CN113999539B - 3D printing composite material with CT imaging effect and preparation method and application thereof - Google Patents

3D printing composite material with CT imaging effect and preparation method and application thereof Download PDF

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CN113999539B
CN113999539B CN202111232839.4A CN202111232839A CN113999539B CN 113999539 B CN113999539 B CN 113999539B CN 202111232839 A CN202111232839 A CN 202111232839A CN 113999539 B CN113999539 B CN 113999539B
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CN113999539A (en
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李开南
李虎
龙涛
胡旭麟
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00Materials specially adapted for additive manufacturing
    • B33Y70/10Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • C08K2003/321Phosphates
    • C08K2003/325Calcium, strontium or barium phosphate
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2203/00Applications
    • C08L2203/02Applications for biomedical use
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    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
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Abstract

The invention discloses a 3D printing composite material with a CT (computed tomography) imaging effect and a preparation method and application thereof. The 3D printing composite material comprises the following components in percentage by mass: 40-70 wt% of photosensitive resin, 5wt% of dispersing agent, 20-50 wt% of hydroxyapatite and 5wt% of titanium dioxide. According to the invention, the printing parameters of the photocuring 3D printer are adjusted, the printing slurry with the CT imaging effect is configured, and the skeleton model and the preoperative guide plate with the CT imaging effect can be printed, so that a doctor can perform preoperative drilling of an orthopedic operation under a CT image, and the success rate of the operation is effectively improved.

Description

3D printing composite material with CT imaging effect and preparation method and application thereof
Technical Field
The invention belongs to the technical field of medical materials, and relates to a 3D printing composite material with a CT (computed tomography) imaging effect, a preparation method thereof and a model making method.
Background
In recent years, 3D printing technology is rapidly developed, and is emerging in the aspect of manufacturing a preoperative guide plate or a preoperative model for orthopedics department, people can establish a 3-dimensional model of the damaged skeleton of a patient through CT slicing technology, and then print the model of the damaged skeleton of the patient through 3D printing technology, and a doctor can design an operation scheme through the model and perform operation exercise under the guidance of CT images, so that an implant can be accurately implanted into the body of the patient, the operation time is shortened, the operation cost is reduced, and the operation risk is reduced, and the 3D printing material with the CT imaging effect is very important under the background.
At present, no team carries out deep research on a 3D printing material for simulating the human skeleton CT imaging effect, scientific researchers only use the inherent image of the material for operation, almost no precedent for improving or researching the imaging effect of the material exists, and the defect of using the material is that the space structure of a model cannot be seen clearly under the CT image, and the positioning accuracy is poor in the process of guiding the placement of a human implant.
Disclosure of Invention
Aiming at the defects and problems of the prior art, the 3D printing composite material with the CT imaging effect, the preparation method thereof and the model manufacturing method are provided, and the problem of poor CT imaging effect of a 3D printing skeleton model is solved.
In order to achieve the purpose, the invention provides the following technical scheme: A3D printing composite material with CT imaging effect comprises the following components in percentage by mass: 40-70 wt% of photosensitive resin, 5wt% of dispersing agent, 20-50 wt% of hydroxyapatite and 5wt% of titanium dioxide.
Preferably, the hydroxyapatite may be replaced with tricalcium phosphate.
Preferably, the hydroxyapatite is a nano-scale hydroxyapatite.
Preferably, the photosensitive resin is a water-washed photosensitive resin having a viscosity of less than 350 mpa.s.
Preferably, the dispersant is polyacrylic acid.
Preferably, the selected mass fraction of the hydroxyapatite is 40wt%, and the selected mass fraction of the photosensitive resin is 50 wt%.
On the other hand, the invention also provides a preparation method of the 3D printing composite material with the CT imaging effect, and the preparation method comprises the following steps:
the weight percentages are as follows: 50wt% of nano-hydroxyapatite, 40wt% of photosensitive resin, 5wt% of polyacrylic acid and 5wt% of titanium dioxide, and the 3D printing composite material has a CT imaging effect;
the materials of the components are put into a planetary ball mill for ball milling to obtain the slurry after ball milling.
On the other hand, the invention also provides a method for manufacturing a model by using the 3D printing composite material with the CT imaging effect, which is characterized by comprising the following steps: the method comprises the following steps:
placing the slurry of the 3D printing composite material with CT imaging effect prepared according to any one of the claims 7-8 into a tank of a photocuring 3D printer;
slicing a pre-designed 3D model by using slicing software, setting the thickness of the slice to be 0.05mm, setting the exposure time to be 3.0 seconds, setting the number of layers of a master plate to be 6, setting the exposure time of the base layer to be 20 seconds, raising the printing platform by 4mm, setting the rising and falling speeds to be 200mm/min, and setting the waiting time to be 2 seconds after stopping;
after the setting is finished, guiding the model into a photocuring 3D printer, and after the slurry is paved on the whole trough, starting the printing model;
and after the model is printed, closing the photocuring 3D printer and taking out the model.
Preferably, the rotation speed of the star ball mill is 300rmp, the ball milling time is 2h, and the star ball mill rotates forwards for 30min and then rotates backwards for 30min for 2 reciprocating cycles.
Preferably, after the model is taken out, the printed model is subjected to a CT test, and a model with an image value of 845-1524Hu under CT is screened out.
Compared with the prior art, the invention has the beneficial effects that:
the 3D printing composite material which can be used for 3D printing of the simulated human skeleton and has the CT imaging effect is simple in formula, scientific in design, simple to prepare and excellent in CT imaging effect. According to the invention, the printing parameters of the photocuring 3D printer are adjusted, the printing slurry with the CT imaging effect is configured, and the skeleton model and the preoperative guide plate with the CT imaging effect can be printed, so that a doctor can perform preoperative drilling of an orthopedic operation under a CT image, and the success rate of the operation can be effectively improved under more real drilling operation conditions; and carrying out CT test on the printed model to screen out the model meeting the human bone standard.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
Fig. 1 is a CT image (numbered from left to right as numbers 1-12 in sequence) presented by a bone model made of a 3D printed composite material according to an embodiment of the present invention.
Detailed Description
In order to further understand and understand the present invention, the technical solutions of the present invention are further described below with reference to the accompanying drawings and the detailed description.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and are used herein for the purpose of describing particular embodiments only and are not intended to limit the scope of the present invention.
For convenience of explanation, the main raw materials described in the present invention are listed below, and are commercially available unless their preparation methods are specifically described.
The embodiment provides a 3D printing composite material with a CT imaging effect, which comprises the following components in percentage by mass:
40-70 wt% of photosensitive resin;
5wt% of a dispersant;
20-50 wt% of hydroxyapatite;
5wt% of titanium dioxide.
The hydroxyapatite is selected as the nano-grade hydroxyapatite, the photosensitive resin is selected as the water-washing photosensitive resin with the viscosity of less than 350MPa.s, and the dispersant is selected as polyacrylic acid.
The mass fraction of the hydroxyapatite in the raw materials is 20-50 wt%, and the mass fraction of the photosensitive resin is correspondingly changed in the process, so that the imaging effect of the photosensitive resin is weakened to different degrees in the process.
The photosensitive resin plays a role of a matrix, the photosensitive resin with low viscosity is more beneficial to the forming of the final slurry, the hydroxyapatite is a main inorganic component of human skeleton, so the photosensitive resin is similar to the human skeleton in the aspect of CT imaging effect, a good CT imaging effect can be obtained by adding a proper amount of hydroxyapatite in a simulated human skeleton model, and the titanium dioxide can generate chemical bonds with the hydroxyapatite to form functional groups, so the stability of the hydroxyapatite can be well improved, the stability of the slurry can be improved by adding a proper amount of titanium dioxide, the hydroxyapatite and the titanium dioxide in the slurry can be uniformly distributed by adding the dispersing agent, and the slurry is prevented from settling, so the forming of photocuring printing is further influenced.
Example 1:
A3D printing composite material with a CT imaging effect comprises the following components in percentage by mass:
washing 45 wt% of photosensitive resin;
5wt% of polyacrylic acid;
45 wt% of nano-hydroxyapatite;
5wt% of titanium dioxide.
The 3D printing composite material with the CT imaging effect is placed into a planetary ball mill for ball milling to obtain ball-milled slurry, the ball milling time is set to be 2 hours at the rotating speed of 300rmp, and the 3D printing composite material is rotated forwards for 30 minutes and then rotated backwards for 30 minutes for 2 reciprocating cycles. The size of the number 1 3D printing composite material was obtained by this preparation method.
Example 2
A3D printing composite material with a CT imaging effect comprises the following components in percentage by mass:
washing photosensitive resin by 50 wt%;
5wt% of polyacrylic acid;
40wt% of nano-hydroxyapatite;
5wt% of titanium dioxide.
The slurry of the 3D printing composite material No. 2 was prepared according to the method of example 1 for preparing a 3D printing composite material having CT imaging effect.
Example 3
A3D printing composite material with a CT imaging effect comprises the following components in percentage by mass:
washing the photosensitive resin with water to 55 wt%;
5wt% of polyacrylic acid;
35 wt% of nano-hydroxyapatite;
5wt% of titanium dioxide.
The slurry of the 3D printing composite material No. 3 was prepared according to the method of example 1 for preparing a 3D printing composite material having CT imaging effect.
Example 4
A3D printing composite material with a CT imaging effect comprises the following components in percentage by mass:
40wt% of water-washed photosensitive resin;
5wt% of polyacrylic acid;
50wt% of nano-grade hydroxyapatite;
5wt% of titanium dioxide.
The slurry of the 3D printing composite material No. 4 was prepared according to the method of example 1 for preparing a 3D printing composite material having CT imaging effect.
Example 5
A3D printing composite material with a CT imaging effect comprises the following components in percentage by mass:
washing photosensitive resin by 60 wt%;
5wt% of polyacrylic acid;
30 wt% of nano-grade hydroxyapatite;
5wt% of titanium dioxide.
A slurry of No. 5 3D printed composite was prepared according to the method of example 1 for preparing 3D printed composite with CT imaging effect.
Example 6
A3D printing composite material with a CT imaging effect comprises the following components in percentage by mass:
washing photosensitive resin by 70 wt%;
5wt% of polyacrylic acid;
20 wt% of nano-hydroxyapatite;
5wt% of titanium dioxide.
A slurry of No. 6 3D printed composite was prepared according to the method of example 1 for preparing 3D printed composite with CT imaging effect.
The hydroxyapatite in the technical scheme of the embodiment can be replaced by tricalcium phosphate.
The paste of the 3D printing composite material with the CT imaging effect obtained in the above embodiment is used to obtain a 3D printing bone model with the CT imaging effect according to the following method for manufacturing a bone model by using the 3D printing composite material with the CT imaging effect. The method for making the bone model comprises the following steps:
placing the prepared slurry of the 3D printing composite material with the CT imaging effect into a material groove of a photocuring 3D printer;
designing a 3D model through Solidworks, slicing the designed 3D model by using slicing software, setting the thickness of the slice to be 0.05mm, setting the exposure time to be 3.0 seconds, setting the number of layers of a bottom plate to be 6, setting the exposure time of the bottom layer to be 20 seconds, raising the printing platform by 4mm, setting the rising and falling speeds to be 200mm/min, and setting the waiting time after stopping to be 2 seconds;
after the setting is finished, the model is led into a photocuring 3D printer, and after the slurry is paved on the whole trough, the printing model is started;
and after the model is printed, closing the photocuring 3D printer and taking out the model.
Further, the step of taking out the model further comprises the step of carrying out CT test on the printed model.
Specifically, the printed model is subjected to CT test, and the image value of the model under CT is obtained so as to measure that the CT imaging effect of the product reaches the human bone standard.
The 3D printing composite paste prepared in the above examples 1 to 6 was printed into a bone model according to the above bone model printing method, and the printed bone model was subjected to CT test, with the test results shown in table 1:
table 1: bone model CT test value
Figure BDA0003316694540000081
After CT test, the obtained image value of the bone model under CT is 532-1524Hu, and the CT value of the human skeleton is 500-1500Hu, so the CT imaging effect of the product reaches the human bone standard.
Taking the bone model made of the 3D printing composite material No. 4 in example 4 as an example, the CT layering test results are shown in table 2, and the CT image is shown in fig. 1. The difference of the CT values is because the CT scanning is one layer, the difference of the CT values of different layers is larger, and the difference of the same layer is smaller. Meanwhile, the difference value range of the CT minimum value and the CT maximum value of the embodiment is minimum through the CT test result value of the layered bone model, and the CT test effect of the bone model manufactured by the embodiment is optimal.
Table 2: CT test result value of layered bone model
Figure BDA0003316694540000082
The product is finally subjected to standardized test by CT equipment in a hospital, and the CT value is obtained at 845-1524Hu (the human skeleton CT value is 500-1500Hu) according to the test result of the bone model made of the No. 4 3D printing composite material in the embodiment 4, is similar to the human skeleton image, and meets the design requirement.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.

Claims (6)

1. 3D prints combined material with CT image science effect, its characterized in that: the composite material comprises the following components in percentage by mass: 40-70 wt% of water-washing photosensitive resin, 5wt% of polyacrylic acid, 20-50 wt% of nano-grade hydroxyapatite and 5wt% of titanium dioxide.
2. 3D printed composite material with CT-imaging effect according to claim 1, characterized in that: the water-washing photosensitive resin is the water-washing photosensitive resin with the viscosity of less than 350MPa.
3. 3D printed composite material with CT-imaging effect according to claim 1, characterized in that: the mass fraction of the nano-hydroxyapatite is 40wt%, and the mass fraction of the water-washed photosensitive resin is 50 wt%.
4. A method of preparing a 3D printed composite with CT imaging effects according to any of claims 1 to 3, characterized in that: the method comprises the following steps:
the weight percentages are as follows: 50wt% of nano-hydroxyapatite, 40wt% of water-washing photosensitive resin, 5wt% of polyacrylic acid and 5wt% of titanium dioxide, and the 3D printing composite material has a CT imaging effect;
the materials of the components are put into a planetary ball mill for ball milling to obtain the slurry after ball milling.
5. The method of preparing a 3D printed composite material with CT imaging effect according to claim 4, characterized in that: the rotating speed of the planetary ball mill is 300rmp, the ball milling time is 2h, and the planetary ball mill firstly rotates forwards for 30min and then rotates backwards for 30min to reciprocate for 2 cycles.
6. A method for manufacturing a bone model by using a 3D printing composite material with CT imaging effect is characterized in that: the method comprises the following steps:
placing the slurry of the 3D printing composite material with CT imaging effect prepared according to any one of the claims 4-5 into a tank of a photocuring 3D printer;
slicing the designed 3D model by using slicing software, setting the thickness of the slice to be 0.05mm, setting the exposure time to be 3.0 seconds, setting the number of layers of the master plate to be 6, setting the exposure time of the base layer to be 20 seconds, raising the printing platform by 4mm, setting the rising and falling speeds to be 200mm/min, and setting the waiting time after stopping to be 2 seconds;
after the setting is finished, the model is led into a photocuring 3D printer, and after the slurry is paved on the whole trough, the printing model is started;
after the model is printed, closing the photocuring 3D printer and taking out the model;
and after the model is taken out, performing CT test on the printed model, and screening out the model with the image value of 845-1524Hu under CT.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109095917A (en) * 2018-09-10 2018-12-28 北京工业大学 A kind of preparation method of the bioactivity, porous hydroxyapatite/Ti acid barium composite ceramics based on 3D printing
CN109180175A (en) * 2018-10-25 2019-01-11 河北大洲智造科技有限公司 A kind of photocuring 3D printing bioceramic slurry and preparation method thereof, bone tissue engineering scaffold and its application
CN109808035A (en) * 2019-01-21 2019-05-28 北京工业大学 A kind of compound porous bioceramic scaffold production method of hydroxyapatite/silica based on 3D printing
CN110272273A (en) * 2019-07-22 2019-09-24 上海应用技术大学 The controlled pore hydroxyl apatite bioceramic bracket and preparation method of 3D printing
CN111035802A (en) * 2019-12-18 2020-04-21 北京工业大学 Preparation method of hydroxyapatite/titanium dioxide composite biological ceramic with three-period extremely-small curved surface structure through photocuring 3D printing
CN111909320A (en) * 2020-07-30 2020-11-10 武汉工程大学 Photocuring 3D printing modified polylactic acid composite photosensitive resin and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109095917A (en) * 2018-09-10 2018-12-28 北京工业大学 A kind of preparation method of the bioactivity, porous hydroxyapatite/Ti acid barium composite ceramics based on 3D printing
CN109180175A (en) * 2018-10-25 2019-01-11 河北大洲智造科技有限公司 A kind of photocuring 3D printing bioceramic slurry and preparation method thereof, bone tissue engineering scaffold and its application
CN109808035A (en) * 2019-01-21 2019-05-28 北京工业大学 A kind of compound porous bioceramic scaffold production method of hydroxyapatite/silica based on 3D printing
CN110272273A (en) * 2019-07-22 2019-09-24 上海应用技术大学 The controlled pore hydroxyl apatite bioceramic bracket and preparation method of 3D printing
CN111035802A (en) * 2019-12-18 2020-04-21 北京工业大学 Preparation method of hydroxyapatite/titanium dioxide composite biological ceramic with three-period extremely-small curved surface structure through photocuring 3D printing
CN111909320A (en) * 2020-07-30 2020-11-10 武汉工程大学 Photocuring 3D printing modified polylactic acid composite photosensitive resin and preparation method thereof

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