CN113666753B - Bionic human bone based on digital light processing molding technology and preparation method thereof - Google Patents
Bionic human bone based on digital light processing molding technology and preparation method thereof Download PDFInfo
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- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 66
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 59
- 238000012545 processing Methods 0.000 title claims abstract description 20
- 238000005516 engineering process Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000465 moulding Methods 0.000 title claims description 18
- 239000000919 ceramic Substances 0.000 claims abstract description 75
- 238000005245 sintering Methods 0.000 claims abstract description 43
- 239000007787 solid Substances 0.000 claims abstract description 43
- 238000005238 degreasing Methods 0.000 claims abstract description 30
- 239000007790 solid phase Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000013461 design Methods 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 238000007639 printing Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 21
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 229910010293 ceramic material Inorganic materials 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 239000012071 phase Substances 0.000 claims description 3
- 238000002474 experimental method Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 30
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
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- 239000003519 biomedical and dental material Substances 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
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- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- -1 PPTTA Chemical compound 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
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- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
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Abstract
The invention discloses a bionic human bone based on a digital light processing forming technology and a preparation method thereof, and relates to the technical field of ceramic bionic human bones. The method comprises the following steps: s1, preparing ceramic slurry with gradient solid phase content; s2, printing out green bodies with solid phase contents; s3, degreasing and sintering the blank to obtain ceramic pieces with solid phase content, and measuring the shrinkage rate of each ceramic piece; s4, adjusting the design size of the adjacent layers of ceramic pieces of the reference ceramic piece according to the multi-layer structure model of the bionic human bone by taking the shrinkage rate of the ceramic piece with one solid content as a reference; and S5, printing a blank according to the adjusted bionic human bone model, degreasing and sintering to obtain the bionic human bone. The invention obtains the ceramic piece with gradient solid content and the shrinkage rate in advance, redesigns the dimension of the bionic human bone model, and further prepares the bionic human bone of the gradient material, and the joint surface of each layer in the bionic human bone can not crack and bend, and the porosity and the bending strength in the bionic human bone are in gradient change.
Description
Technical Field
The invention relates to the technical field of ceramic bionic human bones, in particular to a bionic human bone based on a digital light processing molding technology and a preparation method thereof.
Background
Silicon nitride (Si) 3 N 4 ) The ceramic is a high-performance structural ceramic, and has high strength, high hardness, good chemical stability, antifriction and wear resistance. The method is widely applied to the high-end technical fields of aerospace, mechano-electronics, chemical metallurgy and the like. At the same time, scholars research and discover Si 3 N 4 Has good biocompatibility and partial ray permeability. For example: when taking X-ray film, the most clear image is obtained of human skeleton tissue. Bone tissue containing calcium salt is the most dense normal human tissue, and contains calcium element capable of absorbing X-rays in a large amount. As with human bones, various metals can also absorb a great deal of X-raysLeaving its shadow on the photo negative. Many metals are even fully X-ray absorbing. When taking X-ray films, the patient is provided with necklace, coin or metal implant and other metal articles, which can cover the human body structure which the doctor wants to see and influence the examination effect. The high density of metal articles leaves behind large, abnormal images with metallic foreign objects as the core, called metallic artifacts, on the computer reconstructed X-ray projection images. The artifact not only can shade human tissues around the metal, so that the image quality is reduced, but also can form a large-scale position-offset shadow, so that the image cannot be observed at all. Thus Si is 3 N 4 Ceramics are also regarded as novel biomedical materials capable of replacing metal alloys, and have great application potential in the field of repairing or replacing bone defects.
In the field of high-end biomedical applications, biomedical material products are often required to have complex structures and functions. For example: human bone is essentially a heterogeneous structure with pores and young's modulus that gradually change from outside to inside. Therefore, the material with single performance is difficult to prepare the material which is completely similar to human bone in terms of structure and function, and the biomedical material with the structure and performance which is more similar to human body is hopeful to be prepared by using multi-material or gradient material. The ceramic material has the characteristics of high hardness and low toughness, and the traditional process (such as grinding, injection molding and the like) cannot be used for processing complex structural parts or parts with higher geometric curved surfaces. Digital Light Processing (DLP) molding has the characteristics of no mold molding, high automation degree in the molding process, high dimensional accuracy and higher system resolution, is very suitable for manufacturing models or parts with complex structures, and can prepare complex structures according to individual requirements, thereby providing a feasible method for preparing products with complex structures and functions.
The current problem of the gradient material 3D printing ceramic is that stress is generated at the joint surface of adjacent layers due to different degreasing and shrinkage rates after sintering of different layers in the gradient material, so that cracks are generated at the joint surface, and a bending phenomenon occurs. For example: printing Si with 3D 3 N 4 In the preparation of biological ceramic human skeleton, si is required 3 N 4 Porosity of the porous materialSequentially increasing from outside to inside. After being printed by DLP, the shrinkage rate of each layer is inconsistent when degreasing and cofiring due to the gradient layer in the bionic human bone. In order to reduce the mismatch of sintering shrinkage, the shrinkage behavior of the two must be made as close as possible. However, in the case of a fixed composition and particle size of the bionic human bone material, the corresponding adjustment space for the sintering shrinkage is limited.
Disclosure of Invention
The invention aims to solve the technical problems that the composition and the particle size of the bionic human bone gradient ceramic material are fixed, and the sintering shrinkage rates of different layers are mismatched, so that cracks appear on a joint surface and the quality is affected.
In this regard, the invention provides a bionic human bone prepared based on a digital light processing molding technology and a method thereof. The principle is as follows: firstly, testing the linear shrinkage rate of a single solid phase after sintering through experiments; then, when designing the bionic human bone print model, the size of one layer of the adjacent layers is proportionally enlarged or reduced by taking the shrinkage rate of the other layer as a reference, so that the sizes of the two adjacent layers after sintering are consistent.
Specifically, the technical scheme of the invention is as follows:
a bionic human bone preparation method based on digital light processing molding technology comprises the following steps:
s1, preparing ceramic slurry with gradient solid phase content;
s2, printing out green bodies with solid phase contents by adopting a digital light processing molding technology;
s3, degreasing and sintering the blank to obtain ceramic pieces with solid phase content, and measuring the shrinkage rate of each ceramic piece;
s4, adjusting the design size of the adjacent layers of ceramic pieces of the reference ceramic piece according to the multi-layer structure model of the bionic human bone by taking the shrinkage rate of the ceramic piece with one solid content as a reference;
and S5, printing out each layer of green body according to the adjusted bionic human bone model, degreasing and sintering to obtain the bionic human bone.
Specifically, the adjustment mode of S4 is to enlarge or reduce the design size of the adjacent layer ceramic piece.
Further, the solid phase content of the ceramic slurry ranges from 30vol% to 45 vol%.
Further, the ceramic slurry comprises silicon nitride powder, a sintering aid, a silane coupling agent, resin, a photoinitiator and a dispersing agent.
Further, the sintering aid accounts for 5-15 wt% of the sum of the sintering aid and the silicon nitride powder.
Further, the usage amount of the silane coupling agent accounts for 1-3 wt% of the sum of the sintering aid and the silicon nitride powder.
Further, the sintering aid is selected from any two of alumina, yttria, and magnesia.
Further, the silane coupling agent is selected from at least one of KH550, KH560 and KH 570.
Furthermore, the silicon nitride powder is alpha-phase silicon nitride, and the purity is more than 99.8%.
Specifically, when ceramic slurry is prepared, firstly, ball milling is carried out on a sintering aid and silicon nitride powder for 4-8 hours at 320-380r/min by using a planetary ball mill, and then, drying and sieving are carried out; the drying temperature is 50-70deg.C, and the sieving is 80-120 mesh.
Further, the degreasing mode is a combination of vacuum degreasing and air degreasing, and the degreasing is a vacuum and air 2-step degreasing method.
Further, the sintering temperature is 1600-2000 ℃, preferably 1800 ℃.
The invention also provides a bionic human bone made of the gradient ceramic material, and the bionic human bone is prepared by the bionic human bone preparation method based on the digital light processing molding technology.
Compared with the prior art, the invention has the following technical effects:
according to the bionic human bone preparation method based on the digital light processing molding technology, according to the ceramic piece with the gradient solid content and the corresponding shrinkage rate obtained in advance, the design size of the adjacent layer ceramic piece of the reference ceramic piece is adjusted based on the shrinkage rate of the ceramic piece with the solid content, and the bionic human bone model is redesigned to obtain, so that the bionic human bone can be prepared by using the ceramic material with the gradient solid content, cracks and bending do not occur on the joint surface of each layer in the bionic human bone, and the porosity and the bending strength in the bionic human bone are changed in a gradient manner.
Drawings
FIG. 1 is a three-dimensional model of a biomimetic human bone, wherein (a) is a single layer model; (b) a pre-adjusted simulated human bone model; (c) a re-designed bionic human bone model after adjustment;
FIG. 2 is a physical diagram of different embodiments;
FIG. 3 is an SEM image of a ceramic part having different solids contents, wherein (a) is the SEM morphology of the ceramic part having a solids content of 35 vol%; (b) SEM morphology of the ceramic part with a solids content of 38 vol%.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments. It will be apparent that the embodiments described below are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be understood that the terms "comprises" and "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of embodiments of the invention. As used in the specification of the embodiments of the invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The embodiment of the invention provides a bionic human bone preparation method based on a digital light processing molding technology, which comprises the following steps of:
s1, preparing ceramic slurry with gradient solid phase content;
in specific implementation, the ceramic slurry comprises silicon nitride powder, a sintering aid, a silane coupling agent, resin, a photoinitiator and a dispersing agent.
The sintering aid accounts for 8wt% of the sum of the sintering aid and the silicon nitride powder.
The usage amount of the silane coupling agent is 1.5 weight percent of the sum of the sintering aid and the silicon nitride powder.
The sintering aid is selected from the group consisting of a mixture of yttria and magnesia.
The silane coupling agent is selected from KH560.
The silicon nitride powder is alpha-phase silicon nitride with purity more than 99.8%.
The resin is selected from BPA10EODMA, HDDA, PPTTA, n-octanol
In the concrete implementation, when preparing the ceramic slurry, firstly, ball milling the sintering aid and the silicon nitride powder for 6 hours at 350r/min by using a planetary ball mill, fully and uniformly mixing, drying and sieving; the drying temperature is 60 ℃, and the powder is sieved by a 100-mesh sieve.
In a specific implementation, the solid phase content of the ceramic slurry ranges from 30vol% to 45 vol%.
For example, in one embodiment, ceramic slurries having solids contents of 35vol%,38vol%,40vol%,42vol%,45vol% are separately prepared.
S2, printing out green bodies with solid phase contents by adopting a digital light processing molding technology;
in specific implementation, referring to fig. 1, as shown in fig. 1 (a), according to the single-layer printing model of fig. 1 (a), a blank with each solid phase content is printed by using a digital light processing forming technology.
S3, degreasing and sintering the blank to obtain ceramic pieces with solid phase content, and measuring the shrinkage rate of each ceramic piece;
in the concrete implementation, degreasing and sintering the blank to obtain the ceramic piece.
The degreasing mode is a combination of vacuum degreasing and air degreasing, and the degreasing is a vacuum and air 2-step degreasing method.
Sintering the ceramic at 1800 ℃ to obtain ceramic pieces with various solid phase contents.
For example, in one embodiment, a blank printed according to the model shown in fig. 1 (a) is shown in fig. 2 (a); the physical diagram of the blank after degreasing is shown in (b) of fig. 2; the ceramic part physical diagram obtained after sintering is shown in (c) of fig. 2; from the above figures, it is clear that, when a single layer of the model is printed, the sample will not crack or bend after degreasing and sintering for any single solid content sample.
Shrinkage and other properties of each solid content ceramic part were measured and the results are shown in Table 1 below.
TABLE 1 Properties of the ceramic parts with solids content
| Ceramic part numbering | 11 | 12 | 13 | 14 | 15 |
| Solid content | 35vol％ | 38vol％ | 40vol％ | 42vol％ | 45vol％ |
| Shrinkage/% | 25.41 | 24.25 | 23.63 | 21.53 | 20.27 |
| Porosity/% | 28.42 | 26.36 | 25.01 | 23.47 | 21.25 |
| Flexural Strength/MPa | 442.3 | 453.4 | 468.7 | 488.2 | 497.1 |
Wherein, the SEM morphology of the ceramic members 11, 12 with the solid content of 35vol% and 38vol% is shown in (a) and (b) of FIG. 3.
S4, adjusting the design size of the adjacent layers of ceramic pieces of the reference ceramic piece according to the multi-layer structure model of the bionic human bone by taking the shrinkage rate of the ceramic piece with one solid content as a reference;
and S5, printing out each layer of green body according to the adjusted bionic human bone model, degreasing and sintering to obtain the bionic human bone.
For example, in one embodiment, the ceramic part 11 with a solid content of 35vol% is used as a reference ceramic part, and the solid content of the ceramic part of the adjacent layer is 38vol%, and as shown in the results of table 1, the shrinkage of 38vol% of the solid content is smaller, and the design size with 38vol% of the solid content needs to be enlarged, so as to obtain a redesigned bionic human bone model, as shown in fig. 1 (c).
In one embodiment, the ceramic part 12 with a solid content of 38vol% is used as a reference ceramic part, and the solid content of the ceramic part in the adjacent layer is 40vol%, and as shown in the results of table 1, the shrinkage rate of 40vol% of the solid content is smaller, and the design size with the solid content of 40vol% needs to be enlarged, so as to obtain the redesigned bionic human bone model.
In one embodiment, the ceramic piece 13 with a solid content of 40vol% is used as a reference ceramic piece, the solid content of the ceramic piece in the adjacent layer is 42vol%, and according to the results in table 1, the shrinkage rate of the solid content of 42vol% is smaller, and the design size with the solid content of 42vol% needs to be enlarged, so as to obtain the redesigned bionic human bone model.
In one embodiment, the ceramic part 14 with a solid content of 42vol% is used as a reference ceramic part, and the solid content of the ceramic part in the adjacent layer is 45vol%, and as shown in the results of table 1, the shrinkage rate of the solid content of 45vol% is smaller, and the design size with the solid content of 45vol% needs to be enlarged, so as to obtain the redesigned bionic human bone model.
In one embodiment, the redesigned model of the bionic human bone is shown in fig. 1 (c), and the blank printed from this model is shown in fig. 2 (g); the physical diagram of the blank after degreasing is shown in (h) of fig. 2; the ceramic part real object diagram obtained after sintering is shown in (i) of fig. 2; from the above figures, it can be seen that, when a model with a gradient solid content is printed, the shrinkage of the sample with different solid contents is known, so that the dimension of the model with the bionic human bone is redesigned according to the shrinkage, and the sample with the double-layer structure can not crack and bend after degreasing and sintering. Three or more layers of ceramic materials with gradient solid content can be prepared by similar methods.
Comparative example
Preparing gradient bionic human bone with solid content of 42vol% and 45vol%, wherein the sizes of layers in the bionic human bone model are consistent, the model is shown in a figure 1 (b), and the bionic human bone prepared by the model can crack and bend on the joint surfaces with different solid contents after degreasing and sintering, and the figure is shown as (e) and (f) in a figure 2; (e) The degreased physical image, (f) the sintered physical image, and (d) in fig. 2 is a green body physical image printed according to the model of fig. 1 (b). As can be seen from the figure, the silicon nitride solid phase content in each gradient layer is different, and the silicon nitride solid phase content has different linear shrinkage rates in the sintering process, so that stress is generated on the bonding surface of the adjacent layers, cracks appear, and the silicon nitride solid phase layer bends towards the direction with low solid content.
In summary, according to the bionic human bone preparation method based on the digital light processing molding technology, according to the ceramic piece with gradient solid content and the corresponding shrinkage rate obtained in advance, the design size of the adjacent layer ceramic piece of the reference ceramic piece is adjusted based on the shrinkage rate of the ceramic piece with one solid content, and the bionic human bone model is redesigned to obtain, so that the bionic human bone can be prepared by using the ceramic material with the gradient solid content, and the joint surface of each layer in the bionic human bone does not crack or bend, and the porosity and the bending strength in the bionic human bone have the technical effect of gradient change.
In the foregoing embodiments, the descriptions of the embodiments are focused on, and for those portions of one embodiment that are not described in detail, reference may be made to the related descriptions of other embodiments.
While the invention has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions of equivalents may be made and equivalents will be apparent to those skilled in the art without departing from the scope of the invention. Therefore, the protection scope of the invention is subject to the protection scope of the claims.
Claims (4)
1. The bionic human bone preparation method based on the digital light processing forming technology is characterized by comprising the following steps of:
s1, preparing ceramic slurry with gradient solid phase content ranging from 30vol% to 45 vol%;
s2, printing out green bodies with solid phase contents by adopting a digital light processing molding technology;
s3, degreasing and sintering the blank to obtain ceramic pieces with solid phase content, and measuring the shrinkage rate of each ceramic piece;
s4, adjusting the design size of the adjacent layers of ceramic pieces of the reference ceramic piece according to the multi-layer structure model of the bionic human bone by taking the shrinkage rate of the ceramic piece with one solid content as a reference;
s5, printing each layer of green body according to the adjusted bionic human bone model, degreasing and sintering to obtain the bionic human bone;
the principle of adjusting the design size of the adjacent layer ceramic piece is as follows: firstly, testing the linear shrinkage rate of a ceramic piece with single solid content after sintering through experiments; then, when designing the bionic human bone printing model, the size of one layer of the adjacent layers is proportionally enlarged or reduced by taking the shrinkage rate of the other layer as a reference, so that the sizes of the two adjacent layers after sintering are consistent;
the ceramic slurry comprises silicon nitride powder, a sintering aid, a silane coupling agent, resin, a photoinitiator and a dispersing agent; wherein the sintering aid accounts for 5-15 wt% of the total weight of the sintering aid and the silicon nitride powder; the dosage of the silane coupling agent accounts for 1-3 wt percent of the sum of the sintering aid and the silicon nitride powder; the sintering aid is any two selected from aluminum oxide, yttrium oxide and magnesium oxide; the silicon nitride powder is alpha-phase silicon nitride with purity more than 99.8%.
2. The method for preparing a bionic human bone based on digital light processing molding according to claim 1, wherein the silane coupling agent is at least one selected from KH550, KH560 and KH 570.
3. The method for preparing the bionic human bone based on the digital light processing molding technology as claimed in claim 1, wherein the degreasing is a 2-step degreasing method of vacuum degreasing and air degreasing; the temperature during sintering is 1600-2000 ℃.
4. A bionic human bone, characterized in that the material is a gradient ceramic material, and the bionic human bone is prepared by the bionic human bone preparation method based on the digital light processing molding technology as set forth in any one of claims 1-3.
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