CN107236940B - A kind of preparation method of calcium monohydrogen phosphate cladding magnesium powder - Google Patents
A kind of preparation method of calcium monohydrogen phosphate cladding magnesium powder Download PDFInfo
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- CN107236940B CN107236940B CN201710335787.0A CN201710335787A CN107236940B CN 107236940 B CN107236940 B CN 107236940B CN 201710335787 A CN201710335787 A CN 201710335787A CN 107236940 B CN107236940 B CN 107236940B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1637—Composition of the substrate metallic substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
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Abstract
The present invention relates to a kind of preparation methods of calcium phosphate coated magnesium powder, the present invention uses the deposition solution prepared by a certain percentage by calcium nitrate, potassium dihydrogen phosphate and disodium ethylene diamine tetraacetate, deposition reaction, sedimentary condition are carried out using the pure magnesium dust of aerosolization are as follows: pH value 3.6 ~ 4.8, depositing temperature are 10 ~ 20 DEG C, 200 ~ 400rpm of stirring rate.Preparation method of the present invention prepares one layer of complete, uniform clad on pure magnesium dust surface, and the main object of the clad is mutually dicalcium phosphate dihydrate and a small amount of magnesium monohydrogen phosphate, and corrosion resistance of the magnesium powder in environment containing chlorine can be improved.
Description
Technical field
The present invention relates to the preparation methods of covered composite yarn dusty material, and in particular to a kind of to use chemical liquid deposition system
The method of standby dicalcium phosphate dihydrate covered composite yarn magnesium powder.
Background technique
With the development of modern society, human lives' tempo increase, the extension of human longevity, traffic accident, natural calamity
It is increasingly improved with the requirement of Frequent Accidents and the people to quality of life and living standard such as various unexpected injuries, and phase therewith
Pair be human organ contribute cause stagnation so that organ and tissue replacement it is increasing so that people are to medical life
The demand of object graft materials, biologic replacement materials, biological filler etc. steeply rises.
Magnesium not only has the function of self degradation as macroelement needed by human in vivo, while also having good
Good biocompatibility and good synosteosis and osteoinductive, and the elasticity modulus to match with bone；And magnesium
Storage is abundant in the earth's crust, accounts for about 2 % of earth's crust gross mass, therefore magnesium can be used as the gold of a kind of function admirable and abundance
Belong to biomaterial.
However since degradation speed is fast in vivo for magnesium and magnesium alloy, Chang Yinqi structural failure, wound inflammation etc. and lead
Cause graft failure.Synthos are a kind of bioceramics with good biocompatibility, osteoacusis and osteoinductive, and with day
The ingredient of right bone tissue is close, but its brittleness is big, it is difficult to form.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of calcium monohydrogen phosphate cladding magnesium powder, this method is heavy using chemical liquid phase
Area method prepares calcium monohydrogen phosphate cladding magnesium powder, prepares one layer of complete, uniform calcium monohydrogen phosphate ceramic coatings in magnesium powder particle surface
Layer, becoming surface layer is calcium monohydrogen phosphate, the covered composite yarn powder that inside is magnesium granules, to improve the corrosion resistance of magnesium powder；
The calcium monohydrogen phosphate cladding magnesium powder has good biocompatibility, compression strength and the elasticity modulus to match with human body, together
When the corrosion resistance that has also had and more superior biology performance, to prepare magnesium in the future and the entirety of calcium phosphate is compound
Material provides basic material.
Technical scheme is as follows:
The preparation method of calcium monohydrogen phosphate ceramic coatings magnesium powder, there is following steps:
1) 0.01mol/L calcium nitrate and 0.01mol/L potassium dihydrogen phosphate are configured, second two is added into calcium nitrate solution
Amine tetraacethyl disodium is stirred to after completely dissolution, is slowly added in potassium dihydrogen phosphate, is uniformly mixed, molten with sodium hydroxide
The pH value that liquid adjusts solution is 3.6 ~ 4.8, controls 10 DEG C ~ 20 DEG C of temperature of solution, obtains deposition solution；
2) it takes magnesium powder to be slowly added into deposition solution described in step 1), stirs 10 ~ 30min, divide magnesium dust uniformly
It dissipates and deposition reaction occurs in the solution, after reaction, filter out powder, it is dry, obtain calcium monohydrogen phosphate ceramic coatings magnesium powder.
Calcium nitrate described in step 1): potassium dihydrogen phosphate: the molar ratio of disodium ethylene diamine tetraacetate is 2:2:1.
The amount of the magnesium powder of addition described in step 2 is every liter of solution 0.4mol.
The partial size of magnesium powder described in step 2 is 250 mesh.
The speed of stirring described in step 2 is 200 ~ 400rpm/h.
The deposition solution of the invention includes calcium nitrate, potassium dihydrogen phosphate and disodium ethylene diamine tetraacetate, the ratio of three
Example is 2:2:1.After solution prepares, pH value is adjusted to 3.8 ~ 4.8 with sodium hydroxide solution, and solution temperature is controlled 10
℃~20℃；Then magnesium powder progress deposition processes are being added, wherein
The calcium nitrate is mainly to provide calcium constituent required for forming calcium monohydrogen phosphate, and the effect of potassium dihydrogen phosphate is to mention
For hydrogen phosphate；Both reagents have biggish solubility in water, are easy to be prepared into uniform aqueous solution.
The disodium ethylene diamine tetraacetate is dissolved in the solution of calcic as complexing agent, can be effective by calcium ion
Ground complexing, in deposition process, since calcium ion is by complexing and slow release, so the formation speed of dicalcium phosphate dihydrate
It will receive inhibition, to efficiently control dicalcium phosphate dihydrate in the speed of growth on magnesium granules surface, so that clad is more equal
It is even, fine and close；Meanwhile the slow release of calcium ion also effectively prevents dicalcium phosphate dihydrate free sedimentation from solution and is precipitated,
Guarantee that it can sufficiently be coated on magnesium powder particle surface.
The control of liquid pH value is deposited 3.8 ~ 4.8, if pH value is too low, magnesium powder in the solution can rapid corrosion dissolution, it is difficult to
To cladding powder；If pH value is excessively high, dicalcium phosphate dihydrate settling velocity is too fast, the hydrogen phosphate dihydrate of magnesium powder particle surface deposition
Calcium crystal can mushroom out, it is difficult to obtain complete, uniform clad.
Deposition reaction temperature is controlled at 10 DEG C ~ 20 DEG C, if temperature is excessively high, one side magnesium powder corrosion dissolution speed is accelerated,
Another aspect hydrogen phosphate dihydrate calcium precipitate and the speed of growth are too fast, are unable to get complete, fine and close clad；If temperature mistake
Low, then deposition reaction speed is too slow, it is difficult to guarantee the integrality of cladding.
It is stirred during deposition reaction with the speed of 200rpm ~ 400rpm, if mixing speed is too low, magnesium powder particle
It is difficult to evenly dispersed in deposition liquid, it is difficult to the powder particle being evenly coated, in some instances it may even be possible to there is magnesium granules reunion, that is,
Two or more magnesium granules are covered by together；If mixing speed is excessively high, solution convection velocity is accelerated, to powder
The souring of particle surface increases, and the dicalcium phosphate dihydrate for being deposited on magnesium granules surface, which can be washed, to fall off, serious to reduce packet
Cover efficiency.
Calcium monohydrogen phosphate ceramics/magnesium base composite material, the density contrast of calcium monohydrogen phosphate and magnesium are prepared due to traditional blending processes of powders
Different larger, the two is difficult to be uniformly mixed, and substantially reduces the performance of composite material.Calcium monohydrogen phosphate cladding magnesium powder of the present invention
Preparation method prepares one layer of complete, uniform calcium monohydrogen phosphate clad (main object phase of the clad in magnesium powder particle surface
For dicalcium phosphate dihydrate and a small amount of magnesium monohydrogen phosphate, corrosion resistance of the magnesium powder in environment containing chlorine can be improved), it is used to prepare phosphoric acid
Hydrogen calcium ceramics/magnesium base composite material, it is ensured that the uniformity of ingredient improves composite property.With single magnesium or magnesium alloy
It prepares calcium monohydrogen phosphate ceramics/magnesium base composite material with calcium monohydrogen phosphate ceramics and traditional blending processes of powders to compare, phosphorus of the present invention
The advantages of sour hydrogen calcium ceramics/magnesium base composite material combines calcium monohydrogen phosphate ceramic layer and magnesium, not only have good biocompatibility,
Compression strength and the elasticity modulus to match with human body, while the corrosion resistance also having had and more superior biology
Performance.
The technical effects of the invention are that；
A process for preparing dicalcium phosphate dihydrate ceramic coatings magnesium powder powder maintain magnesium powder original-shape substantially, coat
Coating structure is tiny and uniform, fine and close；Relative to uncoated pure magnesium dust, the corrosion resistance of this covered composite yarn powder is obtained
Great raising has been arrived, meanwhile, this preparation method equipment is simple, easy to operate.
Detailed description of the invention
Fig. 1 is cladding powder exterior appearance of the invention.
Fig. 2 is cladding powder Cross Section Morphology of the invention, in which: the 1. hydrogen phosphate dihydrate to be coated on magnesium granules surface
2. calcium is magnesium granules, rest part is inlay used in sample preparation.
Specific embodiment
Embodiment 1
Ca (the NO of 0.01mol/L is prepared respectively3)2And KH2PO4Each 100ml of solution, in Ca (NO3)22 g are added in solution
Complexing agent C10H14N2Na2O8•2H20, after completely dissolution to it, under magnetic stirrer (400 r/min), by KH2PO4It is slow
It is slow that Ca (NO is added3)2Until being uniformly mixed in solution, pH value finally is adjusted to 3.6 with 1mol/L sodium hydroxide solution, is adjusted molten
Liquid temperature is to 10 DEG C.It weighs 2 g magnesium powders to be added slowly in above-mentioned solution, keeps powder equal using the mixing speed of 400r/min
Even dispersion in the solution, then reduces mixing speed to 200r/min, react after 30min terminates, and powder is taken out and is centrifuged
It is dried in drying box after drying, dicalcium phosphate dihydrate is made and coats magnesium powder powder.
Embodiment 2
Ca (the NO of 0.01 mol/L is prepared respectively3)2And KH2PO4Each 100ml of solution, in Ca (NO3)22 g are added in solution
Complexing agent C10H14N2Na2O8•2H20, after completely dissolution to it, under magnetic stirrer (300 r/min), by KH2PO4It is slow
It is slow that Ca (NO is added3)2Until being uniformly mixed in solution, pH value finally is adjusted to 4.2 with 1mol/L sodium hydroxide solution, is adjusted molten
Liquid temperature is to 15 DEG C.It weighs 2 g magnesium powders to be added slowly in above-mentioned solution, the mixing speed using 300 r/min makes powder
Evenly dispersed then to reduce mixing speed to 200r/min in the solution, react after 25min terminates, by powder take out progress from
It is dried in drying box after the heart is dry, dicalcium phosphate dihydrate is made and coats magnesium powder powder.
Embodiment 3
Ca (the NO of 0.01mol/L is prepared respectively3)2And KH2PO4Each 100ml of solution, in Ca (NO3)22 g are added in solution
Complexing agent C10H14N2Na2O8•2H2O, after completely dissolution to it, under magnetic stirrer (250 r/min), by KH2PO4It is slow
It is slow that Ca (NO is added3)2Until being uniformly mixed in solution, pH value finally is adjusted to 4.8 with 1 mol/L sodium hydroxide solution, is adjusted molten
Liquid temperature is to 20 DEG C.It weighs 2 g magnesium powders to be added slowly in above-mentioned solution, the mixing speed using 250 r/min makes powder
Evenly dispersed in the solution and deposition reaction to occur, reacting after 20min terminates, and powder is taken out and is being dried after carrying out centrifugal drying
It is dried in case, dicalcium phosphate dihydrate is made and coats magnesium powder powder.
Embodiment 4
Ca (the NO of 0.01mol/L is prepared respectively3)2And KH2PO4Each 100 ml of solution, in Ca (NO3)22 g are added in solution
Complexing agent C10H14N2Na2O8•2H20, after completely dissolution to it, under magnetic stirrer (200 r/min), by KH2PO4It is slow
It is slow that Ca (NO is added3)2Until being uniformly mixed in solution, pH value finally is adjusted to 4.5 with 1 mol/L sodium hydroxide solution, is adjusted molten
Liquid temperature is to 18 DEG C.It weighs 2 g magnesium powders to be added slowly in above-mentioned solution, keeps powder equal using the mixing speed of 200r/min
Even dispersion in the solution, is kept stirring 200 r/min of speed, and reacting after 15min terminates, and powder is taken out after carrying out centrifugal drying
It is dried in drying box, dicalcium phosphate dihydrate is made and coats magnesium powder powder.
Claims (3)
1. a kind of preparation method of calcium monohydrogen phosphate cladding magnesium powder, which is characterized in that there is following steps:
1) 0.01mol/L calcium nitrate and 0.01mol/L potassium dihydrogen phosphate are configured, ethylenediamine tetraacetic is added into calcium nitrate solution
Acetic acid disodium is stirred to after completely dissolution, is slowly added in potassium dihydrogen phosphate, is uniformly mixed, with sodium hydroxide solution tune
The pH value for saving solution is 3.6 ~ 4.8, controls 10 DEG C ~ 20 DEG C of temperature of solution, obtains deposition solution；
The calcium nitrate: potassium dihydrogen phosphate: the molar ratio of disodium ethylene diamine tetraacetate is 2:2:1；
2) magnesium powder is taken to be slowly added into deposition solution described in step 1), stir 10 ~ 30min, stirring speed be 200 ~
400 r/min filter out powder, dry, obtain calcium monohydrogen phosphate cladding magnesium powder.
2. preparation method according to claim 1, it is characterised in that: the amount of the magnesium powder of addition described in step 2 is every liter molten
Liquid 0.4mol.
3. preparation method according to claim 1, it is characterised in that: the partial size of magnesium powder described in step 2 is 250 mesh.
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| US20210198152A1 (en) * | 2019-12-26 | 2021-07-01 | Metal Industries Research & Development Centre | Ceramic particle and method for producing the same |
| CN113199021B (en) * | 2021-04-09 | 2022-12-13 | 宁波职业技术学院 | High-performance magnesium alloy composite powder for building material and preparation method thereof |
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| CN102220551A (en) * | 2011-05-27 | 2011-10-19 | 华南理工大学 | Method for plasma spraying of Ca-P bioactive coating on surface of magnesium alloy |
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