CN108118526A - A kind of preparation method of surface flowers shape super large piece calcium phosphate dibasic dihydrate - Google Patents

A kind of preparation method of surface flowers shape super large piece calcium phosphate dibasic dihydrate Download PDF

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CN108118526A
CN108118526A CN201711328466.4A CN201711328466A CN108118526A CN 108118526 A CN108118526 A CN 108118526A CN 201711328466 A CN201711328466 A CN 201711328466A CN 108118526 A CN108118526 A CN 108118526A
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solution
phosphate dibasic
calcium phosphate
dibasic dihydrate
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CN108118526B (en
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张磊磊
裴李娜
李贺军
李克智
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Northwestern Polytechnical University
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • D06M11/71Salts of phosphoric acids
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54Electroplating of non-metallic surfaces
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/06Wires; Strips; Foils
    • C25D7/0607Wires
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00Electrolytic coating other than with metals
    • C25D9/04Electrolytic coating other than with metals with inorganic materials
    • C25D9/08Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40Fibres of carbon

Abstract

The present invention relates to a kind of preparation methods of surface flowers shape super large piece calcium phosphate dibasic dihydrate, using carbon fiber as basis material, its surface texture is improved by chemical vapor deposition process, for quickly generating for calcium phosphate dibasic dihydrate is promoted to provide suitable forming core site, calcium phosphate dibasic dihydrate is then prepared using pulse electrodeposition technique.For the maximum average growth rate of calcium phosphate dibasic dihydrate prepared by the present invention up to 1290 μm/h, which is 12.9 times of the speed of growth maximum of background technology report calcium phosphate dibasic dihydrate.In addition, flowers shape is presented in calcium phosphate dibasic dihydrate surface prepared by the present invention, flowers shape surface texture is conducive to the attachment with cell and the formation of bone tissue.

Description

A kind of preparation method of surface flowers shape super large piece calcium phosphate dibasic dihydrate
Technical field
The invention belongs to the preparation methods of biomaterial, are related to a kind of surface flowers shape super large piece calcium phosphate dibasic dihydrate Preparation method.
Background technology
Calcium phosphorus kind bioceramic mainly includes hydroxyapatite (Ca10(PO4)6(OH)2, HA), calcium phosphate dibasic dihydrate (CaHPO4·2H2O, DCPD), tricalcium phosphate (Ca3(PO4)2,TCP).Wherein calcium phosphate dibasic dihydrate is because with excellent life Object compatibility and osteoconductive energy and be widely used as biomedical material.It has similar to the ingredient and structure of people's bone Property, there is low solubility in body fluid or blood plasma, be implanted into human body it is nontoxic, harmless, without carcinogenesis, and with good Bioactivity, osteoconductive and biocompatibility are widely used in the reparation of damaged bony tissues, the root of the tooth reparation of alveolar ridge, hip Joint and knee-joint prosthesis, the face coat of bone tissue prosthese etc..Therefore many researchers have carried out calcium phosphate dibasic dihydrate Preparation research.
" Liu G Y, Tang S W, Wang C, the et al.Formation characteristic of Ca-P of document 1 Coatings on magnesium alloy surface. China YouSes Acta Metallurgica Sinicas (English edition), 2013,23 (8):2294- 2299 " report that length is prepared when small with 3 is 1~40 μm of sheet calcium phosphate dibasic dihydrate, and maximum length is 40 μm, surface Smooth, maximum average growth rate is 13 μm/h.
" Zhao C L, Wu H L, Hou P, the et al.Enhanced corrosion resistance and of document 2 antibacterial property of Zn doped DCPD coating on biodegradable Mg.Materials Letters,2016,180:42-46 " report with 1 it is small when to prepare length be 50-100 μm of sheet calcium phosphate dibasic dihydrate, most Long length is 100 μm, and surface is smooth, and maximum average growth rate is 100 μm/h.
" Zhang C Y, Zeng R C, Chen R S, the et al.Preparation of calcium of document 3 Phosphate coatings on Mg-1.0Ca alloy. China YouSes Acta Metallurgica Sinicas (English edition), 2010,20 (s2): S655-s659. " reporting and the calcium phosphate dibasic dihydrate that length is 20-200 μm is prepared when small with 2, maximum length is 200 μm, Surface is smooth, and maximum average growth rate is 100 μm/h.
Above-mentioned document has been successfully prepared out calcium phosphate dibasic dihydrate, but the maximum for preparing calcium phosphate dibasic dihydrate is put down The equal speed of growth is respectively less than 100 μm/h, and the speed of growth is slower.And the surface of the calcium phosphate dibasic dihydrate prepared presents smooth Shape is unfavorable for cell in the attachment on its surface and the formation of bone tissue.
The content of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes a kind of two hypophosphite monohydrate hydrogen of surface flowers shape super large piece The preparation method of calcium using carbon fiber as basis material, improves its surface texture, to promote two water by chemical vapor deposition process It closes quickly generating for calcium monohydrogen phosphate and suitable forming core site is provided, two hypophosphite monohydrate hydrogen are then prepared using pulse electrodeposition technique Calcium.The maximum average growth rate of calcium phosphate dibasic dihydrate prepared by the present invention is background technology up to 1290 μm/h, the numerical value Report the speed of growth maximum of calcium phosphate dibasic dihydrate 12.9 times.
Technical solution
A kind of preparation method of surface flowers shape super large piece calcium phosphate dibasic dihydrate, it is characterised in that step is as follows:
Step 1:Carbon fiber is placed in chemical vapor deposition stove and is deposited, parameter is:With the rate of 8-10 DEG C/min 1050-1200 DEG C is warming up to, then passes to the methane that flow is 0.4-0.6L/min, flow is the argon gas of 0.1-0.2L/min, Flow be 0.3-0.6L/min hydrogen, sedimentation time 1.5-2.5h;
The carbon fiber that deposition is completed is dried after being cleaned by ultrasonic using acetone;
Step 2:The carbon fiber that step 1 is deposited to completion is placed in solution, using graphite flake as anode, is completed with deposition Carbon fiber is cathode, applies voltage 3-5V, sedimentation time 15-25min between the two poles of the earth, and depositing temperature is 40-60 degree;It is described The pulsewidth of voltage is 50-100ms, is 100-200ms between arteries and veins;Distance is 30-50mm between the cathode and anode;
The solution is:Ammonium dihydrogen phosphate is dissolved in the solution that 60-150mmol/L is configured in deionized water, is added Calcium nitrate obtains solution after stirring evenly;The molar ratio of the calcium nitrate and ammonium dihydrogen phosphate is 1.7-2.0;
Step 3:By step 2, treated that carbon fiber is placed in gold spraying instrument, is 4 × 10 in pressure-2-6×10-2Pa, electric current For metal spraying 60-100s under the conditions of 6-8mA;
Step 4:Sample C is placed in solution, using graphite flake as anode, sample C applies voltage and be arranged to as cathode 1-3V, sedimentation time 5-10min, depositing temperature are 60-70 degree, take out sample drying after reaction, obtain surface flowers Shape super large piece calcium phosphate dibasic dihydrate;
The voltage pulse width is 20-40ms, is 50-100ms between arteries and veins;
Distance is 30-50mm between the cathode and anode;
The solution is:Ammonium dihydrogen phosphate is dissolved in the solution that 10-30mmol/L is prepared in deionized water, adds nitric acid Calcium is uniformly mixing to obtain solution;The molar ratio of the calcium nitrate and ammonium dihydrogen phosphate is 1.0-1.5.
It is described that 5-10min is cleaned by ultrasonic using acetone.
Advantageous effect
The preparation method of a kind of surface flowers shape super large piece calcium phosphate dibasic dihydrate proposed by the present invention, using carbon fiber as base Body material improves its surface texture by chemical vapor deposition process, for quickly generating for calcium phosphate dibasic dihydrate is promoted to provide Suitable forming core site, then prepares calcium phosphate dibasic dihydrate using pulse electrodeposition technique.Two hydration phosphorus prepared by the present invention For the maximum average growth rate of sour hydrogen calcium up to 1290 μm/h, which is the growth of background technology report calcium phosphate dibasic dihydrate 12.9 times of speed maximum.In addition, flowers shape, flowers shape surface knot is presented in calcium phosphate dibasic dihydrate surface prepared by the present invention Structure is conducive to the attachment with cell and the formation of bone tissue.
Description of the drawings
Fig. 1 is the stereoscan photograph of calcium phosphate dibasic dihydrate prepared by example 2
Fig. 2 is the X ray diffracting spectrum of calcium phosphate dibasic dihydrate prepared by example 2
Specific embodiment
In conjunction with embodiment, attached drawing, the invention will be further described:
Embodiment 1:
(1) carbon fiber is placed in chemical vapor deposition stove, is warming up to 1050 DEG C according to the rate of 8 DEG C/min, Ran Houtong Inbound traffics are the methane of 0.4L/min, and flow is the argon gas of 0.1L/min, and flow is the hydrogen of 0.3L/min, and sedimentation time is 1.5h.It deposits the sample completed and is cleaned by ultrasonic 5min with acetone successively, gained sample marking is A after drying;
(2) ammonium dihydrogen phosphate is dissolved in the solution that 60mmol/L is configured in deionized water, according to calcium nitrate and di(2-ethylhexyl)phosphate The molar ratio of hydrogen ammonium prepares calcium nitrate solution for 1.7, and calcium nitrate and ammonium dihydrogen phosphate are uniformly mixed, are denoted as solution I.By phosphoric acid Ammonium dihydrogen is dissolved in the solution that 10mmol/L is prepared in deionized water, matches somebody with somebody according to the molar ratio of calcium nitrate and ammonium dihydrogen phosphate for 1.0 Calcium nitrate solution processed uniformly mixes calcium nitrate and ammonium dihydrogen phosphate, is denoted as solution II;
(3) Sample A is placed in solution I, using graphite flake as anode, Sample A is as cathode, the spacing of cathode and anode From for 30mm, applying voltage 3V, pulsewidth 50ms is 100ms between arteries and veins, and sedimentation time 15min, depositing temperature is 40 degree, instead Gained sample marking is B after answering;
(4) sample B is placed in gold spraying instrument, is 4 × 10 in pressure-2Pa, electric current be 6mA under the conditions of metal spraying 60s, gained sample Labeled as C;
(5) sample C is placed in solution II, using graphite flake as anode, sample C is as cathode, between cathode and anode Distance applies voltage and is arranged to 1V for 30mm, pulsewidth 20ms, is 50ms, sedimentation time 5min, depositing temperature 60 between arteries and veins Degree.Sample drying is taken out after reaction, you can obtains surface flowers shape super large piece calcium phosphate dibasic dihydrate.
The average growth rate of calcium phosphate dibasic dihydrate prepared by this example 1 is 620 μm/h.
Embodiment 2:
(1) carbon fiber is placed in chemical vapor deposition stove, is warming up to 1100 DEG C according to the rate of 10 DEG C/min, Ran Houtong Inbound traffics are the methane of 0.5L/min, and flow is the argon gas of 0.2L/min, and flow is the hydrogen of 0.5L/min, and sedimentation time is 2.0h.It deposits the sample completed and is cleaned by ultrasonic 10min with acetone successively, gained sample marking is A after drying;
(2) ammonium dihydrogen phosphate is dissolved in the solution that 100mmol/L is configured in deionized water, according to calcium nitrate and di(2-ethylhexyl)phosphate The molar ratio of hydrogen ammonium prepares calcium nitrate solution for 1.7, and calcium nitrate and ammonium dihydrogen phosphate are uniformly mixed, are denoted as solution I.By phosphoric acid Ammonium dihydrogen is dissolved in the solution that 20mmol/L is prepared in deionized water, matches somebody with somebody according to the molar ratio of calcium nitrate and ammonium dihydrogen phosphate for 1.0 Calcium nitrate solution processed uniformly mixes calcium nitrate and ammonium dihydrogen phosphate, is denoted as solution II;
(3) Sample A is placed in solution I, using graphite flake as anode, Sample A is as cathode, the spacing of cathode and anode From for 50mm, applying voltage 4V, pulsewidth 80ms is 100ms between arteries and veins, and sedimentation time 20min, depositing temperature is 50 degree, instead Gained sample marking is B after answering;
(4) sample B is placed in gold spraying instrument, is 6 × 10 in pressure-2Pa, electric current be 8mA under the conditions of metal spraying 80s, gained sample Labeled as C;
(5) sample C is placed in solution II, using graphite flake as anode, sample C is as cathode, between cathode and anode Distance applies voltage and is arranged to 2V for 30mm, pulsewidth 30ms, is 80ms, sedimentation time 8min, depositing temperature 60 between arteries and veins Degree.Sample drying is taken out after reaction, you can obtains surface flowers shape super large piece calcium phosphate dibasic dihydrate.
Fig. 1 is the stereoscan photograph of calcium phosphate dibasic dihydrate prepared by example 2, by Fig. 1 it can be found that two hypophosphite monohydrates Flowers shape is presented in the surface of hydrogen calcium sheet.Fig. 2 is the X ray diffracting spectrum of calcium phosphate dibasic dihydrate prepared by example 2, by scheming 2 it can be found that the object phase constituent for preparing substance is calcium phosphate dibasic dihydrate, without other impurity.
The average growth rate of calcium phosphate dibasic dihydrate prepared by this example 2 is 1290 μm/h.
Embodiment 3:
(1) carbon fiber is placed in chemical vapor deposition stove, is warming up to 1050 DEG C according to the rate of 10 DEG C/min, Ran Houtong Inbound traffics are the methane of 0.6L/min, and flow is the argon gas of 0.2L/min, and flow is the hydrogen of 0.6L/min, and sedimentation time is 2.5h.It deposits the sample completed and is cleaned by ultrasonic 10min with acetone successively, gained sample marking is A after drying;
(2) ammonium dihydrogen phosphate is dissolved in the solution that 150mmol/L is configured in deionized water, according to calcium nitrate and di(2-ethylhexyl)phosphate The molar ratio of hydrogen ammonium prepares calcium nitrate solution for 2.0, and calcium nitrate and ammonium dihydrogen phosphate are uniformly mixed, are denoted as solution I.By phosphoric acid Ammonium dihydrogen is dissolved in the solution that 30mmol/L is prepared in deionized water, matches somebody with somebody according to the molar ratio of calcium nitrate and ammonium dihydrogen phosphate for 1.5 Calcium nitrate solution processed uniformly mixes calcium nitrate and ammonium dihydrogen phosphate, is denoted as solution II;
(3) Sample A is placed in solution I, using graphite flake as anode, Sample A is as cathode, the spacing of cathode and anode From for 50mm, applying voltage 5V, pulsewidth 100ms is 200ms between arteries and veins, and sedimentation time 25min, depositing temperature is 60 degree, instead Gained sample marking is B after answering;
(4) sample B is placed in gold spraying instrument, is 6 × 10 in pressure-2Pa, electric current are metal spraying 100s under the conditions of 8mA, and gained tries Sample is labeled as C;
(5) sample C is placed in solution II, using graphite flake as anode, sample C is as cathode, between cathode and anode Distance applies voltage and is arranged to 3V for 50mm, pulsewidth 40ms, is 100ms between arteries and veins, sedimentation time 10min, and depositing temperature is 70 degree.Sample drying is taken out after reaction, you can obtains surface flowers shape super large piece calcium phosphate dibasic dihydrate.
The average growth rate of calcium phosphate dibasic dihydrate prepared by this example 3 is 1010 μm/h.
Embodiment 4:
(1) carbon fiber is placed in chemical vapor deposition stove, is warming up to 1200 DEG C according to the rate of 8 DEG C/min, Ran Houtong Inbound traffics are the methane of 0.4L/min, and flow is the argon gas of 0.2L/min, and flow is the hydrogen of 0.3L/min, and sedimentation time is 1.5h.It deposits the sample completed and is cleaned by ultrasonic 10min with acetone successively, gained sample marking is A after drying;
(2) ammonium dihydrogen phosphate is dissolved in the solution that 60mmol/L is configured in deionized water, according to calcium nitrate and di(2-ethylhexyl)phosphate The molar ratio of hydrogen ammonium prepares calcium nitrate solution for 2.0, and calcium nitrate and ammonium dihydrogen phosphate are uniformly mixed, are denoted as solution I.By phosphoric acid Ammonium dihydrogen is dissolved in the solution that 10mmol/L is prepared in deionized water, matches somebody with somebody according to the molar ratio of calcium nitrate and ammonium dihydrogen phosphate for 1.5 Calcium nitrate solution processed uniformly mixes calcium nitrate and ammonium dihydrogen phosphate, is denoted as solution II;
(3) Sample A is placed in solution I, using graphite flake as anode, Sample A is as cathode, the spacing of cathode and anode From for 30mm, applying voltage 5V, pulsewidth 50ms is 200ms between arteries and veins, and sedimentation time 15min, depositing temperature is 60 degree, instead Gained sample marking is B after answering;
(4) sample B is placed in gold spraying instrument, is 4 × 10 in pressure-2Pa, electric current be 8mA under the conditions of metal spraying 60s, gained sample Labeled as C;
(5) sample C is placed in solution II, using graphite flake as anode, sample C is as cathode, between cathode and anode Distance applies voltage and is arranged to 1V for 50mm, pulsewidth 40ms, is 50ms between arteries and veins, sedimentation time 10min, and depositing temperature is 60 degree.Sample drying is taken out after reaction, you can obtains surface flowers shape super large piece calcium phosphate dibasic dihydrate.
The average growth rate of calcium phosphate dibasic dihydrate prepared by this example 4 is 930 μm/h.
Embodiment 5:
(1) carbon fiber is placed in chemical vapor deposition stove, is warming up to 1000 DEG C according to the rate of 10 DEG C/min, Ran Houtong Inbound traffics are the methane of 0.5L/min, and flow is the argon gas of 0.1L/min, and flow is the hydrogen of 0.5L/min, and sedimentation time is 2.0h.It deposits the sample completed and is cleaned by ultrasonic 5min with acetone successively, gained sample marking is A after drying;
(2) ammonium dihydrogen phosphate is dissolved in the solution that 80mmol/L is configured in deionized water, according to calcium nitrate and di(2-ethylhexyl)phosphate The molar ratio of hydrogen ammonium prepares calcium nitrate solution for 2.0, and calcium nitrate and ammonium dihydrogen phosphate are uniformly mixed, are denoted as solution I.By phosphoric acid Ammonium dihydrogen is dissolved in the solution that 20mmol/L is prepared in deionized water, matches somebody with somebody according to the molar ratio of calcium nitrate and ammonium dihydrogen phosphate for 1.5 Calcium nitrate solution processed uniformly mixes calcium nitrate and ammonium dihydrogen phosphate, is denoted as solution II;
(3) Sample A is placed in solution I, using graphite flake as anode, Sample A is as cathode, the spacing of cathode and anode From for 40mm, applying voltage 4V, pulsewidth 80ms is 100ms between arteries and veins, and sedimentation time 20min, depositing temperature is 50 degree, instead Gained sample marking is B after answering;
(4) sample B is placed in gold spraying instrument, is 5 × 10 in pressure-2Pa, electric current are metal spraying 100s under the conditions of 6mA, and gained tries Sample is labeled as C;
(5) sample C is placed in solution II, using graphite flake as anode, sample C is as cathode, between cathode and anode Distance applies voltage and is arranged to 2V for 50mm, pulsewidth 30ms, is 100ms between arteries and veins, sedimentation time 10min, and depositing temperature is 70 degree.Sample drying is taken out after reaction, you can obtains surface flowers shape super large piece calcium phosphate dibasic dihydrate.
The average growth rate of calcium phosphate dibasic dihydrate prepared by this example 5 is 850 μm/h.

Claims (2)

1. a kind of preparation method of surface flowers shape super large piece calcium phosphate dibasic dihydrate, it is characterised in that step is as follows:
Step 1:Carbon fiber is placed in chemical vapor deposition stove and is deposited, parameter is:It is heated up with the rate of 8-10 DEG C/min To 1050-1200 DEG C, then pass to flow be 0.4-0.6L/min methane, flow be 0.1-0.2L/min argon gas, flow For the hydrogen of 0.3-0.6L/min, sedimentation time 1.5-2.5h;
The carbon fiber that deposition is completed is dried after being cleaned by ultrasonic using acetone;
Step 2:The carbon fiber that step 1 is deposited to completion is placed in solution, and using graphite flake as anode, the carbon completed with deposition is fine It ties up as cathode, applies voltage 3-5V, sedimentation time 15-25min between the two poles of the earth, depositing temperature is 40-60 degree;The voltage Pulsewidth for 50-100ms, between arteries and veins be 100-200ms;Distance is 30-50mm between the cathode and anode;
The solution is:Ammonium dihydrogen phosphate is dissolved in the solution that 60-150mmol/L is configured in deionized water, adds nitric acid Calcium obtains solution after stirring evenly;The molar ratio of the calcium nitrate and ammonium dihydrogen phosphate is 1.7-2.0;
Step 3:By step 2, treated that carbon fiber is placed in gold spraying instrument, is 4 × 10 in pressure-2-6×10-2Pa, electric current 6- Metal spraying 60-100s under the conditions of 8mA;
Step 4:Sample C is placed in solution, using graphite flake as anode, sample C applies voltage and be arranged to 1- as cathode 3V, sedimentation time 5-10min, depositing temperature are 60-70 degree, take out sample drying after reaction, obtain surface flowers shape Super large piece calcium phosphate dibasic dihydrate;
The voltage pulse width is 20-40ms, is 50-100ms between arteries and veins;
Distance is 30-50mm between the cathode and anode;
The solution is:Ammonium dihydrogen phosphate is dissolved in the solution that 10-30mmol/L is prepared in deionized water, calcium nitrate is added and stirs It mixes and uniformly obtains solution;The molar ratio of the calcium nitrate and ammonium dihydrogen phosphate is 1.0-1.5.
2. the preparation method of surface flowers shape super large piece calcium phosphate dibasic dihydrate according to claim 1, it is characterised in that:
It is described that 5-10min is cleaned by ultrasonic using acetone.
CN201711328466.4A 2017-12-13 2017-12-13 Preparation method of super-large calcium hydrogen phosphate dihydrate with surface in flower cluster shape Active CN108118526B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102552978A (en) * 2012-02-20 2012-07-11 西北工业大学 Method for preparing hydroxyapatite bioactive coating
WO2013067049A1 (en) * 2011-10-31 2013-05-10 The University Of Toledo Method for modifying surfaces for better osseointegration
CN103147280A (en) * 2013-02-06 2013-06-12 西北工业大学 Biological activity modified method of carbon fiber surface

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013067049A1 (en) * 2011-10-31 2013-05-10 The University Of Toledo Method for modifying surfaces for better osseointegration
CN102552978A (en) * 2012-02-20 2012-07-11 西北工业大学 Method for preparing hydroxyapatite bioactive coating
CN103147280A (en) * 2013-02-06 2013-06-12 西北工业大学 Biological activity modified method of carbon fiber surface

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