CN110054492A - The method that hydroxyapatite in-situ containing calcium defect prepares tricalcium phosphate porous material - Google Patents
The method that hydroxyapatite in-situ containing calcium defect prepares tricalcium phosphate porous material Download PDFInfo
- Publication number
- CN110054492A CN110054492A CN201910350306.2A CN201910350306A CN110054492A CN 110054492 A CN110054492 A CN 110054492A CN 201910350306 A CN201910350306 A CN 201910350306A CN 110054492 A CN110054492 A CN 110054492A
- Authority
- CN
- China
- Prior art keywords
- containing calcium
- hydroxyapatite
- tricalcium phosphate
- slurry
- porous material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
-
- C04B35/803—
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/0615—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
- C04B38/068—Carbonaceous materials, e.g. coal, carbon, graphite, hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
The present invention relates to bioceramic material technical fields, a kind of method for preparing tricalcium phosphate porous material more particularly to hydroxyapatite in-situ containing calcium defect, it uses a certain proportion of hydroxyapatite containing calcium defect and biological glass powder for raw material, is added after auxiliary agent molding and is fired into the tricalcium phosphate porous material through high-temp in-situ.The tricalcium phosphate of preparation is the porous support materials that principal crystalline phase is bata-tricalcium phosphate, effectively improve the mechanical property of the degradable tricalcium phosphate porous support materials of tradition, porosity, connectivity, method of the invention utilizes the characteristics of bata-tricalcium phosphate and other synthos are mutually deformed under the hydroxyapatite hot conditions containing calcium defect, both the mechanical performance of hydroxyapatite enhancing porous support materials had been can use, optimize the pore structure of porous material, the phase composition ingredient of the additive amount control material of bioactivity glass can also be utilized, reach control degradation rate, to match with the growth rate of freshman bone tissue.
Description
Technical field
The present invention relates to bioceramic material technical fields, and in particular to a kind of preparation of hydroxyapatite in-situ containing calcium defect
The method of tricalcium phosphate porous material.
Background technique
With the quickening of modern society's aging process, due to a variety of causes such as self-defect, wound infection and tumours
Caused by bone defect case it is more and more, the exploitation of the reparative regeneration material of tissue receives significant attention.Hydroxyapatite
(Hydroxyapatite, chemical formula Ca10(PO4)6(OH)2, abbreviation HA) and tricalcium phosphate (Tricalcium
Phosphate, chemical formula Ca3(PO4)2, abbreviation TCP) and similar to nature bone on the Nomenclature Composition and Structure of Complexes, there is good biology
Compatibility and bioactivity after being implanted into human body, can form very strong chemical bonding with body bone tissue, and can shorten knitting
Time is widely used to field of biomedicine.But since hydroxyapatite degradation rate is slow, material fragility is big, mechanical property
The disadvantages of poor, clinical application are very limited;Bata-tricalcium phosphate (β-TCP) has good biocompatibility and self-bone grafting
Performance and suitable biological degradability, and porous ceramics is prepared into using various methods, it has also become bone defect healing is the most
A kind of ideal filling and repair materials.
Traditional β-TCP porous bio-ceramic is mainly raw material using the β-TCP powder and bio-vitric of synthesis, passes through bubble
The preparation of the methods of foam infusion process, foaming and addition pore-foaming agent.The pore structure of porous ceramics vulnerable to β-TCP powder constituent,
Particle size and distribution and the influence of various pore-forming techniques, and the porosity of porous ceramics is generally less than 70%, it is difficult to it prepares
High porosity, controlled porosity, three-dimensional communication, the bioceramic that macropore, aperture and micropore are reasonably distributed are provided.β-TCP pottery
Porcelain poor mechanical property, brittleness is big, and flexural strength is low, degradation speed is too fast, with bone uptake and Bone Defect Repari rate mismatch and material
The problems such as ostosis amount is less after implanting and bone depth of penetration is limited has become current biodegradable bioceramic application urgently
A problem to be solved.
Summary of the invention
The purpose of the present invention is to provide a kind of hydroxyapatite in-situs containing calcium defect to prepare tricalcium phosphate porous material
Method effectively improves mechanical property, porosity, the connectivity of the degradable tricalcium phosphate porous support materials of tradition, can be reasonable
The degradation rate of timbering material is controlled, to be expected to obtain the timbering material to match with bone uptake and reparation rate.
The present invention solves scheme used by above-mentioned technical problem: one kind hydroxyapatite in-situ containing calcium defect prepares phosphorus
The method of sour tricalcium porous material, uses a certain proportion of hydroxyapatite containing calcium defect and biological glass powder for raw material, is added
The tricalcium phosphate porous material is fired into through high-temp in-situ after auxiliary agent molding.
The thermal stability of hydroxyapatite is generally related to its crystallinity, stoichiometric ratio and doped chemical etc..Calcic lacks
Sunken hydroxyapatite is since there are a degree of distortions of lattice, it is suppressed that the crystallization of crystal, so that the knot of hydroxyapatite
Brilliant degree reduces, and thermal stability is deteriorated, and general temperature can decompose in the case where being higher than 900 DEG C, and phase transformation generates β-TCP and other phosphorus
Acid calcium salt (such as reaction equation 1 and 2).In addition, addition of the bio-vitric as high-temperature agglomerant, in the process for promoting material firing
In, [PO can be promoted in bio-vitric along with the melting of bio-vitric4] tetrahedron and Ca4P2O9Reaction generates TCP (as reacted
Formula 3 and 4) is decomposed or phase transformation generation TCP to accelerate hydroxyapatite containing calcium defect.The present invention is based on the above hydroxyls containing calcium defect
The principle of TCP is formed in situ in base apatite, has successfully prepared that comprehensive performance is good, with high porosity, high connected ratio it is more
The netted structure stand material in hole.
Ca10-x(HPO4)x(PO4)6-x(OH)2-x→(1-x)Ca10(PO4)6(OH)2+3x Ca3(PO4)2+H2O
(1)
Ca10(PO4)6(OH)2→2Ca3(PO4)2+Ca4P2O9+H2O (2)
3Ca4P2O9+2P2O5→2Ca3(PO4)2+3Ca2P2O7 (3)
3Ca4P2O9+P2O5→4Ca3(PO4)2 (4)
The present invention uses conventional molding process technology, and the novel degradable phosphoric acid for providing porous network structure is prepared in situ
Tricalcium (TCP) porous support materials effectively improve mechanical property, the hole of the degradable tricalcium phosphate porous support materials of tradition
Rate, connectivity.
For the mechanical property for effectively improving degradable calcium phosphate biological stephanoporate ceramics, prepare similar with body bone tissue
Porous support materials, method of the invention utilize the hydroxyapatite crystal whisker containing calcium defect and hydroxyapatite powder containing calcium defect
For raw material, moulding process appropriate is chosen, after molding and drying, degradable β-TCP is prepared in situ in high temperature sintering procedure
Porous support materials.This method equipment is simple and convenient to operate, and pore property is convenient for artificial adjustment.Method of the invention utilizes
The characteristics of β-TCP and other synthos are mutually deformed under hydroxyapatite hot conditions containing calcium defect, both can use hydroxyl
Base apatite enhances the mechanical performance of porous support materials, optimizes the pore structure of porous material, can also utilize bioactivity glass
The phase composition ingredient of the additive amount control material of glass, reaches control degradation rate, so as to the growth rate phase with freshman bone tissue
Matching.Method of the invention is suitable for the moldings such as addition pore-foaming agent, chemical blowing process, foam impregnation method and vacuum freeze-drying method
Method can be effectively improved the comprehensive performance of degradable β-TCP porous ceramics and its at home and abroad using competitiveness.
Preferably, the ratio of the hydroxyapatite containing calcium defect and biological glass powder is (75-85) wt%:(15-25)
Wt%.
Preferably, the hydroxyapatite containing calcium defect by hydroxyapatite crystal whisker containing calcium defect/fiber and contains calcium defect
Hydroxyapatite powder is mixed according to mass ratio for 1.5-4:1.
Preferably, the apatite whiskers containing calcium defect/fiber Ca/P is 1.58-1.62,180-240 μm long, major diameter
Than 70-90, the Ca/P of the hydroxyapatite powder containing calcium defect is 1.62-1.65, partial size is 10-50 μm.
Preferably, the biological glass powder is the 42%-50%P according to following mass percent2O5, 12%-17%
SiO2, 13%-20%CaCO3, 10%-16%Na2O, 3%-8%%ZnO, 1%-3%CaF2Matched with 3%-10% MgO
Material, and be melted at a temperature of 1050-1150 DEG C, it through chilling, grinds, the partial size of the biological glass powder is 10-50 μm.
Preferably, the forming method is pore-foaming agent method, in foam impregnation method, chemical blowing process, vacuum freeze-drying method
Any one.
Preferably, the step of preparing the tricalcium phosphate porous material using pore-foaming agent method is as follows: according to hydroxyl containing calcium defect
2wt%-10wt% pore-foaming agent, 1wt% sodium carboxymethylcellulose, 0.1wt%- is added in base apatite and biological glass powder gross mass
Slurry is made in 0.3wt% Sodium Polyacrylate, uniform stirring, and the solid content of the slurry is 20 wt%-30wt%, by the material
After starching injection forming, is demoulded, dried, finally high temperature is fired at 850 DEG C -1000 DEG C.
Pore-foaming agent method: will contain after calcium defect hydroxyapatite and biological glass powder mixing into solid mixture, mixed with solid
Closing material is butt, and choosing polymeric foam microballoon or activated carbon microballon etc. is pore-foaming agent, by the 2wt%- of solid mixture
10wt% weighs pore-foaming agent.1wt% sodium carboxymethylcellulose, the 0.1wt%-0.3wt% polypropylene of solid mixture is added
The additives such as sour sodium and corresponding aqueous solution control its solid content between 20 wt%-30wt%, form material through mechanical stirring
Slurry.Alleged pore-foaming agent is uniformly mixed in above-mentioned slurry, slurry injects injection forming in gypsum mold, can demould to blank
Afterwards, it moves into 80-105 DEG C of drying box, until drying.Shaping blank is put into high temperature furnace, with the heating of 4-10 DEG C/min
Rate is warming up to 800 DEG C -900 DEG C, and keeps the temperature 10-30min, finally with the heating rate of 5-8 DEG C/min be warming up to 1050 DEG C -
1100 DEG C of firings.
Preferably, the step of preparing the tricalcium phosphate porous material using chemical blowing process is as follows: according to containing calcium defect
1wt% sodium carboxymethylcellulose, 0.1wt%-0.3wt% polyacrylic acid is added in hydroxyapatite and biological glass powder gross mass
Slurry is made in sodium, uniform stirring, and the solid content of the slurry is 20wt%-30wt%, is then added in slurry and contains calcium defect
The foaming agent of hydroxyapatite and biological glass powder gross mass 2wt%-8wt% utilizes slip casting at normal temperature using stirring foaming
Gained foaming slurry injection forming is demoulded, is dried by the method for forming;Finally high temperature is fired at 850 DEG C -1000 DEG C.
Chemical blowing process: will contain calcium defect hydroxyapatite and biological glass powder mixing after at solid mixture, with solid
Mixture is butt, chooses ammonium hydrogen carbonate or hydrogen peroxide as foaming agent and weighs foaming by the 2wt%-8wt% of solid mixture
Agent.First by additives such as the 1wt% sodium carboxymethylcellulose of solid mixture, 0.1wt%-0.3wt% Sodium Polyacrylates and
Corresponding aqueous solution, uniform stirring form slurry, control its solid content between 20wt%-30wt%.Then add in slurry
Enter foaming agent, after being foamed under normal temperature environment using mechanical stirring, inject in gypsum grinding tool, after blank can demould, moves into 80-
In 105 DEG C of drying box, until drying.Shaping blank is put into high temperature furnace, is warming up to the heating rate of 4-10 DEG C/min
800 DEG C -900 DEG C, and 10-30min is kept the temperature, 1050 DEG C of -1100 DEG C of firings are finally warming up to the heating rate of 5-8 DEG C/min.
Preferably, the step of preparing the tricalcium phosphate porous material using foam impregnation method is as follows: according to containing calcium defect
1wt% sodium carboxymethylcellulose, 0.1wt%-0.3wt% polyacrylic acid is added in hydroxyapatite and biological glass powder gross mass
Slurry is made in sodium, uniform stirring, and the solid content of the slurry is 20wt%-30wt%, then submerges polymeric foam sponge
In gained slurry, taken out after completing midge, after to be dried, midge sponge repeats above-mentioned steps for several times, until midge is completed,
After being demoulded, being dried, high temperature is fired at 850 DEG C -1000 DEG C.
Foam impregnation method: will contain calcium defect hydroxyapatite and biological glass powder mixing after at solid mixture, with solid
Mixture is butt, and choosing polymeric foam sponge is dipping template, and first in above-mentioned solid mixture, solid mixing is added
Additives and the corresponding aqueous solutions such as the 2wt% sodium carboxymethylcellulose of material, 0.1wt%-0.3wt% Sodium Polyacrylate, uniformly
Slurry is stirred into, solid content is controlled in 20wt%-30wt%.Then it is taken out after sponge being impregnated 2min in slurry, to nothing
After slurry oozes, 2min is impregnated in slurry again, which repeats 3-5 times.After blank is slightly dry, 80-105 DEG C is moved into
Drying box in, until drying.Shaping blank is put into high temperature furnace, with the heating rate of 4-10 DEG C/min be warming up to 800 DEG C-
900 DEG C, and 10-30min is kept the temperature, 1050 DEG C of -1100 DEG C of firings are finally warming up to the heating rate of 5-8 DEG C/min.
Preferably, the step of preparing the tricalcium phosphate porous material using vacuum freeze-drying method is as follows: according to calcic
1wt% sodium carboxymethylcellulose, 0.1wt%-0.3wt% poly- third is added in defect hydroxyapatite and biological glass powder gross mass
Slurry is made in olefin(e) acid sodium, uniform stirring, and the solid content of the slurry is 20 wt%-30wt%, is then injected into gained slurry
Row freezing processing after freeze forming, sloughs moisture, is finally warming up to 450 DEG C of heat preservation 1h with the heating rate of 4-10 DEG C/min, it
After be warming up to 900 DEG C of -950 DEG C of heat preservation 10min-30min and fire.
Freeze-drying: will contain calcium defect hydroxyapatite and biological glass powder mixing after at solid mixture, with solid
Mixture is butt, and 10wt%-20wt% dehydrated alcohol and 1wt% carboxymethyl cellulose are added in above-mentioned solid mixture
Sodium, 0.1wt%-0.3wt% Sodium Polyacrylate are configured to slurry according to solid content 20wt%-30wt%.Above-mentioned slurry mixing is equal
It after even, pours into polytetrafluoroethylene (PTFE) grinding tool, and is put into low temperature thermostat bath and carries out freeze forming according to the freezing system of setting, it
The dry body being freeze-dried is placed in Muffle furnace afterwards, 900-950 DEG C of heat preservation is warming up to the heating rate of 4-10 DEG C/min
10-30min firing.
Beneficial effects of the present invention are as follows: method of the invention is original with hydroxyapatite containing calcium defect and bio-vitric
Material, using conventional molding process technology, be prepared in situ provide porous network structure novel degradable tricalcium phosphate (TCP) it is more
Hole timbering material, the tricalcium phosphate of preparation are the porous support materials that principal crystalline phase is bata-tricalcium phosphate (β-TCP), are effectively improved
Mechanical property, porosity, the connectivity of the degradable tricalcium phosphate porous support materials of tradition, method equipment letter of the invention
Single, easy to operate, pore property is convenient for artificial adjustment, and method of the invention utilizes the hydroxyapatite high temperature item containing calcium defect
The characteristics of β-TCP and other synthos are mutually deformed under part both can use hydroxyapatite enhancing porous support materials
Mechanical performance optimizes the pore structure of porous material, can also utilize the phase composition of the additive amount control material of bioactivity glass
Ingredient reaches control degradation rate, to match with the growth rate of freshman bone tissue.
Method of the invention is suitable for addition pore-foaming agent, chemical blowing process, foam impregnation method and vacuum freeze-drying method etc.
Forming method can be effectively improved the comprehensive performance of degradable β-TCP porous ceramics and its at home and abroad using competitiveness.
The TCP porous material of method preparation of the invention compared with traditional degradable TCP porous support materials, have with
Under major advantage: (1) traditional TCP porous support materials porosity is generally below 70%, and TCP timbering material of the invention
The porosity, up to 75%-90%;
(2) β-TCP porous support materials of the invention have the porous network structure of three-dimensional communication, macropore, aperture and micro-
Pore size distribution is uniformly reasonable, and pore structure regulation is convenient, can close by adjusting the type and content and molding parameter of pore former
The pore structure of reason control material;
(3) present invention is improving the same of material three-dimensional connectivity using hydroxyapatite crystal whisker containing calcium defect as primary raw material
When, improve the mechanical performance of material;
(4) ratio of the present invention by adjusting hydroxyapatite crystal whisker containing calcium defect and hydroxy apatite powder, Yi Jisheng
The ratio of object glass can rationally control the degradation rate of timbering material, to be expected to obtain and bone uptake and reparation rate phase
The timbering material matched;
(5) pore structure of β-TCP porous support materials prepared by the present invention regulates and controls convenient, and material porosity obtained exists
Between 75%-90%, between 100-200 μm of aperture, compression strength is up to 1.2-5.2MPa.
Detailed description of the invention
Fig. 1 is the XRD diagram of different bio-vitric powder content samples in the present invention;
Fig. 2 is the microstructure figure of hydroxyapatite crystal whisker used in the present invention;
Fig. 3 is the pore structure shape appearance figure of tricalcium phosphate porous material prepared by the embodiment of the present invention 8.
Specific embodiment
For a better understanding of the present invention, the following examples are to further explanation of the invention, but the contents of the present invention
It is not limited solely to the following examples.
Embodiment 1:
(1) raw material
Hydroxyapatite crystal whisker containing calcium defect: 180-240 μm long, draw ratio 70-90, Ca/P:1.62
Hydroxyapatite powder containing calcium defect: 10-50 μm of partial size, Ca/P:1.62
Biological glass powder: 10-50 μm of partial size
Polyurethane foam microballoon: partial size crosses 60-100 mesh standard sieve
Other reagents: sodium carboxymethylcellulose, Sodium Polyacrylate
(2) prepared by slurry
After hydroxyapatite crystal whisker containing calcium defect and powder are mixed according to the ratio of mass ratio 4:1, hydroxyl containing calcium defect is pressed
The mass percent of apatite and biological glass powder is that 75wt% and 25wt% weighs material, is mixed after mixing at solid
Material.It is 20wt% according to solid content, solid mixture 1wt% sodium carboxymethylcellulose, 0.2wt% Sodium Polyacrylate etc. is added
Additive and suitable water through mechanical stirring, are modulated into the slurry of suitable slip casting or foaming.
(3) it forms and is burnt into
The polyurethane foam microballoon for weighing solid mixture 2wt% is pore-foaming agent, and after being sufficiently mixed with slurry, by slurry
Injection forming in gypsum mold is injected, after blank can demould, is moved into 80-105 DEG C of drying box, until drying.It will molding
Blank is put into high temperature furnace, 800 DEG C is warming up to the heating rate of 10 DEG C/min, and keep the temperature 10min, finally with 5 DEG C/min's
Heating rate is warming up to 1050 DEG C of firings.
(4) performance test
According to the porosity about 83% of sample obtained by above-mentioned process system, compression strength 4.35MPa, aperture 130-170 μ
m。
Embodiment 2:
(1) raw material
Hydroxyapatite crystal whisker containing calcium defect: 180-240 μm long, draw ratio 70-90, Ca/P:1.58
Hydroxyapatite powder containing calcium defect: 10-50 μm of partial size, Ca/P:1.65
Biological glass powder: 10-50 μm of partial size
Polyurethane foam microballoon: partial size crosses 60-100 mesh standard sieve
Other reagents: sodium carboxymethylcellulose, Sodium Polyacrylate
(2) prepared by slurry
After hydroxyapatite crystal whisker containing calcium defect and powder are mixed according to the ratio of mass ratio 3:2, hydroxyl containing calcium defect is pressed
Apatite and biological glass powder mass percent are that 80wt% and 20wt% weighs material, after mixing at solid mixture.
It is 30wt% according to solid content, it is additional that solid mixture 1wt% sodium carboxymethylcellulose, 0.2wt% Sodium Polyacrylate etc. is added
Agent and suitable water through mechanical stirring, are modulated into the slurry of suitable slip casting or foaming.
(3) it forms and is burnt into
The polyurethane foam microballoon for weighing solid mixture 10wt% is pore-foaming agent, and after being sufficiently mixed with slurry, will be expected
Injection forming moves into 80-105 DEG C of drying box after blank can demould in slurry injection gypsum mold, until drying.It will be at
Parison material is put into high temperature furnace, 900 DEG C is warming up to the heating rate of 4 DEG C/min, and keep the temperature 30min, finally with 8 DEG C/min's
Heating rate is warming up to 1100 DEG C of firings.
(4) performance test
According to the porosity about 80% of sample obtained by above-mentioned process system, compression strength 2.98MPa, aperture 120-180 μ
m。
Embodiment 3:
(1) raw material
Hydroxyapatite crystal whisker containing calcium defect: 180-240 μm long, draw ratio 70-90, Ca/P:1.58
Hydroxyapatite powder containing calcium defect: 10-50 μm of partial size, Ca/P:1.65
Biological glass powder: 10-50 μm of partial size
Foaming agent: hydrogen peroxide
Other reagents: sodium carboxymethylcellulose, Sodium Polyacrylate
(2) prepared by slurry
After hydroxyapatite crystal whisker containing calcium defect and powder are mixed according to the ratio of mass ratio 4:1, hydroxyl containing calcium defect is pressed
Apatite and biological glass powder mass percent are that 85wt% and 15wt% weighs material, after mixing at solid mixture.
It is 20wt% according to solid content, it is additional that solid mixture 1wt% sodium carboxymethylcellulose, 0.2wt% Sodium Polyacrylate etc. is added
Agent and suitable water through mechanical stirring, are modulated into the slurry of suitable slip casting or foaming.
(3) it forms and is burnt into
Selection hydrogen peroxide weighs foaming agent by the 2wt% of solid mixture for foaming agent.Add in above-mentioned gained slurry
Enter foaming agent, after foaming under normal temperature environment using mechanical stirring, slurry is injected into injection forming in gypsum mold, it can to blank
It after demoulding, moves into 80-105 DEG C of drying box, until drying.Shaping blank is put into high temperature furnace, with 4-10 DEG C/min's
Heating rate is warming up to 800 DEG C -900 DEG C, and keeps the temperature 10min, is finally warming up to 1050 DEG C DEG C with the heating rate of 5 DEG C/min
Firing.
(4) performance test
According to the porosity about 75% of sample obtained by above-mentioned process system, compression strength 4.92MPa, aperture 100-150 μ
m。
Embodiment 4:
(1) raw material
Hydroxyapatite crystal whisker containing calcium defect: 180-240 μm long, draw ratio 70-90, Ca/P:1.59
Hydroxyapatite powder containing calcium defect: 10-50 μm of partial size, Ca/P:1.64
Biological glass powder: 10-50 μm of partial size
Foaming agent: hydrogen peroxide
Other reagents: sodium carboxymethylcellulose, Sodium Polyacrylate
(2) prepared by slurry
After hydroxyapatite crystal whisker containing calcium defect and powder are mixed according to the ratio of mass ratio 3:2, hydroxyl containing calcium defect is pressed
Apatite and biological glass powder mass percent are that 80wt% and 20wt% weighs material, after mixing at solid mixture.
It is 30wt% according to solid content, it is additional that solid mixture 1wt% sodium carboxymethylcellulose, 0.2wt% Sodium Polyacrylate etc. is added
Agent and suitable water through mechanical stirring, are modulated into the slurry of suitable slip casting or foaming.
(3) it forms and is burnt into
Selection hydrogen peroxide weighs foaming agent by the 8wt% of solid mixture for foaming agent.Add in above-mentioned gained slurry
Enter foaming agent, after foaming under normal temperature environment using mechanical stirring, slurry is injected into injection forming in gypsum mold, it can to blank
It after demoulding, moves into 80-105 DEG C of drying box, until drying.Shaping blank is put into high temperature furnace, with the liter of 10 DEG C/min
Warm rate is warming up to 900 DEG C, and keeps the temperature 30min, is finally warming up to 1050 DEG C of DEG C of firings with the heating rate of 5-8 DEG C/min.
(4) performance test
According to the porosity about 78% of sample obtained by above-mentioned process system, compression strength 3.72MPa, aperture 110-150 μ
m。
Embodiment 5:
(1) raw material
Hydroxyapatite crystal whisker containing calcium defect: 180-240 μm long, draw ratio 70-90, Ca/P:1.58
Hydroxyapatite powder containing calcium defect: 10-50 μm of partial size, Ca/P:1.65
Biological glass powder: 10-50 μm of partial size
Polyurethane foam sponge: 35PPI mesoporous
Other reagents: sodium carboxymethylcellulose, Sodium Polyacrylate
(2) prepared by slurry
After hydroxyapatite crystal whisker containing calcium defect and powder are mixed according to the ratio of mass ratio 4:1, hydroxyl containing calcium defect is pressed
Apatite and biological glass powder mass percent are that 75wt% and 25wt% weighs material, after mixing at solid mixture.
It is 20wt% according to solid content, it is additional that solid mixture 2wt% sodium carboxymethylcellulose, 0.2wt% Sodium Polyacrylate etc. is added
Agent and suitable water through mechanical stirring, are modulated into the slurry of suitable slip casting or foaming.
(3) it forms and is burnt into
Choosing polyurethane foam sponge is dipping template, takes out after sponge is impregnated 2min in slurry, drips to no slurry
After out, 2min is impregnated in slurry again, which repeats 3-5 times.After blank is slightly dry, 80-105 DEG C of drying is moved into
In case, until drying.Shaping blank is put into high temperature furnace, is warming up to 800 DEG C with the heating rate of 4 DEG C/min, and keep the temperature
10min is finally warming up to 1050 DEG C of firings with the heating rate of 5 DEG C/min.
(4) performance test
According to the porosity about 85% of sample obtained by above-mentioned process system, compression strength about 2.8MPa, aperture 100-150 μ
m。
Embodiment 6:
(1) raw material
Hydroxyapatite crystal whisker containing calcium defect: 180-240 μm long, draw ratio 70-90, Ca/P:1.59
Hydroxyapatite powder containing calcium defect: 10-50 μm of partial size, Ca/P:1.62
Biological glass powder: 10-50 μm of partial size
Polyurethane foam sponge: 35PPI mesoporous
Other reagents: sodium carboxymethylcellulose, Sodium Polyacrylate
(2) prepared by slurry
After hydroxyapatite crystal whisker containing calcium defect and powder are mixed according to the ratio of mass ratio 3:2, hydroxyl containing calcium defect is pressed
Apatite and biological glass powder mass percent are that 80wt% and 20wt% weighs material, after mixing at solid mixture.
It is 30wt% according to solid content, it is additional that solid mixture 1wt% sodium carboxymethylcellulose, 0.2wt% Sodium Polyacrylate etc. is added
Agent and suitable water through mechanical stirring, are modulated into the slurry of suitable slip casting or foaming.
(3) it forms and is burnt into
Choosing polyurethane foam sponge is dipping template, and 2wt%CMC binder is added in solid mixture slurry, and
It stirs evenly.It is taken out after sponge is impregnated 2min in slurry, after no slurry oozes, impregnates 2min in slurry again, it should
Process repeats 3-5 times.It after blank is slightly dry, moves into 80-105 DEG C of drying box, until drying.Shaping blank is put into
In high temperature furnace, 900 DEG C are warming up to the heating rate of 10 DEG C/min, and keep the temperature 10min, finally with the heating rate of 8 DEG C/min
It is warming up to 1100 DEG C of firings.
(4) performance test
According to the porosity about 79% of sample obtained by above-mentioned process system, compression strength 3.06MPa, aperture 110-150 μ
m。
Embodiment 7:
(1) raw material
Hydroxyapatite crystal whisker containing calcium defect: 180-240 μm long, draw ratio 70-90, Ca/P:1.58
Hydroxyapatite powder containing calcium defect: 10-50 μm of partial size, Ca/P:1.64
Biological glass powder: 10-50 μm of partial size
Other reagents: dehydrated alcohol, sodium carboxymethylcellulose, Sodium Polyacrylate
(2) prepared by slurry
After hydroxyapatite crystal whisker containing calcium defect and powder are mixed according to the ratio of mass ratio 4:1, hydroxyl containing calcium defect is pressed
Apatite and biological glass powder mass percent are that 75wt% and 25wt% weighs material, after mixing at solid mixture.
It is 20wt% according to solid content, it is poly- that solid mixture 10wt% dehydrated alcohol, 1wt% sodium carboxymethylcellulose, 0.1wt% is added
The additives such as sodium acrylate and suitable water through mechanical stirring, are modulated into the slurry of suitable slip casting or foaming.
(3) it forms and is burnt into
After mixing by above-mentioned slurry, it pours into Teflon mould, and is put into low temperature thermostat bath according to setting
Freezing system carry out freezing processing, the dry body being freeze-dried is placed in Muffle furnace later, with the heating rate of 4 DEG C/min
It is warming up to 950 DEG C of heat preservation 10min.
(4) performance test
According to the porosity about 90% of sample obtained by above-mentioned process system, compression strength about 1.2MPa, aperture 120-200 μ
m。
Embodiment 8:
(1) raw material
Hydroxyapatite crystal whisker containing calcium defect: 180-240 μm long, draw ratio 70-90, Ca/P:1.58
Hydroxyapatite powder containing calcium defect: 10-50 μm of partial size, Ca/P:1.62
Biological glass powder: 10-50 μm of partial size
Other reagents: dehydrated alcohol, sodium carboxymethylcellulose, Sodium Polyacrylate
(2) prepared by slurry
After hydroxyapatite crystal whisker containing calcium defect and powder are mixed according to the ratio of mass ratio 4:1, hydroxyl containing calcium defect is pressed
Apatite and biological glass powder mass percent are that 75wt% and 25wt% weighs material, after mixing at solid mixture.
It is 20wt% according to solid content, it is poly- that solid mixture 20wt% dehydrated alcohol, 1wt% sodium carboxymethylcellulose, 0.3wt% is added
The additives such as sodium acrylate and suitable water through mechanical stirring, are modulated into the slurry of suitable slip casting or foaming.
(3) it forms and is burnt into
After mixing by above-mentioned slurry, it pours into Teflon mould, and is put into low temperature thermostat bath according to setting
Freezing system carry out freezing processing, dry body be freeze-dried is placed in Muffle furnace later, it is fast with the heating of 10 DEG C/min
Rate is warming up to 900 DEG C of heat preservation 30min.
(4) performance test
According to the porosity about 85% of sample obtained by above-mentioned process system, compression strength about 2.2MPa, aperture 110-150 μ
m。
Fig. 1 is the XRD diagram of different bio-vitric powder content samples in the present invention;As can be seen from Figure with bio-vitric
The principal crystalline phase of the increase of powder content, the tricalcium phosphate of preparation is changed into β-TCP by HA, while there are also a small amount of pyrophosphates
(Ca2P2O7) presence.
Fig. 2 is the microstructure figure of hydroxyapatite crystal whisker used in the present invention;As can be seen from Figure, hydroxyl containing calcium defect
The Whiskers shape of apatite whiskers is uniformly regular, is in needle bar shape, soilless sticking phenomenon is 180-240 μm long, draw ratio 70-90.
Fig. 3 is the pore structure shape appearance figure of tricalcium phosphate porous material prepared by the embodiment of the present invention 8, as can be seen from Figure
The pore size distribution$ of the tricalcium phosphate porous material of preparation is uniform, and connectivity is good and substantially in the same direction, and aperture is in 110-150
Between μm.
The above is a preferred embodiment of the present invention, cannot limit the right model of the present invention with this certainly
It encloses, it is noted that for those skilled in the art, without departing from the principle of the present invention, may be used also
To make several improvement and variation, these, which improve and change, is also considered as protection scope of the present invention.
Claims (10)
1. a kind of method that hydroxyapatite in-situ containing calcium defect prepares tricalcium phosphate porous material, it is characterised in that: use one
The hydroxyapatite containing calcium defect and biological glass powder of certainty ratio are raw material, are added after auxiliary agent molding and are fired into institute through high-temp in-situ
State tricalcium phosphate porous material.
2. the method that hydroxyapatite in-situ containing calcium defect according to claim 1 prepares tricalcium phosphate porous material,
Be characterized in that: the ratio of the hydroxyapatite containing calcium defect and biological glass powder is (75-85) wt%:(15-25) wt%.
3. the method that hydroxyapatite in-situ containing calcium defect according to claim 1 prepares tricalcium phosphate porous material,
Be characterized in that: the hydroxyapatite containing calcium defect is by hydroxyapatite crystal whisker containing calcium defect/fiber and the phosphorus of hydroxyl containing calcium defect
Lime stone powder is mixed according to mass ratio for 1.5-4:1.
4. the method that hydroxyapatite in-situ containing calcium defect according to claim 3 prepares tricalcium phosphate porous material,
Be characterized in that: the apatite whiskers containing calcium defect/fiber Ca/P is 1.58-1.62,180-240 μm long, draw ratio 70-
90, the Ca/P of the hydroxyapatite powder containing calcium defect is 1.62-1.65, partial size is 10-50 μm.
5. the method that hydroxyapatite in-situ containing calcium defect according to claim 1 prepares tricalcium phosphate porous material,
Be characterized in that: the biological glass powder is the 42%-50%P according to following mass percent2O5, 12%-17%SiO2, 13%-
20%CaCO3, 10%-16%Na2O, 3%-8%%ZnO, 1%-3%CaF2With 3%-10%MgO carry out ingredient, and
It is melted at a temperature of 1050-1150 DEG C, through chilling, grinds, the partial size of the biological glass powder is 10-50 μm.
6. the method that hydroxyapatite in-situ containing calcium defect according to claim 1 prepares tricalcium phosphate porous material,
Be characterized in that: the forming method is pore-foaming agent method, foam impregnation method, chemical blowing process, any in vacuum freeze-drying method
It is a kind of.
7. the method that hydroxyapatite in-situ containing calcium defect according to claim 6 prepares tricalcium phosphate porous material,
Be characterized in that: the step of preparing the tricalcium phosphate porous material using pore-foaming agent method is as follows: according to hydroxy-apatite containing calcium defect
2wt%-10wt% pore-foaming agent, 1wt% sodium carboxymethylcellulose, 0.1wt%- is added in stone and biological glass powder gross mass
Slurry is made in 0.3wt% Sodium Polyacrylate, uniform stirring, and the solid content of the slurry is 20wt%-30wt%, by the slurry
It after injection forming, demoulded, dried, finally high temperature is fired at 850 DEG C -1000 DEG C.
8. the method that hydroxyapatite in-situ containing calcium defect according to claim 6 prepares tricalcium phosphate porous material,
Be characterized in that: the step of preparing the tricalcium phosphate porous material using chemical blowing process is as follows: according to the phosphorus of hydroxyl containing calcium defect
1wt% sodium carboxymethylcellulose, 0.1wt%-0.3wt% Sodium Polyacrylate is added in lime stone and biological glass powder gross mass, uniformly
It stirs and slurry is made, the solid content of the slurry is 20wt%-30wt%, and hydroxy-apatite containing calcium defect is then added in slurry
The foaming agent of stone and biological glass powder gross mass 2wt%-8wt% will using slip casting at normal temperature using stirring foaming
Gained foaming slurry injection forming, is demoulded, is dried;Finally high temperature is fired at 850 DEG C -1000 DEG C.
9. the method that hydroxyapatite in-situ containing calcium defect according to claim 6 prepares tricalcium phosphate porous material,
Be characterized in that: the step of preparing the tricalcium phosphate porous material using foam impregnation method is as follows: according to the phosphorus of hydroxyl containing calcium defect
1wt% sodium carboxymethylcellulose, 0.1wt%-0.3wt% Sodium Polyacrylate is added in lime stone and biological glass powder gross mass, uniformly
It stirs and slurry is made, the solid content of the slurry is 20wt%-30wt%, and polymeric foam sponge is then immersed in gained material
In slurry, taken out after completing midge, after to be dried, midge sponge repeats above-mentioned steps for several times, until midge is completed, demoulded,
After drying, high temperature is fired at 850 DEG C -1000 DEG C.
10. the method that hydroxyapatite in-situ containing calcium defect according to claim 6 prepares tricalcium phosphate porous material,
Be characterized in that: the step of preparing the tricalcium phosphate porous material using vacuum freeze-drying method is as follows: according to hydroxyl containing calcium defect
1wt% sodium carboxymethylcellulose, 0.1wt%-0.3wt% Sodium Polyacrylate is added in base apatite and biological glass powder gross mass,
Slurry is made in uniform stirring, and the solid content of the slurry is 20wt%-30wt%, then carries out the injection of gained slurry at freezing
It manages, after freeze forming, sloughs moisture, 450 DEG C of heat preservation 1h are finally warming up to the heating rate of 4-10 DEG C/min, are warming up to later
900 DEG C of -950 DEG C of heat preservation 10min-30min are fired.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910350306.2A CN110054492A (en) | 2019-04-28 | 2019-04-28 | The method that hydroxyapatite in-situ containing calcium defect prepares tricalcium phosphate porous material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910350306.2A CN110054492A (en) | 2019-04-28 | 2019-04-28 | The method that hydroxyapatite in-situ containing calcium defect prepares tricalcium phosphate porous material |
Publications (1)
Publication Number | Publication Date |
---|---|
CN110054492A true CN110054492A (en) | 2019-07-26 |
Family
ID=67321363
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910350306.2A Pending CN110054492A (en) | 2019-04-28 | 2019-04-28 | The method that hydroxyapatite in-situ containing calcium defect prepares tricalcium phosphate porous material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110054492A (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004050095A1 (en) * | 2003-10-14 | 2005-05-19 | Pentax Corp. | Ca0-Mg0-SiO2-based biologically active glass and sintered calcium phosphate glass |
CN107986750A (en) * | 2017-11-30 | 2018-05-04 | 明光市泰丰新材料有限公司 | A kind of bioceramic material and preparation method |
CN109133907A (en) * | 2018-08-16 | 2019-01-04 | 迈海新型材料科技(固安)有限公司 | A kind of artificial bone and preparation method thereof comprising hydroxyapatite crystal whisker and biphase calcium phosphor |
-
2019
- 2019-04-28 CN CN201910350306.2A patent/CN110054492A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004050095A1 (en) * | 2003-10-14 | 2005-05-19 | Pentax Corp. | Ca0-Mg0-SiO2-based biologically active glass and sintered calcium phosphate glass |
CN107986750A (en) * | 2017-11-30 | 2018-05-04 | 明光市泰丰新材料有限公司 | A kind of bioceramic material and preparation method |
CN109133907A (en) * | 2018-08-16 | 2019-01-04 | 迈海新型材料科技(固安)有限公司 | A kind of artificial bone and preparation method thereof comprising hydroxyapatite crystal whisker and biphase calcium phosphor |
Non-Patent Citations (4)
Title |
---|
汤顺清等: "《无机生物材料学》", 31 October 2008, 华南理工大学出版社 * |
王迎军: "《生物医用陶瓷材料》", 31 October 2010, 华南理工大学出版社 * |
赵彦涛: "几种纳米羟基磷灰石材料的合成与生物相容性研究", 《中国优秀博硕士学位论文全文数据库(硕士)医药卫生科技辑》 * |
郑卫: "HA混合生物玻璃制备TCP陶瓷支架及其性能的研究", 《中国生物医学工程学报》 * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7119038B2 (en) | Method for making a porous calcium phosphate article | |
EP1335757B1 (en) | Porous calcium phosphate cement | |
JP5688010B2 (en) | Calcium phosphate cement composition for bone filling material and kit thereof | |
CN101407414A (en) | Method for preparing calcium polyphosphate / tricalcium phosphate two-phase biological ceramic | |
CN107141022B (en) | Whitlockite coating constructed on surface of calcium phosphate biological ceramic matrix and preparation method thereof | |
CN103585677B (en) | A kind of HA micro-nano whisker reinforcement calcium phosphate ceramic material and its preparation method and application | |
CN1240637C (en) | Porous calcium phosphate bioceramic material and preparing method thereof | |
CN106310381A (en) | Degradable magnesium-containing calcium phosphate-calcium sulfate porous composite biological scaffold | |
CN107185033A (en) | A kind of anti-infection bio ceramic artificial bone and its application | |
CN103585672A (en) | Preparation method of bioglass fiber reinforced hydroxyapatite porous composite material | |
CN101274108B (en) | Compound porous bracket and method of producing the same | |
CN101716369B (en) | Preparation method for calcium polyphosphate-tricalcium phosphate bone bracket | |
CN102764450B (en) | Cuttlebone transformation series porous composite bio-ceramic, its preparation method and application | |
CN111773432A (en) | Magnesium-based amorphous-calcium phosphate/calcium silicate composite filler and preparation and application thereof | |
CN101148778A (en) | Hydroxyapatite crystal whisker with high length-diameter ratio and preparation method thereof | |
TWI573776B (en) | Dicalcium phosphate ceramics, dicalcium phosphate/hydroxyapatite biphasic ceramics and method of manufacturing the same | |
CN113582680B (en) | Hydroxyapatite ceramic and preparation method and application thereof | |
CN103830774B (en) | A kind of bone cement and preparation method thereof | |
CN110054492A (en) | The method that hydroxyapatite in-situ containing calcium defect prepares tricalcium phosphate porous material | |
KR102328412B1 (en) | Method for preparation of bone filler having cells and drug and bone filler prepared thereby | |
CN105536059B (en) | A kind of selfreparing injecting bone cement and preparation method | |
CN108498860B (en) | Method for preparing 3D ceramic scaffold by doping hydroxyapatite with metal elements | |
Siek et al. | Biodegradable cement type bone implant materials based on calcium phosphates and calcium sulphate | |
JP2004269333A (en) | Carbon fiber reinforced composite material molding containing calcium phosphate-based material, method of manufacturing the same, and artificial bone using the same | |
CN101857372B (en) | Nanometer metallic in-situ grown and enhanced porous calcium-phosphorus glass ceramic and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190726 |
|
RJ01 | Rejection of invention patent application after publication |