CN109330744B

CN109330744B - 3D printing artificial finger bone of customized degradable multi-element multi-layer nano composite

Info

Publication number: CN109330744B
Application number: CN201811127845.1A
Authority: CN
Inventors: 徐淑波; 刘建营; 王瀚林
Original assignee: Shandong Jianzhu University
Current assignee: Shandong Jianzhu University
Priority date: 2018-09-27
Filing date: 2018-09-27
Publication date: 2020-08-25
Anticipated expiration: 2038-09-27
Also published as: CN109330744A

Abstract

The invention relates to an implant prosthesis, in particular to a 3D printing finger bone of a customized degradable multi-element multi-layer nano composite. The invention uses CT scanning to scan broken finger to obtain CT tomographic image data of the broken finger, establishes an artificial finger three-dimensional model according with the broken finger according to the CT tomographic image data, mixes various metals of Ti powder, Mg, Si, Ca, Cu, Ag, niobium powder and molybdenum powder as matrix materials of finger bone, adds ternary nano composite mixed powder of carbon nano tube/hydroxyapatite/wollastonite fiber in different proportions, and prints the finger bone layer by layer. Compared with the titanium alloy and magnesium alloy finger bone manufactured by the traditional method, the finger bone printed by the method has better strength, toughness and biocompatibility.

Description

3D printing artificial finger bone of customized degradable multi-element multi-layer nano composite

Technical Field

The invention relates to an implant prosthesis, in particular to a 3D printing artificial finger bone made of a customized degradable multi-element multi-layer nano composite.

Background

China is a developing country, and with the rapid development of the industry, agriculture and transportation industry, a large number of hand trauma patients appear, wherein finger distant injury is the most common. The finger distal segment injury is common injury of hand surgery, the currently adopted method is bone transplantation and bone reconstruction, the bone transplantation is to find bones similar to missing bones in a bone bank and transplant the bones to the severed finger, and then the finger is replanted by using the modern medical technology; the bone reconstruction method comprises the steps of scanning the broken finger by CT to obtain broken finger data, reconstructing a bone similar to or identical to a lost bone by using three-dimensional software, and compared with bone transplantation, the bone reconstruction method does not need to consider the loss of bone resources and the rejection of an immune system, but the bone reconstructed by the bone mainly comprises a metal bone, and the strength, toughness and modulus of the metal are far greater than those of a cortical bone, so that porous design and material design of the metal bone are required.

Most of bone materials used for bone reconstruction in modern medical treatment are titanium alloy, and titanium is an ideal medical metal material due to the non-toxicity, high strength and excellent biocompatibility of titanium. However, the skeleton made of titanium alloy is still very different from the original skeleton, and the invention aims to restore the original skeleton, so the material of the finger bone should have certain degradability. The metal nano composite powder is used as a base material of the artificial finger bone, and the base material and the ternary nano composite powder of the multi-wall carbon nano tube, the hydroxyapatite and the wollastonite fiber are mixed according to different proportions and are covered on the base material layer by layer, so that the printed artificial finger bone has better biocompatibility.

Compared with the titanium alloy and magnesium alloy finger bone manufactured by the traditional method, the finger bone printed by the method is degraded finally to generate new bone with the same or better performance as the lost bone, and has better strength, toughness and biocompatibility.

Disclosure of Invention

The invention aims to provide a preparation method of a customized degradable multi-element multi-layer nano composite 3D printing finger bone, and the finger bone prepared by the method has excellent biocompatibility and mechanical property.

The technical scheme of the invention is as follows: CT scanning is carried out on broken fingers to obtain CT tomographic image data of the broken fingers, a three-dimensional model of the artificial finger conforming to the broken fingers is established according to the CT tomographic image data, and the three-dimensional model of the artificial finger is printed into the artificial finger bone by a 3D printer in a layered distribution mode, wherein the three-dimensional model of the artificial finger conforms to the broken fingers and is formed by mixing medical nano-porous titanium magnesium composite powder and multi-walled carbon nano-tubes/hydroxyapatite/polyether-ether-ketone ternary nano-composites in different. The specific scheme is as follows:

1. building a three-dimensional model

And (3) adopting CT to scan two hands to obtain CT tomographic image data of the residual finger, and obtaining the size and the shape of the metal implant in the finger bone by using three-dimensional reconstruction software according to the missing degree of the residual finger bone and the inner diameter of the residual end bone.

2. Preparation of nanocomposite powder

Metal Ti powder, Mg particles (the purity is 99.6 percent), Si particles (the purity is 99.9 percent), Ca particles, Cu particles, Ag particles, niobium powder and molybdenum powder are mixed according to the molar weight ratio of (20-40): (10-20): (38-45): (15-18): (5-8): (3-5): (5-10): (0.1-0.5), and performing ball milling treatment on the mixture until the maximum ball diameter is not more than 40 mu m to obtain superfine powder.

The niobium metal has excellent corrosion resistance and stability, hardly reacts with various liquid substances in a human body, and has good biocompatibility.

The molybdenum is a component of various enzymes in human body, and can improve the growth rate of bone cells and the degradation rate of metal skeleton.

Calcium element is inorganic salt with the largest content in human body, is the most important substance for forming bones, and means that calcium element in bones can be used as a raw material for bone cell growth, and the growth speed of bone cells can be greatly improved.

3. Preparation of ternary nano composite powder of carbon nano tube/hydroxyapatite/wollastonite fiber

Dissolving dispersant sodium dodecyl sulfate in deionized water, adding carbon nano tubes, and magnetically stirring to completely wet the carbon nano tubes by the aqueous solution for about 30 min. And then, carrying out ultrasonic treatment by using an ultrasonic instrument with the power set to 700W for 60min, and after the ultrasonic treatment is finished, carrying out centrifugal sedimentation on the dispersion liquid to remove undispersed agglomerated particles. The centrifugation speed is 3000 r/min, the centrifugation time is 40 min, and stable dispersion liquid with certain carbon nano tube content is obtained for standby.

Wollastonite fibers are fully dissolved by concentrated hydrochloric acid and diluted to a pH value of 7.3 or less. And (3) performing ultrasonic treatment on the diluted solution to uniformly diffuse the wollastonite fiber. Under the stirring condition, the carbon nano tube dispersion liquid is slowly added, and the mass fraction of the carbon nano tube is kept at 6%. Then, the dispersed HA nanoparticles with the mass fraction of 30% are added into the raw materials, and the stirring is continued for 6 hours. Finally, the mixture is filtered by suction and dried to constant weight under the condition of vacuum 120 ℃. The resulting ternary premix.

And performing ball milling treatment on the obtained ternary premix to ensure that the maximum ball diameter of the ternary premix is not more than 40 mu m, thereby obtaining the ternary composite nano powder.

4. 3D prints meaning and indicates bone

Fully mixing the metal ultrafine powder and the ternary composite nano powder according to the mass fraction ratio of 3:1, 2:1 and 1:1 respectively, sequentially naming the obtained powder as powder 2, powder 3 and powder 4, and taking the metal powder as powder 1 and the ternary composite nano powder as powder 5 until the preparation work of the finger bone is completely finished.

Guiding the three-dimensional model manufactured in the first step into a 3D printer, firstly printing a phalanx 'kernel' with the thickness of 1 mm-3 mm by using powder 1, wherein the laser spot diameter of the 3D printer is (40-100 mu m), and the scanning speed is 15.2 m/s; then, continuously printing the powder 2 with the thickness of 1 mm-2 mm on the basis of the inner core of the phalangeal skeleton, wherein the diameter of a laser spot is 40-100 mu m, and the scanning speed is 15.2 m/s; then, continuously printing the powder 3 with the thickness of 1 mm-2 mm on the basis of the powder 2, wherein the laser spot diameter is (40-100 mu m), and the scanning speed is 15.2 m/s; and then continuously printing the semi-finished product with the thickness of 1 mm-2 mm by using powder 4 on the basis of the powder 3, wherein the diameter of a laser spot is 40-100 mu m, the scanning speed is 15.2m/s, so as to finish the semi-finished product of the finger prosthesis, then carrying out stress removal treatment on the semi-finished product of the finger bone to eliminate the residual stress of the finger bone, and finally plating a layer of ceramic film with the thickness of 1 mm-3 mm on the semi-finished product of the finger bone by using powder 5, as shown in figure 1. The plated ceramic film is a compact degradable ceramic film, and can improve the biocompatibility and the bioactivity of the skeleton of the finger bone.

Drawings

FIG. 1 is a cross-section of a 3D printed distal phalanx, with FIG. 1 being a ceramic coating; 2, mixing the metal ultrafine powder and the ternary composite nano powder according to a ratio of 1: 1; 3, mixing the metal ultrafine powder and the ternary composite nano powder according to a ratio of 2: 1; 4, mixing the metal ultrafine powder and the ternary composite nano powder according to a ratio of 3: 1; 5 is metal superfine powder inner core.

Detailed Description

The first step is as follows: and (3) adopting CT to scan two hands to obtain CT tomographic image data of the residual finger, and obtaining the size and the shape of the metal implant in the finger bone by using three-dimensional reconstruction software according to the missing degree of the residual finger bone and the inner diameter of the residual end bone.

The second step is that: dissolving dispersant sodium dodecyl sulfate in deionized water, adding carbon nano tubes, and magnetically stirring to completely wet the carbon nano tubes by the aqueous solution for about 30 min. And then, carrying out ultrasonic treatment by using an ultrasonic instrument with the power set to 700W for 60min, and after the ultrasonic treatment is finished, carrying out centrifugal sedimentation on the dispersion liquid to remove undispersed agglomerated particles. The centrifugation speed is 3000 r/min, the centrifugation time is 40 min, and stable dispersion liquid with certain carbon nano tube content is obtained for standby.

The third step: metal Ti powder, Mg particles (the purity is 99.6 percent), Si particles (the purity is 99.9 percent), Ca particles, Cu particles, Ag particles, niobium powder and molybdenum powder are mixed according to the molar weight ratio of (20-40): (10-20): (38-45): (15-18): (5-8): (3-5): (5-10): (0.1-0.5), and performing ball milling treatment on the mixture until the maximum ball diameter is not more than 40 mu m to obtain superfine powder.

The fourth step: fully mixing metal mixed powder and ternary composite nano powder according to the mass fraction ratio of 3:1, 2:1 and 1:1 respectively, sequentially naming the obtained powder as powder 2, powder 3 and powder 4, and taking the metal powder as powder 1 and the ternary composite nano powder as powder 5 until the preparation work of the finger bone is completely finished.

The fifth step: guiding the three-dimensional model manufactured in the first step into a 3D printer, firstly printing a phalange 'kernel' with the thickness of 2mm by using powder 1, wherein the diameter of a laser spot of the 3D printer is 40 mu m, and the scanning speed is 15.2 m/s; then, continuously printing the powder 2 with the thickness of 1.5mm on the basis of the 'core' of the phalange skeleton, wherein the diameter of a laser spot is 50 mu m, and the scanning speed is 15.2 m/s; then, continuously printing the powder 3 with the thickness of 1.5mm on the basis of the powder 2, wherein the laser spot diameter is 60 mu m, and the scanning speed is 15.2 m/s; then, continuously printing the powder 4 with the thickness of 1mm on the basis of the powder 3, wherein the diameter of a laser spot is 80 mu m, and the scanning speed is 15.2 m/s; thus, the semi-finished product of the finger is finished.

And a sixth step: and (3) performing stress relief treatment on the finger bone semi-finished product completed in the fifth step to eliminate residual stress in the finger bone, plating a layer of ceramic film with the thickness of 2mm on the finger bone semi-finished product by using powder 5, and performing detail treatment on the finger bone of the artificial finger according to the CT sectional image data of the residual finger obtained in the first step to enable the finger bone to be more connected with a broken finger part.

Claims

1. A preparation method of a 3D printing finger phalanx of a customized multi-element multi-layer nano composite is characterized by comprising the following steps: CT scanning broken fingers to obtain CT tomographic image data of the broken fingers, establishing a three-dimensional model of the broken fingers according to the CT tomographic image data, mixing various metals of Ti powder, Mg, Si, Ca, Cu, Ag, niobium powder and molybdenum powder to serve as a matrix material of finger bone, adding ternary nano-composite mixed powder of carbon nano tubes/hydroxyapatite/wollastonite fibers in different proportions, and printing the finger bone layer by layer, wherein the finger bone prepared by the method has excellent biocompatibility and mechanical property; the specific process steps for preparing the finger bone are as follows:

(a) establishing a three-dimensional model: CT scanning is adopted to scan two hands to obtain CT tomographic image data of the residual finger, and according to the loss degree of the residual finger bone and the inner diameter of the residual end bone, three-dimensional reconstruction software is utilized to obtain the size and the shape of the metal implant in the finger bone;

(b) preparation of metal nanocomposite powder: metal Ti powder, Mg particles with the purity of 99.6 percent, Si particles with the purity of 99.9 percent, Ca particles, Cu particles, Ag particles, niobium powder, molybdenum powder and platinum powder are mixed according to the molar weight ratio of (20-40): (10-20): (38-45): (15-18): (5-8): (3-5): (5-10): (0.1-0.5): (0.8-2) after uniformly mixing and preparing, carrying out ball milling treatment on the mixture to ensure that the maximum ball diameter of the mixture is not more than 40 mu m, thus obtaining metal composite superfine powder;

(c) preparation of ternary nano composite powder of carbon nano tube/hydroxyapatite/wollastonite fiber

Dissolving a dispersing agent sodium dodecyl sulfate in deionized water, adding the carbon nano tube, and magnetically stirring to completely wet the carbon nano tube by the aqueous solution for about 30 min; then, carrying out ultrasonic treatment by using an ultrasonic instrument, setting the power to be 700W, carrying out ultrasonic treatment for 60min, and after the ultrasonic treatment is finished, carrying out centrifugal sedimentation on the dispersion liquid to remove undispersed agglomerated particles; centrifuging at 3000 r/min for 40 min to obtain stable dispersion liquid with certain carbon nanotube content; fully dissolving wollastonite fiber with concentrated hydrochloric acid, and diluting the wollastonite fiber until the pH value is less than or equal to 7.3; carrying out ultrasonic treatment on the diluted solution to uniformly diffuse wollastonite fibers; slowly adding the carbon nano tube dispersion liquid under the stirring condition, and keeping the mass fraction of the carbon nano tubes to be 6%; then adding the dispersed HA nanoparticles with the mass fraction of 30% into the raw materials, and continuously stirring for 6 hours; finally, carrying out suction filtration, and drying at the temperature of 120 ℃ in vacuum to constant weight; the resulting ternary premix; performing ball milling treatment on the obtained ternary premix to ensure that the maximum ball diameter of the ternary premix is not more than 40 mu m, thus obtaining ternary composite nano powder;

(d) obtaining a 3D printed finger phalanx: fully mixing the metal ultrafine powder and the ternary composite nano powder according to the mass fraction ratio of 3:1, 2:1 and 1:1 respectively, sequentially naming the obtained powder as powder 2, powder 3 and powder 4, and taking the metal powder as powder 1 and the ternary composite nano powder as powder 5 until the preparation work of the finger bone is completely finished;

(e) guiding the three-dimensional model manufactured in the first step into a 3D printer, firstly printing a phalange 'kernel' with the thickness of 1 mm-3 mm by using powder 1, wherein the diameter of a laser spot of the 3D printer is 40-100 mu m, and the scanning speed is 15.2 m/s; then, continuously printing the powder 2 with the thickness of 1 mm-2 mm on the basis of the inner core of the phalangeal skeleton, wherein the diameter of a laser spot is 40-100 mu m, and the scanning speed is 15.2 m/s; then, continuously printing the powder 3 with the thickness of 1 mm-2 mm on the basis of the powder 2, wherein the laser spot diameter is 40-100 mu m, and the scanning speed is 15.2 m/s; and then, continuously printing the powder 4 with the thickness of 1 mm-2 mm on the basis of the powder 3, wherein the diameter of a laser spot is 40-100 mu m, and the scanning speed is 15.2m/s, so as to finish the semi-finished product of the phalange, then performing stress removal treatment on the semi-finished product of the phalange to eliminate the residual stress of the phalange, and finally plating a layer of ceramic film with the thickness of 1 mm-3 mm on the semi-finished product of the phalange by using the powder 5, wherein the plated ceramic film is a layer of compact degradable ceramic film, so that the biocompatibility and the bioactivity of the phalange can be improved.