calcine 2 hours at 1000 DEG C, its crystalline phase is 100% Tetragonal, and equation (Scherrer is strangled according to thanking Equation the grain size) calculated is 28.3nm.

A kind of press body, is sintered by the Zirconium powder and is made, therefore its composition and than the radiation activity and oxidation Zirconium powder body phase is same.The press body is 6.06g/cm by the density measured of ISO 18754³, the crystal grain measured according to ASTM E112 Between 100 nanometers to 360 nanometers.

The press body its preparation method is specific as follows：

A, the Zirconium powder provided the present invention are first after 70MPa compression moldings, then the isostatic cool pressing pressure under 200MPa Type is made.

B, above-mentioned press body is sintered in air atmosphere, from electrical heating.It is being raised to maximum sintering temperature Kept for 1.0 hours, 1450 DEG C of maximum sintering temperature, kept for 2.0 hours in maximum sintering temperature at 500 DEG C before.The liter of sintering Warm speed is set as 600 DEG C/h.

A kind of ceramic material, including the press body that the present invention is provided, its density are 6.06g/cm³, hardness be 13.7GPa, Intensity is 1359MPa, is 80Bq/kg. than radiation activity.The ceramic material, the artificial tooth that is particularly suitable for use in processing grinding blank, tool Body such as orthodontic bracket, or artificial bone turned blank, it is specific such as artificial femur joint.

Embodiment 2

A kind of Zirconium oxide powder, its key component is ZrO₂+HfO₂+Y₂O₃, wherein Y₂O₃Account for the Mole percent of main component Than for 2.5%, the main component accounts for the mass percent 99.9% of Zirconium powder.Containing other metal oxides, it is specifically shown in Table 2, chlorine element mass percent is 0.043%.

Other metal oxide contents (mass fraction) of table 2

Note：Detection is limited to 0.00001%

The Zirconium powder, according to ISO 13356：The 2008 ratio radiation activity 75Bq/kg measured.It is wherein cubic and vertical The content of prismatic crystal phase is 99.5%.

(1) by 1.2mol/L zirconium nitrate solution, heating chemically react so that zirconium it is cation ic-converted into zirconium oxide, Zirconium hydroxide or its hydrate, react to zirconium cationic monomer conversion 99.2%, and reactant mixture containing zirconium is made.

250 DEG C of heating response temperature, pressure 1.5MPa.

(2) by obtained reactant mixture containing zirconium in step (1), with urea regulation pH=1.6, then 6000 × g from Centrifuged 30 minutes under mental and physical efforts, carry out separation of solid and liquid processing, obtain solid containing zirconium and solution A.

(3) obtained solid containing zirconium in step (2) is configured to mass concentration with pure water and is 50% slurries containing zirconium, and added Plus relative to the yttrium chloride that key component is 5.0 moles of %.

(4) by obtained slurries containing zirconium in step (3), pH=8.0 is adjusted using ammoniacal liquor, then in 5000 × g centrifugal force Lower centrifugation 30 minutes, carries out separation of solid and liquid processing, obtains main component precursor solid and solution B.

(5) obtained main component precursor solid in step (4) is dried in vacuo and calcined, institute is made after washing granulation State Zirconium powder.

The calcining step, in air atmosphere, using electrical heating.950 DEG C of highest calcining heat, in highest calcining heat Kept for 2.5 hours.The heating rate of calcining is set as 200 DEG C/h.

The granulation step, can to Zirconium powder add pure water carry out, be put into ball grinder, with a diameter of 6mm and 2mm zirconia ball ball milling 5 hours together, added during physical crushing toughener aluminum oxide nanoparticle (particle diameter 10 to 20nm) and Adhesive polyethylene alcohol, until average grain diameter is less than after 1.0 microns, then is spray-dried.

A kind of press body, is sintered by the Zirconium powder and is made, therefore its composition and than the radiation activity and oxidation Zirconium powder body phase is same.The press body by ISO 18754 measure it is close be 6.03g/cm³, exist according to the crystal grain that ASTM E112 are measured Between 50 nanometers to 300 nanometers.

The press body its preparation method is specific as follows：

A, the Zirconium powder provided the present invention, are first pressed in 70MPa compression moldings, then in 200MPa isostatic cool pressings Type is made.

B, above-mentioned press body is sintered in air atmosphere, from electrical heating.It is being raised to maximum sintering temperature Kept for 0.5 hour, 1350 DEG C of maximum sintering temperature, kept for 2.5 hours in maximum sintering temperature at 550 DEG C before.The liter of sintering Warm speed is set as 300 DEG C/h.

A kind of ceramic material, including the press body that the present invention is provided, its density are 6.03g/cm³, hardness be 13.1GPa, Intensity is 1230MPa, is 75Bq/kg than radiation activity.The ceramic material, the artificial tooth that is particularly suitable for use in processing grinding blank, tool Body such as orthodontic bracket, or artificial bone turned blank, specific such as artificial femur joint.

Embodiment 3

A kind of Zirconium oxide powder, its key component is ZrO₂+HfO₂+Y₂O₃, wherein Y₂O₃Account for the Mole percent of main component Than for 3.5%, the main component accounts for the mass percent 99.9% of Zirconium powder.Containing other metal oxides, it is specifically shown in Table 3, chlorine element mass percent is 0.038%.

Other metal oxide contents (mass fraction) of table 3

Note：Detection is limited to 0.00001%

The Zirconium powder, according to ISO 13356：The 2008 ratio radiation activity 68Bq/kg measured.It is wherein cubic and vertical The content of prismatic crystal phase is 98.7%.

(1) by 0.3mol/L zirconium oxychloride solution, heating chemically reacts so that zirconium is cation ic-converted into oxidation Zirconium, zirconium hydroxide or its hydrate, reaction to zirconium cationic monomer conversion are 98.2%, and reactant mixture containing zirconium is made.

400 DEG C of heating response temperature, pressure 3.25MPa.

(2) by obtained reactant mixture containing zirconium in step (1), with ammoniacal liquor regulation pH=1.8, then 6000 × g from Centrifuged 30 minutes under mental and physical efforts, carry out separation of solid and liquid processing, obtain solid containing zirconium and solution A.

(3) obtained solid containing zirconium in step (2) is configured to mass concentration with pure water and is 60% slurries containing zirconium, and added Plus relative to 7.0 moles of % of key component yttrium chloride.

(4) by obtained slurries containing zirconium in step (3), pH=7.0 is adjusted using ammoniacal liquor, is then centrifuged for, be 0.1 with aperture The cellulose membrane of micron carries out suction filtration as filter membrane, reaches the purpose of separation of solid and liquid, obtains main component precursor solid and solution B。

(5) obtained main component precursor solid in step (4) is air-dried and calcined in room temperature, be made after washing granulation The Zirconium powder.

The calcining step, in air atmosphere, using electrical heating.900 DEG C of highest calcining heat, in highest calcining heat Kept for 3.0 hours.The heating rate of calcining is set as 450 DEG C/h.

The granulation step, can to Zirconium powder add pure water carry out, be put into ball grinder, with a diameter of 6mm and 2mm zirconia ball ball milling 5 hours together, toughener aluminum oxide nanoparticle is added during physical crushing, and (particle diameter is 10 to 20nm Between) and adhesive polymethylacrylic acid, until after obtaining particle diameter less than 1.0 microns, then be spray-dried.

A kind of press body, is sintered by the Zirconium powder and is made, therefore its composition and than the radiation activity and oxidation Zirconium powder body phase is same.The press body is 6.08g/cm by the density measured of ISO 18754³, the crystal grain measured according to ASTM E112 Between 30 nanometers to 200 nanometers.

The press body its preparation method is specific as follows：

A, the Zirconium powder provided the present invention are first in 70MPa compression moldings, then the isostatic cool pressing compacting under 200MPa Shaping.

B, above-mentioned press body is sintered in air atmosphere, from electrical heating, is being raised to maximum sintering temperature Kept for 4.0 hours, 1300 DEG C of maximum sintering temperature, kept for 1.0 hours in maximum sintering temperature at 600 DEG C before.The liter of sintering Warm speed is set as 800 DEG C/h.

A kind of ceramic material, including the press body that the present invention is provided, its density are 6.08g/cm³, hardness be 13.8GPa, Intensity is 1385MPa, is 68Bq/kg than radiation activity.The ceramic material, the artificial tooth that is particularly suitable for use in processing grinding blank, tool Body such as orthodontic bracket, or artificial bone turned blank, specific such as artificial femur joint.

Embodiment 4

A kind of Zirconium oxide powder, its key component is ZrO₂+HfO₂+Y₂O₃, wherein Y₂O₃Account for the Mole percent of main component Than for 2.0%, the main component accounts for the mass percent 99.9% of Zirconium powder.Containing other metal oxides, it is specifically shown in Table 4, chlorine element mass percent is 0.026%.

Other metal oxide contents (mass fraction) of table 4

Note：Detection is limited to 0.00001%

The Zirconium powder, according to ISO 13356：The 2008 ratio radiation activity measured are 95Bq/kg.Wherein four directions and The content of cube crystalline phase is 95%.

(1) by 2.0mol/L sulfuric acid zirconium solution, heating chemically react so that zirconium it is cation ic-converted into zirconium oxide, Zirconium hydroxide or its hydrate, react to zirconium cationic monomer conversion 95.3%, and reactant mixture containing zirconium is made.

110 DEG C of heating response temperature, pressure 0.15MPa.

(2) by obtained reactant mixture containing zirconium in step (1), with ammoniacal liquor regulation pH=0.56, then 6000 × g from Centrifuged 30 minutes under mental and physical efforts, carry out separation of solid and liquid processing, obtain solid containing zirconium and solution A.

(3) obtained solid containing zirconium in step (2) is configured to mass concentration with pure water and is 70% slurries containing zirconium, and added Plus relative to the yttrium chloride that key component is 4.0 moles of %.

(4) by obtained slurries containing zirconium in step (3), pH=6.0 is adjusted using ammoniacal liquor, then in 6000 × g centrifugal force Lower centrifugation 30 minutes, carries out separation of solid and liquid processing, obtains main component precursor solid and solution B.

(5) obtained main component precursor solid in step (4) is spray-dried and calcined, institute is made after washing granulation State Zirconium powder.

The calcining step, in nitrogen atmosphere, using electrical heating.1100 DEG C of highest calcining heat, temperature is calcined in highest Degree is kept for 0.5 hour.The heating rate of calcining is set as 600 DEG C/h.

The granulation step, can to Zirconium powder add pure water carry out, be put into ball grinder, with a diameter of 6mm and 2mm zirconia ball ball milling 5 hours together, toughener aluminum oxide nanoparticle is added during physical crushing, and (particle diameter is 10 to 20nm Between) and adhesive carboxymethyl cellulose, until after obtaining particle diameter less than 1.0 microns, then be spray-dried.

A kind of press body, is sintered by the Zirconium powder and is made, therefore composition and than the radiation activity and zirconium oxide Powder is identical.The press body by ISO 18754 measure it is close be 6.08g/cm³, exist according to the crystal grain that ASTM E112 are measured Between 150 nanometers to 400 nanometers.

The press body its preparation method is specific as follows：

A, the Zirconium powder first compression molding under 70MPa provided the present invention, then the isostatic cool pressing pressure under 200MPa Type is made.

B, above-mentioned press body is sintered in nitrogen atmosphere, heated from microwave.It is being raised to highest sintering temperature Kept for 0.1 hour, 1600 DEG C of maximum sintering temperature, kept for 0.5 hour in maximum sintering temperature at 1100 DEG C before degree.Sintering Heating rate is set as 1200 DEG C/h.

A kind of ceramic material, including the press body that the present invention is provided, density 6.08g/cm³, hardness 13.9GPa, intensity 1506MPa, than radiation activity 49Bq/kg.The ceramic material, the artificial tooth that is particularly suitable for use in processing grinding blank is specific such as correction Bracket, or artificial bone turned blank, specific such as artificial femur joint.

Embodiment 5

A kind of Zirconium oxide powder, its key component is ZrO₂+HfO₂+TiO₂+Y₂O₃, wherein TiO₂And Y₂O₃Account for main respectively The molar percentage of component is 12.0% and 3.0%, and the main component accounts for the mass percent 99.8% of Zirconium powder.Contain Other metal oxides, are specifically shown in Table 5, chlorine element mass percent is 0.045%.

Other metal oxide contents (mass fraction) of table 5

Note：Detection is limited to 0.00001%

The Zirconium powder, according to ISO 13356：The 2008 ratio radiation activity 98Bq/kg measured.It is wherein cubic and vertical The content of prismatic crystal phase is 90.5%.

(1) by 5.0mol/L zirconium oxychloride solution, heating chemically reacts so that zirconium is cation ic-converted into oxidation Zirconium, zirconium hydroxide or its hydrate, react to zirconium cationic monomer conversion 90%, and reactant mixture containing zirconium is made.

80 DEG C of heating response temperature, pressure 0.1MPa.

(2) by obtained reactant mixture containing zirconium in step (1), with ammoniacal liquor regulation pH=0.1, then, 6000 × g from Centrifuged 30 minutes under mental and physical efforts, carry out separation of solid and liquid processing, obtain solid containing zirconium and solution A.

(3) obtained solid containing zirconium in step (2) is configured to mass concentration with pure water and is 20% slurries containing zirconium, and added Plus relative to the yttrium chloride and 12.0 moles of % titanium chloride that key component is 6.0 moles of %.

(4) by obtained slurries containing zirconium in step (3), pH=10.5 is adjusted using sodium hydroxide, then using 4000 × g Centrifugal force carries out separation of solid and liquid processing in 30 minutes, obtains main component precursor solid and solution B.

The calcining step, in air atmosphere, using electrical heating.850 DEG C of highest calcining heat, in highest calcining heat Kept for 5.0 hours.The heating rate of calcining is set as 1200 DEG C/h.

Washing step one-level as defined in foundation national standard GB 6682-2000 be (U.S. clinical pathology meeting CAP's Type I are suitable) pure water carry out elution 5 times.

The granulation step, can to Zirconium powder add pure water carry out, be put into ball grinder, with a diameter of 6mm and 2mm zirconia ball ball milling 5 hours together, toughener aluminum oxide nanoparticle is added during physical crushing, and (particle diameter is 10 to 20nm Between) and adhesive polyacrylic acid, until after obtaining particle diameter less than 1.0 microns, then be spray-dried.

A kind of press body, is sintered by the Zirconium powder and is made, therefore its composition and than the radiation activity and oxidation Zirconium powder body phase is same.The press body is 6.01g/cm by the density measured of ISO 18754³, the crystal grain measured according to ASTM E112 Between 35 nanometers to 390 nanometers.

The press body its preparation method is specific as follows：

A, the Zirconium powder provided the present invention first carry out hot static pressure compacting in 70MPa compression moldings, again in 200MPa Shaping.

B, above-mentioned press body is sintered in air atmosphere, from electrical heating.It is being raised to maximum sintering temperature Kept for 8.0 hours, then kept for 2 hours at 500 DEG C, 1500 DEG C of maximum sintering temperature, in maximum sintering temperature at 110 DEG C before Kept for 1.5 hours.The heating rate of sintering is set as 200 DEG C/h.

A kind of ceramic material, including the press body that the present invention is provided, density 6.01g/cm³, hardness 12.9GPa, intensity be 1120MPa.The ceramic material, the artificial tooth that is particularly suitable for use in processing grinding blank is specific as orthodontic bracket, or artificial bone are processed Blank, specific such as artificial femur joint.

Embodiment 6

A kind of Zirconium oxide powder, its key component is ZrO₂+HfO₂+MgO+Y₂O₃, wherein MgO and Y₂O₃Account for main component Molar percentage is respectively 5.0 moles of % and 3.0 mole of %, and the main component accounts for the mass percent of Zirconium powder 99.87%.Containing other metal oxides, 6 are specifically shown in Table, chlorine element mass percent is 0.039%.

Other metal oxide contents (mass fraction) of table 6

Note：Detection is limited to 0.00001%

The Zirconium powder, according to ISO 13356：The 2008 ratio radiation activity 76Bq/kg measured.It is wherein cubic and vertical The content of prismatic crystal phase is 92.1%

(1) by 0.1mol/L zirconium oxychloride solution, heating chemically reacts so that zirconium is cation ic-converted into oxidation Zirconium, zirconium hydroxide or its hydrate, react to zirconium cationic monomer conversion 99.9%, and reactant mixture containing zirconium is made.

40 DEG C of heating response temperature, pressure 0.1MPa.

(2) by obtained reactant mixture containing zirconium in step (1), pH=2.0 is adjusted with HCl, is then centrifuged in 6000 × g Centrifuged 30 minutes under power, carry out separation of solid and liquid processing, obtain solid containing zirconium and solution A.

(3) obtained solid containing zirconium in step (2) is configured to mass concentration with pure water and is 5% slurries containing zirconium, and added Plus relative to the magnesium chloride that key component is 6.0 moles of % yttrium chlorides and 5.0 moles of %.

(4) by obtained slurries containing zirconium in step (3), using sodium hydroxide regulation pH=11.0, then 3000 × g from Centrifuged 30 minutes under mental and physical efforts, carry out separation of solid and liquid processing, obtain main component precursor solid and solution B.

(5) main component precursor solid is in 110 DEG C of low temperature dryings and calcines by obtained in step (4), after washing granulation The Zirconium powder is made.

The calcining step, in air atmosphere, using electrical heating.600 DEG C of highest calcining heat, in highest calcining heat Kept for 5.0 hours.The heating rate of calcining is set as 300 DEG C/h.

The granulation step, can to Zirconium powder add pure water carry out, be put into ball grinder, with a diameter of 6mm and 2mm zirconia ball ball milling 5 hours together, toughener aluminum oxide nanoparticle is added during physical crushing, and (particle diameter is 10 to 20nm Between) and adhesive POLYPROPYLENE GLYCOL, until after obtaining particle diameter less than 1.0 microns, then be spray-dried.

A kind of press body, is sintered by the Zirconium powder and is made, therefore its composition and than the radiation activity and oxidation Zirconium powder body phase is same.The press body is 6.02g/cm by the density measured of ISO 18754³, the crystal grain measured according to ASTM E112 Between 30 nanometers to 50 nanometers.

The press body its preparation method is specific as follows：

A, the Zirconium powder elder generation provided the present invention are pressed into 70MPa compression moldings, then in 200MPa isostatic cool pressings Type.

B, above-mentioned press body is sintered in air atmosphere, from electrical heating.It is being raised to maximum sintering temperature Kept for 2.0 hours, 1200 DEG C of maximum sintering temperature, kept for 5.0 hours in maximum sintering temperature at 650 DEG C before.The liter of sintering Warm speed is set as 500 DEG C/h.

A kind of ceramic material, including the press body that the present invention is provided, density is 6.02g/cm³, hardness be 11.3GPa, it is strong Spend for 1009MPa, be 76Bq/kg than radiation activity.The ceramic material, the artificial tooth that is particularly suitable for use in processing grinding blank, specifically Such as orthodontic bracket, or artificial bone turned blank, specific such as artificial femur joint.

Embodiment 7

A kind of Zirconium oxide powder, its key component is ZrO₂+HfO₂+Y₂O₃, wherein Y₂O₃Account for the Mole percent of main component Than for 8.0%, the mass percent that the main component accounts for Zirconium powder is 99.9%.Containing other metal oxides, specifically 7 are shown in Table, chlorine element mass percent is 0.047%.

Other metal oxide contents (mass fraction) of table 7

Note：Detection is limited to 0.00001%

The Zirconium powder, according to ISO 13356：The 2008 ratio radiation activity measured are 45Bq/kg.Its is cubic and vertical The content of prismatic crystal phase is 99.9%.

(1) by 0.6mol/L zirconium oxychloride solution, heating chemically reacts so that zirconium is cation ic-converted into oxidation Zirconium, zirconium hydroxide or its hydrate, react to zirconium cationic monomer conversion 99.7%, and reactant mixture containing zirconium is made.

Heating response temperature 50 C, pressure 0.1MPa.

(2) by obtained reactant mixture containing zirconium in step (1), with ammoniacal liquor regulation pH=0.23, then 6000 × g from Centrifuged 30 minutes under mental and physical efforts, carry out separation of solid and liquid processing, obtain solid containing zirconium and solution A.

(3) obtained solid containing zirconium in step (2) is configured to mass concentration with pure water and is 35% slurries containing zirconium, and added Plus relative to the yttrium chloride that key component is 16.0 moles of %.

(4) by obtained slurries containing zirconium in step (3), pH value=8.5 is adjusted using ammoniacal liquor, are then centrifuged in 4000 × g Centrifuged 30 minutes under power, carry out separation of solid and liquid processing, obtain main component precursor solid and solution B.

The calcining step, in air atmosphere, using electrical heating.1050 DEG C of highest calcining heat, temperature is calcined in highest Degree is kept for 1.5 hours.The heating rate of calcining can be set as 300 DEG C/h.

A kind of press body, is sintered by the Zirconium powder and is made, therefore its composition and than the radiation activity and oxidation Zirconium powder body phase is same.The press body is 6.04g/cm by the density measured of ISO 18754³, the crystal grain measured according to ASTM E112 Size is between 30 nanometers to 300 nanometers.

The press body its preparation method is specific as follows：

A, to the Zirconium powder that provides of the present invention, the first compression molding under 70MPa, then under 200MPa isostatic cool pressing into Type.

B, above-mentioned press body is sintered in air atmosphere, from electrical heating.It is being raised to maximum sintering temperature Kept for 2.0 hours, 1100 DEG C of maximum sintering temperature, kept for 10.0 hours in maximum sintering temperature at 700 DEG C before.The liter of sintering Warm speed is set as 200 DEG C/h.

A kind of ceramic material, including the press body that the present invention is provided, its density are 6.05g/cm³, hardness be 10.5GPa, Intensity is 970MPa, is 45Bq/kg than radiation activity.The ceramic material, the artificial tooth that is particularly suitable for use in processing grinding blank, specifically Such as orthodontic bracket, or artificial bone turned blank, specific such as artificial femur joint.

Embodiment 8

A kind of Zirconium oxide powder, its key component is ZrO₂+HfO₂+CeO₂+Y₂O₃, CeO₂And Y₂O₃Account for rubbing for main component Your percentage is respectively 8.0% and 3.0%, and the mass percent that the main component accounts for Zirconium powder is 99.7%.Containing it His metal oxide content, is specifically shown in Table 8, chlorine element mass percent is 0.042%.

Other metal oxide contents (mass fraction) of table 8

Note：Detection is limited to 0.00001%

The Zirconium powder, according to ISO 13356：The 2008 ratio radiation activity 59Bq/kg measured.It is wherein cubic and vertical The content of prismatic crystal phase is 99.7%.

(1) by 2.5mol/L zirconium oxychloride solution, heating chemically reacts so that zirconium is cation ic-converted into oxidation Zirconium, zirconium hydroxide or its hydrate, react to zirconium cationic monomer conversion 94.8%, and reactant mixture containing zirconium is made.

105 DEG C of heating response temperature, pressure 0.12MPa.

(2) by obtained reactant mixture containing zirconium in step (1), with ammoniacal liquor regulation pH=0.46, then 6000 × g from Centrifuged 30 minutes under mental and physical efforts, carry out separation of solid and liquid processing, obtain solid containing zirconium and solution A.

(3) obtained solid containing zirconium in step (2) is configured to mass concentration with pure water and is 40% slurries containing zirconium, and added Plus relative to the yttrium chloride and 8.0 moles of % cerium chloride that key component is 6.0 moles of %.

(4) by obtained slurries containing zirconium in step (3), pH=9.0 is adjusted using ammoniacal liquor, then in 4000 × g centrifugal force Lower centrifugation 30 minutes, carries out separation of solid and liquid processing, obtains main component precursor solid and solution B.

The calcining step, in air atmosphere, using electrical heating.1000 DEG C of highest calcining heat, temperature is calcined in highest Degree is kept for 1.0 hours.The heating rate of calcining is 300 DEG C/h.

The granulation step, can to Zirconium powder add pure water carry out, be put into ball grinder, with a diameter of 6mm and 2mm zirconia ball ball milling 5 hours together, toughener aluminum oxide nanoparticle is added during physical crushing, and (particle diameter is 10 to 20nm Between) and adhesive polyacrylic acid, until average grain diameter is less than after 1.0 microns, then be spray-dried obtaining Zirconium powder.

A kind of press body, is sintered by the Zirconium powder and is made, therefore its composition and than the radiation activity and oxidation Zirconium powder body phase is same.The press body is 6.04g/cm by the density measured of ISO 18754³, the crystal grain measured according to ASTM E112 Between 30 nanometers to 350 nanometers.

The press body its preparation method is specific as follows：

B, above-mentioned press body is sintered in air atmosphere, from electrical heating.It is being raised to maximum sintering temperature Kept for 2.0 hours, 1400 DEG C of maximum sintering temperature, kept for 3.0 hours in maximum sintering temperature at 500 DEG C before.The liter of sintering Warm speed is set as 600 DEG C/h.

A kind of ceramic material, including the press body that the present invention is provided, its density are 6.04g/cm³, hardness be 12.0GPa, Intensity is 1005MPa, is 59Bq/kg. than radiation activity.The ceramic material, the artificial tooth that is particularly suitable for use in processing grinding blank, tool Body such as orthodontic bracket, or artificial bone turned blank, it is specific such as artificial femur joint.

Embodiment 9

A kind of Zirconium oxide powder, its key component is ZrO₂+HfO₂+Y₂O₃, Y₂O₃The molar percentage for accounting for main component is 3.0%, the mass percent that the main component accounts for Zirconium powder is 99.9%.Containing other metal oxide contents, specifically 9 are shown in Table, chlorine element mass percent is 0.034%.

Other metal oxide contents (mass fraction) of table 9

Note：Detection is limited to 0.00001%

The Zirconium powder, according to ISO 13356：The 2008 ratio radiation activity measured are 91Bq/kg.Its is cubic and vertical The content of prismatic crystal phase is 99.9%.

Described Zirconium oxide powder, its preparation method is same as Example 1, and only step (2) pH is adjusted to 1.0.

Embodiment 10

A kind of Zirconium oxide powder, its key component is ZrO₂+HfO₂+Y₂O₃, Y₂O₃The molar percentage for accounting for main component is 3.0%, the mass percent that the main component accounts for Zirconium powder is 99.9%.Containing other metal oxide contents, specifically 10 are shown in Table, chlorine element mass percent is 0.034%.

Other metal oxide contents (mass fraction) of table 10

Note：Detection is limited to 0.00001%

The Zirconium powder, according to ISO 13356：The 2008 ratio radiation activity measured are 72Bq/kg.Its is cubic and vertical The content of prismatic crystal phase is 99.9%.

Described Zirconium oxide powder, its preparation method is same as Example 1, and only step (4) pH is adjusted to 7.0.

Embodiment 11 (comparative example)

A kind of Zirconium oxide powder, its key component is ZrO₂+HfO₂+Y₂O₃, wherein Y₂O₃Account for the Mole percent of main component Than for 2.8%, the main component accounts for the mass percent 96.6% of Zirconium powder.Containing other metal oxides, it is specifically shown in Table 11, chlorine element mass percent is 1.34%.

Other metal oxide contents (mass fraction) of table 11

Note：Detection is limited to 0.00001%

The Zirconium powder, according to ISO 13356：The 2008 ratio radiation activity measured are 357Bq/kg.Its four directions and The content of cube crystalline phase is 85%.

(1) by 0.5mol/L basic zirconium chloride, heating chemically reacts so that zirconium is cation ic-converted into zirconium oxide, hydrogen Zirconium oxide or its hydrate, react to zirconium cationic monomer conversion 98.6%, and reactant mixture containing zirconium is made.

150 DEG C of heating response temperature, pressure 0.41MPa.

(2) it is 5.6 moles of % chlorinations to be added into step (1) in obtained reactant mixture containing zirconium relative to key component Yttrium.It is spray-dried and calcines after stirring, is made to compare after washing granulation and uses Zirconium powder.

The calcining step, in air atmosphere, using electrical heating.1000 DEG C of highest calcining heat, temperature is calcined in highest Degree is kept for 2.0 hours.The heating rate of calcining is set as 300 DEG C/h.

The granulation step, can to Zirconium powder add pure water carry out, be put into ball grinder, with a diameter of 6mm and 2mm zirconia ball ball milling 5 hours together, add adhesive polyacrylic acid during physical crushing, until it is micro- less than 1.0 to obtain particle diameter Meter Hou, then be spray-dried.

A kind of press body, is sintered by the Zirconium powder and is made, therefore its composition and than the radiation activity and oxidation Zirconium powder body phase is same.The press body is 5.6g/cm by the density measured of ISO 18754³, the crystal grain measured according to ASTM E112 Size is between 350 to 4000 nanometers.

The press body its preparation method is specific as follows：

A, to the Zirconium powder that provides of the present invention using first under 70MPa compression molding, again under 200MPa it is cold etc. quiet Pressure is compressing

B, above-mentioned press body is sintered in air atmosphere, from electrical heating.It is being raised to maximum sintering temperature Kept for 1.0 hours, 1450 DEG C of maximum sintering temperature, kept for 2.0 hours in maximum sintering temperature at 500 DEG C before.The liter of sintering Warm speed is 600 DEG C/h.

The ceramic material that comparative example is provided, including the press body that comparative example is provided, density 5.6g/cm³, hardness 8.7GPa, Intensity 650MPa, than radiation activity 357Bq/kg.Obtained ceramic material is not suitable for artificial tooth processing grinding blank or artificial bone Bone turned blank.

Compare understand the present invention by regulate and control pH twice and separation of solid and liquid can remove Si, Al, Fe for containing in raw material and The impurity such as radioactive element so that the impurity content and ratio radiation activity of obtained Zirconium powder are significantly reduced, can be complete Meet ISO 13356：The corresponding requirements of 2008 pairs of bioceramics.Furthermore it is also possible to find out in second of centrifugal process, add Yttrium presoma be not almost lost in, so there is no any influence to the structural stability of final Zirconium powder.

The X-ray diffracting spectrum that zirconium oxide made from embodiment 1 and comparative example 11 is measured before calcination is as shown in Figure 2.By Fig. 2 is visible, Zirconium powder made from comparative example 11 before being calcined, without being more than less than or equal to 2.0 and pH in pH or Equal to the separation of solid and liquid under the conditions of 6.0 two, except the impurity such as Si, Al, Fe and radioactive element will not be removed, and come from The acid or alkali added when chlorion and the pH regulation and control of raw material can form crystallization in the drying process.In subsequent calcination process, These impurity can be converted into the corrosivity such as chlorine, hydrogen chloride, NOx and environmental contaminants.And the method for the embodiment of the present invention 1 is made Zirconium powder before being calcined, after separation of solid and liquid twice, the crystallization of ammonium chloride is not just detected, follow-up Will not also be formed in calcination process has corrosiveness and gas influential on environment on equipment.

As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not used to The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include Within protection scope of the present invention.

Claims

1. a kind of preparation method of Zirconium powder, it is characterised in that comprise the following steps：

(1) heating of zirconium precursor liquid solution is chemically reacted so that zirconium is cation ic-converted into zirconium oxide, zirconium hydroxide or its water Compound, reaction to zirconium cationic monomer conversion is more than or equal to 90%, and reactant mixture containing zirconium is made；The zirconium precursor liquid solution, Its zirconium cation concn is less than or equal to 5.0mol/L；

(2) by obtained reactant mixture containing zirconium in step (1), regulation pH is less than or equal to 2.0, then carried out at separation of solid and liquid Reason, obtains solid containing zirconium and filter solution A；

(3) obtained solid containing zirconium in step (2) is configured to mass concentration being starched containing zirconium between 5% to 70% with pure water Liquid, and metal oxide M is added into the slurries containing zirconium according to required stoichiometric proportion_xO_yPresoma, M be selected from yttrium, calcium, One or more in magnesium, cerium, praseodymium, vanadium, molybdenum and titanium elements；

(4) by obtained slurries containing zirconium in step (3), then regulation pH value is carried out at separation of solid and liquid to more than or equal to 6.0 Reason, obtains key component precursor solid and solution B；

(5) obtained key component precursor solid in step (4) is dried and calcined, the zirconium oxide is made after washing granulation Powder.

2. preparation method as claimed in claim 1, it is characterised in that step (1) the zirconium precursor body is basic zirconium chloride, chlorination One or more combinations in zirconium, zirconium nitrate, zirconium sulfate, zirconium carbonate and basic zirconium phosphate, reaction temperature 40 DEG C to 400 DEG C it Between, pressure is in 0.1MPa between 3.25MPa.

3. preparation method as claimed in claim 2, it is characterised in that the temperature is between 50 DEG C to 250 DEG C, the pressure In 0.1MPa between 1.2MPa.

4. preparation method as claimed in claim 3, it is characterised in that the temperature is between 80 DEG C to 150 DEG C, the pressure In 0.1MPa between 0.5MPa.

5. preparation method as claimed in claim 1, it is characterised in that step (5) calcining heat is at 600 DEG C to 1100 DEG C Between, heating rate maintains calcining maximum temperature 0.5 hour to 5 hours between 200 DEG C/h to 1200 DEG C/h.

6. a kind of preparation method of press body, it is characterised in that the press body is just like described in claim 1 to 5 any one Preparation method made from zirconium oxide split compacting sintering be made.

7. the preparation method of press body as claimed in claim 6, it is characterised in that sintering temperature 1100 DEG C to 1600 DEG C it Between, sintering time 0.5 hour to 10 hours.

8. a kind of press body, it is characterised in that prepared according to preparation method as claimed in claims 6 or 7.

9. press body as claimed in claim 8, it is characterised in that its key component is ZrO₂+HfO₂+M_xO_y, wherein M_xO_yFor Metal oxide, its content is less than or equal to 15 moles of %, the one kind of M in yttrium, calcium, magnesium, cerium, praseodymium, vanadium, molybdenum and titanium elements Or it is a variety of, the key component accounts for the mass percent of Zirconium powder more than 90%, other metals outside key component The every kind of mass fraction for accounting for the Zirconium powder of oxide is less than or equal to 0.01%；Preferably, according to ISO13356：2008 Its measured is less than or equal to 100Bq/kg than radiation activity, is more than or equal to 6.0g/ according to the density that ISO18754 is measured Cm3, the grain size that foundation ASTME112 is measured is between 30 nanometers to 400 nanometers.

10. a kind of ceramic material, it is characterised in that including press body as claimed in claim 8 or 9.