CN114306101A - Novel double-layer film coated magnetic conductive alloy powder, preparation method and application - Google Patents
Novel double-layer film coated magnetic conductive alloy powder, preparation method and application Download PDFInfo
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Abstract
The invention provides a novel double-layer film coated magnetic conductive alloy powder, a preparation method and application. The preparation method of the double-layer film coated magnetic conductive alloy powder comprises the following steps: the magnetic conductive alloy powder coated by the hydroxyapatite/magnesium-iron bimetal oxide double-layer film is obtained by sintering, wherein the magnetic conductive powder coated by the double-layer film has excellent mechanical property. Cell experiments prove that: the magnetic powder coated by the double-layer film is nontoxic and has good biocompatibility, and can be used for cleaning teeth under the magnetic control condition, and the magnetic powder is specifically as follows: the tooth crown polishing device can generate relative motion with the tooth crown under the action of a magnetic field, polish the tooth crown, comprehensively clean the adjacent surface gap between the tooth surface and the tooth body and the fossa point gap on the tooth surface, and effectively remove dental plaque.
Description
Technical Field
The invention belongs to the field of material processing, and particularly relates to novel double-layer film coated magnetic conductive alloy powder, a preparation method and application.
Background
At present, the international method for cleaning teeth mainly comprises a tooth crown polishing method, particularly, a rubber cup and polishing paste are used for polishing tooth surfaces at a low speed, or supragingival and subgingival sand blasting is used for polishing the tooth surfaces, but due to the existence of anatomical structures with different tooth surfaces and tooth root forms, irritants in the interior of teeth and in tooth gaps are difficult to remove completely, the cleaned tooth surfaces are often provided with deep scratches through observation by an optical microscope and a scanning electron microscope, the scratches are easy to adhere to dental plaques and form dental calculus crystal nuclei, and the dental calculus can grow rapidly to cause periodontal inflammation. The above disadvantages are the problems to be solved in the current tooth crown polishing materials and techniques.
Disclosure of Invention
In order to solve the technical problem, the invention provides a novel double-layer film coated magnetic conductive alloy powder, which is prepared by the following method steps:
(1) taking soluble magnesium salt and soluble ferric salt as solutes and deionized water as a solvent, stirring until the solutes are completely dissolved in the solvent to obtain a solution A, wherein Mg in the solution A2+With Fe3+The ion molar ratio is 2-6: 1; using soluble alkali and soluble carbonate or bicarbonate as solutes and deionized water as a solvent, stirring until the solutes are completely dissolved in the solvent to obtain a solution B, wherein OH in the solution B-And CO3 2-The ion molar ratio is 1-3: 1; adding the solution B into the solution A, and continuously stirring to obtain a suspension C, wherein the pH value of the solution is 9.0-11.5;
(2) putting the magnetic conductive alloy powder into absolute ethyl alcohol for ultrasonic cleaning, drying and preserving heat for 10-30 min at 60-100 ℃ after cleaning to obtain dry and clean magnetic conductive alloy powder, putting the dry powder into a hydrothermal reaction kettle, adding the suspension C obtained in the step (1) into the reaction kettle, preserving heat for 12-24 h at 120-160 ℃ to obtain powder after hydrothermal reaction, cleaning with deionized water, and drying for 10-30 min at 60-100 ℃ to obtain magnetic conductive alloy powder coated with magnesium-iron layered double hydroxides;
(3) respectively dissolving soluble calcium salt and phosphorus pentoxide in absolute ethyl alcohol, stirring for 10-30 min to obtain precursor solutions containing Ca and P, wherein the molar ratio of Ca to P in the two solutions is 1.67, slowly dripping the precursor solution containing P into the precursor solution containing Ca, simultaneously dripping ammonia water, adjusting the pH value of the solution to 9.0-11.5, stirring for 10-30 min, standing and aging for 24-48 h to obtain hydroxyapatite gel;
(4) adding the hydroxyapatite gel obtained in the step (3) into the magnetic conductive alloy powder coated by the magnesium-iron layered double hydroxide obtained in the step (2), and performing ultrasonic dispersion for 10-30 min to obtain hydroxyapatite gel/magnesium-iron layered double hydroxide coated magnetic conductive alloy powder;
(5) and (3) putting the magnetic conductive alloy powder coated by the hydroxyapatite gel/the magnesium-iron layered double-metal hydroxide obtained in the step (4) into a heat treatment furnace for sintering, heating to 500-650 ℃ at a heating rate of 4-6 ℃/min, preserving heat for 2-4 h, and cooling to obtain novel double-layer film coated magnetic conductive alloy powder, wherein the novel double-layer film coated magnetic conductive alloy powder is the magnetic conductive alloy powder coated by the hydroxyapatite/magnesium-iron layered double-metal hydroxide.
Further, the soluble magnesium salt in the step (1) is any combination of magnesium nitrate, magnesium chloride or magnesium sulfate, and the soluble iron salt is any combination of ferric nitrate, ferric chloride or ferric sulfate.
Further, the soluble alkali in the step (1) is any combination of sodium hydroxide or potassium hydroxide, the soluble carbonate is any combination of sodium carbonate or potassium carbonate, and the bicarbonate is any combination of sodium bicarbonate or potassium bicarbonate.
Further, the magnetic conductive alloy powder in the step (2) is any combination of iron-chromium alloy, iron-nickel alloy or iron-cobalt alloy.
Further, the soluble calcium salt in the step (3) is any combination of calcium nitrate, calcium chloride or calcium sulfate.
The invention also provides application of the novel double-layer film coated magnetic conductive alloy powder in the field of tooth surface cleaning materials, under the action of a magnetic field, the double-layer film coated magnetic conductive alloy powder and a tooth crown generate relative motion to polish the tooth crown, and the powder can clean and polish the tooth surface, the adjacent surface gap between tooth bodies and the pit and groove point gap on the tooth surface, so that the teeth can be effectively cleaned and plaque can be removed.
The invention has the beneficial effects that:
the invention provides a tooth magnetic control polishing material, which has magnetic conductivity under the condition of a magnetic field, and simultaneously, the coated polishing medium meets the polishing hardness range and has good mechanical property and biocompatibility. The invention solves the problem of weak bonding force between the hydroxyapatite film layer and the metal powder substrate by preparing the bimetallic hydroxide layer on the surface of the magnetic conductive metal powder in advance and then preparing the hydroxyapatite composite film layer. The magnetic conductive alloy powder coated by the double-layer film is of a composite film structure, wherein the composite film layer is complete in shape and good in combination between layers, can be applied to the field of tooth surface polishing, and solves the problems that tooth crown abrasion, tooth body adjacent surface gaps and surface pit and groove point gaps are difficult to clean and the like which cannot be solved in the polishing process by a conventional polishing method when teeth are cleaned. The composite membrane layer material has the beneficial effects that:
(1) an interlayer of magnesium-iron Layered double hydroxide (LDH for short) with good biocompatibility grows in situ on the surface of the magnetic conductive alloy powder, and the interlayer is tightly combined with the magnetic conductive alloy powder. When the magnetic conductive alloy powder coated with the magnesium-iron layered double hydroxide is mixed with hydroxyapatite gel, ammonia water in the gel can activate the magnesium-iron layered double hydroxide, wherein part of magnesium ions and iron ions can enter the hydroxyapatite gel, and after sintering, hydroxyapatite doped with magnesium elements and iron elements is formed between the hydroxyapatite layer and a magnesium-iron double oxide (LDO) layer, so that the close combination of the magnesium-iron layered double hydroxide layer and an outer hydroxyapatite film layer is promoted. Therefore, the magnesium-iron bimetal oxide layer is used as the intermediate layer of the magnetic alloy powder and the hydroxyapatite film layer, so that the bonding strength between the film layer and the substrate is enhanced, the growth condition of the hydroxyapatite film layer is improved, the toughness of the film layer is increased, and the integrity of the film layer is ensured.
(2) The layered double hydroxide is introduced to be used as the intermediate layer of the hydroxyapatite and the alloy powder, and in consideration of strict safety requirements of biomedical equipment, the layered double hydroxide intermediate layer is constructed by selecting trace elements magnesium and iron which are necessary for a human body, wherein the magnesium is one of important trace elements of the human body, plays an important role in promoting bone formation and bone regeneration, and is also helpful for maintaining the strength and density of bones and teeth, and the iron is an important component of hemoglobin and participates in oxygen transportation and storage. In addition, the magnetic conductive alloy powder coated by the double-layer film has good biocompatibility, and is non-toxic when detected by a cytotoxicity test.
(3) The magnetic conductive alloy powder coated by the hydroxyapatite/magnesium-iron bimetal oxide double-layer film obtained by the invention is round and spherical, has uniform dispersion, good fluidity, proper and narrow particle size distribution of the powder, and controllable diameter of 50-125 μm.
(4) The prepared hydroxyapatite/magnesium-iron double-metal oxide double-layer film can completely wrap the magnetic conductive alloy powder, so that the direct contact between the surface of the alloy powder and the tooth crown is avoided in the practical application process, and the damage to the tooth crown caused in the polishing process is eliminated; and the outer apatite film layer has the mechanical property similar to that of the tooth tissue, so that the tooth crown can be polished without damage, painless cleaning can be realized, and the comfort level in the cleaning process is improved.
(5) The magnetic control polishing utilizes the distribution of a magnetic field to generate a stable magnetic induction effect, so that the material and the polishing solution are fully ground in all directions and at multiple angles, and the aims of quickly removing rust, removing dead corners, removing burrs, removing oxidation films and the like are fulfilled. The applied magnetic field intensity is small, and no adverse effect is caused to human tissues. By combining the characteristics of magnetic polishing technology and tooth surface polishing, the powder prepared by the invention has good magnetic conductivity, can clean narrow positions such as tooth surfaces, adjacent surface gaps, surface pit gaps and the like in an all-around way under the action of magnetic force to effectively remove irritants on the tooth surfaces and in the teeth, is more suitable for cleaning the tooth surfaces and deep structures in tooth roots, and makes up for the defects of the existing polishing technology.
(6) Compared with the traditional tooth crown polishing technology, the material obtained by the invention is used in the technical field of magnetic control polishing, has the advantages of no loss of health, rapidness, high efficiency, higher cleanliness, low damage degree to teeth and the like, and reduces the polishing time by 50-80%.
Drawings
FIG. 1 is a chart showing the results of hemolysis test on iron-chromium alloy powder coated with a double-layer film of hydroxyapatite/magnesium-iron bimetal oxide prepared in step (5) of example 1;
FIG. 2 is an XRD (X-ray diffraction) spectrum of a surface film layer of the Mg-Fe layered double-metal hydroxide film-coated magnetically conductive alloy powder prepared in the step (2) of example 1;
FIG. 3 is a SEM image of the surface of the Fe-Cr alloy powder coated with the Mg-Fe bimetal hydroxide film prepared in step (2) of example 1;
fig. 4a) and b) are SEM images of the hydroxyapatite/magnesium iron bimetal oxide double-layer film coated iron-chromium alloy powder prepared in the step (5) of example 1, which are magnified by 200 times and 1000 times, respectively;
fig. 5a) and b) are SEM comparison images of the iron-chromium alloy powder coated with the hydroxyapatite/magnesium-iron bimetallic oxide double-layer film prepared in step (5) of example 1 before and after crown polishing, respectively;
FIG. 6 is an SEM photograph of the hydroxyapatite-coated iron-chromium alloy powder obtained in step (4) of comparative example 1.
Detailed Description
Example 1
The preparation method of the iron-chromium alloy powder I coated with the hydroxyapatite/magnesium-iron bimetallic oxide double-layer film comprises the following steps:
(1) taking 5.75g of magnesium nitrate and 3.03g of ferric nitrate as solutes, and measuring 25mL of deionized water as a solvent by using a measuring cylinder to obtain Mg in the solution2+With Fe3+The ion ratio is 3:1, stirring is carried out until the solute is completely dissolved in the solvent, and a solution A is obtained; taking 1.92g of sodium hydroxide and 1.69g of sodium carbonate as solutes, and taking 100mL of deionized water as a solvent by a measuring cylinder, so that OH in the solution-And CO3 2-The ion ratio is 3:1, stirringDissolving the solute in the solvent completely to obtain a solution B; adding the solution B into the solution A, and continuously stirring until the pH value of the mixed solution is 10 to obtain a suspension C;
(2) taking iron-chromium alloy powder, putting the iron-chromium alloy powder into absolute ethyl alcohol for ultrasonic cleaning, putting the iron-chromium alloy powder into a 60 ℃ blast drying oven after the cleaning, and keeping the temperature for 10min to obtain dry and clean iron-chromium alloy powder; putting the dried powder into a hydrothermal reaction kettle, then pouring the suspension C prepared in the step (1) into the reaction kettle, and keeping the temperature at 160 ℃ for 24 hours; taking out the powder after the hydrothermal reaction, washing the powder by using deionized water, and putting the powder into a forced air drying oven at 60 ℃ for 10min to obtain dry iron-chromium alloy powder with a magnesium-iron layered double hydroxide intermediate layer;
(3) respectively taking 7.88g of calcium nitrate and 1.42g of phosphorus pentoxide as solutes, taking 30mL of absolute ethanol as a solvent, and stirring for 30min to obtain a 1.113mol/L calcium nitrate ethanol solution and a 0.333mol/L phosphorus pentoxide ethanol solution; slowly dropping a precursor solution containing P into the precursor solution containing Ca according to the molar ratio of Ca/P of 1.67, dropping ammonia water in the process, adjusting the pH value of the sol to 10, stirring for 30min, taking out, standing and aging for 24h to obtain hydroxyapatite gel;
(4) slowly dripping the hydroxyapatite gel obtained in the step (3) into the iron-chromium alloy powder coated by the magnesium-iron layered double hydroxide intermediate layer prepared in the step (2), and performing ultrasonic dispersion for 10min to ensure that the powder is fully contacted with the gel to obtain hydroxyapatite gel/magnesium-iron layered double hydroxide coated iron-chromium alloy powder;
(5) and (4) putting the product obtained in the step (4) into a heat treatment furnace for sintering, heating the heat treatment furnace to 550 ℃ at the heating rate of 4 ℃/min, preserving the heat for 2 hours, and cooling along with the furnace to obtain the iron-chromium alloy powder I coated with the hydroxyapatite/magnesium-iron double-metal oxide double-layer film.
FIG. 1 shows the results of a hemolysis assay. A is a hemolysis control group, wherein Triton-X100 is a control reagent and can dissolve lipid, the solution of the group A is clear and red, no erythrocyte residue is left at the bottom of a test tube, and the test tube is fully hemolyzed; and B is the iron-chromium alloy powder I coated by the hydroxyapatite/magnesium-iron double metal oxide (HAp/LDO) double-layer film obtained in the step (5) of the example 1, the solution is colorless and transparent, and erythrocytes are deposited at the bottom of the test tube without hemolysis. The iron-chromium alloy powder i coated with the hydroxyapatite/magnesium-iron bimetallic oxide double-layer film obtained in the embodiment 1 is nontoxic and has good biocompatibility.
Fig. 2 is an XRD spectrum of the surface film layer of the magnetic alloy powder coated with the magnesium-iron layered double hydroxide (Mg-Fe LDH) film prepared in step (2) of example 1, and the characteristic peaks (003) and (006) in the XRD spectrum are consistent with those of the layered double hydroxide, indicating that the magnesium-iron layered double hydroxide layer is formed on the powder substrate.
Fig. 3 is an SEM image of the surface of the ferrochrome powder coated with the mg-fe layered double hydroxide film prepared in step (2) of example 1, in which it can be clearly seen that a film layer with a lamellar structure grows on the ferrochrome surface, which shows the morphological characteristics of the layered double hydroxide, and the film layer is compact and complete, has no cracks, no pores, etc., and is tightly bonded to the substrate.
Fig. 4 is an SEM image of the iron-chromium alloy powder i coated with the hydroxyapatite/magnesium-iron bimetallic oxide double-layer film prepared in step (5) of example 1, and it can be seen from fig. 4a) that the iron-chromium alloy powder particles with the composite film layer are round and spherical, uniformly dispersed, and have a narrow size distribution; and FIG. 4b) is a partial enlarged view of FIG. 4a), wherein the particle diameter is 50-125 μm, and the outer surface of the particle is coated with a complete, compact and defect-free hydroxyapatite/magnesium-iron bimetallic oxide composite film.
Example 2
The preparation method of the iron-chromium alloy powder II coated with the hydroxyapatite/magnesium-iron bimetallic oxide double-layer film comprises the following steps:
(1) taking 3.04g of magnesium chloride and 2.03g of ferric chloride as solutes, and measuring 25mL of deionized water as a solvent by using a measuring cylinder to obtain Mg in the solution2+With Fe3+The ion ratio is 2:1, stirring is carried out until the solute is completely dissolved in the solvent, and a solution A is obtained; taking 1.92g of sodium hydroxide and 1.69g of sodium carbonate as solutes, and taking 100mL of deionized water as a solvent by a measuring cylinder, so that OH in the solution-And CO3 2-The ion ratio is 3:1, and stirring is carried out until the solute is completely dissolvedDissolving in solvent to obtain solution B; adding the solution B into the solution A, and continuously stirring until the pH value of the mixed solution is 10 to obtain a suspension C;
(2) taking iron-chromium alloy powder, putting the iron-chromium alloy powder into absolute ethyl alcohol for ultrasonic cleaning, putting the iron-chromium alloy powder into a 60 ℃ blast drying oven after the cleaning, and keeping the temperature for 10min to obtain dry and clean iron-chromium alloy powder; putting the dried powder into a hydrothermal reaction kettle, then pouring the suspension C prepared in the step (1) into the reaction kettle, and keeping the temperature at 160 ℃ for 24 hours; taking out the powder after the hydrothermal reaction, washing the powder by using deionized water, and putting the powder into a forced air drying oven at 60 ℃ for 10min to obtain dry iron-chromium alloy powder with a magnesium-iron layered double hydroxide intermediate layer;
(3) respectively taking 5.91g of calcium nitrate and 1.065g of phosphorus pentoxide as solutes and 30mL of absolute ethanol as a solvent, and stirring for 30min to obtain 0.835mol/L calcium nitrate ethanol solution and 0.25mol/L phosphorus pentoxide ethanol solution; slowly dropping a precursor solution containing P into the precursor solution containing Ca according to the molar ratio of Ca/P of 1.67, dropping ammonia water in the process, adjusting the pH value of the sol to 10, stirring for 30min, taking out, standing and aging for 24h to obtain hydroxyapatite gel;
(4) slowly dripping the hydroxyapatite gel obtained in the step (3) into the iron-chromium alloy powder coated by the magnesium-iron layered double hydroxide intermediate layer prepared in the step (2), and performing ultrasonic dispersion for 10min to ensure that the powder is fully contacted with the gel to obtain hydroxyapatite gel/magnesium-iron layered double hydroxide coated iron-chromium alloy powder;
(5) and (4) putting the product obtained in the step (4) into a heat treatment furnace for sintering, heating the heat treatment furnace to 600 ℃ at the heating rate of 4 ℃/min, preserving the heat for 2h, and cooling along with the furnace to obtain the iron-chromium alloy powder II coated with the hydroxyapatite/magnesium-iron double-metal oxide double-layer film.
Example 3
The preparation method of the iron-nickel alloy powder III coated by the hydroxyapatite/magnesium-iron bimetallic oxide double-layer film comprises the following steps:
(1) taking 5.75g of magnesium nitrate and 3.03g of ferric nitrate as solutes, and measuring 25mL of deionized water as a solvent by using a measuring cylinder to obtain Mg in the solution2+With Fe3+The ion ratio is 3:1, stirring is carried out until the solute is completely dissolved in the solvent, and a solution A is obtained; 2.8g of potassium hydroxide and 3.46g of potassium carbonate were taken as solutes, and 100mL of deionized water was taken as a solvent in a measuring cylinder, so that OH in the solution was brought about-And CO3 2-The ion ratio is 1:1, stirring is carried out until the solute is completely dissolved in the solvent, and a solution B is obtained; adding the solution B into the solution A, and continuously stirring until the pH value of the mixed solution is 9 to obtain a suspension C;
(2) taking iron-nickel alloy powder, putting the iron-nickel alloy powder into absolute ethyl alcohol for ultrasonic cleaning, putting the iron-nickel alloy powder into a 60 ℃ blast drying oven after the cleaning, and keeping the temperature for 10min to obtain dry and clean iron-nickel alloy powder; putting the dried powder into a hydrothermal reaction kettle, then pouring the suspension C prepared in the step (1) into the reaction kettle, and keeping the temperature at 160 ℃ for 24 hours; taking out the powder after the hydrothermal reaction, washing the powder by using deionized water, and putting the powder into a 60 ℃ forced air drying oven for 10min to obtain dry iron-nickel alloy powder with a magnesium-iron layered double hydroxide intermediate layer;
(3) respectively taking 3.94g of calcium nitrate and 0.71g of phosphorus pentoxide as solutes and 30mL of absolute ethanol as a solvent, and stirring for 30min to obtain 0.557mol/L of calcium nitrate ethanol solution and 0.165mol/L of phosphorus pentoxide ethanol solution; slowly dropping a precursor solution containing P into the precursor solution containing Ca according to the molar ratio of Ca/P of 1.67, dropping ammonia water in the process, adjusting the pH value of the sol to 10, stirring for 30min, taking out, standing and aging for 24h to obtain hydroxyapatite gel;
(4) slowly dripping the hydroxyapatite gel obtained in the step (3) into the iron-nickel alloy powder coated by the magnesium-iron layered double hydroxide intermediate layer prepared in the step (2), and performing ultrasonic dispersion for 10min to ensure that the powder is fully contacted with the gel to obtain the iron-nickel alloy powder coated by the hydroxyapatite gel/magnesium-iron layered double hydroxide;
(5) and (4) putting the product obtained in the step (4) into a heat treatment furnace for sintering, heating the heat treatment furnace to 600 ℃ at the heating rate of 6 ℃/min, preserving the heat for 2h, and cooling along with the furnace to obtain the iron-nickel alloy powder III coated with the hydroxyapatite/magnesium-iron double-metal oxide double-layer film.
Example 4
The preparation method of the iron-chromium alloy powder IV coated with the hydroxyapatite/magnesium-iron bimetallic oxide double-layer film comprises the following steps:
(1) 11.07g of magnesium sulfate and 3.81g of ferric sulfate are taken as solutes, and 25mL of deionized water is taken as a solvent by a measuring cylinder, so that Mg is contained in the solution2+With Fe3+The ion ratio is 6:1, and stirring is carried out until the solute is completely dissolved in the solvent, so as to obtain a solution A; 8.4g of potassium hydroxide and 3.46g of potassium carbonate were taken as solutes, and 100mL of deionized water was taken as a solvent by a measuring cylinder, so that OH in the solution was brought about-And CO3 2-The ion ratio is 3:1, and stirring is carried out until the solute is completely dissolved in the solvent, so as to obtain a solution B; adding the solution B into the solution A, and continuously stirring until the pH value of the mixed solution is 11 to obtain a suspension C;
(2) taking iron-chromium alloy powder, putting the iron-chromium alloy powder into absolute ethyl alcohol for ultrasonic cleaning, putting the iron-chromium alloy powder into a 60 ℃ blast drying oven after the cleaning, and keeping the temperature for 10min to obtain dry and clean iron-chromium alloy powder; putting the dried powder into a hydrothermal reaction kettle, then pouring the suspension C prepared in the step (1) into the reaction kettle, and keeping the temperature at 160 ℃ for 24 hours; taking out the powder after the hydrothermal reaction, washing the powder by using deionized water, and putting the powder into a forced air drying oven at 60 ℃ for 10min to obtain dry iron-chromium alloy powder with a magnesium-iron layered double hydroxide intermediate layer;
(3) respectively taking 1.97g of calcium nitrate and 0.355g of phosphorus pentoxide as solutes and 30mL of absolute ethanol as a solvent, and stirring for 30min to obtain 0.278mol/L calcium nitrate ethanol solution and 0.083mol/L phosphorus pentoxide ethanol solution; slowly dropping a precursor solution containing P into the precursor solution containing Ca according to the molar ratio of Ca/P of 1.67, dropping ammonia water in the process, adjusting the pH value of the sol to 10, stirring for 30min, taking out, standing and aging for 24h to obtain hydroxyapatite gel;
(4) slowly dripping the hydroxyapatite gel obtained in the step (3) into the iron-chromium alloy powder coated by the magnesium-iron layered double hydroxide intermediate layer prepared in the step (2), and performing ultrasonic dispersion for 10min to ensure that the powder is fully contacted with the gel to obtain hydroxyapatite gel/magnesium-iron layered double hydroxide coated iron-chromium alloy powder;
(5) and (4) putting the product obtained in the step (4) into a heat treatment furnace for sintering, heating the heat treatment furnace to 550 ℃ at the heating rate of 4 ℃/min, preserving the heat for 4h, and cooling along with the furnace to obtain the iron-chromium alloy powder IV coated with the hydroxyapatite/magnesium-iron double-metal oxide double-layer film.
Example 5
And (3) coating iron-chromium alloy powder I, II, III and IV by using part of the hydroxyapatite/magnesium-iron bimetal oxide double-layer films prepared in the embodiments 1, 2, 3 and 4 respectively, placing the iron-chromium alloy powder I, II, III and IV in a magnetic control device, and carrying out a tooth crown polishing experiment. Under the action of a magnetic field, the iron-chromium alloy powder coated by the hydroxyapatite/magnesium-iron bimetal oxide double-layer film and the tooth crown generate relative motion, and the tooth crown is polished.
Compared with the prior art, the time consumption of the hydroxyapatite/magnesium-iron bimetal oxide double-layer film coated iron-chromium alloy powder obtained by the invention for tooth magnetic control polishing is reduced by 50-80%, wherein the time consumption of the hydroxyapatite/magnesium-iron bimetal oxide double-layer film coated iron-chromium alloy powder I prepared in the example 1 is reduced by about 80% when being used for magnetic control polishing compared with the prior polishing technology, and the time consumption of the hydroxyapatite/magnesium-iron bimetal oxide double-layer film coated iron-chromium alloy powder IV prepared in the example 4 is reduced by about 50% when being used for magnetic control polishing compared with the prior polishing technology.
Fig. 5 is SEM images of the iron-chromium alloy powder i coated with the hydroxyapatite/magnesium-iron double metal oxide double layer film of example 1 before and after tooth surface polishing. FIG. 5a) is an SEM image of a crown before polishing, in which it can be seen that the crown surface is rough, thus illustrating the attachment of a large amount of contaminants to the surface of the crown of a sample tooth; fig. 5b) is an SEM image obtained after the tooth crown is polished by coating the iron-chromium alloy powder i with the hydroxyapatite/magnesium-iron bimetal oxide double-layer film according to example 1, and it can be seen from the SEM image that the tooth crown after polishing has a smooth surface, no obvious scratches, and a good polishing effect.
Comparative example 1
(1) Respectively taking 7.88g of calcium nitrate and 1.42g of phosphorus pentoxide as solutes, taking 30mL of absolute ethanol as a solvent, and stirring for 30min to obtain a 1.113mol/L calcium nitrate ethanol solution and a 0.333mol/L phosphorus pentoxide ethanol solution; slowly dropping a precursor solution containing P into the precursor solution containing Ca according to the molar ratio of Ca/P of 1.67, dropping ammonia water in the process, adjusting the pH value of the sol to 10, stirring for 30min, taking out, standing and aging for 24h to obtain hydroxyapatite gel;
(2) taking iron-chromium alloy powder, putting the iron-chromium alloy powder into absolute ethyl alcohol for ultrasonic cleaning, putting the iron-chromium alloy powder into a 60 ℃ blast drying oven after the cleaning, and keeping the temperature for 10min to obtain dry and clean iron-chromium alloy powder;
(3) slowly dripping the gel obtained in the step (1) into the iron-chromium alloy powder cleaned and dried in the step (2) until the gel is just immersed, and performing ultrasonic dispersion for 10min to ensure that the powder is fully contacted with the gel to obtain iron-chromium alloy powder wrapped by hydroxyapatite gel;
(4) and (4) putting the product obtained in the step (3) into a heat treatment furnace for sintering, heating the heat treatment furnace to 550 ℃ at the heating rate of 4 ℃/min, preserving the heat for 2 hours, and cooling along with the furnace to obtain the hydroxyapatite-coated iron-chromium alloy powder.
Fig. 6 is an SEM image of the hydroxyapatite-coated iron-chromium alloy powder of comparative example 1, and it can be seen that there is a significant crack and a peeling phenomenon in a partial region of the film layer on the base alloy powder. Fig. 4a) and b) of the hydroxyapatite/magnesium-iron bimetal oxide composite film layer obtained in example 1 show that the iron-chromium alloy powder coated with the hydroxyapatite/magnesium-iron bimetal oxide composite film layer obtained in example 1 has the advantages of complete structure, no damage and excellent mechanical properties.
To sum up: compared with the prior art, the composite material has the following advantages by optimizing the components and the synergistic effect of the process: the composite material has the advantages of good mechanical property, good biocompatibility, no toxicity, no side effect, good magnetic permeability, close interlayer combination of composite material layers, spherical powder, uniform dispersion and narrow size distribution, and can better clean dirt in tooth gaps under the action of a magnetic field when the composite material is used for cleaning teeth. The close combination of the composite material layers can prevent the material from brittle fracture or falling off when cleaning teeth, and simultaneously accelerate the speed of cleaning teeth (compared with the prior art, the time consumption can be reduced by about 50-80 percent), reduce the pain in the cleaning process and be suitable for industrialized production.
Claims (6)
1. A novel magnetic conductive alloy powder coated by a double-layer film is characterized by being prepared by the following method steps:
(1) taking soluble magnesium salt and soluble ferric salt as solutes and deionized water as a solvent, stirring until the solutes are completely dissolved in the solvent to obtain a solution A, wherein Mg in the solution A2+With Fe3+The ion molar ratio is 2-6: 1; using soluble alkali and soluble carbonate or bicarbonate as solutes and deionized water as a solvent, stirring until the solutes are completely dissolved in the solvent to obtain a solution B, wherein OH in the solution B-And CO3 2-The ion molar ratio is 1-3: 1; adding the solution B into the solution A, and continuously stirring to obtain a suspension C, wherein the pH value of the solution is 9.0-11.5;
(2) putting the magnetic conductive alloy powder into absolute ethyl alcohol for ultrasonic cleaning, drying and preserving heat for 10-30 min at 60-100 ℃ after cleaning to obtain dry and clean magnetic conductive alloy powder, putting the dry powder into a hydrothermal reaction kettle, adding the suspension C obtained in the step (1) into the reaction kettle, preserving heat for 12-24 h at 120-160 ℃ to obtain powder after hydrothermal reaction, cleaning with deionized water, and drying for 10-30 min at 60-100 ℃ to obtain magnetic conductive alloy powder coated with magnesium-iron layered double hydroxides;
(3) respectively dissolving soluble calcium salt and phosphorus pentoxide in absolute ethyl alcohol, stirring for 10-30 min to obtain precursor solutions containing Ca and P, wherein the molar ratio of Ca to P in the two solutions is 1.67, slowly dripping the precursor solution containing P into the precursor solution containing Ca, simultaneously dripping ammonia water, adjusting the pH value of the solution to 9.0-11.5, stirring for 10-30 min, standing and aging for 24-48 h to obtain hydroxyapatite gel;
(4) adding the hydroxyapatite gel obtained in the step (3) into the magnetic conductive alloy powder coated by the magnesium-iron layered double hydroxide obtained in the step (2), and performing ultrasonic dispersion for 10-30 min to obtain hydroxyapatite gel/magnesium-iron layered double hydroxide coated magnetic conductive alloy powder;
(5) and (3) putting the magnetic conductive alloy powder coated by the hydroxyapatite gel/the magnesium-iron layered double-metal hydroxide obtained in the step (4) into a heat treatment furnace for sintering, heating to 500-650 ℃ at a heating rate of 4-6 ℃/min, preserving heat for 2-4 h, and cooling to obtain novel double-layer film coated magnetic conductive alloy powder, wherein the novel double-layer film coated magnetic conductive alloy powder is the magnetic conductive alloy powder coated by the hydroxyapatite/magnesium-iron layered double-metal hydroxide.
2. The novel double-layer film coated magnetically conductive alloy powder according to claim 1, wherein the soluble magnesium salt in step (1) is any combination of magnesium nitrate, magnesium chloride or magnesium sulfate, and the soluble ferric salt is any combination of ferric nitrate, ferric chloride or ferric sulfate.
3. The novel double-layer film coated magnetically conductive alloy powder of claim 1, wherein the soluble alkali in step (1) is any combination of sodium hydroxide or potassium hydroxide, the soluble carbonate is any combination of sodium carbonate or potassium carbonate, and the bicarbonate is any combination of sodium bicarbonate or potassium bicarbonate.
4. The novel double-layer film-coated magnetic conductive alloy powder according to claim 1, wherein the magnetic conductive alloy powder in the step (2) is any combination of iron-chromium alloy, iron-nickel alloy or iron-cobalt alloy.
5. The novel double-layer film coated magnetically conductive alloy powder of claim 1, wherein the soluble calcium salt in step (3) is any combination of calcium nitrate, calcium chloride or calcium sulfate.
6. The application of the novel double-layer film coated magnetic conductive alloy powder in the field of tooth surface cleaning materials is characterized in that under the action of a magnetic field, the double-layer film coated magnetic conductive alloy powder and a tooth crown generate relative motion to polish the tooth crown, and the powder can clean and polish the adjacent surface gap between the tooth surface and a tooth body and the pit and groove point gap on the tooth surface, so that teeth can be effectively cleaned and plaque can be removed.
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