CN110818403B - Method for preparing transparent calcium phosphate biological ceramic by atmosphere protection and normal pressure sintering - Google Patents
Method for preparing transparent calcium phosphate biological ceramic by atmosphere protection and normal pressure sintering Download PDFInfo
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- CN110818403B CN110818403B CN201810907431.4A CN201810907431A CN110818403B CN 110818403 B CN110818403 B CN 110818403B CN 201810907431 A CN201810907431 A CN 201810907431A CN 110818403 B CN110818403 B CN 110818403B
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 title claims abstract description 145
- 238000005245 sintering Methods 0.000 title claims abstract description 102
- 229910000389 calcium phosphate Inorganic materials 0.000 title claims abstract description 71
- 239000001506 calcium phosphate Substances 0.000 title claims abstract description 71
- 235000011010 calcium phosphates Nutrition 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000000919 ceramic Substances 0.000 title claims abstract description 19
- 239000012298 atmosphere Substances 0.000 title claims abstract description 16
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 86
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 82
- 239000003462 bioceramic Substances 0.000 claims abstract description 62
- 239000000843 powder Substances 0.000 claims abstract description 46
- 238000002834 transmittance Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- 238000000498 ball milling Methods 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 31
- 238000000465 moulding Methods 0.000 claims description 20
- 238000009694 cold isostatic pressing Methods 0.000 claims description 18
- 238000004537 pulping Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000007921 spray Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 238000005238 degreasing Methods 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000003754 machining Methods 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 230000002572 peristaltic effect Effects 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 238000005056 compaction Methods 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 8
- 238000010923 batch production Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 210000003074 dental pulp Anatomy 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 238000005452 bending Methods 0.000 description 13
- 238000005507 spraying Methods 0.000 description 11
- 239000011148 porous material Substances 0.000 description 8
- 238000001513 hot isostatic pressing Methods 0.000 description 6
- 238000000280 densification Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000009768 microwave sintering Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004068 calcium phosphate ceramic Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000002449 bone cell Anatomy 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 230000024245 cell differentiation Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 230000004663 cell proliferation Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000002188 osteogenic effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
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Abstract
The invention provides a method for preparing transparent calcium phosphate bioceramic by atmosphere protection and normal pressure sintering, belonging to the technical field of biomedical materials. The transparent calcium phosphate biological ceramic with the light transmittance of 50-95% is obtained by taking high-purity nano Hydroxyapatite (HA) and/or high-purity nano beta-tricalcium phosphate (beta-TCP) powder as a raw material, adding no sintering aid, adopting steam protection, and sintering under atmospheric pressure in a sectional and normal pressure manner. The phase composition of the transparent calcium phosphate bioceramic is HA single-phase, beta-TCP single-phase or HA/beta-TCP two-phase mixture. The invention has simple process, small equipment investment and short production period, can meet the requirement of batch production, and the obtained transparent calcium phosphate bioceramic has the relative density of more than 99.5 percent, uniform and fine crystal grains, no impurity phase and higher mechanical strength, can be used as a good base material for observing the interaction of cells and tissues and the calcium phosphate bioceramic, and can also be used in the field of repairing tooth roots, dental pulp, artificial eyes and the like.
Description
Technical Field
The invention relates to the technical field of biomedical materials, in particular to a method for preparing transparent calcium phosphate bioceramic by atmosphere protection and normal pressure sintering.
Background
Hydroxyapatite (HA), beta-tricalcium Phosphate (beta-TCP) and hydroxyapatite/beta-tricalcium Phosphate two-phase composite ceramic (BCP for short) have excellent biocompatibility, can quickly conduct bone cell regeneration, can be directly bonded with bones without an intermediate medium, serve as a good biological hard tissue filling, repairing and replacing material, and are widely applied in clinic.
When the calcium phosphate bioceramic with certain light transmittance is used as a cell culture substrate, the biological properties of cell growth, proliferation, differentiation and the like can be directly observed in real time by using a transmission optical microscope without dyeing cells, and the method has profound significance for evaluating the osteogenic capacity of the calcium phosphate bioceramic implanted in vivo and exploring the interaction mechanism of the cells and the substrate in vitro. Meanwhile, the transparent calcium phosphate biological ceramic has higher mechanical strength and aesthetic property, and can also be used in the field of repairing tooth roots, dental pulp, artificial eyes and the like.
It is well known that when light passes through a medium, the intensity of the light is attenuated by absorption, scattering, refraction, and the like. For transparent ceramics, this attenuation, in addition to being composition-dependent, depends primarily on the microstructure, with grain boundaries and residual porosity being the primary factors affecting light transmission. In general, many pores are formed in the ceramic in the final sintering stage due to rapid growth of crystal grains, and the pores at the grain boundaries can be discharged along with the movement of the grain boundaries, but the closed pores in the crystal are difficult to remove particularly when the closed pores contain phases such as water vapor, nitrogen and carbon. Therefore, since the refractive indexes of the phases at both sides of the pore interface are different, refraction and reflection of light occur, thereby reducing the light transmittance of the ceramic.
In order to satisfy the requirement of minimizing absorption, refraction and scattering of light, in addition to high purity, the inside of the transparent ceramic should be reduced as much as possible in the content of pores, grain boundaries and the relative content of the second phase from the viewpoint of the texture, and should be a single-phase or multi-phase ceramic having close refractive indices of the respective phases. Data show that the refractive indexes of HA and beta-TCP are very close to each other, namely 1.64-1.65 and 1.63, so that the transparent BCP two-phase composite ceramic can be obtained through process control. Meanwhile, in order to improve the light transmittance of the calcium phosphate bioceramic and meet the strength requirement in clinical practical application, further grain refinement while densification is necessary.
In order to achieve the above purpose, at present, the main methods for preparing transparent calcium phosphate ceramics include hot-pressing sintering, hot isostatic pressing sintering, microwave sintering, pulse current sintering and the like. The preparation of pure β -TCP, pure HA, and β -TCP/20 wt% HA (BCP20), β -TCP/40 wt% HA (BCP40), β -TCP/60 wt% HA (BCP60) and β -TCP/80 wt% HA (BCP80) transparent calcium phosphate ceramics was reported in the literature (Processing and properties of biophase calcium carbonate associated by pressurized sintering and hot isostatic pressing, journal of European Ceramic Society 33(2013) 1270) by Michel Descams et al, achieving relative densities greater than 99.9% and phase grain sizes less than 1 micron. However, the method needs to be performed by pre-sintering and then hot isostatic pressing sintering at 1000-1100 ℃ under 150MPa, and Ar-20 vol% O needs to be adopted in the sintering process2The mixed gas protection not only has complex sintering process, but also has large equipment investment, and can not realize batch production. CN1793022 discloses a preparation method of a transparent beta-tricalcium phosphate biological ceramic material, which adopts a discharge plasma sintering technology to obtain compact and transparent beta-tricalcium phosphate biological ceramic, but the sintering process of the method still needs pressure auxiliary sintering. Meanwhile, the method needs a special graphite die, so that the production cost is high, and batch production cannot be realized.
Therefore, the traditional technologies such as hot-pressing sintering, hot isostatic pressing sintering, microwave sintering, pulse current sintering and the like mostly need to be sintered under special conditions such as vacuum, argon and nitrogen atmosphere or electric pulse, pressure assistance, microwave and the like, the operation procedure is complex, the equipment investment and technical requirements are high, batch production cannot be realized, the process difficulty is greatly increased, and the production cost is increased.
Disclosure of Invention
The invention aims to provide a method for preparing transparent calcium phosphate bioceramic by atmosphere protection and normal pressure sintering.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing transparent calcium phosphate bioceramic through atmosphere protection and normal pressure sintering is characterized in that high-purity nano hydroxyapatite and/or high-purity nano beta-tricalcium phosphate powder is used as a raw material, the transparent calcium phosphate bioceramic with the light transmittance of 50-95% is obtained through segmented high-temperature normal pressure sintering, and water vapor protection can be selected in the sintering process.
As a further improved technical scheme of the invention, the transparent calcium phosphate bioceramic is hydroxyapatite, beta-tricalcium phosphate single-phase or hydroxyapatite/beta-tricalcium phosphate two-phase composite ceramic.
As a further improved technical scheme of the invention, the relative density of the transparent calcium phosphate bioceramic is more than 99.5%, and the grain size of each phase is less than 10 μm.
As a further improved technical scheme of the invention, the method comprises the following steps:
s1, weighing high-purity nano hydroxyapatite and/or high-purity nano beta-tricalcium phosphate powder according to different proportions of two phases of hydroxyapatite and beta-tricalcium phosphate, mixing, ball-milling, pulping, and spray granulating;
s2, filling the granulated powder into a die, performing prepressing molding by using a dry press, and then performing cold isostatic pressing to obtain a blank body, wherein the relative density of the blank body is more than 55%;
s3, placing the blank in an electric furnace for sectional sintering, and optionally slowly injecting deionized water into the hearth by using a peristaltic pump to sinter the blank in a high-temperature water vapor environment;
and S4, performing surface grinding and polishing machining treatment on the sintered transparent calcium phosphate bioceramic.
As a further improved technical scheme of the invention, the purity of the high-purity nano hydroxyapatite and the high-purity nano beta-tricalcium phosphate powder is more than 99.9 percent, and the grain size of each powder is 10-300 nm.
As a further improved technical scheme of the present invention, in step S1, the high purity nano hydroxyapatite and/or high purity nano β -tricalcium phosphate powder is subjected to ball milling after mixing, adding a proper amount of dispersant and defoaming agent, using zirconia balls as a ball milling medium, using ethanol or deionized water as a ball milling solvent, and the mass ratio of the mixed powder, the ball milling medium and the ball milling solvent is 1: 1-5: 1-3, the rotating speed of the ball mill is 100-400 r/min, and the ball milling time is 1-10 hours.
As a further improved technical scheme of the invention, after the high-purity nano-hydroxyapatite and/or high-purity nano-beta-tricalcium phosphate powder in the step S1 is mixed, ball-milled and pulped, the microspheres with the diameter of 10-200 microns are obtained through spray granulation.
As a further improved technical scheme of the invention, the pressure of the pre-pressing molding in the step S2 is 20-50 MPa, and the pressure of the cold isostatic pressing molding is 100-350 MPa.
As a further improved technical scheme, in the step S3, firstly, the temperature is raised to 350-650 ℃ at the speed of 1-5 ℃/min, the temperature is kept for 1-10 h for degreasing, and then two-stage sintering is carried out, wherein the first-stage sintering temperature is 750-1250 ℃, and the temperature keeping time is 0.1-30 h; and then heating or cooling for second-stage sintering, wherein the sintering temperature is 750-1300 ℃, the heat preservation time is 0.1-30 h, then the temperature is controlled to be 600 ℃, and then the material is naturally cooled to the room temperature, the heating rate before the two-stage sintering is 10-500 ℃/min, and the cooling rate is controlled to be 1-50 ℃/min.
As a further improved technical scheme of the invention, in step S3, when the temperature of the hearth rises to 700 ℃, deionized water is continuously injected into the furnace, the injection rate is 0-10 ml/min, and after the heat preservation is finished, the injection of the deionized water is stopped when the temperature of the hearth drops to 600 ℃.
Compared with the prior art, the invention has the technical effects that:
(1) the adoption of steam for protection sintering not only is more beneficial to removing closed pores in the crystal, but also can avoid the decomposition of hydroxyapatite and the formation of impurity phases;
(2) no sintering aid is added, no impurity pollution is caused, and the sintering process does not need special conditions (vacuum environment, high pressure or special gas and special equipment) requirements;
(3) the obtained transparent calcium phosphate biological ceramic has the light transmittance of 50-95%, the grain size of each phase is less than 10 mu m, the bending strength is not lower than 125MPa, and the requirement of clinical surgical implantation can be met.
(4) The process is simple, the equipment investment is small, the production period is short, and the requirement of batch production can be met;
drawings
FIG. 1 is a schematic flow chart of a method for preparing a transparent calcium phosphate bioceramic by atmosphere protection and atmospheric pressure sintering according to an embodiment of the present invention;
FIG. 2 is an X-ray diffraction spectrum of a transparent calcium phosphate bioceramic.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments shown in the drawings. These embodiments are not intended to limit the present invention, and variations in formulation, phase composition, organization, method, or function, which may be made by one of ordinary skill in the art according to these embodiments, are within the scope of the invention.
It is well known that densification is critical to increase the transparency of calcium phosphate bioceramics by reducing light scattering, since calcium phosphate is inherently non-absorbing to visible light. The transparent calcium phosphate bioceramic (HA, beta-TCP or BCP) adopts special sintering technologies such as hot-pressing sintering, microwave sintering, hot isostatic pressing sintering, pulse current sintering and the like, and aims to reduce the sintering temperature (lower than 1100 ℃) and realize densification while refining grains; another important objective is to prevent the decomposition reaction of calcium phosphate at too high sintering temperature to form a heterogeneous phase, the decomposition reaction principle is:
Ca10(PO4)6(OH)2→3β-Ca3(PO4)2+CaO+H2o (decomposing water vapor)
According to the method for preparing the transparent calcium phosphate biological ceramic by atmosphere protection and normal pressure sintering, provided by the invention, the calcium phosphate biological ceramic with better transparency can be obtained by high-temperature normal pressure segmented sintering at 750-1300 ℃ under the condition of water vapor. In comparison, although the highest temperature of the segmented sintering is higher than the sintering temperature adopted by special technologies such as hot-pressing sintering, microwave sintering, hot isostatic pressing sintering, pulse current sintering and the like, the hydroxyapatite is ensured not to be decomposed even at a higher sintering temperature due to the introduction of the water vapor protection. Meanwhile, the high-temperature sintering is carried out under the condition of water vapor, so that the water vapor in the closed pores in the crystal easily enters HA crystal lattices, and the shrinkage and densification of the micropores in the crystal are facilitated. And secondly, the method for preparing the transparent calcium phosphate bioceramic through atmosphere protection and normal pressure sintering further adopts 750-1300 ℃ sectional sintering, and can realize densification and further refinement of crystal grains of each phase by controlling the first-stage sintering temperature and the second-stage sintering temperature and time. Therefore, the method for preparing the transparent calcium phosphate bioceramic through atmosphere protection and normal pressure sintering, provided by the invention, has a positive effect of simultaneously improving the biocompatibility, strength and light transmittance of the calcium phosphate bioceramic.
Referring to fig. 1 to 2, a method for preparing transparent calcium phosphate bioceramic by atmosphere protection and normal pressure sintering is provided, which comprises the steps of taking high-purity nano hydroxyapatite and/or high-purity nano beta-tricalcium phosphate powder as a raw material, sintering at high temperature and normal pressure in a segmented manner to obtain the transparent calcium phosphate bioceramic with the light transmittance of 50-95%, and optionally carrying out steam protection in the sintering process.
Further, the transparent calcium phosphate bioceramic is hydroxyapatite, beta-tricalcium phosphate single-phase or hydroxyapatite/beta-tricalcium phosphate two-phase composite ceramic.
Further, the transparent calcium phosphate bioceramic has a relative density of more than 99.5% and a grain size of each phase of less than 10 μm.
Further, the method comprises the following steps:
s1, weighing high-purity nano hydroxyapatite and/or high-purity nano beta-tricalcium phosphate powder according to different proportions of two phases of hydroxyapatite and beta-tricalcium phosphate, mixing, ball-milling, pulping, and spray granulating;
s2, filling the granulated powder into a die, performing prepressing molding by using a dry press, and then performing cold isostatic pressing to obtain a blank body, wherein the relative density of the blank body is more than 55%;
s3, placing the blank in an electric furnace for sectional sintering, and optionally slowly injecting deionized water into the hearth by using a peristaltic pump to sinter the blank in a high-temperature water vapor environment;
and S4, performing surface grinding and polishing machining treatment on the sintered transparent calcium phosphate bioceramic.
Furthermore, the purity of the high-purity nano hydroxyapatite and the high-purity nano beta-tricalcium phosphate powder is more than 99.9 percent, and the grain size of each powder is 10-300 nm.
Further, in step S1, the high-purity nano-hydroxyapatite and/or high-purity nano- β -tricalcium phosphate powder is mixed, added with a proper amount of dispersant and defoamer, and then ball-milled, using zirconia balls as ball-milling media, using ethanol or deionized water as ball-milling solvent, wherein the mass ratio of the mixed powder, the ball-milling media and the ball-milling solvent is 1: 1-5: 1-3, the rotating speed of the ball mill is 100-400 r/min, and the ball milling time is 1-10 hours.
Further, after the high-purity nano hydroxyapatite and/or high-purity nano beta-tricalcium phosphate powder is mixed, ball-milled and pulped in the step S1, the microspheres with the diameter of 10-200 microns are obtained through spray granulation.
Further, the pressure of the pre-pressing molding in the step S2 is 20-50 MPa, and the pressure of the cold isostatic pressing molding is 100-350 MPa.
Further, in the step S3, firstly, the temperature is raised to 350-650 ℃ at the speed of 1-5 ℃/min, the temperature is kept for 1-10 hours for degreasing, and then two-stage sintering is carried out, wherein the first-stage sintering temperature is 750-1250 ℃, and the temperature keeping time is 0.1-30 hours; and then heating or cooling for second-stage sintering, wherein the sintering temperature is 750-1300 ℃, the heat preservation time is 0.1-30 h, then the temperature is controlled to be 600 ℃, and then the material is naturally cooled to the room temperature, the heating rate before the two-stage sintering is 10-500 ℃/min, and the cooling rate is controlled to be 1-50 ℃/min.
Further, in step S3, when the temperature of the furnace chamber rises to 700 ℃, continuously injecting deionized water into the furnace at an injection rate of 0-10 ml/min, and after the heat preservation is finished, stopping injecting deionized water when the temperature of the furnace chamber drops to 600 ℃.
Example 1
(100 wt% beta-TCP +0 wt% HA) transparent calcium phosphate bioceramic
Weighing 100 wt% of high-purity nano beta-TCP powder, ball-milling, pulping, spraying, granulating, placing the granulated powder into a die, prepressing for forming under 20MPa, then carrying out cold isostatic pressing for forming under 250MPa, and placing the formed blank into a box-type electric furnace for sintering. The sintering system is as follows: heating to 550 ℃ at the speed of 2 ℃/min, preserving heat for 2 hours, heating to 820 ℃ at the speed of 10 ℃/min, preserving heat for 5 hours, continuously heating to 950 ℃ at the speed of 10 ℃/min, preserving heat for 10 hours, cooling to 600 ℃ at the speed of 2 ℃/min, and naturally cooling to room temperature to prepare the beta-TCP single-phase transparent calcium phosphate bioceramic, wherein the average grain size is 235nm and the relative density is 99.5%. The light transmittance is 95 percent, and the bending strength is 178 MP.
Example 2
(0 wt% beta-TCP +100 wt% HA) transparent calcium phosphate bioceramic
Weighing 100 wt% of high-purity nano HA powder, ball-milling, pulping, spraying and granulating, putting the granulated powder into a die, prepressing and molding at 30MPa, then carrying out cold isostatic pressing at 280MPa, and sintering the molded blank in a box-type electric furnace. The sintering system is as follows: heating to 550 ℃ at the speed of 2 ℃/min, preserving heat for 2 hours, then heating to 700 ℃ at the speed of 15 ℃/min, introducing deionized water at the speed of 5ml/min, then continuously heating to 1000 ℃ at the speed of 15 ℃/min, preserving heat for 5 hours, heating to 1250 ℃ at the speed of 15 ℃/min, preserving heat for 1 hour, finally cooling to 600 ℃ at the speed of 4 ℃/min, stopping introducing the deionized water, and naturally cooling to room temperature to prepare the HA single-phase transparent calcium phosphate bioceramic, wherein the average grain size is 156nm, and the relative density is 99.5%. The light transmittance is 92%, and the bending strength is 125 MP.
Example 3
(10 wt% beta-TCP +90 wt% HA) transparent calcium phosphate bioceramic
Mixing and ball-milling 90 wt% of high-purity nano HA and 10 wt% of high-purity nano beta-TCP powder, pulping, spraying and granulating, putting the granulated powder into a die, prepressing and molding at 40MPa, then carrying out cold isostatic pressing at 300MPa, and sintering the molded blank in a box type electric furnace. The sintering system is as follows: heating to 550 ℃ at the speed of 2 ℃/min, preserving heat for 2 hours, then introducing deionized water at the speed of 4ml/min when heating to 700 ℃ at the speed of 20 ℃/min, continuing heating to 1000 ℃ and preserving heat for 8 hours, then heating to 1250 ℃ at the speed of 15 ℃/min, preserving heat for 4 hours, finally cooling to 600 ℃ at the speed of 3 ℃/min, stopping introducing the deionized water, and naturally cooling to room temperature to prepare the 10 wt% beta-TCP +90 wt% HA two-phase transparent calcium phosphate bioceramic, wherein the average grain size of the beta-TCP phase is 360nm, the average grain size of the HA phase is 260nm, and the relative density is 99.5%. The light transmittance is 90 percent, and the bending strength is 135 MP.
Example 4
(20 wt% beta-TCP +80 wt% HA) transparent calcium phosphate bioceramic
Mixing and ball-milling 80 wt% of high-purity nano HA and 20 wt% of high-purity nano beta-TCP powder, pulping, spraying and granulating, putting the granulated powder into a die, prepressing and molding at 50MPa, then carrying out cold isostatic pressing at 320MPa, and sintering the molded blank in a box type electric furnace. The sintering system is as follows: heating to 550 ℃ at the speed of 3 ℃/min, preserving heat for 5 hours, then introducing deionized water at the speed of 3ml/min when heating to 700 ℃ at the speed of 16 ℃/min, continuing heating to 1000 ℃ and preserving heat for 8 hours, then heating to 1250 ℃ at the speed of 15 ℃/min, preserving heat for 2 hours, finally cooling to 600 ℃ at the speed of 3 ℃/min, stopping introducing the deionized water, and naturally cooling to room temperature to prepare the 20 wt% beta-TCP +80 wt% HA two-phase transparent calcium phosphate bioceramic, wherein the average grain size of the beta-TCP phase is 470nm, the average grain size of the HA phase is 280nm, and the relative density is 99.6%. The light transmittance was 87% and the bending strength was 156 MP.
Example 5
(30 wt% beta-TCP +70 wt% HA) transparent calcium phosphate bioceramic
Mixing and ball-milling 70 wt% of high-purity nano HA and 30 wt% of high-purity nano beta-TCP powder, pulping, spraying and granulating, putting the granulated powder into a die, prepressing and molding at 45MPa, then carrying out cold isostatic pressing at 200MPa, and sintering the molded blank in a box type electric furnace. The sintering system is as follows: heating to 550 ℃ at the speed of 2 ℃/min, preserving heat for 2 hours, then introducing deionized water at the speed of 4ml/min when heating to 700 ℃ at the speed of 12 ℃/min, continuing heating to 950 ℃ and preserving heat for 8 hours, then heating to 1300 ℃ at the speed of 15 ℃/min, preserving heat for 2 hours, finally cooling to 600 ℃ at the speed of 3 ℃/min, stopping introducing the deionized water, and naturally cooling to room temperature to prepare the 30 wt% beta-TCP +70 wt% HA two-phase transparent calcium phosphate bioceramic, wherein the average grain size of the beta-TCP phase is 450nm, the average grain size of the HA phase is 320nm, and the relative density is 99.5%. The light transmittance is 85 percent, and the bending strength is 162 MP.
Example 6
(40 wt% beta-TCP +60 wt% HA) transparent calcium phosphate bioceramic
Mixing and ball-milling 60 wt% of high-purity nano HA and 40 wt% of high-purity nano beta-TCP powder, pulping, spraying and granulating, putting the granulated powder into a die, prepressing and molding at 35MPa, then carrying out cold isostatic pressing at 300MPa, and sintering the molded blank in a box type electric furnace. The sintering system is as follows: heating to 600 ℃ at the speed of 5 ℃/min, keeping the temperature for 3 hours, then heating to 700 ℃ at the speed of 50 ℃/min, introducing deionized water at the speed of 3.5ml/min, continuing heating to 950 ℃ and keeping the temperature for 15 hours, then heating to 1280 ℃ at the speed of 50 ℃/min, keeping the temperature for 2 hours, finally cooling to 600 ℃ at the speed of 3 ℃/min, stopping introducing the deionized water, and naturally cooling to room temperature to prepare 40 wt% of beta-TCP +60 wt% of HA two-phase transparent calcium phosphate bioceramic, wherein the average grain size of the beta-TCP phase is 420nm, the average grain size of the HA phase is 310nm, and the relative density is 99.7%. The light transmittance is 82%, and the bending strength is 165 MP.
Example 7
(50 wt% beta-TCP +50 wt% HA) transparent calcium phosphate bioceramic
Mixing and ball-milling 50 wt% of high-purity nano HA and 50 wt% of high-purity nano beta-TCP powder, then carrying out pulping and spray granulation, putting the granulated powder into a die, carrying out 28MPa pre-pressing molding, then carrying out 290MPa cold isostatic pressing molding, and placing the molded blank into a box type electric furnace for sintering. The sintering system is as follows: heating to 500 ℃ at the speed of 1 ℃/min, keeping the temperature for 10 hours, then heating to 700 ℃ at the speed of 30 ℃/min, introducing deionized water at the speed of 3.0ml/min, continuing heating to 950 ℃ and keeping the temperature for 15 hours, then heating to 1200 ℃ at the speed of 30 ℃/min, keeping the temperature for 2 hours, finally cooling to 600 ℃ at the speed of 3 ℃/min, stopping introducing the deionized water, and naturally cooling to room temperature to prepare the 50 wt% beta-TCP +50 wt% HA two-phase transparent calcium phosphate bioceramic, wherein the average grain size of the beta-TCP phase is 412nm, the average grain size of the HA phase is 253nm, and the relative density is 99.5%. The light transmittance is 80%, and the bending strength is 172 MP.
Example 8
(60 wt% beta-TCP +40 wt% HA) transparent calcium phosphate bioceramic
Mixing and ball-milling 40 wt% of high-purity nano HA and 60 wt% of high-purity nano beta-TCP powder, pulping, spraying and granulating, putting the granulated powder into a die, prepressing and molding at 42MPa, then carrying out cold isostatic pressing at 260MPa, and sintering the molded blank in a box type electric furnace. The sintering system is as follows: heating to 550 ℃ at the speed of 2 ℃/min, preserving heat for 5 hours, then heating to 700 ℃ at the speed of 25 ℃/min, introducing deionized water at the speed of 2.5ml/min, continuing heating to 900 ℃ and preserving heat for 15 hours, then heating to 1180 ℃ at the speed of 25 ℃/min, preserving heat for 8 hours, finally cooling to 600 ℃ at the speed of 3 ℃/min, stopping introducing the deionized water, and naturally cooling to room temperature to prepare 60 wt% beta-TCP +40 wt% HA two-phase transparent calcium phosphate bioceramic, wherein the average grain size of the beta-TCP phase is 353nm, the average grain size of the HA phase is 234nm, and the relative density is 99.6%. The light transmittance is 86 percent, and the bending strength is 175 MP.
Example 9
(70 wt% beta-TCP +30 wt% HA) transparent calcium phosphate bioceramic
Mixing and ball-milling 30 wt% of high-purity nano HA and 70 wt% of high-purity nano beta-TCP powder, pulping, spraying and granulating, putting the granulated powder into a die, pre-pressing and molding at 48MPa, then performing cold isostatic pressing at 310MPa, and sintering the molded blank in a box type electric furnace. The sintering system is as follows: heating to 650 ℃ at the speed of 1 ℃/min, preserving heat for 5 hours, then heating to 700 ℃ at the speed of 30 ℃/min, introducing deionized water at the speed of 2.0ml/min, continuing heating to 800 ℃ and preserving heat for 25 hours, then heating to 1150 ℃ at the speed of 30 ℃/min, preserving heat for 10 hours, finally cooling to 600 ℃ at the speed of 3 ℃/min, stopping introducing the deionized water, and naturally cooling to room temperature to prepare the 70 wt% beta-TCP +30 wt% HA two-phase transparent calcium phosphate bioceramic, wherein the average grain size of the beta-TCP phase is 450nm, the average grain size of the HA phase is 215nm, and the relative density is 99.7%. The light transmittance is 88 percent, and the bending strength is 177 MP.
Example 10
(80 wt% beta-TCP +20 wt% HA) transparent calcium phosphate bioceramic
Mixing and ball-milling 20 wt% of high-purity nano HA and 80 wt% of high-purity nano beta-TCP powder, pulping, spraying and granulating, putting the granulated powder into a die, prepressing and molding at 39MPa, then carrying out cold isostatic pressing at 330MPa, and sintering the molded blank in a box type electric furnace. The sintering system is as follows: heating to 550 ℃ at the speed of 2 ℃/min, preserving heat for 5 hours, then heating to 700 ℃ at the speed of 100 ℃/min, introducing deionized water at the speed of 1.5ml/min, continuing heating to 850 ℃ and preserving heat for 20 hours, then heating to 1200 ℃ at the speed of 100 ℃/min, preserving heat for 2 hours, finally cooling to 600 ℃ at the speed of 3 ℃/min, stopping introducing the deionized water, and naturally cooling to room temperature to prepare the 80 wt% beta-TCP +20 wt% HA two-phase transparent calcium phosphate bioceramic, wherein the average grain size of the beta-TCP phase is 450nm, the average grain size of the HA phase is 365nm, and the relative density is 99.6%. The light transmittance is 90 percent, and the bending strength is 180 MP.
Example 11
(90 wt% beta-TCP +10 wt% HA) transparent calcium phosphate bioceramic
Mixing and ball-milling 10 wt% of high-purity nano HA and 90 wt% of high-purity nano beta-TCP powder, pulping, spraying and granulating, putting the granulated powder into a die, pre-pressing and molding at 44MPa, then performing cold isostatic pressing at 300MPa, and sintering the molded blank in a box type electric furnace. The sintering system is as follows: heating to 550 ℃ at the speed of 2 ℃/min, preserving heat for 8 hours, then heating to 700 ℃ at the speed of 200 ℃/min, namely introducing deionized water at the speed of 1.0ml/min, continuing heating to 750 ℃ and preserving heat for 30 hours, then heating to 1250 ℃ at the speed of 200 ℃/min, preserving heat for 0.5 hours, finally cooling to 600 ℃ at the speed of 3 ℃/min, stopping introducing the deionized water, and naturally cooling to room temperature to prepare the 90 wt% beta-TCP +10 wt% HA two-phase transparent calcium phosphate bioceramic, wherein the average grain size of the beta-TCP phase is 380nm, the average grain size of the HA phase is 220nm, and the relative density is 99.8%. The light transmittance is 95 percent, and the bending strength is 185 MP.
Example 12
(95 wt% beta-TCP +5 wt% HA) transparent calcium phosphate bioceramic
Mixing and ball-milling 5 wt% of high-purity nano HA and 95 wt% of high-purity nano beta-TCP powder, pulping, spraying and granulating, putting the granulated powder into a die, prepressing and molding at 50MPa, then carrying out cold isostatic pressing at 350MPa, and sintering the molded blank in a box type electric furnace. The sintering system is as follows: heating to 650 ℃ at the speed of 1 ℃/min, keeping the temperature for 5 hours, then heating to 700 ℃ at the speed of 300 ℃/min, introducing deionized water at the speed of 0.8ml/min, continuing heating to 1200 ℃, keeping the temperature for 0.1 hour, then cooling to 850 ℃ at the speed of 50 ℃/min, keeping the temperature for 15 hours, finally cooling to 600 ℃ at the speed of 3 ℃/min, stopping introducing the deionized water, and naturally cooling to room temperature to prepare the 95 wt% beta-TCP +5 wt% HA two-phase transparent calcium phosphate bioceramic, wherein the average grain size of the beta-TCP phase is 220nm, the average grain size of the HA phase is 180nm, and the relative density is 99.6%. The light transmittance was 93% and the bending strength was 185 MP.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may be modified or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A method for preparing transparent calcium phosphate bioceramic by atmosphere protection and normal pressure sintering is characterized in that high-purity nano hydroxyapatite or a mixture of the high-purity nano hydroxyapatite and high-purity nano beta-tricalcium phosphate powder is used as a raw material, the transparent calcium phosphate bioceramic with the light transmittance of 80-95% is obtained by segmented high-temperature normal pressure sintering,
the sintering process comprises the steps of firstly heating to 350-650 ℃ at a speed of 1-5 ℃/min, preserving heat for 1-10 hours for degreasing, and then sintering in two sections, wherein the first section sintering temperature is 750-1250 ℃, and the preserving heat time is 0.1-30 hours; then heating or cooling for second-stage sintering, wherein the sintering temperature is 750-1300 ℃, the heat preservation time is 0.1-30 h, then the temperature is controlled to be 600 ℃, and then the material is naturally cooled to the room temperature, the heating rate before the two-stage sintering is 10-500 ℃/min, and the cooling rate is controlled to be 1-50 ℃/min;
and when the temperature of the hearth rises to 700 ℃, continuously injecting deionized water into the furnace, wherein the injection rate is 0-10 ml/min and is not 0, and after the heat preservation is finished, stopping injecting the deionized water when the temperature of the hearth drops to 600 ℃.
2. The method for preparing transparent calcium phosphate bioceramic according to claim 1, wherein the transparent calcium phosphate bioceramic is hydroxyapatite single-phase or hydroxyapatite/β -tricalcium phosphate two-phase composite ceramic.
3. The method for preparing transparent calcium phosphate bioceramic according to claim 1, wherein the transparent calcium phosphate bioceramic has a relative density of more than 99.5% and a grain size of each phase of less than 10 μm.
4. The method for preparing transparent calcium phosphate bioceramic through atmosphere protection and atmospheric pressure sintering according to claim 1, comprising the following steps:
s1, weighing high-purity nano hydroxyapatite and/or high-purity nano beta-tricalcium phosphate powder according to different proportions of two phases of hydroxyapatite and beta-tricalcium phosphate, mixing, ball-milling, pulping, and spray granulating;
s2, filling the granulated powder into a die, performing prepressing molding by using a dry press, and then performing cold isostatic pressing to obtain a blank body, wherein the relative density of the blank body is more than 55%;
s3, placing the blank in an electric furnace for sectional sintering, and slowly injecting deionized water into the hearth by using a peristaltic pump to sinter the blank in a high-temperature water vapor environment;
and S4, performing surface grinding and polishing machining treatment on the sintered transparent calcium phosphate bioceramic.
5. The method for preparing transparent calcium phosphate bioceramic through atmosphere protection and atmospheric pressure sintering according to claim 1 or 4, wherein the purity of the high-purity nano-hydroxyapatite and high-purity nano-beta-tricalcium phosphate powder is greater than 99.9%, and the grain size of each powder is 10-300 nm.
6. The method for preparing transparent calcium phosphate bioceramic through atmosphere protection and normal pressure sintering according to claim 4, wherein in step S1, the high-purity nano-hydroxyapatite and/or high-purity nano-beta-tricalcium phosphate powder is subjected to ball milling after being mixed, added with a proper amount of dispersant and defoaming agent, zirconia balls are used as ball milling media, ethanol or deionized water is used as ball milling solvents, and the mass ratio of the mixed powder to the ball milling media to the ball milling solvents is 1: 1-5: 1-3, the rotating speed of the ball mill is 100-400 r/min, and the ball milling time is 1-10 hours.
7. The method for preparing transparent calcium phosphate bioceramic through atmosphere protection and normal pressure sintering according to claim 4, wherein the microspheres with the diameter of 10-200 microns are obtained through spray granulation after the high-purity nano hydroxyapatite and/or high-purity nano beta-tricalcium phosphate powder is mixed, ball-milled and pulped in the step S1.
8. The method for preparing transparent calcium phosphate bioceramic through atmosphere-protection atmospheric-pressure sintering according to claim 4, wherein the pressure of the pre-compaction molding in the step S2 is 20-50 MPa, and the pressure of the cold isostatic pressing is 100-350 MPa.
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