CN107056258B

CN107056258B - A kind of biologically active nano-oxide ceramic membrane of organic precursor liquid solution plated film preparation

Info

Publication number: CN107056258B
Application number: CN201710362316.9A
Authority: CN
Inventors: 李廷凯; 沈志坚; 张�杰; 赵武元; 陶力
Original assignee: HANGZHOU ERRAN TECHNOLOGY Co Ltd
Current assignee: HANGZHOU ERRAN TECHNOLOGY Co Ltd
Priority date: 2017-05-22
Filing date: 2017-05-22
Publication date: 2019-11-05
Anticipated expiration: 2037-05-22
Also published as: CN107056258A

Abstract

The invention discloses a kind of biologically active nano-oxide ceramic membranes of organic precursor liquid solution plated film preparation, are prepared by the following method and obtain: (1) forming the surface texture that design needs by CAD and Computer aided building on the substrate of bio-medical engineering material；(2) the organic precursor method coating liquid of pore former is added or is not added in preparation；(3) using organic precursor method coating liquid on the surface texture of step (1) treated substrate plated film, coating process decomposes thin-film technique using sol-gel films technique or organic compound, roasting, natural cooling, the simple film with nanoaperture is obtained after cleaning, or internal layer is micro-void film, outer layer is the composite membrane of nanoporous film.The present invention significantly improves the biocompatibility and bioactivity of bio-medical engineering material especially zirconium oxide.

Description

A kind of biologically active nano-oxide of organic precursor liquid solution plated film preparation Ceramic membrane

Technical field

The present invention relates to bio-medical engineering material technical field, in particular to a kind of organic precursor liquid solution plated film preparation Biologically active nano-oxide ceramic membrane.

Background technique

Biological engineering material is the material of the substance for being related to interacting with biosystem, surface or structure.As A science, about 50 years history of biological engineering material.The research of biomaterial is referred to as biomaterial science or raw Object material engineering has also had extensive research.In its history, many governments, research institution and company are all thrown A large amount of fund is entered to research and develop new material and products thereof.Biomaterial science has included medicine, biology, change The content of, organizational project and material science etc..Any material contacted with living tissue, organism or microorganism, all The problem of its biocompatibility and bioactivity must be taken into consideration.

There are two methods for the biocompatibility and bioactivity for solving the problems, such as biological engineering material: first is that using having life Material of the object similar to chemical composition.Biofacies such as hydroxyapatite coating layer as the improved hip joint of hip implant Capacitive and bioactivity.But this kind of material usually has lower intensity and fracture toughness, and strong with the connection of basis material It spends very poor, limits their application.Another kind is to use chemically inert material, and it is allowed to have the knot similar with organism Structure improves their biocompatibility and bioactivity.Biomaterial can be a kind of self, allosome for graft materials Or xenograft material.

Self assembly is the most common term of modern science circle, and it is (former to occur particle under the influence of not by any external force Son, molecule, colloid, micella etc.) spontaneous aggregation, and form thermodynamically stable structure.Such as 7 in metallurgy and mineralogy The discovery (such as face-centered cubic, body-centered cubic) of a crystal system, is exactly an example of atom self assembly.Molecule from group Dress also universally present in biosystem among, form the biological structure of various complexity.We can be found that with superior machine The microstructure characteristic of the biomaterial of tool performance and it, meanwhile, self assembly also becomes the new of chemical synthesis and nanotechnology Strategy.All generations of molecular crystal, liquid crystal, colloid, micella, lotion, the polymer mutually separated, film and self-assembled monolayer The structure of the high-sequential of table is all the example using these technologies.Almost all of natural material is had across scale Hierarchical structure.In biomaterial, this across scale hierarchical structure is intrinsic microstructure.In the history of structure biology On, Astbury and Woods scatter the hierarchical structure for determining hair and wool using X-ray.Protein is the basic of organism Unit, the diameter of protein molecule gelatine principle about between 1-100 nanometers are to form three by the primitive that diameter is 1.5nm The organic molecule of helical structure.These ossein molecules are mingled with mineral facies (such as hydroxyapatite, calcium phosphate) by alternating direction Form helical fiber structural unit.These " units " are the basic building blocks of bone, organic that 60/40 is about pressed between inorganic phase Volume fraction distribution.Further investigation revealed that hydroxyapatite crystal therein be with about 70-100 nanometers of diameter and With a thickness of 1 nanometer of plate structure.Almost all of biomaterial all has the basic structure of nanomorphic.Gelatine original molecule can It is adsorbed by these nanostructures, hydroxyapatite crystal molecule is grown in gap therebetween, produces good bioactivity.Cause This prepares bionical nano structure membrane, and chemically inert biological engineering material can be made to have good biocompatibility and life Object activity.Currently, biomaterial is widely used, such as joint replacement, bone plate, bone cement, artificial ligament and tendon, tooth Surgical implant is fixed for tooth, blood vessel prosthesis, heart valve, skin repair device (artificial organ), cochlea displacement, stealthy eye Mirror, breast implant, drug delivery mechanism, sustainable material, vasotransplantation, bracket, nerve trachea, surgical suture are cut Volume and wound suture etc..Since zirconium oxide has very high intensity and fracture toughness, obtained in recent years in biological engineering material field To being widely applied.On the other hand, due to zirconium oxide be it is chemically inert, there is certain biocompatibility, but do not have Bioactivity makes its application receive certain limitation.

Summary of the invention

The purpose of the present invention is to provide a kind of biologically active nano oxygens of organic precursor liquid solution plated film preparation Compound ceramic membrane significantly improves the biocompatibility and bioactivity of bio-medical engineering material especially zirconium oxide.

The technical solution adopted by the present invention to solve the technical problems is:

A kind of biologically active nano-oxide ceramic membrane of organic precursor liquid solution plated film preparation, by following Method is prepared:

(1) it is set on the substrate of bio-medical engineering material by CAD and Computer aided building formation Count the surface texture needed；The bio-medical engineering material is aluminium oxide, zirconium oxide, yttrium partially stabilized zirconium oxide, aluminium oxide Adulterate one of yttrium partially stabilized zirconium oxide；This surface texture can be the rough surface of micron order and micron order or more Macrostructure includes polymorphic structure, is also possible to smooth finish surface.The design of surface texture is according to bio-medical engineering material What the needs of purposes designed.

(2) the organic precursor method coating liquid of pore former, the organic precursor method coating liquid are added or are not added in preparation To form the precursor complex liquid of aluminum oxide film, the precursor complex liquid for forming yttrium partially stabilized zirconia film, forming oxygen Change aluminium and adulterates one of precursor complex liquid of yttrium partially stabilized zirconia film；

(3) using organic precursor method coating liquid on the surface texture of step (1) treated substrate plated film, coating process Thin-film technique, roasting are decomposed using sol-gel films technique or organic compound, natural cooling obtains simple tool after cleaning There is the film of nanoaperture or internal layer is micro-void film, outer layer is the composite membrane of nanoporous film.

The grain size in nano-oxide ceramic membrane its film that the present invention is formed is at 100-500 microns.Such shape At material and product present not only have high intensity and toughness, but also have good biocompatibility and bioactivity.

Chemically inert ceramic material, if be formed on its surface and protein molecule or bone collagen molecular size phase Matched nanostructure, protein molecule or bone collagen molecule will be adsorbed on development growth in this nanostructure, present good Good bioactivity.Further study show that nano-pore topological structure and nano pore inner surface water and constitution water form pair Material hydrophilic has decisive influence to absorption serum, protein, drug and growth factor；It is induced by adsorption protein Cell selective attachment with hyperplasia can generate respectively bionical periodontal in the zirconia nanopowder ceramic surface containing nano-pore structure Film soft tissue or bionic tone tissue.The present invention exactly utilizes this principle, and bionical nano structure membrane, pole are prepared on matrix The earth improves the biocompatibility and bioactivity of zirconium oxide biomaterial and product.

It is proved by zoopery, this kind of aluminium oxide with micro--bionic nano porosity gradient, yttrium partially stabilized oxidation Zirconium, the biological engineering material of alumina doped yttrium partially stabilized zirconia film structure and product present good bio-compatible Property and bioactivity.

The nano-oxide ceramic membrane that the present invention processes, can be the film of simple nanoaperture, be also possible to interior Side micro-void layer film, the composite membrane of outside nanoaperture layer film.The nano-oxide ceramic membrane that the present invention processes can To be used for dental material, can also be used in includes maxillofacial bone frame, skull, hip joint, meniscus etc. above all artificial bones.

The film of simple nanoaperture can play a role with the surface texture cooperation processed on matrix, such as surface texture By the pattern of micron-sized figure constitution, 0.3-0.5 microns of thickness, the film of such surface texture (micron)-nanoaperture (is received Rice) micro-nano gradient-structure is formed, it is also possible to micro-void layer film on the inside of film itself, outside nanoaperture layer film Composite membrane formed film micro-nano gradient-structure.

Preferably, the coating liquid of the sol-gel films technique is the preparation method comprises the following steps: using metal alkoxide as precursor material Material, precursor material is dissolved in dehydrated alcohol, is configured to the precursor solution that concentration is 0.1-0.5 moles every liter；Then to The deionized water solution that ethyl alcohol is added in precursor solution (if directly adding water, can cause localized metallic alkoxide fast hydrolyzing not Be formed uniformly gel, so plus when water, to be added in a manner of ethanol water, uniform colloidal sol could be formed, rather than straight Connecing becomes gel), it stirs evenly, obtains mixed solution, then DMF is added in the mixed solution, form composite solution, it is described multiple Close component molar proportion in solution are as follows: the amount of precursor solution: the amount of alcohol in the deionized water solution of ethyl alcohol: deionized water Amount: amount=1:1-4:5-10:0.2-0.4 of DMF；The micron or nanoaperture shape for accounting for precursor quantity of material 1-5wt% is added At agent, 10-15min is stirred, finally sealing is parked 0.5-2 hours at room temperature, and obtaining precursor complex liquid is coating liquid.It is molten The plated film of gel film technique stops 10s-15s after plated film, forms wet gel film；The diaphragm for forming wet gel film is put into In drying box, 30mL-40mL ethyl alcohol is added, is to slowly warm up to 80-120 DEG C, freeze-day with constant temperature 1-2h, obtains one at 80-120 DEG C Diaphragm after secondary drying；Repeatedly to reach required thicknesses of layers.

Preferably, the precursor material for forming the precursor complex liquid of aluminum oxide film is the metal alkoxide containing Al；Shape Precursor material at the precursor complex liquid of yttrium partially stabilized zirconia film is the metal alkoxide containing Zr and Y；Form oxidation The precursor material that aluminium adulterates the precursor complex liquid of yttrium partially stabilized zirconia film is the metal alkoxide containing Al, Zr and Y.

Preferably, the organic compound decomposes the coating liquid of thin-film technique the preparation method comprises the following steps: to contain metal ion 2- ethyl hexyl hydrochlorate be precursor material, the in the mixed solvent that precursor material dissolves in 2 ethyl hexanoic acid and toluene is prepared The precursor solution for being 0.1-0.5 moles every liter at precursor material concentration, in the mixed solvent 2 ethyl hexanoic acid and toluene rub You are than being 1:1-2；Be added and account for the micron or nanoaperture forming agent of precursor quantity of material 1-5wt%, temperature be 60 DEG C- 10-30min is stirred at 80 DEG C, forms the organic precursor solution of homogeneous transparent, sealing is parked 0.5-2 hours at room temperature, is obtained Precursor complex liquid is coating liquid.Organic compound decomposes thin-film technique plated film, will stop 1-5 seconds after solution plated film, is formed The diaphragm for forming wet gel film is directly put to heating 3-5 minutes on 220 DEG C -250 DEG C of heater and is removed rapidly by wet gel film Solvent, then plated film are removed, is reheated, repeatedly to reach required thicknesses of layers.

Preferably, the precursor material for forming the precursor complex liquid of aluminum oxide film is the 2- containing metal ion Al Ethyl hexyl hydrochlorate；The precursor material for forming the precursor complex liquid of yttrium partially stabilized zirconia film is containing metal ion Zr With the 2 ethyl hexanoic acid salt of Y；Form the precursor material of the precursor complex liquid of alumina doped yttrium partially stabilized zirconia film Material is the 2 ethyl hexanoic acid salt containing metal ion Al, Zr and Y.

Preferably, the micro-void forming agent be selected from polyethylene glycol, NC Nitroncellulose, polyacrylic acid, poly- Propanolamine, Polyethylene, polyvinyl chloride, polybutadiene, polystyrene, polyacrylonitrile, polyphenyl phenol, polyformaldehyde, polyamide, gathers in polypropylene One or more of amide, polyarylether, Nomex, polyimides carbonic ester, terephthalic acid (TPA) methyl methacrylate；Institute It states nanoaperture forming agent and is selected from carbonyl diamide, Propanolamine, citric acid, ethylene, propylene, vinyl chloride, butadiene, styrene, third One or more of alkene nitrile, phenol, formaldehyde, amide, caprolactam, aryl oxide, fragrant amide, acid imide carbonic ester, ethylene glycol.It is micro- Metre hole gap forming agent is used to form 0.2-0.5 microns of pore structure, and nanoaperture forming agent is used to form 1-100 nanoaperture Structure and diameter are 1-10nm, the linear structure and their combination of a length of 50nm-500nm.

Preferably, the content of yttrium is 2-6mol%, alumina doped yttrium partially stabilized oxygen in yttrium partially stabilized zirconium oxide Aluminium content is 1-5mol% in change zirconium, yttrium content is 2-6mol%.

Preferably, the cleaning in step (3) specifically: successively using SC1 cleaning solution, SC2 cleaning solution, SC3 cleaning solution, Acetone, alcohol and distilled water are cleaned by ultrasonic 10-30min respectively；SC1 cleans formula of liquid are as follows: NH₄OH:H₂O₂:H₂O volume ratio is 1:1-2:5-7, cleaning temperature control are 65-80 DEG C；

SC2 cleans formula of liquid are as follows: H₂SO₄:H₂O₂:H₂O volume ratio is 1:1-2:6-8, and cleaning temperature control is 65-80 DEG C； SC3 cleans formula of liquid are as follows: NH₄OH:H₂O₂:H₂O volume ratio is 1:1:3, and cleaning temperature control is 100-130 DEG C.Preferably, In step (3): the simple film thickness with nanoaperture is 0.3-3 microns, and the micro-void film thickness of internal layer is 0.3-3 microns, the nanoporous film of outer layer is with a thickness of 0.3-3 microns.

Preferably, the specific preparation method of biologically active nano-oxide ceramic membrane selects following scheme One of:

Scheme 1: pass through CAD and Computer aided building shape on the substrate of bio-medical engineering material At the surface texture that design needs, 120-200 DEG C of 1-2 hours dry, control surface is warming up to the heating rate of 1-10 DEG C/s Then humidity uses organic precursor method coating liquid plated film on the surface texture of substrate, before roasting first pre-burning stove to 50-60 DEG C, Then roasting is divided into three phases: the 1st stage was warming up to 250- under mild oxidation atmosphere (partial pressure of oxygen 20-50vol%) 350 DEG C, heating rate is 1-5 DEG C/min, after reaching 300 DEG C, keeps the temperature 0.5-1h；2nd stage, in strong oxidizing atmosphere (partial pressure of oxygen To be warming up to 500-600 DEG C under 80-100vol%), heating rate is 5-10 DEG C/min, after reaching 500-600 DEG C, keeps the temperature 1- 2h, phase III are rapidly heated to 1400-1700 DEG C, and heating rate is 50-100 DEG C/s, keeps the temperature 1-2h；Then natural cooling Cooling is successively cleaned by ultrasonic 10- using SC1 cleaning solution, SC2 cleaning solution, SC3 cleaning solution, acetone, alcohol and distilled water respectively 30min；

Scheme 2: pass through CAD and Computer aided building shape on the substrate of bio-medical engineering material At the surface texture that design needs, it is 1-2 hours dry that 120-200 DEG C is warming up to the heating rate of 1-10 DEG C/s, then with 10-50 DEG C/heating rate of s is warming up to 700-1100 DEG C of biscuiting 1-2 hours, it is placed in clear water, with ultrasonic cleaning, after dry, with third Ketone cleaning, then uses organic precursor method coating liquid plated film on the surface texture of substrate, roasts preceding first pre-burning stove to 50-60 DEG C, roasting is then divided into three phases: the 1st stage was warming up under mild oxidation atmosphere (partial pressure of oxygen 20-50vol%) 250-350 DEG C, heating rate is 1-5 DEG C/min, after reaching 300 DEG C, keeps the temperature 0.5-1h；2nd stage, in strong oxidizing atmosphere (oxygen For partial pressure to be warming up to 500-600 DEG C under 80-100vol%), heating rate is 5-10 DEG C/min, after reaching 500-600 DEG C, is protected Warm 1-2h, phase III are rapidly heated to 1400-1700 DEG C, and heating rate is 50-100 DEG C/s, keeps the temperature 1-2h；Then natural It cools, is successively cleaned by ultrasonic respectively using SC1 cleaning solution, SC2 cleaning solution, SC3 cleaning solution, acetone, alcohol and distilled water 10-30min；

Scheme 3: the substrate of bio-medical engineering material is warming up to 120-200 DEG C of dry 1- with the heating rate of 1-10 DEG C/s It 2 hours, is then set on the substrate of bio-medical engineering material by CAD and Computer aided building formation The surface texture needed is counted, surface moisture is controlled, using the organic precursor method coating liquid added with micro-void forming agent in base Then plated film on the surface texture of material is warming up to 700-1100 DEG C of biscuiting 1-2 hours with the heating rate of 10-50 DEG C/s, is placed in In clear water, cleaned after dry with acetone with ultrasonic cleaning, then using the organic precursor for being added with nanoaperture forming agent Body coating liquid continues plated film, is finally warming up to 1400-1700 DEG C with the heating rate of 1-10 DEG C/s, keeps the temperature 1-2h；Then natural It cools, is successively cleaned by ultrasonic respectively using SC1 cleaning solution, SC2 cleaning solution, SC3 cleaning solution, acetone, alcohol and distilled water 10-30min.

The beneficial effects of the present invention are: in order to adapt to the needs of biomedical engineering, in existing biologically inert engineering in medicine The surface of material, has prepared the aluminium oxide gradient pore structured with bionical micro-nano, and yttrium stable zirconium oxide and aluminium oxide are mixed The membrane structure of miscellaneous yttrium stable zirconium oxide.To make this kind of biological engineering material and product with high intensity and high tenacity, it is in Now come good biocompatibility and bioactivity.This kind of material and product will obtain widely in biomedical engineering field Using.

Detailed description of the invention

Fig. 1 is that have bionical micron-nanometer porosity gradient thin film bio engineering material schematic diagram；

Fig. 1 a has special-shaped macrostructure and bionic nano porosity gradient thin film bio engineering material and product,

Fig. 1 b has smooth finish surface structure and bionic nano porosity gradient thin film bio engineering material and product,

Fig. 1 c has special-shaped macrostructure and bionical micro-nano porosity gradient thin film bio engineering material and product,

Fig. 1 d has smooth finish surface and bionical micro-nano porosity gradient thin film bio engineering material and product.

Fig. 2 is the schematic diagram of the bionical micron-nanometer pore structure of the present invention, and wherein Fig. 2 a is with bionic nano single hole hole The form of gap structure, Fig. 2 b are the side view forms for having bionical micron-nanometer gradient pore structured, and Fig. 2 c is with bionic nano The form of linear pore structure, Fig. 2 d are the forms with bionic nano single hole, porous and linear combination pore structure.

In figure: 1, substrate, 2, surface texture, the plated film of 31 micro-voids, the plated film of 32 nanoapertures.

Specific embodiment

Below by specific embodiment, technical scheme of the present invention will be further explained in detail.

In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art. Method in following embodiments is unless otherwise instructed the conventional method of this field.

Embodiment:

1. raw material, reagent and cleaning formulation and technique:

Zirconium hydroxide (ZrO (OH)₂·nH₂O >=99%)；Basic zirconium chloride (ZrOCl₂·8H₂O >=99%), zirconium nitrate (Zr (NO₃)₄·5H₂O >=99%), yttrium oxide (Y₂O₃>=99.99%)；Yttrium nitrate Y (NO₃)₃·6H₂O, yttrium chloride (YCI₃·6H₂O >=99.99%)；Aluminium hydroxide (Al (OH)₃>=99%)；Aluminium chloride (AlCl₃>=99%), aluminum nitrate (Al (NO₃)₃·9H₂O), Dehydrated alcohol, C₂H₅OH is analyzed pure；Distilled water H₂O；Ammonium hydroxide (NH₃·H₂O, it analyzes pure)；Carbonyl diamide (NH)₂), CO poly- second two Alcohol (PEG1000), NC Nitroncellulose, polyacrylic acid, polyvinyl alcohol, Propanolamine, citric acid and have different molecular weight and difference The high molecular material of form organic group, such as ethylene, propylene, vinyl chloride, butadiene, styrene, acrylonitrile, phenol, formaldehyde, acyl Amine, caprolactam, aryl oxide, fragrant amide, acid imide carbonic ester, ethylene glycol and terephthalic acid (TPA) methyl methacrylate etc. and they Polymer.Sol-gel films technology, which is selected from, contains metal ion Zr, Al, Y metal alkoxide, such as Y (OC₃H₇)₃、Al (OC₃H₇)₃、Zr(OC₃H₇)₄Etc.；Organic compound decomposes film process technology and is selected from 2 ethyl hexanoic acid salt and 2 ethyl hexanoic acid； Such as 2 ethyl hexanoic acid yttrium Y (C₇H₁₅COO)₃, 2 ethyl hexanoic acid aluminium Al (C₇H₁₅COO)₃, 2 ethyl hexanoic acid zirconium Zr (C₇H₁₅COO)₄, Sulfuric acid, hydrochloric acid, ammonium hydroxide, hydrogen peroxide, deionized water, acetone, alcohol.

The formula and technique of three kinds of cleaning agents: its formula of SC1 cleaning solution is NH₄OH:H₂O₂: H₂O=1:1:5 to 1:2:7； Cleaning temperature is 65-80 DEG C；Its formula of SC2 cleaning solution is HCl:H₂O₂: H₂O=1:1:6 to 1:2:8；Cleaning temperature is 65-80 DEG C, its formula of SC3 cleaning solution is H₂SO₄: H₂O₂: H₂O=1:1:3；Cleaning temperature is 100-130 DEG C.

2. experimental facilities

Conventional glass instrument；Drier；Pure water system；Full-automatic electronic assay balance；Constant temperature blender with magnetic force；Electric heating is permanent Warm water tank；PH acidometer；Vacuum filtration system (filtering of band nanometer scale ceramics and quantitative filter paper)；Centrifuge；Electric heating constant temperature is dry Case；Agate grinds alms bowl；High-temperature gas Protection furnace, normal working temperature reach 1700 DEG C.Testing sieve extension set (325 mesh, 400 mesh, 500 mesh, electricity vibration), vent cabinet, gas shield glove box, CAM machining tool etc..

3. the measurement testing program of powder the efficiency of formation

3.1, test objective

The powder the efficiency of formation of Al, Y, Zr after precipitating, drying and calcination is individually investigated, calculates material implementing to be co-precipitated Theoretical value is corrected when proportion, to guarantee the formation of accuracy and pure phase that Zr-Al-Y is formed.

3.2, principle

Individually to Al, Y, the solution of Zr precipitated, drying and calcination experiment, measurement be actually formed the coefficient of amount of powder= It is actually formed amount of powder/theoretical value.Formula value=theoretical value/is actually formed the coefficient of amount of powder.

3.2.1 Al₂O₃Powder the efficiency of formation

2Al(NO₃)₃·9H2O→Al₂O₃

2mol Al(NO₃)₃9H2O is converted into 1mol Al₂O₃。Al(NO₃)₃9H2O molal weight is 375.13, Al₂O₃ Molal weight is 101.96, if conversion ratio is 100%, 750.26 grams of Al (NO₃)₃9H2O is after precipitating, drying and calcination It should obtain 101.96 grams of Al₂O₃.Aluminium hydroxide (Al (OH) can similarly be calculated₃>=99%) and aluminium chloride (ZrCl₃≥ 99%) powder the efficiency of formation.

3.2.2Y₂O₃Powder the efficiency of formation

2Y(NO₃)₃·6H₂O→Y₂O₃

2mol Y(NO₃)₃·6H₂O is converted into 1mol Y₂O₃。Y(NO₃)₃·6H₂O molal weight is 383.06, Y₂O₃Mole Quality is 225.81, if conversion ratio is 100%, 766.12 grams of Y (NO₃)₃·6H₂O is deserved after precipitating, drying and calcination To 225.81 grams of Y₂O₃.Yttrium chloride (YCI can similarly be calculated₃·6H₂O >=99.99%) powder the efficiency of formation.

3.2.3ZrO₂Powder the efficiency of formation

Zr(NO₃)₄·5H2O→ZrO₂

Theoretically, 1mol Zr (NO₃)₄5H2O is converted into 1mol ZrO₂。Zr(NO₃)₄5H2O molal weight is 519.32, ZrO₂Molal weight is 123.22, if conversion ratio is 100%, 519.32 grams of Zr (NO₃)₄5H2O through precipitating, 123.22 grams of ZrO should be obtained after drying and calcination₂.Zirconium hydroxide (ZrO (OH) can similarly be calculated₂·nH₂O >=99%) and Basic zirconium chloride (ZrOCl₂·8H₂O >=99%) powder the efficiency of formation.

Other zirconium hydroxides (ZrO (OH)₂·nH₂O >=99%)；Basic zirconium chloride (ZrOCl₂·8H₂O >=99%)；Yttrium oxide (Y₂O₃>=99.99%)；Yttrium chloride (YCI₃·6H₂O >=99.99%)；Aluminium hydroxide (Al (OH)₃>=99%)；Aluminium chloride (AlCl₃>=99%) powder the efficiency of formation etc. is measured by above-mentioned principle.By the measurement of Al, Y, Zr powder the efficiency of formation, protect It demonstrate,proves Al doping Y and stablizes ZrO₂The formation of the accuracy and pure phase of composition.

4. aluminium oxide, Y portion stablizes ZrO₂Stablize ZrO with aluminium doping Y portion₂Powder manufacturing process method example:

4.1. alumina powder method of manufacturing technology example:

4.1.1. alumina powder A method of manufacturing technology example: preparing alumina slurry using the anti-method dripped, and uses Aluminium compound is precursor, outfield heat by way of and be precisely controlled liquid phase coprecipitation reaction, the technique and addition of calcining Agent produces the pure phase nanometer grade aluminum oxide powder with different grain sizes.Precipitating reagent uses NH₄HCO₃(10-50%)+ NH₃·H₂The mixed solution of O；Prepared precipitating reagent is placed in conical flask, conical flask is placed in magnetic stirring apparatus or with stirring In water bath with thermostatic control reactor, contain Al³⁺Female saline solution is aluminium hydroxide (Al (OH)₃>=99%)；Aluminium chloride (AlCl₃>=99%), nitre Sour aluminium (Al (NO₃)₃·9H₂O) one such；It is slowly dropped into precipitating reagent, and strong stirring reacts it sufficiently, has reacted Be aged 8-12 hour or more after finishing, with centrifuge quick separating, and vacuum filtration will be precipitated, and with distilled water, ethanol washing, obtained Al₂O₃Presoma.It is 1-2 hours dry at a temperature of 100-200 DEG C, obtain alumina powder A.4.1.2 alumina powder B is manufactured Process example:

It uses hydro-thermal-hydrolysis method of manufacturing technology: concentration is added to instead for the aluminium hydroxide suspension of 0.5-1mol/L It answers in device, reactor is heated to 40-60 DEG C, keeps the temperature 2-3 hours, the poly- of 0.5-1wt% (dosage for accounting for aluminium hydroxide) is added Vinyl alcohol is then heated to 200-250 DEG C, keeps the temperature 55-65 hours progress hydro-thermal-hydrolysis.Holding internal pressure is 2- 3MPa is allowed to gradually hydrolytic precipitation.With centrifuge quick separating, and will precipitating vacuum filtration, with distilled water, ethanol washing, obtain To the presoma of aluminium oxide.It is 1-2 hours dry at a temperature of 100-200 DEG C, obtain alumina powder B.

4.2.Y partially stabilized ZrO₂Powder manufacturing process method example:

4.2.1.Y (2-6mol%) partially stabilized ZrO₂Powders A manufacture example is as follows: preparing Y using the anti-method dripped Partially stabilized ZrO₂Slurry, prepared precipitating reagent NH₄HCO₃(10-50%)+NH₃·H₂O solution is placed in conical flask, cone Shape bottle is placed in magnetic stirring apparatus or water bath with thermostatic control reactor with stirring, contains Y for prepared³⁺、Zr⁴⁺Mother liquor includes hydrogen-oxygen Change zirconium (ZrO (OH)₂·nH₂O >=99%), basic zirconium chloride (ZrOCl₂·8H₂O >=99%), zirconium nitrate (Zr (NO₃)₄·5H₂O >=99%) one such；Yttrium nitrate Y (NO₃)₃·6H₂O, yttrium chloride (YCI₃·6H₂O >=99.99%) it is one such；It is slow It is slow to instill in precipitating reagent, and strong stirring reacts it sufficiently, be aged 8-12 hours after completion of the reaction or more, it is quick with centrifuge Separation, and precipitating is filtered by vacuum, it is 1-2 hours dry at a temperature of 100-200 DEG C with distilled water, ethanol washing, obtain the portion Y Divide and stablizes ZrO₂Powder A.

4.2.2.Y (2-6mol%) partially stabilized ZrO₂Powder C example is as follows: the Zr for being 0.5-1mol/L by concentration⁴⁺'s Zirconium hydroxide (ZrO (OH)₂·nH₂O >=99%) suspension is added in reactor, then yttrium oxide point is added to for 3 to 5 times In reactor.Reactor is heated to 40-60 DEG C, keeps the temperature 2-3 hours, after yttrium oxide to be added is completely dissolved, hydrogen-oxygen is added The polyvinyl alcohol for changing zirconium weight 0.5-1wt% is then heated to 200-250 DEG C, and heat preservation progress hydro-thermal-hydrolysis in 55-65 hours is anti- It answers.Holding internal pressure is 2-3MPa, is allowed to gradually hydrolytic precipitation.With centrifuge quick separating, and will precipitating vacuum filtration, use Distilled water, ethanol washing, it is 1-2 hours dry at a temperature of 100-200 DEG C, it obtains Y portion and stablizes ZrO₂Powder C.

4.2.3.Y (2-6mol%) partially stabilized ZrO₂Powder D method of manufacturing technology example is as follows: being 0.5- by concentration The Zr of 1mol/L⁴⁺Zirconium hydroxide (ZrO (OH)₂·nH₂O >=99%) suspension is added in reactor, then yttrium oxide Divide 3 to 5 times and is added in reactor.Reactor is heated to 40-60 DEG C, keeps the temperature 2-3 hours, yttrium oxide to be added is complete After dissolution, be added zirconium hydroxide weight 0.5-1wt% polyacrylic acid and polyvinyl alcohol 1:1 weight ratio mixture, then plus Heat keeps the temperature 55-65 hours progress hydro-thermal-hydrolysis to 200-250 DEG C.Holding internal pressure is 2-3MPa, is allowed to gradually water Solution precipitating.With centrifuge quick separating, and will precipitating vacuum filtration, with distilled water, ethanol washing, at a temperature of 100-200 DEG C It is 1-2 hours dry, it obtains Y portion and stablizes ZrO₂Powder D.

4.2.4.Y (2-6mol%) partially stabilized ZrO₂It is as follows that powder E manufactures example: being 0.5-0.6mol/L's by concentration Basic zirconium chloride (ZrOCl₂·8H₂O >=99%) solution and 1mol/L carbonyl diamide (NH)₂CO it) is added to instead by the volume ratio of 1:1 It answers in device, reactor is heated to 150 DEG C of progress hydro-thermal reactions, keeps the temperature 2-4 hours, generates gel.It is obtained after taking out hydro-thermal reaction The gel obtained, adding a certain amount of (1:1) former reaction solution, (former reaction solution refers to the zirconium oxychloride solution and carbonyl diamide of front By the mixture of the volume ratio of 1:1), this solution is stirred in the flask configured with reflux condenser, while boiling at 100-150 DEG C Continue hydrolysis at a temperature of rising.Gained is hydrated ZrO₂The conversion ratio of colloidal sol reaches 99%.Yttrium nitrate is added to hydration ZrO₂In colloidal sol, this solution is stirred, after yttrium nitrate to be added is completely dissolved, is allowed to gradually hydrolytic precipitation.It is quick with centrifuge Separation, and precipitating is filtered by vacuum, it is 1-2 hours dry at a temperature of 100-200 DEG C with distilled water, ethanol washing, obtain the portion Y Divide and stablizes ZrO₂Powder E.

4.3.Al doping Y portion stablizes ZrO₂Powder manufacturing process method example:

4.2.1.Al (1-5mol%) adulterates Y (2-6mol%) partially stabilized ZrO₂It is as follows that powder F manufactures example: using anti- The method of drop stablizes ZrO to prepare Al doping Y₂Slurry, prepared precipitating reagent NH₄HCO₃(10-50%)+NH₃·H₂O is molten Liquid is placed in conical flask, and conical flask is placed in magnetic stirring apparatus or water bath with thermostatic control reactor with stirring, contains Al for prepared³ ⁺、Y³⁺、Zr⁴⁺Mother liquor includes zirconium hydroxide (ZrO (OH)₂·nH₂O >=99%), basic zirconium chloride (ZrOCl₂·8H₂O >=99%), Zirconium nitrate (Zr (NO₃)₄·5H₂One of O >=99%)；Yttrium nitrate Y (NO₃)₃·6H₂O, yttrium chloride (YCI₃·6H₂O≥ One of 99.99%)；Aluminium hydroxide (Al (OH)₃>=99%), aluminium chloride (AlCl₃>=99%), aluminum nitrate (Al (NO₃)₃· 9H₂One of O)；It is slowly dropped into precipitating reagent, and strong stirring reacts it sufficiently, is aged 8~12 hours after completion of the reaction More than, it is done at a temperature of 100-200 DEG C with centrifuge quick separating, and by precipitating vacuum filtration with distilled water, ethanol washing It is 1-2 hours dry, it obtains Al doping Y portion and stablizes ZrO₂Powder F.

4.3.2.Al (1-5mol%) adulterates Y (2-6mol%) partially stabilized ZrO₂It is as follows that powder H manufactures example: by concentration For the Zr of 0.5-1mol/L⁴⁺Zirconium hydroxide (ZrO (OH)₂·nH₂O >=99%) suspension and aluminium hydroxide (Al (OH)₃≥ 99%) it is added in reactor, then yttrium oxide is divided 3 to 5 times and is added in reactor.Reactor is heated to 40-60 DEG C, 2-3 hours are kept the temperature, after yttrium oxide to be added is completely dissolved, the polyvinyl alcohol of zirconium hydroxide amount 0.5-1wt% is added, so After be heated to 200-250 DEG C, keep the temperature 55-65 hours progress hydro-thermal-hydrolysis.Holding internal pressure be 2-3MPa, be allowed to by Gradually hydrolytic precipitation.With centrifuge quick separating, and will precipitating vacuum filtration, with distilled water, ethanol washing, in 100-200 DEG C of temperature Degree is lower 1-2 hours dry, obtains Al doping Y portion and stablizes ZrO₂Powder H.

4.3.3.Al (1-5mol%) adulterates Y (2-6mol%) partially stabilized ZrO₂It is as follows that powder I manufactures example: by concentration For the Zr of 0.5-1mol/L⁴⁺Zirconium hydroxide (ZrO (OH)₂·nH₂O >=99%) suspension and aluminium hydroxide (Al (OH)₃≥ 99%) it is added in reactor, then yttrium oxide is divided 3 to 5 times and is added in reactor.Reactor is heated to 40-60 DEG C, 2-3 hours are kept the temperature, after yttrium oxide to be added is completely dissolved, the polyacrylic acid of zirconium hydroxide amount 0.5-1wt% is added and gathers The mixture of vinyl alcohol 1:1 is then heated to 200-250 DEG C, keeps the temperature 55-65 hours progress hydro-thermal-hydrolysis.Keep internal Pressure is 2-3MPa, is allowed to gradually hydrolytic precipitation.With centrifuge quick separating, and will precipitating vacuum filtration, with distilled water, ethyl alcohol Washing, it is 1-2 hours dry at a temperature of 100-200 DEG C, it obtains Al doping Y portion and stablizes ZrO₂Powder I.

4.3.4.Al (1-5mol%) adulterates Y (2-6mol%) partially stabilized ZrO₂It is as follows that powder J manufactures example: by concentration For the carbonyl diamide of the zirconium oxychloride solution of 0.5-0.6mol/L, 1mol/L, by the volume of 1:1, when aluminium hydroxide is added to instead It answers in device, zirconium oxychloride solution and carbonyl diamide are matched by the volume ratio of 1:1, and it is anti-that reactor is heated to 150 DEG C of progress hydro-thermals It answers, keeps the temperature 2-4 hours, generate gel；Gel is taken out, (former reaction solution refers to the oxychloride of front with former reaction solution by gel Zirconium solution is with carbonyl diamide by the mixture of the volume ratio of 1:1) it is mixed according to the weight ratio of 1:1, it is being configured with reflux condenser Flask in, under stirring condition, continue hydrolysis under 100-150 DEG C of boiling temperature.Gained is hydrated ZrO₂Colloidal sol Conversion ratio reach 99%.Yttrium nitrate is added to hydration ZrO₂In colloidal sol, this solution is stirred, yttrium nitrate to be added is completely dissolved Afterwards, it is allowed to gradually hydrolytic precipitation.With centrifuge quick separating, and will precipitating vacuum filtration, with distilled water, ethanol washing, In It is 1-2 hours dry at a temperature of 100-200 DEG C, obtain the Al doping partially stabilized ZrO of Y₂Powder J.

5. aluminium oxide, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized zirconium oxide organic precursor method plated film are molten The preparating example of liquid.

Micro-void forming agent is the high molecular material with different molecular weight and different shape organic group, such as poly- second two Alcohol (PEG1000), NC Nitroncellulose, polyacrylic acid, polyvinyl alcohol, poly- Propanolamine, polyethylene, polyvinyl chloride, gather polypropylene Butadiene, polystyrene, polyacrylonitrile, polyphenyl phenol, polyformaldehyde, polyamide, polycaprolactam, polyarylether, Nomex, polyamides Imido-carbonic ester, terephthalic acid (TPA) methyl methacrylate and their combination etc. are used to form 0.2-0.5 microns of hole knot Structure.Nanoaperture forming agent is the high molecular material with different molecular weight and different shape organic group, such as carbonyl diamide, Propanolamine, citric acid, ethylene, propylene, vinyl chloride, butadiene, styrene, acrylonitrile, phenol, formaldehyde, amide, caprolactam, Aryl oxide, fragrant amide, acid imide carbonic ester, ethylene glycol and their combination etc. are used to form and protein molecule or bone collagen point The 1-100 nanoaperture structure and diameter that sub- size matches be 1-10nm, the linear structure of a length of 50nm-500nm and they Combination.

The preparating example of 5.1 aluminium oxide organic precursor method coated solutions

5.1.1 aluminium oxide organic precursor method coated solution A example

Select the metal alkoxide containing metal ion Al for precursor material such as Al (OC₃H₇)₃, by precursor material Al (OC₃H₇)₃It dissolves in dehydrated alcohol and is configured to the precursor solution that concentration is 0.1-0.5 moles every liter；Then to precursor solution The middle deionized water solution that ethyl alcohol is added, stirs evenly, obtains mixed solution, then DMF is added in the mixed solution, is formed Composite solution, component molar proportion in the composite solution are as follows: the amount of precursor solution: the second in the deionized water solution of ethyl alcohol Alcohol amount: the amount of deionized water: amount=1:1-4:5-10:0.2-0.4 of DMF；The micron for accounting for precursor quantity of material 1-5wt% is added Or nanoaperture forming agent, stir 10-15min, finally sealing is parked 0.5-2 hours at room temperature, obtain being formed micron or The precursor composite solution of the aluminum oxide film of person's nanoaperture.

5.1.2 aluminium oxide organic precursor method coated solution B example

Select the 2 ethyl hexanoic acid salt containing metal ion Al for precursor material such as 2 ethyl hexanoic acid aluminium Al (C₇H₁₅COO)₃；By precursor material Al (C₇H₁₅COO)₃It dissolves in the solvent of 2 ethyl hexanoic acid and toluene and is configured to precursor material Expect that concentration is 0.1-0.5 moles every liter of precursor solution, wherein the molar ratio of 2 ethyl hexanoic acid and toluene is 1: 1-2；It is added The micron of precursor quantity of material 1-5wt% or the pore former of nanometer are accounted for, stirs 10- at being 60 DEG C -80 DEG C in temperature 30min forms the organic precursor solution of homogeneous transparent, and sealing is parked 0.5-2 hours at room temperature, obtain being formed micron or The precursor composite solution of the hole aluminum oxide film of nanometer.

5.2 yttrium partially stabilized zirconium oxide organic precursor method coated solution method of manufacturing technology examples

5.2.1 yttrium partially stabilized zirconium oxide organic precursor method coated solution A method of manufacturing technology example

Select such as Y (OC of the metal alkoxide containing metal ion Zr and Y₃H₇)₃、Zr(OC₃H₇)₄Etc. for precursor material, According to composition proportion by precursor material Y (OC₃H₇)₃、Zr(OC₃H₇)₄It dissolves in dehydrated alcohol and is configured to concentration and rubs for 0.1-0.5 The precursor solution of every liter of that；Then the deionized water solution of ethyl alcohol is added into precursor solution, stirs evenly, must mix molten Liquid, then DMF is added in the mixed solution, composite solution is formed, component molar proportion in the composite solution are as follows: precursor The amount of solution: the amount of alcohol in the deionized water solution of ethyl alcohol: the amount of deionized water: amount=1:1-4:5-10:0.2- of DMF 0.4；The micron or nanoaperture forming agent for accounting for precursor quantity of material 1-5wt% is added.Then stir 10-15min, finally in Sealing is parked 0.5-2 hours at room temperature, obtains the yttrium partially stabilized zirconium oxide coated solution to form micron or nanoaperture.

5.2.2 yttrium partially stabilized zirconium oxide organic precursor method coated solution B method of manufacturing technology example

Select the 2 ethyl hexanoic acid salt containing metal ion Zr and Y for precursor material such as 2 ethyl hexanoic acid yttrium Y (C₇H₁₅COO)₃, 2 ethyl hexanoic acid zirconium Zr (C₇H₁₅COO)₄.By precursor material 2 ethyl hexanoic acid yttrium Y (C₇H₁₅COO)₃, 2- second Base zirconium hexanoate Zr (C₇H₁₅COO)₄It is dissolved according to composition proportion in the solvent of 2 ethyl hexanoic acid and toluene and is configured to precursor material The precursor solution that concentration is 0.1-0.5 moles every liter, wherein the molar ratio of 2 ethyl hexanoic acid and toluene is 1: 1-2；Addition accounts for The micron of precursor material amount 1-5wt% or the pore former of nanometer.Then 10- is stirred at being 60 DEG C -80 DEG C in temperature 30min forms the organic precursor solution of homogeneous transparent, and sealing is parked 0.5-2 hours at room temperature, obtains forming micron or receive The yttrium partially stabilized zirconium oxide plated film composite solution of the hole of rice.

5.3 alumina doped yttrium partially stabilized zirconium oxide organic precursor method coated solution method of manufacturing technology examples

5.3.1 alumina doped yttrium partially stabilized zirconium oxide organic precursor method coated solution A method of manufacturing technology example

Selection contains the metal alkoxide such as Y (OC of metal ion Al, Zr and Y₃H₇)₃、Al(OC₃H₇)₃、Zr(OC₃H₇)₄Etc. For precursor material, according to composition proportion by precursor material Y (OC₃H₇)₃、Al(OC₃H₇)₃、Zr(OC₃H₇)₄Dissolve in dehydrated alcohol In to be configured to concentration be 0.1-0.5 moles every liter of precursor solution；Then the deionization of ethyl alcohol is added into precursor solution Aqueous solution stirs evenly, and obtains mixed solution, then DMF is added in the mixed solution, forms composite solution, described compound molten Component molar matches in liquid are as follows: the amount of precursor solution: the amount of alcohol in the deionized water solution of ethyl alcohol: the amount of deionized water: Amount=1:1-4:5-10:0.2-0.4 of DMF；The micron for accounting for precursor quantity of material 1-5wt% is added or nanoaperture is formed Agent.Then 10-15min is stirred, finally sealing is parked 0.5-2 hours at room temperature, obtains being formed micron or nanoaperture Alumina doped yttrium partially stabilized zirconium oxide coated solution.

5.3.2 alumina doped yttrium partially stabilized zirconium oxide organic precursor method coated solution B method of manufacturing technology example

2 ethyl hexanoic acid salt of the selection containing metal ion Al, Zr and Y is precursor material such as 2 ethyl hexanoic acid yttrium Y (C₇H₁₅COO)₃, 2 ethyl hexanoic acid aluminium Al (C₇H₁₅COO)₃, 2 ethyl hexanoic acid zirconium Zr (C₇H₁₅COO)₄.By precursor material 2- second Base caproic acid yttrium Y (C₇H₁₅COO)₃, 2 ethyl hexanoic acid aluminium Al (C₇H₁₅COO)₃, 2 ethyl hexanoic acid zirconium Zr (C₇H₁₅COO)₄According to ingredient It matches and is configured to the precursor that precursor material concentration is 0.1-0.5 moles every liter in the solvent for dissolving in 2 ethyl hexanoic acid and toluene Solution, wherein the molar ratio of 2 ethyl hexanoic acid and toluene is 1: 1-2；Be added account for precursor quantity of material 1-5wt% micron or The pore former of nanometer.Then 10-30min is stirred at being 60 DEG C -80 DEG C in temperature, the organic precursor for forming homogeneous transparent is molten Liquid, sealing is parked 0.5-2 hours at room temperature, obtains the alumina doped yttrium partially stabilized of the hole to form micron or nanometer Zirconium oxide plated film composite solution.

6. having bionical micro-nano porosity gradient aluminium oxide, yttrium partially stabilized zirconium oxide and alumina doped yttrium part are steady Determine the biological engineering material and product manufacturing example of zirconia film structure

Any matrix of 6.1 aluminium oxide, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized zirconium oxide and The biological engineering material and product manufacturing example of surface biomimetic micro-nano porosity gradient aluminum oxide film membrane structure.

6.1.1 there is the aluminium oxide of special-shaped macrostructure, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized Any matrix of zirconium oxide and the biological engineering material and product system of surface biomimetic nanoaperture graded oxidation aluminium film structure Make example 1.

The aluminium oxide prepared with coprecipitation method and hydro-thermal method for hydrolysis, yttrium partially stabilized zirconium oxide and alumina doped yttrium Partially stabilized zirconia powder compacting prepares aluminium oxide, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized zirconium oxide Biscuit passes through the method for counting machine Computer Aided Design (CAD) and counting machine secondary process (CAM) on biscuit substrate, is formed and is needed Compromise face and 0.3-0.5 microns of microstructure, it is small that 120-200 DEG C of dry 1-2 is warming up to 1-10 DEG C/s of heating rate When, control surface moisture.When using have nanovoids additive aluminium oxide organic precursor method coated solution A carry out immersion plating, Spraying plating, coating and rotation mode layer plated film remove redundant solution.In 120-200 DEG C of drying, then plated film.Re-dry, according to needs It can be repeated several times；When the aluminium oxide organic precursor method coated solution B progress immersion plating using nanovoids additive, spraying plating, coating With rotation mode layer plated film, redundant solution is removed, the diaphragm of wet gel film is directly put to heating on 220-250 DEG C of heater Solvent is rapidly removed within 3-5 minutes, and repeats plated film and obtains the thicknesses of layers needed.Answer first pre-burning stove to 50 DEG C -60 before roasting DEG C, roasting is then divided into three phases: the 1st stage, is warming up to 250- in the case where partial pressure of oxygen is the mild oxidation atmosphere of 20-50% 350 DEG C, heating rate is 1-5 DEG C/min, after reaching 300 DEG C, keeps the temperature 0.5-1h；2nd stage was 80-100%'s in partial pressure of oxygen 500-600 DEG C is warming up under strong oxidizing atmosphere, heating rate is 5-10 DEG C/min；After reaching 500-600 DEG C, 1-2h is kept the temperature, the Three stages were rapidly heated to 1450-1700 DEG C, and heating rate is 50-100 DEG C/s, keeps the temperature 1-2h；Then natural cooling cools down, Successively SC1, SC2, SC3 and acetone, the ultrasonic cleaning in 10-30 minutes of alcohol and distilled water, being formed has micron order and micron Grade or more macrostructure and bionic nano graded oxidation aluminium film structure biological engineering material and product (Fig. 1).

6.1.2 there is the aluminium oxide of special-shaped macrostructure, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized Any matrix of zirconium oxide and the biological engineering material and product system of surface biomimetic nanoaperture graded oxidation aluminium film structure Make example 2.

Pass through the method for counting machine Computer Aided Design (CAD) and counting machine secondary process (CAM) on biscuit substrate, being formed needs The microstructure of compromise face and 0.3-0.5 microns is wanted, it is small to be warming up to 120-200 DEG C of dry 1-2 with 1-10 DEG C/s of heating rate When.Again according to needing to be warming up to 700-1100 DEG C of biscuiting with the heating rate of 10-50 DEG C/s, 1-2 hours are kept the temperature.It is placed in clear water In, it is cleaned after dry with acetone with ultrasonic cleaning.When using the aluminium oxide organic precursor method with nanovoids additive Coated solution A carries out immersion plating, spraying plating, coating and rotation mode layer plated film, removes redundant solution.In 120-200 DEG C of drying, then Plated film.Re-dry can be repeated several times according to needs；When the aluminium oxide organic precursor method coated solution using nanovoids additive B carries out immersion plating, spraying plating, coating and rotation mode layer plated film, removes redundant solution, and the diaphragm of wet gel film is directly put to 220- It is heated on 250 DEG C of heater and rapidly removes within 3-5 minutes solvent, and repeated plated film and obtain the thicknesses of layers needed.It is answered before roasting Then roasting is divided into three phases: the 1st stage to 50 DEG C -60 DEG C by first pre-burning stove, in the slight oxygen that partial pressure of oxygen is 20-50% Change and be warming up to 250-350 DEG C under atmosphere, heating rate is 1-5 DEG C/min, after reaching 300 DEG C, keeps the temperature 0.5-1 h；2nd stage, It is warming up to 500-600 DEG C in the case where partial pressure of oxygen is the strong oxidizing atmosphere of 80-100%, heating rate is 10 DEG C/min of 5-, is reached After 500-600 DEG C, 1-2h is kept the temperature, the phase III is rapidly heated to 1450-1700 DEG C, and heating rate is 50-100 DEG C/s, heat preservation 1-2h；Then natural cooling cools down, successively SC1, SC2, SC3 and acetone, the ultrasonic cleaning in 10-30 minutes of alcohol and distilled water, Form the bioengineering material with micron order and the above macrostructure of micron order and bionic nano graded oxidation aluminium film structure Material and product.

6.1.3 with the aluminium oxide of smooth finish surface, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized oxidation Any matrix of zirconium and the biological engineering material and product manufacturing of surface biomimetic nanoaperture graded oxidation aluminium film structure are real Example 3.

This example and 6.1.1 on biscuit substrate the difference is that pass through counting machine Computer Aided Design (CAD) and counting machine The method of secondary process (CAM) forms the smooth finish surface needed, other same 6.1.1.

6.1.4 with the aluminium oxide of smooth finish surface, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized oxidation Any matrix of zirconium and the biological engineering material and product manufacturing of surface biomimetic nanoaperture graded oxidation aluminium film structure are real Example 4.

This example and 6.1.2 on biscuit substrate the difference is that pass through counting machine Computer Aided Design (CAD) and counting machine The method of secondary process (CAM) forms the smooth finish surface needed, other same 6.1.2.

6.1.5 with the aluminium oxide of compromise face, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized oxidation Any matrix of zirconium and the biological engineering material and product manufacturing of surface biomimetic micro-nano porosity gradient aluminum oxide film membrane structure Example 5 (Fig. 2).

Biscuit substrate with 1-10 DEG C/s of heating rate be warming up to 120-200 DEG C it is 1-2 hours dry.Pass through on biscuit substrate The method of counting machine Computer Aided Design (CAD) and counting machine secondary process (CAM) forms the compromise face structure of needs, control table Then surface humidity carries out immersion plating, spray using the precursor complex liquid of the formation aluminum oxide film added with micro-void forming agent Plating, coating and rotation mode layer plated film remove redundant solution.When using the aluminium oxide organic precursor with micron spacers additive Body coated solution A carries out immersion plating, spraying plating, coating and rotation mode layer plated film, removes redundant solution.In 120-200 DEG C of drying, then Plated film.Re-dry can be repeated several times according to needs；When the aluminium oxide organic precursor method coated solution using micron spacers additive B carries out immersion plating, spraying plating, coating and rotation mode layer plated film, removes redundant solution, and the diaphragm of wet gel film is directly put to 220- It is heated on 250 DEG C of heater and rapidly removes within 3-5 minutes solvent, and repeated plated film and obtain the thicknesses of layers needed.Then 700-1100 DEG C of biscuiting 1-2 hours is warming up to the heating rate of 10-50 DEG C/s.It is placed in clear water, it is dry with ultrasonic cleaning Afterwards, it is cleaned with acetone.Then continued using the precursor complex liquid of the formation aluminum oxide film added with nanoaperture forming agent Plated film.When using have nanovoids additive aluminium oxide organic precursor method coated solution A carry out immersion plating, spraying plating, coating and Rotation mode layer plated film removes redundant solution.In 120-200 DEG C of drying, then plated film.Re-dry can be repeated several times according to needs； When the aluminium oxide organic precursor method coated solution B progress immersion plating using nanovoids additive, spraying plating, coating and rotation mode layer Plated film, removes redundant solution, and the diaphragm of wet gel film, which is directly put to heating 3-5 minutes on 220-250 DEG C of heater, to be removed rapidly Solvent is removed, and repeats plated film and obtains the thicknesses of layers needed.Diaphragm after the drying finally obtained, which is put into roaster, to be roasted It burns.It answers first pre-burning stove to 50 DEG C -60 DEG C before roasting, roasting is then divided into three phases: the 1st stage, be 20- in partial pressure of oxygen 250-350 DEG C is warming up under 50% mild oxidation atmosphere, heating rate is 1-5 DEG C/min, after reaching 300 DEG C, keeps the temperature 0.5- 1h；2nd stage was warming up to 500-600 DEG C in the case where partial pressure of oxygen is the strong oxidizing atmosphere of 80-100%, and heating rate is 5-10 DEG C/ Min after reaching 500-600 DEG C, keeps the temperature 1- 2h, and the phase III is rapidly heated to 1450-1500 DEG C, heating rate 50-100 DEG C/s, keep the temperature 1-2h；Then natural cooling cools down, successively SC1, SC2, SC3 and acetone, alcohol and distilled water 10-30 minutes Ultrasonic cleaning, formed the biological engineering material with special-shaped macrostructure and bionical micro-nano graded oxidation aluminium film structure and Product.

6.1.6 with the aluminium oxide of any surface finish structure, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized Any matrix of zirconium oxide and the biological engineering material and product of surface biomimetic micro-nano porosity gradient aluminum oxide film membrane structure Manufacture example 6.

This example and 6.1.5 on biscuit substrate the difference is that pass through counting machine Computer Aided Design (CAD) and counting machine The method of secondary process (CAM) forms the smooth finish surface needed, other same 6.1.5.

6.1.7 with the aluminium oxide of compromise face, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized oxidation Any matrix of zirconium and the biological engineering material and product manufacturing of surface biomimetic micro-nano porosity gradient aluminum oxide film membrane structure Example 7.

Biscuit substrate with 1-10 DEG C/s of heating rate be warming up to 120-200 DEG C it is 1-2 hours dry.Pass through on biscuit substrate The method of counting machine Computer Aided Design (CAD) and counting machine secondary process (CAM) forms the compromise face structure of needs, control table Then surface humidity carries out immersion plating, spray using the precursor complex liquid of the formation aluminum oxide film added with micro-void forming agent Plating, coating and rotation mode layer plated film remove redundant solution.When using the aluminium oxide organic precursor with micron spacers additive Body coated solution A carries out immersion plating, spraying plating, coating and rotation mode layer plated film, removes redundant solution.In 120-200 DEG C of drying, then Plated film.Re-dry can be repeated several times according to needs；When the aluminium oxide organic precursor method coated solution using micron spacers additive B carries out immersion plating, spraying plating, coating and rotation mode layer plated film, removes redundant solution, and the diaphragm of wet gel film is directly put to 220- It is heated on 250 DEG C of heater and rapidly removes within 3-5 minutes solvent, and repeated plated film and obtain the thicknesses of layers needed.Then it uses The precursor complex liquid of formation aluminum oxide film added with nanoaperture forming agent continues plated film.When using with nanovoids The aluminium oxide organic precursor method coated solution A of additive carries out immersion plating, spraying plating, coating and rotation mode layer plated film, and it is extra to remove Solution.In 120-200 DEG C of drying, then plated film.Re-dry can be repeated several times according to needs；When using nanovoids additive Aluminium oxide organic precursor method coated solution B carries out immersion plating, spraying plating, coating and rotation mode layer plated film, removes redundant solution, wet solidifying The diaphragm of glue film is directly put to heating on 220-250 DEG C of heater and rapidly removes within 3-5 minutes solvent, and repeats plated film and needed The thicknesses of layers wanted.Diaphragm after the drying finally obtained, which is put into roaster, to be roasted.Answer first pre-burning stove to 50 before roasting DEG C -60 DEG C, roasting is then divided into three phases: the 1st stage, is heated up in the case where partial pressure of oxygen is the mild oxidation atmosphere of 20-50% To 250-350 DEG C, heating rate is 1-5 DEG C/min, after reaching 300 DEG C, keeps the temperature 0.5-1h；2nd stage was 80- in partial pressure of oxygen 500-600 DEG C is warming up under 100% strong oxidizing atmosphere, heating rate is 5-10 DEG C/min, after reaching 500-600 DEG C, heat preservation 1-2h, phase III are rapidly heated to 1450-1500 DEG C, and heating rate is 50-100 DEG C/s, keeps the temperature 1-2h；Then naturally cold But cool down, successively SC1, SC2, SC3 and acetone, the ultrasonic cleaning in 10-30 minutes of alcohol and distilled water, being formed has abnormity macro See the biological engineering material and product of structure and bionical micro--nanometer gradient aluminum oxide film membrane structure.

Any matrix of 6.2 aluminium oxide, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized zirconium oxide and The biological engineering material and product manufacturing example of the yttrium partially stabilized zirconia film structure of surface biomimetic micro-nano porosity gradient.

6.2.1 there is the aluminium oxide of special-shaped macrostructure, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized The bioengineering material of the yttrium partially stabilized zirconia film structure of any matrix and surface biomimetic nanoaperture gradient of zirconium oxide Material and product manufacturing example 1.

The aluminium oxide prepared with coprecipitation method and hydro-thermal method for hydrolysis, yttrium partially stabilized zirconium oxide and alumina doped yttrium Partially stabilized zirconia powder compacting prepares aluminium oxide, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized zirconium oxide Biscuit passes through the method for counting machine Computer Aided Design (CAD) and counting machine secondary process (CAM) on biscuit substrate, is formed and is needed Compromise face and 0.3-0.5 microns of microstructure, it is small that 120-200 DEG C of dry 1-2 is warming up to 1-10 DEG C/s of heating rate When.Surface moisture is controlled, when using the yttrium partially stabilized zirconium oxide organic precursor method coated solution A with nanovoids additive Immersion plating, spraying plating, coating and rotation mode layer plated film are carried out, redundant solution is removed.In 120-200 DEG C of drying, then plated film.It does again It is dry, it can be repeated several times according to needs；When molten using the yttrium partially stabilized zirconium oxide organic precursor method plated film of nanovoids additive Liquid B carries out immersion plating, spraying plating, coating and rotation mode layer plated film, removes redundant solution, and the diaphragm of wet gel film is directly put to 220- It is heated on 250 DEG C of heater and rapidly removes within 3-5 minutes solvent, and repeated plated film and obtain the thicknesses of layers needed.It is answered before roasting Then roasting is divided into three phases: the 1st stage to 50 DEG C -60 DEG C by first pre-burning stove, in mild oxidation atmosphere, (partial pressure of oxygen is 250-350 DEG C is warming up under 20-50%), heating rate is 1-5 DEG C/min, after reaching 300 DEG C, keeps the temperature 0.5-1h；2nd stage, 500-600 DEG C is warming up at strong oxidizing atmosphere (partial pressure of oxygen 80-100%), heating rate is 5-10 DEG C/min, reaches 500- After 600 DEG C, 1-2h is kept the temperature, the phase III is rapidly heated to 1400-1600 DEG C, and heating rate is 50-100 DEG C/s, keeps the temperature 1- 2h；Then natural cooling cools down, successively SC1, SC2, SC3 and acetone, the ultrasonic cleaning in 10-30 minutes of alcohol and distilled water, shape At the life with micron order and the above macrostructure of micron order and the yttrium partially stabilized zirconia film structure of bionic nano gradient Object engineering material and product.

6.2.2 there is the aluminium oxide of special-shaped macrostructure, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized The bioengineering material of the yttrium partially stabilized zirconia film structure of any matrix and surface biomimetic nanoaperture gradient of zirconium oxide Material and product manufacturing example 2.

Pass through the method for counting machine Computer Aided Design (CAD) and counting machine secondary process (CAM) on biscuit substrate, being formed needs The microstructure of compromise face and 0.3-0.5 microns is wanted, it is small to be warming up to 120-200 DEG C of dry 1-2 with 1-10 DEG C/s of heating rate When.Again according to needing to be warming up to 700-1100 DEG C of biscuiting with the heating rate of 10-50 DEG C/s, 1-2 hours are kept the temperature.It is placed in clear water In, it is cleaned after dry with acetone with ultrasonic cleaning, it is then multiple using the precursor for forming yttrium partially stabilized zirconia film It closes liquid plated film: being soaked when using the yttrium partially stabilized zirconium oxide organic precursor method coated solution A with nanovoids additive Plating, spraying plating, coating and rotation mode layer plated film remove redundant solution.In 120-200 DEG C of drying, then plated film.Re-dry, foundation It needs can be repeated several times；It is carried out when using the yttrium partially stabilized zirconium oxide organic precursor method coated solution B of nanovoids additive Immersion plating, spraying plating, coating and rotation mode layer plated film, remove redundant solution, and the diaphragm of wet gel film is directly put to 220-250 DEG C It is heated on heater and rapidly removes within 3-5 minutes solvent, and repeated plated film and obtain the thicknesses of layers needed.First pre-burning stove is answered before roasting To 50 DEG C -60 DEG C, roasting is then divided into three phases: the 1st stage was warming up to 250-350 DEG C under mild oxidation atmosphere, Heating rate is 1-5 DEG C/min, after reaching 300 DEG C, keeps the temperature 0.5-1h；2nd stage was warming up to 500- under strong oxidizing atmosphere 600 DEG C, heating rate is 5-10 DEG C/min；After reaching 500-600 DEG C, 1-2h is kept the temperature, the phase III is rapidly heated to 1400- 1600 DEG C, heating rate is 50-100 DEG C/s, keeps the temperature 1-2h；Then natural cooling cools down, successively SC1, SC2, SC3 and acetone, The ultrasonic cleaning in 10-30 minutes of alcohol and distilled water, being formed has micro-void structures and bionical micro-nano gradient yttrium part steady Determine the biological engineering material and product of zirconia film structure.

6.2.3 with the aluminium oxide of smooth finish surface, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized oxidation The biological engineering material of the yttrium partially stabilized zirconia film structure of any matrix and surface biomimetic nanoaperture gradient of zirconium and Product manufacturing example 3.

This example and 6.2.1 on biscuit substrate the difference is that pass through counting machine Computer Aided Design (CAD) and counting machine The method of secondary process (CAM) forms the smooth finish surface needed, other same 6.2.1.

6.2.4 with the aluminium oxide of smooth finish surface, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized oxidation The biological engineering material of the yttrium partially stabilized zirconia film structure of any matrix and surface biomimetic nanoaperture gradient of zirconium and Product manufacturing example 4.

This example and 6.2.2 on biscuit substrate the difference is that pass through counting machine Computer Aided Design (CAD) and counting machine The method of secondary process (CAM) forms the smooth finish surface needed, other same 6.2.2.

6.2.5 with the aluminium oxide of compromise face, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized oxidation The biological engineering material of the yttrium partially stabilized zirconia film structure of any matrix and surface biomimetic micro-nano porosity gradient of zirconium And product manufacturing example 5.

Biscuit substrate with 1-10 DEG C/s of heating rate be warming up to 120-200 DEG C it is 1-2 hours dry.Pass through on biscuit substrate The method of counting machine Computer Aided Design (CAD) and counting machine secondary process (CAM) forms the compromise face structure of needs, control table Surface humidity, then using the precursor complex liquid plating of the yttrium partially stabilized zirconia film of formation added with micro-void forming agent Film: when using the aluminium oxide organic precursor method coated solution A progress immersion plating with micron spacers additive, spraying plating, coating and rotation Turn mode layer plated film, removes redundant solution.In 120-200 DEG C of drying, then plated film.Re-dry can be repeated several times according to needs；When Immersion plating, spraying plating, coating and the plating of rotation mode layer are carried out using the aluminium oxide organic precursor method coated solution B of micron spacers additive Film, removes redundant solution, and the diaphragm of wet gel film is directly put to heating 3-5 minutes on 220-250 DEG C of heater and rapidly removed Solvent, and repeat plated film and obtain the thicknesses of layers needed.700-1100 DEG C of biscuiting 1- is warming up to the heating rate of 10-50 DEG C/s 2 hours.It is placed in clear water, is cleaned after dry with acetone with ultrasonic cleaning, then using added with nanoaperture forming agent Yttrium partially stabilized zirconia film precursor complex liquid continue plated film: when using have nanovoids additive aluminium oxide Organic precursor method coated solution A carries out immersion plating, spraying plating, coating and rotation mode layer plated film, removes redundant solution.In 120-200 DEG C drying, then plated film.Re-dry can be repeated several times according to needs；When the aluminium oxide organic precursor using nanovoids additive Body coated solution B carries out immersion plating, spraying plating, coating and rotation mode layer plated film, removes redundant solution, and the diaphragm of wet gel film is direct It puts to heating on 220-250 DEG C of heater and rapidly removes within 3-5 minutes solvent, and repeat plated film and obtain the thicknesses of layers needed. Diaphragm after the drying finally obtained, which is put into roaster, to be roasted.It answers first pre-burning stove to 50 DEG C -60 DEG C before roasting, then will Roasting is divided into three phases: the 1st stage, and 250-350 DEG C is warming up under mild oxidation atmosphere (partial pressure of oxygen 20-50%), rises Warm rate is 1-5 DEG C/min, after reaching 300 DEG C, keeps the temperature 0.5-1h；2nd stage, in strong oxidizing atmosphere (partial pressure of oxygen 80- 100%) 500-600 DEG C is warming up under, heating rate is 5-10 DEG C/min, after reaching 500-600 DEG C, keeps the temperature 1-2h, third rank Section is rapidly heated to 1450-1600 DEG C, and heating rate is 50-100 DEG C/s, keeps the temperature 1-2h；Then natural cooling cools down, successively SC1, SC2, SC3 and acetone, the ultrasonic cleaning in 10-30 minutes of alcohol and distilled water, being formed has special-shaped macrostructure and bionical The biological engineering material and product of the yttrium partially stabilized zirconia film structure of micro-nano gradient.

6.2.6 with the aluminium oxide of any surface finish structure, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized The bioengineering of the yttrium partially stabilized zirconia film structure of any matrix and surface biomimetic micro-nano porosity gradient of zirconium oxide Material and product manufacturing example 6.

This example and 6.2.5 on biscuit substrate the difference is that pass through counting machine Computer Aided Design (CAD) and counting machine The method of secondary process (CAM) forms the smooth finish surface needed, other same 6.2.5.

6.2.7 with the aluminium oxide of compromise face, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized oxidation The biological engineering material of the yttrium partially stabilized zirconia film structure of any matrix and surface biomimetic micro-nano porosity gradient of zirconium And product manufacturing example 7.

Biscuit substrate with 1-10 DEG C/s of heating rate be warming up to 120-200 DEG C it is 1-2 hours dry.Pass through on biscuit substrate The method of counting machine Computer Aided Design (CAD) and counting machine secondary process (CAM) forms the compromise face structure of needs, control table Surface humidity, then using the precursor complex liquid of the yttrium partially stabilized zirconia film of formation added with micro-void forming agent into Row plated film: when using have micron spacers additive yttrium partially stabilized zirconium oxide organic precursor method coated solution A carry out immersion plating, Spraying plating, coating and rotation mode layer plated film remove redundant solution.In 120-200 DEG C of drying, then plated film.Re-dry, according to needs It can be repeated several times；When using micron spacers additive yttrium partially stabilized zirconium oxide organic precursor method coated solution B carry out immersion plating, Spraying plating, coating and rotation mode layer plated film, remove redundant solution, and the diaphragm of wet gel film is directly put to 220-250 DEG C of heating It is heated on device and rapidly removes within 3-5 minutes solvent, and repeated plated film and obtain the thicknesses of layers needed.Then using added with nano-pore The precursor complex liquid of the yttrium partially stabilized zirconia film of gap forming agent continues plated film: when using with nanovoids additive Yttrium partially stabilized zirconium oxide organic precursor method coated solution A carry out immersion plating, spraying plating, coating and rotation mode layer plated film remove Redundant solution.In 120-200 DEG C of drying, then plated film.Re-dry can be repeated several times according to needs；It is added when using nanovoids The yttrium partially stabilized zirconium oxide organic precursor method coated solution B of agent carries out immersion plating, spraying plating, coating and rotation mode layer plated film, removes Going redundant solution, the diaphragm of wet gel film is directly put to heating 3-5 minutes on 220-250 DEG C of heater and rapidly removes solvent, And it repeats plated film and obtains the thicknesses of layers needed.Diaphragm after the drying finally obtained, which is put into roaster, to be roasted.Roasting Before answer first pre-burning stove to 50 DEG C -60 DEG C, roasting is then divided into three phases: the 1st stage, in mild oxidation atmosphere (partial pressure of oxygen To be warming up to 250-350 DEG C under 20-50%), heating rate is 1-5 DEG C/min, after reaching 300 DEG C, keeps the temperature 0.5-1h；2nd rank Section is warming up to 500-600 DEG C at strong oxidizing atmosphere (partial pressure of oxygen 80-100%), and heating rate is 5-10 DEG C/min, is reached After 500-600 DEG C, 1-2h is kept the temperature, the phase III is rapidly heated to 1450-1500 DEG C, and heating rate is 50-100 DEG C/s, heat preservation 1-2h；Then natural cooling cools down, successively SC1, SC2, SC3 and acetone, the ultrasonic cleaning in 10-30 minutes of alcohol and distilled water, Formed the biological engineering material with special-shaped macrostructure and the yttrium partially stabilized zirconia film structure of bionical micro-nano gradient and Product.

Any matrix of 6.3 aluminium oxide, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized zirconium oxide and The biological engineering material and product of the alumina doped yttrium partially stabilized zirconia film structure of surface biomimetic micro-nano porosity gradient Manufacture example.

6.3.1 there is the aluminium oxide of special-shaped macrostructure, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized Any matrix and surface biomimetic nanoaperture graded oxidation aluminium of zirconium oxide adulterate yttrium partially stabilized zirconia film structure Biological engineering material and product manufacturing example 1.

This example and 6.2.1 using the precursor complex liquid for forming yttrium partially stabilized zirconia film the difference is that plated Film, other same 6.2.1.

6.3.2 there is the aluminium oxide of special-shaped macrostructure, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized Any matrix and surface biomimetic nanoaperture graded oxidation aluminium of zirconium oxide adulterate yttrium partially stabilized zirconia film structure Biological engineering material and product manufacturing example 2.

This example and 6.2.2 using the precursor complex liquid for forming yttrium partially stabilized zirconia film the difference is that plated Film, other same 6.2.2.

6.3.3 with the aluminium oxide of smooth finish surface, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized oxidation Any matrix and surface biomimetic nanoaperture graded oxidation aluminium of zirconium adulterate the biology of yttrium partially stabilized zirconia film structure Engineering material and product manufacturing example 3.

This example and 6.3.1 on biscuit substrate the difference is that pass through counting machine Computer Aided Design (CAD) and counting machine The method of secondary process (CAM) forms the smooth finish surface needed, other same 6.3.1.

6.3.4 with the aluminium oxide of smooth finish surface, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized oxidation Any matrix and surface biomimetic nanoaperture graded oxidation aluminium of zirconium adulterate the biology of yttrium partially stabilized zirconia film structure Engineering material and product manufacturing example 4.

This example and 6.3.2 on biscuit substrate the difference is that pass through counting machine Computer Aided Design (CAD) and counting machine The method of secondary process (CAM) forms the smooth finish surface needed, other same 6.3.2.

6.3.5 with the aluminium oxide of compromise face, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized oxidation The life of the alumina doped yttrium partially stabilized zirconia film structure of any matrix and surface biomimetic micro-nano porosity gradient of zirconium Object engineering material and product manufacturing example 5.

This example and 6.2.5 using the precursor complex liquid for forming yttrium partially stabilized zirconia film the difference is that plated Film, other same 6.2.5.

6.3.6 with the aluminium oxide of any surface finish structure, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized The alumina doped yttrium partially stabilized zirconia film structure of any matrix and surface biomimetic micro-nano porosity gradient of zirconium oxide Biological engineering material and product manufacturing example 6.

This example and 6.3.5 on biscuit substrate the difference is that pass through counting machine Computer Aided Design (CAD) and counting machine The method of secondary process (CAM) forms the smooth finish surface needed, other same 6.3.5.

6.3.7 with the aluminium oxide of compromise face, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized oxidation The life of the alumina doped yttrium partially stabilized zirconia film structure of any matrix and surface biomimetic micro-nano porosity gradient of zirconium Object engineering material and product manufacturing example 7.

This example and 6.2.7 using the precursor complex liquid for forming yttrium partially stabilized zirconia film the difference is that plated Film, other same 6.2.7.

6.4 have compromise face, the aluminium oxide of micron surface structure and smooth finish surface structure, yttrium partially stabilized zirconium oxide With any matrix of alumina doped yttrium partially stabilized zirconium oxide and the aluminium oxide of surface biomimetic micro-nano porosity gradient, yttrium The biological engineering material of partially stabilized zirconia and alumina doped yttrium partially stabilized zirconium oxide and combinations thereof membrane structure and production Product manufacture example.

With compromise face, the aluminium oxide of micron surface structure and smooth finish surface structure, yttrium partially stabilized zirconium oxide and oxygen Change aluminium and adulterates any matrix of yttrium partially stabilized zirconium oxide and the aluminium oxide of surface biomimetic micro-nano porosity gradient, yttrium part The biological engineering material and product of stabilizing zirconia and alumina doped yttrium partially stabilized zirconium oxide and combinations thereof membrane structure, Manufacturing process is as follows: the aluminium oxide prepared with coprecipitation method and hydro-thermal method for hydrolysis, yttrium partially stabilized zirconium oxide and aluminium oxide It adulterates yttrium partially stabilized Zirconium oxide powder molding and prepares aluminium oxide, yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized Zirconium oxide biscuit, biscuit substrate with the heating rate of 1-10 DEG C/s be warming up to 120-200 DEG C it is 1-2 hours dry.In zirconium oxide The method for passing through counting machine Computer Aided Design (CAD) and counting machine secondary process (CAM) on biscuit substrate, forms the special-shaped table of needs Any, control surface moisture, using above-mentioned identical process flow, In of face structure, micro-void structures and smooth finish surface When coating process, using the aluminium oxide containing micro-void forming agent and nanoaperture forming agent, yttrium partially stabilized zirconium oxide and The composite solution plated film and use variety classes solution alternate plating of alumina doped yttrium partially stabilized zirconium oxide form composite membrane Layer.Finally, before roasting then roasting is divided into three phases: the 1st stage, in mild oxidation atmosphere to 50-60 DEG C by first pre-burning stove Under be warming up to 250-350 DEG C, heating rate is 1-5 DEG C/min, after reaching 300 DEG C, keeps the temperature 0.5-1h；2nd stage, in strong oxygen Change and be warming up to 500-600 DEG C under atmosphere, heating rate is 5-10 DEG C/min, after reaching 500-600 DEG C, keeps the temperature 1-2h, third rank Section, is rapidly heated to 1400-1700 DEG C, keeps the temperature 1-2h；Then natural cooling cools down, and is successively cleaned using SC1 cleaning solution, SC2 Liquid, SC3 cleaning solution, acetone, alcohol and distilled water are cleaned by ultrasonic 10-30min respectively, obtain with compromise face, micron surface knot The aluminium oxide of structure and smooth finish surface structure, any of yttrium partially stabilized zirconium oxide and alumina doped yttrium partially stabilized zirconium oxide The aluminium oxide of kind matrix and surface biomimetic micro-nano porosity gradient, yttrium partially stabilized zirconium oxide and alumina doped yttrium part are steady Determine the biological engineering material and product of zirconium oxide and combinations thereof membrane structure.

The intensity of the zirconium oxide based plating film bio-medical engineering material of production of the invention is tough in 800Mpa-1200Mpa Property is in 10.0Mpa m1/2-20Mpa m1/2.

Zoopery shows that this kind of nano-oxide ceramic membrane has good biocompatibility and bioactivity.

Above-mentioned embodiment is only a preferred solution of the present invention, not the present invention is made in any form Limitation, there are also other variations and modifications on the premise of not exceeding the technical scheme recorded in the claims.

Claims

1. a kind of biologically active nano-oxide ceramic membrane of organic precursor liquid solution plated film preparation, feature exist In being prepared by the following method and obtain:

(1) forming design by CAD and Computer aided building on the substrate of bio-medical engineering material needs The surface texture wanted；The bio-medical engineering material is aluminium oxide, zirconium oxide, yttrium partially stabilized zirconium oxide, alumina doped One of yttrium partially stabilized zirconium oxide；

(2) the organic precursor method coating liquid of pore former is added or is not added in preparation, and the organic precursor method coating liquid is shape At the precursor complex liquid of aluminum oxide film, the precursor complex liquid of the yttrium partially stabilized zirconia film of formation, formation aluminium oxide Adulterate one of the precursor complex liquid of yttrium partially stabilized zirconia film；

(3) using organic precursor method coating liquid, plated film, coating process are used on the surface texture of step (1) treated substrate Sol-gel films technique or organic compound decompose thin-film technique, roasting, and natural cooling obtains simple having and receives after cleaning The film or internal layer of metre hole gap are micro-void film, and outer layer is the composite membrane of nanoporous film；

One of described specific preparation method selection following scheme of biologically active nano-oxide ceramic membrane:

Scheme 1: it is set on the substrate of bio-medical engineering material by CAD and Computer aided building formation Count need surface texture, with the heating rate of 1-10 DEG C/s be warming up to 200 DEG C of 120- it is 1- 2 hours dry, control surface it is wet Then degree uses organic precursor method coating liquid plated film on the surface texture of substrate, first pre-burning stove is to 50-60 DEG C before roasting, so Roasting is divided into three phases: the 1st stage afterwards, is warming up to 250-350 DEG C under mild oxidation atmosphere, heating rate is 1-5 DEG C/ Min after reaching 300 DEG C, keeps the temperature 0.5-1h；2nd stage was warming up to 500-600 DEG C, heating rate 5- under strong oxidizing atmosphere 10 DEG C/min, after reaching 500-600 DEG C, 1-2 h is kept the temperature, the phase III, is rapidly heated to 1400-1700 DEG C, heating rate is 50-100 DEG C/s, keep the temperature 1-2h；Then natural cooling cools down, and successively uses SC1 cleaning solution, SC2 cleaning solution, SC3 cleaning solution, third Ketone, alcohol and distilled water are cleaned by ultrasonic 10-30min respectively；

Scheme 2: it is set on the substrate of bio-medical engineering material by CAD and Computer aided building formation The surface texture needed is counted, it is 1- 2 hours dry to be warming up to 200 DEG C of 120- with the heating rate of 1-10 DEG C/s, then with 10-50 DEG C/heating rate of s is warming up to 700-1100 DEG C of biscuiting 1-2 hours, it is placed in clear water, with ultrasonic cleaning, after dry, with third Ketone cleaning, then uses organic precursor method coating liquid plated film on the surface texture of substrate, roasts preceding first pre-burning stove to 50-60 DEG C, roasting is then divided into three phases: the 1st stage, 250-350 DEG C is warming up under mild oxidation atmosphere, heating rate is 1-5 DEG C/min, after reaching 300 DEG C, keep the temperature 0.5-1h；2nd stage was warming up to 500-600 DEG C, heating speed under strong oxidizing atmosphere Rate is 5-10 DEG C/min；After reaching 500-600 DEG C, 1-2 h is kept the temperature, the phase III is rapidly heated to 1400-1700 DEG C, heats up Rate is 50-100 DEG C/s, keeps the temperature 1-2h；Then natural cooling cools down, successively clear using SC1 cleaning solution, SC2 cleaning solution, SC3 Washing lotion, acetone, alcohol and distilled water are cleaned by ultrasonic 10-30min respectively；

Scheme 3: it is small that the substrate of bio-medical engineering material with the heating rate of 1-10 DEG C/s is warming up to 120-200 DEG C of dry 1- 2 When, then forming design by CAD and Computer aided building on the substrate of bio-medical engineering material needs The surface texture wanted controls surface moisture, using the organic precursor method coating liquid added with micro-void forming agent in substrate Then plated film on surface texture is warming up to 700-1100 DEG C of biscuiting 1-2 hours with the heating rate of 10-50 DEG C/s, is placed in clear water In, it is cleaned after dry with acetone with ultrasonic cleaning, is then plated using the organic precursor method added with nanoaperture forming agent Film liquid continues plated film, is finally warming up to 1400-1700 DEG C with the heating rate of 1-10 DEG C/s, keeps the temperature 1-2h；Then natural cooling Cooling is successively cleaned by ultrasonic 10- using SC1 cleaning solution, SC2 cleaning solution, SC3 cleaning solution, acetone, alcohol and distilled water respectively 30min；

SC1 cleans formula of liquid are as follows: NH₄OH: H₂O₂: H₂O volume ratio is 1:1-2:5-7, and cleaning temperature control is 65-80 DEG C； SC2 cleans formula of liquid are as follows: H₂SO₄: H₂O₂: H₂O volume ratio is 1:1-2:6-8, and cleaning temperature control is 65-80 DEG C；SC3 Clean formula of liquid are as follows: NH₄OH: H₂O₂: H₂O volume ratio is 1:1:3, and cleaning temperature control is 100-130 DEG C.

2. a kind of biologically active nano-oxide of organic precursor liquid solution plated film preparation according to claim 1 Ceramic membrane, which is characterized in that the coating liquid of the sol-gel films technique is the preparation method comprises the following steps: using metal alkoxide as precursor Material dissolves in precursor material in dehydrated alcohol, is configured to the precursor solution that concentration is 0.1-0.5 moles every liter；Then The deionized water solution of ethyl alcohol is added into precursor solution, stirs evenly, obtains mixed solution, then adds in the mixed solution Enter DMF, forms composite solution, component molar proportion in the composite solution are as follows: the amount of precursor solution: the deionized water of ethyl alcohol Amount of alcohol in solution: the amount of deionized water: amount=1:1-4:5-10:0.2-0.4 of DMF；Addition accounts for precursor quantity of material 1- The micron or nanoaperture forming agent of 5wt% stirs 10-15min, and finally sealing is parked 0.5-2 hours at room temperature, obtains It is coating liquid to precursor complex liquid.

3. a kind of biologically active nano-oxide of organic precursor liquid solution plated film preparation according to claim 2 Ceramic membrane, which is characterized in that the precursor material for forming the precursor complex liquid of aluminum oxide film is the metal alkoxide containing Al； The precursor material for forming the precursor complex liquid of yttrium partially stabilized zirconia film is the metal alkoxide containing Zr and Y；Form oxygen The precursor material for changing the precursor complex liquid that aluminium adulterates yttrium partially stabilized zirconia film is the metal alcohol containing Al, Zr and Y Salt.

4. a kind of biologically active nano-oxide of organic precursor liquid solution plated film preparation according to claim 1 Ceramic membrane, which is characterized in that the organic compound decompose the coating liquid of thin-film technique the preparation method comprises the following steps: with containing metal from The 2 ethyl hexanoic acid salt of son is precursor material, and the in the mixed solvent that precursor material dissolves in 2 ethyl hexanoic acid and toluene is prepared The precursor solution for being 0.1-0.5 moles every liter at precursor material concentration, 2-thylhexoic acid of in the mixed solvent and toluene Molar ratio is 1:1-2；Be added and account for the micron or nanoaperture forming agent of precursor quantity of material 1-5 wt%, temperature be 60 DEG C- 10-30 min is stirred at 80 DEG C, forms the organic precursor solution of homogeneous transparent, and sealing is parked 0.5-2 hours at room temperature, is obtained It is coating liquid to precursor complex liquid.

5. a kind of biologically active nano-oxide of organic precursor liquid solution plated film preparation according to claim 4 Ceramic membrane, which is characterized in that the precursor material for forming the precursor complex liquid of aluminum oxide film is containing metal ion Al 2 ethyl hexanoic acid salt；Formed the precursor complex liquid of yttrium partially stabilized zirconia film precursor material be containing metal from The 2 ethyl hexanoic acid salt of sub- Zr and Y；Form the pioneer of the precursor complex liquid of alumina doped yttrium partially stabilized zirconia film Body material is the 2 ethyl hexanoic acid salt containing metal ion Al, Zr and Y.

6. a kind of biologically active nano oxygen of organic precursor liquid solution plated film preparation according to claim 2 or 4 Compound ceramic membrane, which is characterized in that the micro-void forming agent is selected from polyethylene glycol, NC Nitroncellulose, polyacrylic acid, gathers Propanolamine, polyethylene, polypropylene, polyvinyl chloride, polybutadiene, polystyrene, polyacrylonitrile, polyphenyl phenol, polyformaldehyde, polyamides One of amine, polycaprolactam, polyarylether, Nomex, polyimides carbonic ester, terephthalic acid (TPA) methyl methacrylate Or it is several；The nanoaperture forming agent be selected from carbonyl diamide, Propanolamine, citric acid, ethylene, propylene, vinyl chloride, butadiene, Styrene, acrylonitrile, phenol, formaldehyde, amide, caprolactam, aryl oxide, fragrant amide, acid imide carbonic ester, one in ethylene glycol Kind is several.

7. a kind of biologically active nano-oxide of organic precursor liquid solution plated film preparation according to claim 1 Ceramic membrane, which is characterized in that the content of yttrium is 2-6mol% in yttrium partially stabilized zirconium oxide, alumina doped yttrium partially stabilized Aluminium content is 1-5mol% in zirconium oxide, yttrium content is 2-6mol%.

8. a kind of biologically active nano-oxide of organic precursor liquid solution plated film preparation according to claim 1 Ceramic membrane, which is characterized in that in step (3): the simple film thickness with nanoaperture is 0.3-3 microns, internal layer Micro-void film thickness is 0.3-3 microns, and the nanoporous film of outer layer is with a thickness of 0.3-3 microns.