CN108751157A - A kind of iron content hydroxyapatite and preparation method thereof and purposes - Google Patents
A kind of iron content hydroxyapatite and preparation method thereof and purposes Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/325—Preparation by double decomposition
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K6/838—Phosphorus compounds, e.g. apatite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/84—Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The present invention provides a kind of iron content hydroxyapatite and preparation method thereof and purposes, and the position of ferro element calcium in part substituted hydroxy phosphorite crystal in the form of iron ion, obtains the Fe-HA of calcium deficiency type in the iron content hydroxyapatite.Preparation method includes：By (CaNO3)2·4H2O、Fe(NO3)3·9H2O、(NH4)2HPO4It is configured to solution with deionized water；By solution with dilute acid for adjusting pH value to 2.0~2.5, then with weak base pH value is adjusted to 10.0~10.5；Reaction paste is synthesized using ultrasound-microwave cooperating mode；It filters successively later, clean, obtain Fe-HA solids after drying.The present invention also provides purposes of the above-mentioned iron content hydroxyapatite in preparing dental prosthetic material.
Description
Technical field
The invention belongs to technical field of biological materials, and in particular to a kind of iron content hydroxyapatite and preparation method thereof with
On the way.
Background technology
Hydroxyapatite (HA) is the host inorganic constituent of vertebrate skeletal and tooth, hydroxyl in the enamel of people
The content of apatite about 96Wt% (92Vol%), many diseases and wound can lead to the absence of tooth of patient, and therefore, dentistry is repaiied
Research in terms of multiple material is of interest by vast researcher always.Hydroxyapatite has excellent biocompatibility and life
Object activity, and the inducible factor of a kind of bone or tooth is can be used as, there is preferable mine again to tooth in oral hygiene
Change, desensitization and whitening function.
Ferro element is one of the essential element for constituting human body, and iron deficiency influences whether health and the development of human body, iron
It can be utilized repeatedly by body in being metabolized in vivo.The present invention is attempted for the first time using natural animal red iron content enamel as bionical right
As with (NH4)2HPO4、Ca(NO3)2·4(H2) and Fe (NO O3)3·9(H2O it) is used as raw material, utilizes ultrasonic wave added Microwave Water
Thermal synthesis method prepares iron content hydroxyapatite (Fe-HA), it is intended to be solved by promoting mechanical performance and the anti-microbial property of Fe-HA
Enamel decalcification problem, fundamentally prevents dental caries.
Invention content
In view of the problems of the existing technology, the present invention provide a kind of iron content hydroxyapatite and preparation method thereof with
On the way.The technical scheme is that：
The first aspect, the present invention provide a kind of iron content hydroxyapatite, in the iron content hydroxyapatite ferro element with
The position of calcium, obtains the Fe-HA of calcium deficiency type in the form part substituted hydroxy phosphorite crystal of iron ion.
The second aspect, the present invention provide the preparation method of above-mentioned iron content hydroxyapatite, including：
(1) by (CaNO3)2·4H2O、Fe(NO3)3·9H2O、(NH4)2HPO4It is configured to solution with deionized water；
(2) solution is adjusted into pH value to 10.0~10.5 to 2.0~2.5, then with weak base with dilute acid for adjusting pH value, obtained anti-
Answer slurry；
(3) reaction paste is synthesized using ultrasound-microwave cooperating mode；
(4) slurry after the completion of reaction filtered successively, cleaned, obtaining Fe-HA solids after drying.
Further, the detailed process of preparation solution is in the step (1)：According to (CaNO3)2·4H2O、Fe
(NO3)3·9H2O、(NH4)2HPO4Mass ratio be (2.98~2.2)：(0~1)：(0.5:~1.1) then dispensing will
(CaNO3)2·4H2O、Fe(NO3)3·9H2O、(NH4)2HPO4It is configured to solution respectively, in 35~40 DEG C, mixing speed 400
First by Fe (NO under the conditions of~600rpm3)3·9H2O solution is slowly added to (CaNO3)2·4H2It is mixed well in O solution, then will
(NH4)2HPO4Solution is slowly added to and mixes well to obtain the final product.
Further, the diluted acid in the step (2) is the dust technology that mass concentration is 15%.
Further, the weak base in the step (2) is the ammonium hydroxide that mass concentration is 50%.
Further, the specific control parameter of ultrasound-microwave cooperating mode is in the step (3)：Ultrasonic power is 50W
~60W, supersonic frequency are 40~50KHz, and microwave power is 300~400W, and reaction temperature is 70~90 DEG C, and the reaction time is
700~1000s.
Further, specific control parameter dry in the step (4) is：Drying temperature is 70~90 DEG C, when dry
Between be 10~12h.
In terms of third, the present invention provides purposes of the above-mentioned iron content hydroxyapatite in preparing dental prosthetic material.
The beneficial effects of the present invention are：The present invention is with (CaNO3)2·4H2O、Fe(NO3)3·9H2O、(NH4)2HPO4For
Starting material prepares a kind of completely new iron content hydroxyapatite, technique using ultrasound-microwave cooperating mode by bio-mimetic syntheses
Easy to operate, Environmental Safety, cost is relatively low, is suitble to the scale quantization production of high-purity iron content hydroxyapatite.In addition, of the invention
Iron content can arbitrarily be adjusted in 0%-10% in the iron content hydroxyapatite being prepared, and product is in rodlike, uniform in size, dispersion
Property it is good, nano level grain size can reach 40-100nm, and have excellent abrasive resistance, resistance to acid attack and anti-microbial property, can use
In dental prosthetic material field.
Description of the drawings
The SEM figures that Fig. 1 is the Fe-HA that the embodiment of the present invention 1 obtains.
The SEM figures that Fig. 2 is the Fe-HA that the embodiment of the present invention 2 obtains.
The SEM figures that Fig. 3 is the Fe-HA that the embodiment of the present invention 3 obtains.
The SEM figures that Fig. 4 is the Fe-HA that the embodiment of the present invention 4 obtains.
The EDS figures that Fig. 5 is the Fe-HA that the embodiment of the present invention 2 obtains.
The IR figures that Fig. 6 is the Fe-HA that 1-4 of the embodiment of the present invention is obtained.
Fig. 7 is the XRD diagram for the Fe-HA that 1-4 of the embodiment of the present invention is obtained.
Fig. 8 is the hardness test result schematic diagram for the Fe-HA ceramics that 1-4 of the embodiment of the present invention is obtained.
Fig. 9 is the acid etching test result schematic diagram for the Fe-HA ceramics that 1-4 of the embodiment of the present invention is obtained, and wherein 9-1 is
Fe0%The gradual change schematic diagram of the acid corrosion process of-HA ceramics；9-2 is Fe1%The gradual change schematic diagram of the acid corrosion process of-HA ceramics；9-3 is
Fe1.5%The gradual change schematic diagram of the acid corrosion process of-HA ceramics；9-4 is Fe2%The gradual change schematic diagram of the acid corrosion process of-HA；9-5 is 4
Mass loss changes with time schematic diagram in kind of Fe-HA ceramics acid corrosion process.
Figure 10 is the CETR friction and wear test results schematic diagrames for the Fe-HA ceramics that 1-4 of the embodiment of the present invention is obtained, wherein
10-1 is mass loss amount result schematic diagram；10-2 is Fe0%The polishing scratch size and pattern schematic diagram of-HA ceramics；10-3 is Fe1%-
The polishing scratch size and pattern schematic diagram of HA ceramics；10-4 is Fe1.5%The polishing scratch size and pattern schematic diagram of-HA ceramics；10-5 is
Fe2%The polishing scratch size and pattern schematic diagram of-HA ceramics.
Figure 11 is the mechanical experimental results schematic diagram for the compound resin that the embodiment of the present invention 8 obtains, and wherein 11-1 is
Springform spirogram, 11-2 are nano hardness figure.
Figure 12 is the anti-microbial property test result schematic diagram for the compound resin that the embodiment of the present invention 8 obtains.
Specific implementation mode
The present invention is described in further details with specific embodiment below in conjunction with the accompanying drawings, described is the solution to the present invention
It releases rather than limits.
Embodiment 1
The present embodiment provides a kind of iron content hydroxyapatites, wherein ferro element substituted hydroxy phosphorus in part in the form of iron ion
The position of calcium in lime stone crystal, content 0%.Specific preparation process is as follows：According to (CaNO3)2·4H2O、(NH4)2HPO4Quality
Than being 2.98：Two kinds of raw materials are configured to the aqueous solution that mass concentration is 2.3% and 1.3% by 1 dispensing respectively；In 37 DEG C, stirring
Speed be 400rpm under the conditions of by (NH4)2HPO4Solution is slowly added to (CaNO3)2·4H2It is mixed well in O solution；Then it uses
Mass concentration be 15% dust technology regulation system pH value to 2.0, then with mass concentration be 50% ammonium hydroxide adjusting pH value to
10.0, obtain reaction paste；Reaction paste is synthesized using ultrasound-microwave cooperating mode, specific control parameter is：Ultrasound
Power is 50W, supersonic frequency 40KHz, microwave power 300W, and reaction temperature is 80 DEG C, and reaction time 800s will react
After slurry after the completion is placed at room temperature for 6h, it is neutral to be precipitated to pH with deionized water with the rotating speed eccentric cleaning of 4500rpm, then is used
Absolute ethyl alcohol washing precipitation is twice；Under the conditions of being finally 80 DEG C in temperature Fe is obtained after dry 12h0%- HA solid powders, product
In rodlike, uniform in size, favorable dispersibility, nano level grain size can reach 60nm, and the results are shown in Figure 1 by SEM, and IR results are such as
Shown in Fig. 6, the results are shown in Figure 7 by XRD, and hardness test result is as shown in Figure 8.
Embodiment 2
The present embodiment provides a kind of iron content hydroxyapatites, wherein ferro element substituted hydroxy phosphorus in part in the form of iron ion
The position of calcium in lime stone crystal, content 1%.Specific preparation process is as follows：According to (CaNO3)2·4H2O、Fe(NO3)3·
9H2O、(NH4)2HPO4Mass ratio is 2.8：0.13：0.97 dispensing, by three kinds of raw materials be configured to respectively mass concentration be 2.8%,
0.5% and 1.3% aqueous solution；By Fe (NO under the conditions of being 500rpm in 37 DEG C, mixing speed3)3·9H2O solution is slowly added to
To (CaNO3)2·4H2It is mixed well in O solution, then by (NH4)2HPO4Solution is slowly added to and mixes well；Then quality is used
A concentration of 15% dust technology regulation system pH value is to 2.1, then the ammonium hydroxide for being 50% with mass concentration adjusts pH value to 10.2, obtains
To reaction paste；Reaction paste is synthesized using ultrasound-microwave cooperating mode, specific control parameter is：Ultrasonic power is
50W, supersonic frequency 50KHz, microwave power 400W, reaction temperature are 85 DEG C, reaction time 900s, after the completion of reaction
Slurry be placed at room temperature for 6h after, it is neutral to be precipitated to pH with deionized water with the rotating speed eccentric cleaning of 4500rpm, then with anhydrous second
Alcohol washing precipitation is twice；Under the conditions of being finally 80 DEG C in temperature Fe is obtained after dry 12h1%- HA solid powders, product in rodlike,
Uniform in size, favorable dispersibility, nano level grain size can reach 50nm, and the results are shown in Figure 2 by SEM, EDS figure as shown in figure 5,
The results are shown in Figure 6 by IR, and the results are shown in Figure 7 by XRD, and hardness test result is as shown in Figure 8.
Table 1
Embodiment 3
The present embodiment provides a kind of iron content hydroxyapatites, wherein ferro element substituted hydroxy phosphorus in part in the form of iron ion
The position of calcium in lime stone crystal, content 1.5%.Specific preparation process is as follows：According to (CaNO3)2·4H2O、Fe(NO3)3·
9H2O、(NH4)2HPO4Mass ratio is 2.5:0.13:0.88 dispensing, by three kinds of raw materials be configured to respectively mass concentration be 2.7%,
1.1% and 1.3% aqueous solution；By Fe (NO under the conditions of being 550rpm in 38 DEG C, mixing speed3)3·9H2O solution is slowly added to
To (CaNO3)2·4H2It is mixed well in O solution, then by (NH4)2HPO4Solution is slowly added to and mixes well；Then quality is used
A concentration of 15% dust technology regulation system pH value is to 2.2, then the ammonium hydroxide for being 50% with mass concentration adjusts pH value to 10.1, obtains
To reaction paste；Reaction paste is synthesized using ultrasound-microwave cooperating mode, specific control parameter is：Ultrasonic power is
50W, supersonic frequency 40KHz, microwave power 400W, reaction temperature are 80 DEG C, reaction time 850s, after the completion of reaction
Slurry be placed at room temperature for 6h after, it is neutral to be precipitated to pH with deionized water with the rotating speed eccentric cleaning of 4500rpm, then with anhydrous second
Alcohol washing precipitation is twice；Under the conditions of being finally 80 DEG C in temperature Fe is obtained after dry 12h1.5%- HA solid powders, product are in stick
Shape, uniform in size, favorable dispersibility, nano level grain size can reach 40nm, and the results are shown in Figure 3 by SEM, IR results such as Fig. 6
Shown, the results are shown in Figure 7 by XRD, and hardness test result is as shown in Figure 8.
Embodiment 4
The present embodiment provides a kind of iron content hydroxyapatites, wherein ferro element substituted hydroxy phosphorus in part in the form of iron ion
The position of calcium in lime stone crystal, content 2%.Specific preparation process is as follows：According to (CaNO3)2·4H2O、Fe(NO3)3·
9H2O、(NH4)2HPO4Mass ratio is 2.4:0.41:0.89 dispensing, by three kinds of raw materials be configured to respectively mass concentration be 2.6%,
1.8% and 1.3% aqueous solution；By Fe (NO under the conditions of being 600rpm in 39 DEG C, mixing speed3)3·9H2O solution is slowly added to
To (CaNO3)2·4H2It is mixed well in O solution, then by (NH4)2HPO4Solution is slowly added to and mixes well；Then quality is used
A concentration of 15% dust technology regulation system pH value is to 2.3, then the ammonium hydroxide for being 50% with mass concentration adjusts pH value to 10.4, obtains
To reaction paste；Reaction paste is synthesized using ultrasound-microwave cooperating mode, specific control parameter is：Ultrasonic power is
50W, supersonic frequency 50KHz, microwave power 300W, reaction temperature are 80 DEG C, reaction time 800s, after the completion of reaction
Slurry be placed at room temperature for 6h after, it is neutral to be precipitated to pH with deionized water with the rotating speed eccentric cleaning of 4500rpm, then with anhydrous second
Alcohol washing precipitation is twice；Under the conditions of being finally 80 DEG C in temperature Fe is obtained after dry 12h2%- HA solid powders, product in rodlike,
Uniform in size, favorable dispersibility, nano level grain size can reach 70nm, and the results are shown in Figure 4 by SEM, IR results such as Fig. 6 institutes
Show, the results are shown in Figure 7 by XRD, and hardness test result is as shown in Figure 8.
Embodiment 5
The preparation method of Fe-HA ceramics：
Fe-HA powder prepared by embodiment 1-4, is filled into sampling die respectively, using automatic tableting press by Fe-HA
Powder is pressed into cylindric block, and it is 10MPa, dwell time 1min to test pressure used.By the Fe-HA blocks of compression molding, place
Isostatic cool pressing testing machine is put into after reason to suppress again, test pressure 250Mpa, dwell time 1min.Finally block is put into
(test parameters is sintered in Muffle furnace：Heating rate be 2.5 DEG C/min, 1200 DEG C, soaking time 2h of holding temperature, then
900 DEG C are dropped to 2.5 DEG C/min rate of temperature fall, last furnace cooling), obtain 4 kinds of Fe-HA ceramic samples.
Embodiment 6
Acid etching is tested：
4 kinds of Fe-HA ceramics are subjected to sanding and polishing processing.Then, sample is put into the lemon of 50ml0.001mol/l respectively
In lemon acid.Before acid etching, is weighed to each sample, observes its pattern using light microscopic.The 7th day, the 14th day after acid etching,
It is weighed again to sample respectively, morphology observations, is subject to comparative analysis mass loss variation, pattern variation characteristic.Such as Fig. 9-1
Shown in~9-4, it can be seen from the figure that Fe-HA ceramics prepared under conditions of alkaline PH=10 are with immersion number of days
Increase, all test specimen quality are all lost, and the smooth finish of each specimen surface is all declined.This table
Hydroxyapatite in bright ceramics is reacted with citric acid, consumes the part mass of sample.Curve in comparison diagram 9-5
And light microscopic figure is can be found that:Fe is added in HA ceramics, can significantly improve the resistance to acid attack ability of pure HA, mass loss it is upper
The trend of liter is obviously slack-off.When Fe contents are 1.5wt%, Fe1.5%- HA is demonstrated by most excellent acid etch resistance energy；By 14 days
Acid etching immersion test, mass loss is relatively small, specimen surface flatness is best.This shows miserable miscellaneous suitable in HA
Fe can improve the acid etch resistance energy of ceramics.
Embodiment 7
CETR friction-wear tests：
The wear-resisting property of Fe-HA ceramics is tested using UMT-3 multifunction friction wears testing machine (U.S. CE TR companies).It adopts
With the friction mode of ball-face contact, reciprocating thin tail sheep sliding frictional wear experiment is carried out.Select ferroalloy ball (TC4, diameter
10mm) as secondary to mill.
Experimental condition used is as follows：Normal load:Fn=20N, shift reciprocately：D=1.0mm, frequency：F=2Hz, cycle
Number：N=5000 times, test temperature：25 ± 3 DEG C, experimental enviroment：Artificial saliva.
As shown in Figure 10, test result shows：Occur apparent delamination phenomenon in pure HA, in polishing scratch and a large amount of mills are cheated；
Wear surface is mainly adhesive wear；By comparing it can be found that Fe1.5%The polishing scratch of-HA ceramics obviously becomes smaller, without apparent
Mill hole occurs, and illustrates to add Fe in HA bioceramics, can effectively improve its wear-resisting situation.But with Fe contents
Increase (Fe2%- HA), polishing scratch region significantly increases again, and Wear track depth is also obviously deepened, this shows that excessive Fe elements result in
Fe-HA ceramic wear-resisting performances decline.
Embodiment 8
Fe-HA solids prepared by embodiment 3 are added to as inorganic filler in light-cured resin, compound tree is prepared
Fat, find iron content hydroxyapatite addition can improve the mechanical properties such as elasticity modulus, the nano hardness of compound resin and
Anti-microbial property.
The preparation process of compound resin is as follows：
It is 50 to weigh mass ratio first:50 bisphenol-A-glycidyl methacrylate (Bis-GMA) and diluent list
It is uniformly mixed to obtain the final product by body dimethacrylate triethylene glycol fat (TEGDMA) in the vial wrapped up with masking foil
Resin matrix；Then weigh account for resin matrix 1wt.% photoinitiator it is spare, wherein camphorquinone (CQ) and 4- ethyls (diformazan ammonia
Base) benzoic acid (4-EDMAB) mass ratio be 1:4；It is premixed by double center mixing dispersion machines, specific pre-compounding process is：It will
Load weighted inorganic filler is in batches a small amount of to be repeatedly added into resin monomer, so that resin monomer is soaked inorganic filler, then gradually adjust
High dispersive machine rotating speed, holding are done time in advance, are finally reached the purpose of mixing and dispersion；Finally, it is slowly added under the conditions of being protected from light
Photoinitiator uniformly fills the resin samples prepared into the silicon rubber mould of Φ 4mm × 6mm, positive and negative to compound resin
Face cures 60s respectively, obtains compound resin.
Mechanics Performance Testing and antibacterial tests detection are carried out to the compound resin, wherein Mechanics Performance Testing uses Agilent
Nano-hardness tester carries out indentation test to compound resin, then detects elasticity modulus and nano hardness result is as shown in figure 11, knot
Fruit shows that iron content hydroxyapatite is added to as inorganic filler in light-cured resin, can significantly improve the power of light-cured resin
Performance is learned, and works as Fe1.5%When-HA contents are 5%, compound resin has optimal mechanical property.
Antibacterial tests are as follows：
10mL brain heart infusion broths training base (BHI) is entered in the Streptococcus mutans S.mutans (UA159) to after recovery,
Temperature is 37 DEG C, carries out Zengjing Granule under the conditions of amphimicrobian under (70%N2+20%CO2+10%H2)；After cultivating 12h, take
200ul bacterium solutions be added 24 hole Bacteria Culture plates in, be separately added into the orifice plate sterilizing after compound resin sample to be tested and
1800ulBHI is cultivated for 24 hours under the conditions of amphimicrobian；By 106 times of PBS gradient dilutions of the bacterium solution in 24 orifice plates, every group takes
LOOul is added in the tablet of BHI, and every group of 3 samples are cultivated for 24 hours under the conditions of amphimicrobian again after smoothening；It is soft with counting
Part chooses plate count, and takes pictures, and then carries out CFU countings.Residual bacterial quantity result is as shown in figure 12.As a result table
It is bright：Iron content hydroxyapatite is added to as inorganic filler in light-cured resin, has good anti-microbial property, as filler contains
The raising of amount, anti-microbial property enhance therewith.
To sum up, with (CaNO in present invention specific implementation3)2·4H2O、Fe(NO3)3·9H2O、(NH4)2HPO4It is former for starting
Material prepares a kind of completely new iron content hydroxyapatite, technological operation letter using ultrasound-microwave cooperating mode by bio-mimetic syntheses
Single, Environmental Safety, cost is relatively low, is suitble to the scale quantization production of high-purity iron content hydroxyapatite.In addition, the present invention is prepared into
To iron content hydroxyapatite in iron content can arbitrarily be adjusted in 0%-10%, product is uniform in size in rodlike, and dispersibility is good
Good, nano level grain size can reach 40-100nm, and have excellent abrasive resistance, resistance to acid attack and anti-microbial property, can be used for tooth
Dental repair material field.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (8)
1. a kind of iron content hydroxyapatite, which is characterized in that ferro element is in the form of iron ion in the iron content hydroxyapatite
The position of calcium, obtains the Fe-HA of calcium deficiency type in the substituted hydroxy phosphorite crystal of part.
2. a kind of preparation method of iron content hydroxyapatite described in claim 1, which is characterized in that including：
(1) by (CaNO3)2·4H2O、Fe(NO3)3·9H2O、(NH4)2HPO4It is configured to solution with deionized water；
(2) solution is adjusted into pH value to 10.0~10.5 to 2.0~2.5, then with weak base with dilute acid for adjusting pH value, obtains reaction slurry
Material；
(3) reaction paste is synthesized using ultrasound-microwave cooperating mode；
(4) slurry after the completion of reaction filtered successively, cleaned, obtaining Fe-HA solids after drying.
3. a kind of preparation method of iron content hydroxyapatite according to claim 2, which is characterized in that the step (1)
It is middle prepare solution detailed process be：According to (CaNO3)2·4H2O、Fe(NO3)3·9H2O、(NH4)2HPO4Mass ratio be
(2.98~2.2)：(0~1)：(0.5:~1.1) dispensing, then by (CaNO3)2·4H2O、Fe(NO3)3·9H2O、(NH4)2HPO4It is configured to solution respectively, first by Fe (NO under the conditions of being 400~600rpm in 35~40 DEG C, mixing speed3)3·9H2O is molten
Liquid is slowly added to (CaNO3)2·4H2It is mixed well in O solution, then by (NH4)2HPO4Solution is slowly added to and mixes well i.e.
?.
4. a kind of preparation method of iron content hydroxyapatite according to claim 2, which is characterized in that the step (2)
In diluted acid be dust technology that mass concentration is 15%.
5. a kind of preparation method of iron content hydroxyapatite according to claim 2, which is characterized in that the step (2)
In weak base be ammonium hydroxide that mass concentration is 50%.
6. a kind of preparation method of iron content hydroxyapatite according to claim 2, which is characterized in that the step (3)
The specific control parameter of middle ultrasound-microwave cooperating mode is：Ultrasonic power is 50W~60W, and supersonic frequency is 40~50KHz, micro-
Wave power is 300~400W, and reaction temperature is 70~90 DEG C, and the reaction time is 700~1000s.
7. a kind of preparation method of iron content hydroxyapatite according to claim 2, which is characterized in that the step (4)
The specific control parameter of middle drying is：Drying temperature is 70~90 DEG C, and drying time is 10~12h.
8. a kind of purposes of the iron content hydroxyapatite described in claim 1 in preparing dental prosthetic material.
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|---|---|---|---|
| CN201810780047.2A CN108751157A (en) | 2018-07-16 | 2018-07-16 | A kind of iron content hydroxyapatite and preparation method thereof and purposes |
Applications Claiming Priority (1)
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