CN102764453A - Personalized carbon/carbon composite artificial bone and preparation method thereof - Google Patents
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Abstract
The invention relates to a personalized carbon/carbon composite artificial bone and a preparation method of the personalized carbon/carbon composite artificial bone, wherein specific steps are as follows: a. choosing carbon-fiber reinforced carbon matrix as a raw material; b. performing an artificial bone outline by collection of computerized tomography (CT) images, converting the collected artificial bone outline into a non-uniform rational B-spline surface, processing the carbon/carbon composite to form the carbon/carbon composite artificial bone; c. filling argon into a vacuum glow discharge chamber to perform plasma pretreatment on the surface of the carbon-fiber reinforced carbon matrix, placing the processed carbon-fiber reinforced carbon matrix into alcohol solution to perform ultrasonic washing; d. spraying a hydroxyapatite coating onto the surface of the washed carbon-fiber reinforced carbon matrix to form the carbon/carbon composite. According to the personalized carbon/carbon composite artificial bone and preparation method of the personalized carbon/carbon composite artificial bone provided by the invention, the hydroxyapatite coating is sprayed onto the surface of the carbon/carbon composite, the surface activity of the carbon/carbon composite is improved and the release of carbon granules can be decreased effectively.
Description
Technical field
The present invention relates to medical field, especially a kind of personalized carbon-carbon composite artificial bone and preparation method thereof.
Background technology
The artificial bone replacement operation is at home and abroad extensively carried out as the efficacious therapy method.Though people's skeleton is consistent appearance substantially, skeletal structure exists than big-difference, and femoral neck shaft angle can change to 140 ° from 110 °, and average 125 °, unified prosthese can not be applicable to all patients.Common prosthese handle can not be fit to everyone pulp cavity, makes between prosthese and the bone to have the space, can produce small rocking when stressed again, and Bowman SM etc. are through finding that to the fine motion experiment of Os Bovis seu Bubali girder the fine motion meeting produces fatigue damage to bone trabecula.Combining closely of prosthese and bone makes the suffered power of prosthese conduct to skeleton equably simultaneously, reduced osteanabrosis that stress force shelter reaction produced and bone resorption.So the artificial bone prosthetic products has high personalization features, the product of standard, seriation is often improper to some patients, and the artificial prosthesis design parameter part of present domestic use is from American-European ethnic group.The prosthese that therefore will manufacture and design individuation satisfies the requirement of patient bone structure, can manual intervention in design process, thus obtain best artificial bone prosthese.
Carbon is the one of the chief elements of forming organic substance, constitutes the important element of human body especially, and material with carbon element has obtained to use and development aspect many artificial materials such as cardiac valve, skeleton, tooth root, blood vessel, tendon.Carbon/carbon compound material has overcome the fragility of single material with carbon element, has high strength, high tenacity, advantage such as corrosion-resistant, high temperature resistant.Carbon/carbon compound material is the advanced composite material (ACM) with the carbon fiber reinforced carbon matrix body, and elastic modelling quantity and people's bone photo are worked as, and have good biomechanical compatibility.This seminar early-stage Study thinks that the carbon/carbon compound material of process special handling meets country of People's Republic of China (PRC) medical apparatus and instruments biological safe standard.And this seminar is relatively thought through iconography: the carbon/carbon compound material implant can not produce metal artifacts with respect to metal implant and to the ray barrier effect on imaging examination.Carbon/carbon compound material is a kind of potential new bio medical material, and the preparation of individuation carbon/carbon compound material artificial bone is a development trend.But preparation manufacturing cycle with respect to metal implant of individuation carbon/carbon compound material artificial bone is long at present, cost is high, has restricted the development of carbon/carbon compound material artificial bone.Metal restoration is general to obtain two and three dimensions information through CT scan earlier; Carry out generating mould or model after the modeling; Obtain the artificial bone of individuation again through casting; And the carbon/carbon compound material artificial bone is because need be to the arrangement of carbon fiber and the deposition of RESEARCH OF PYROCARBON, so the manufacturing approach of metal implant is inappropriate for the preparation of carbon/carbon compound material artificial bone.
Summary of the invention
The technical problem that the present invention will solve is: in order to overcome the above-mentioned middle problem that exists; A kind of personalized carbon-carbon composite artificial bone and preparation method thereof is provided; The fragility that it has overcome single material with carbon element has high strength, high tenacity, corrosion resistance, resistant to elevated temperatures characteristics.
The technical solution adopted for the present invention to solve the technical problems is: a kind of method for preparing of personalized carbon/carbon compound material artificial bone, and concrete steps are following:
A. select the carbon fiber reinforced carbon matrix body as raw material, the elastic modelling quantity of carbon fiber reinforced carbon matrix body and people's bone photo are worked as, and have good biomechanical compatibility;
B. carry out the artificial bone profile through the collection of CT image; Artificial bone profile after the collection converts the method for non-uniform rational B-spline curved surface to carbon/carbon compound material is handled back formation carbon/carbon compound material artificial bone, and its concrete grammar is following: (1) profile is delineated; (2) generate the two-value volume data; (3) triangle gridding generates; (4) convert nurbs surface to;
C. the carbon fiber reinforced carbon matrix body is put into the vacuum glow discharge chamber; In the vacuum glow discharge chamber, feeding argon carries out plasma pretreatment is carried out in the carbon fiber reinforced carbon matrix surface; The characteristic of the gauffer on RESEARCH OF PYROCARBON surface, fragment, adhesion difference around the removal carbon fiber; Make hydroxyapatite and carbon fiber bond strength improve; Parameters such as the dc source voltage of vacuum glow discharge chamber, the pressure of argon, operating current, working time are adjustable, and carbon fiber reinforced carbon matrix body is after treatment put into alcoholic solution and carried out ultrasonic cleaning, clean argon and bombard the RESEARCH OF PYROCARBON granule that gets off;
D. carry out spraying hydroxyapatite coating formation finished product carbon/carbon compound material to cleaning carbon fiber reinforced carbon matrix surface later; Spray plasma spraying power is 38kw; Spray distance is 110mm; The spray gun rate travel is 180mm/s, and coating layer thickness is 70um, satisfies the requirement of human body to hydroxyapatite figure layer thickness.
The carbon/carbon compound material artificial bone comprises carbon/carbon compound material and hydroxyapatite among the d, and is hydroxyapatite sprayed on the carbon/carbon compound material surface.
The invention has the beneficial effects as follows, a kind of personalized carbon-carbon composite artificial bone of the present invention and preparation method thereof, the carbon/carbon compound material artificial bone that obtains through the CT preparation of images can be consistent with its self bone shape that is replaced; Spraying hydroxyapatite coating on the surface of carbon/carbon compound material can improve the carbon/carbon compound material surface activity, reduces the release of carbon granule effectively; Through the plasma pretreatment, can improve the adhesion between hydroxyapatite coating layer and the carbon/carbon compound material; Its elastic modelling quantity and people's bone photo are worked as, have high strength, high tenacity, corrosion-resistant and resistant to elevated temperatures characteristic, and be artificial joint, the bone prosthetic material of applications well prospect.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
Fig. 1 is a non-uniform rational B-spline curved surface flow chart of the present invention;
Fig. 2 is the sketch map that profile of the present invention is delineated;
Fig. 3 is polygon of the present invention and corresponding image;
Fig. 4 is the carbon/carbon compound material SEM pattern sketch map after the plasma treatment of the present invention;
Fig. 5 is the infrared spectrogram of Cement Composite Treated by Plasma carbon/carbon compound material of the present invention;
Fig. 6 is the coating SEM pattern and the electron spectrum sketch map of hydroxyapatite of the present invention;
Fig. 7 is the infrared absorption spectroscopy sketch map of hydroxyapatite coating layer of the present invention;
Fig. 8 is the XRD diffracting spectrum sketch map of hydroxyapatite coating layer of the present invention;
Fig. 9 is scratch test of the present invention and SEM pattern sketch map.
The specific embodiment
Combine accompanying drawing that the present invention is done further detailed explanation now.These accompanying drawings are the sketch map of simplification, basic structure of the present invention only is described in a schematic way, so it only show the formation relevant with the present invention.
A kind of method for preparing of personalized carbon-carbon composite artificial bone, concrete steps are following: a. selects the carbon fiber reinforced carbon matrix body as raw material;
B. carry out the artificial bone profile through the collection of CT image; Artificial bone profile after the collection converts the method for non-uniform rational B-spline curved surface (like Fig. 1) to carbon/carbon compound material is handled back formation carbon/carbon compound material artificial bone; Its concrete grammar is following: (1) profile is delineated: on DICOM RT, combine automatically and manually through RT struct module and delineate the bone profile; Automatically delineate sketch outline faster, manually delineate relatively accurate but time-consuming.Automatically delineate and adopt the auto-by-threshold technology, promptly be divided into 128 grades to the CT gray scale, convert 64 red greyscale level figure again to, shown in Fig. 2 (a), utilize formula
A certain dotted region grade chromatic graph is a reference value; The zone of this same gray level grade is a profile, regulates window width, the window position of CT, can obtain satisfied profile diagram; Can not well distinguish but regulate the window value, have only through manual differentiation for two adjacent osseous tissues.Fig. 2 (b) is the profile of artificial humeral head, and the profile of the prosthese handle of artificial humeral head is slightly less than the profile of right side humerus medullary cavity, can successfully be inserted in the pulp cavity to guarantee this prosthese handle; Fig. 2 (c) is the result of multilamellar profile stack artificial humeral head; (2) generate the two-value volume data: sign in the polygon that extracts in one individuality (volume) data.Volume is the two-value volume data, and polygon is inner representes that with 0 outside of polygon is represented with 1.So just generated volume data by polygon data, as shown in Figure 3; (3) triangle gridding generates: the transition face in the two-value volume data that above-mentioned steps generates between 0 and 1 is the surface of skeleton.It is 0.5 contour surface that this paper uses marching cubes algorithm to extract above-mentioned volume data intermediate value, obtains a surface triangles grid.Triangular mesh is enough to describe the surface information of a three-dimensional body; (4) convert nurbs surface to: the employed data model of machining adopts non-uniform rational B-spline to represent mostly.Therefore, if the model of wanting to be set up can carry out machining easily, need be converted into the model that NURBS representes.This paper work uses Geomagic Studio 12 softwares to convert triangle gridding to the non-uniform rational B-spline curved surface; Use the grid doctor to analyze and repair polygonal mesh; Generate the patch structure through contour line and boundary line, repair patch again and prevent the curved surface mistake, the structure grid; Nurbs surface of fitting surface existence saves as the iges model file;
C. the carbon fiber reinforced carbon matrix body is put into the vacuum glow discharge chamber; The pressure 60Pa of dc source voltage 600v, working time 20min, argon; In the vacuum glow discharge chamber, feeding argon carries out plasma pretreatment is carried out in the carbon fiber reinforced carbon matrix surface; RESEARCH OF PYROCARBON smooth surface under this condition, and too high voltage and long working time will make surface topography obtain corrosion again, low excessively voltage, short working time article on plasma pretreatment carbon/carbon compound material pattern influence little; Like Fig. 4 (a) is the carbon fiber pattern through the carbon/carbon compound material of 500v, 20min, the processing of 30Pa plasma treatment condition; Similar with the original carbon fiber pattern without the carbon/carbon compound material of plasma treatment, carbon fiber surface has the strip gauffer of tangible convexity, and this is that the RESEARCH OF PYROCARBON deposition causes; Fig. 4 (b) is the carbon fiber pattern through the carbon/carbon compound material of 600v, 20min, the processing of 60Pa plasma treatment condition; Carbon fiber surface is smooth relatively, does not have protruding gauffer, and the carbon fiber that the plasma treatment carbon/carbon compound material is described is effective; But more observing under the high-amplification-factor Electronic Speculum; Carbon fiber surface has been observed the etching pit and has been formed, and Fig. 4 (c) is that carbon fiber surface has the obvious corrosion pit to form through the carbon fiber pattern of the carbon/carbon compound material of 700v, 20min, the processing of 60Pa plasma treatment condition.Through after the Cement Composite Treated by Plasma; Carbonyl, hydroxyl isoreactivity group have been introduced on the carbon/carbon compound material surface; Shown in Fig. 5 (a) infrared spectrogram; Fig. 5 (b) is the carbon/carbon compound material infrared spectrogram without Cement Composite Treated by Plasma, and carbon fiber reinforced carbon matrix body is after treatment put into alcoholic solution and carried out ultrasonic cleaning, cleans argon and bombards the RESEARCH OF PYROCARBON granule that gets off;
D. carry out spraying hydroxyapatite coating formation finished product carbon/carbon compound material to cleaning carbon fiber reinforced carbon matrix surface later; To the carbon/carbon compound material handled through 600v, 20min, 60Pa plasma treatment condition, and the carbon/carbon compound material that does not carry out plasma treatment carry out plasma spraying, see hydroxyapatite coating layer mainly by the granulometric composition that differs in size that has dissolved hydroxyapatite by Fig. 6 (a), Fig. 6 (b), surface irregularity and have the space to exist; Help the growth of seeking connections with of human tissue cell; With the hydroxyapatite coating layer pattern basically identical that forms without the plasma pretreatment carbon/carbon compound material, find that through both electron spectrums (EDS) Fig. 6 (c), Fig. 6 (d) coating that two kinds of methods obtain all contains Ca, P; C; Compositions such as O, O are observed the carbon/carbon compound material of being handled by 600v, 20min, 60Pa plasma treatment condition, the infrared absorption spectroscopy that reaches the carbon/carbon compound material HA coating of not carrying out plasma treatment from matrix; Like Fig. 7,2500cm
-1～3200cm
-1Wide and diffusing peak be the C-H stretching vibration, 1654cm
-1And 3447cm
-1Be the absworption peak of hydroxyl, and at 3582cm
-1The characteristic absorption peak of HA possibly covered by the hydroxyl absworption peak, and the stretching vibration of P-O appears at 1090cm
-1, 1048cm
-1, and 602cm
-1, 569cm
-1, 473cm
-1It then is the absworption peak of P-O bending vibration
[16]The intensity and the width of absworption peak of stretching vibration and bending vibration of P-O that carries out the carbon/carbon compound material HA coating of plasma pretreatment strengthens than the untreated carbon/carbon compound material HA of plasma coating; From the XRD figure spectrum, find; As shown in Figure 8; The part diffraction maximum that has occurred HA crystal face characteristic diffraction peak ((100), (201), (211), (112), (300), (222), (213)) and calcium phosphate, calcium oxide in the collection of illustrative plates of HA coating; The diffraction maximum that has yet occurred other impurity in the collection of illustrative plates possibly totally not exist other sprayed on material relevant with the plasma spray gun cleaning;
Carbon/carbon compound material after the spraying need carry out the cut test; Read the data of scratching instrument and combine SEM cut picture; As shown in Figure 9; Obtain adopting or not adopting plasma pretreatment Tan ∕ carbon composite HA coating critical load to be respectively 14.0N, 8.9N, the former has improved 57.3% than latter critical load, according to formula
H
SBe matrix hardness, L
CBe critical pressure, R is for loading the adamantine tip of pressure head half warp, adopts or do not adopt both shear strengths of plasma treatment Tan ∕ carbon composite HA coating to be respectively 63.3MPa, 50.5MPa.Cut smooth before adopting plasma treatment Tan ∕ carbon composite HA coating to lose efficacy, after inefficacy, coating stripping exposes matrix, and the matrix place is visible to have a spot of coating residual, and this part is residual mainly to be to be arranged in due to the coating of carbon/carbon compound material hole.And bulk disbonding after not losing efficacy with plasma treatment Tan ∕ carbon composite HA coating, coating's adhesion is not strong.
Adopt following than the mechanism that does not adopt plasma pretreatment Tan ∕ carbon composite HA coating critical load to improve: argon ion bombards carbon/carbon compound material at a high speed; Remove carbon fiber defective such as gauffer, the fragment etc. on RESEARCH OF PYROCARBON surface on every side; Gauffers etc. are poor with the adhesion of matrix and hydroxyapatite, be prone to come off, and remove the critical load that RESEARCH OF PYROCARBON blemish such as gauffer can improve the HA coating of Tan ∕ carbon composite.
With above-mentioned foundation desirable embodiment of the present invention is enlightenment, and through above-mentioned description, the related work personnel can carry out various change and modification fully in the scope that does not depart from this invention technological thought.The technical scope of this invention is not limited to the content on the description, must confirm its technical scope according to the claim scope.
Claims (2)
1. the method for preparing of a personalized carbon-carbon composite artificial bone is characterized in that concrete steps are following:
A. select the carbon fiber reinforced carbon matrix body as raw material;
B. carry out the artificial bone profile through the collection of CT image; Artificial bone profile after the collection converts the method for non-uniform rational B-spline curved surface to carbon/carbon compound material is handled back formation carbon/carbon compound material artificial bone, and its concrete grammar is following: (1) profile is delineated; (2) generate the two-value volume data; (3) triangle gridding generates; (4) convert nurbs surface to;
C. the carbon fiber reinforced carbon matrix body is put into the vacuum glow discharge chamber; In the vacuum glow discharge chamber, feed argon and carry out plasma pretreatment is carried out in the carbon fiber reinforced carbon matrix surface, carbon fiber reinforced carbon matrix body is after treatment put into alcoholic solution and is carried out ultrasonic cleaning;
D. carry out spraying hydroxyapatite coating formation finished product carbon/carbon compound material to cleaning carbon fiber reinforced carbon matrix surface later.
2. a kind of personalized carbon-carbon composite artificial bone according to claim 1, it is characterized in that: the carbon/carbon compound material artificial bone comprises carbon/carbon compound material and hydroxyapatite among the d, and is hydroxyapatite sprayed on the carbon/carbon compound material surface.
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Cited By (10)
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| CN103920186A (en) * | 2014-04-17 | 2014-07-16 | 倪昕晔 | Magnesium-containing hydroxyapatite coating on surface of medical material and preparation method of coating |
| CN104587527A (en) * | 2015-01-16 | 2015-05-06 | 中国石油大学(华东) | Bio-functionalized carbon/carbon composite material and preparation method thereof |
| CN105908155A (en) * | 2016-06-16 | 2016-08-31 | 倪昕晔 | Preparing method for magnesium-containing hydroxyapatite coating on surface of carbon/carbon composite |
| CN110680559A (en) * | 2019-09-27 | 2020-01-14 | 长沙晟天新材料有限公司 | Chest lock integrated piece and preparation method thereof |
| CN110841114A (en) * | 2019-09-27 | 2020-02-28 | 长沙晟天新材料有限公司 | Carbon fiber composite material artificial bone and preparation method thereof |
| CN111925226A (en) * | 2020-01-19 | 2020-11-13 | 湖南碳康生物科技有限公司 | Carbon fiber composite skull patch and preparation method thereof |
| CN112370569A (en) * | 2021-01-15 | 2021-02-19 | 湖南碳康生物科技有限公司 | Carbon fiber composite material artificial rib and preparation method thereof |
| CN112843340A (en) * | 2021-01-18 | 2021-05-28 | 湖南碳康生物科技有限公司 | Carbon-based composite material artificial rib and preparation method thereof |
| CN112876269A (en) * | 2021-01-18 | 2021-06-01 | 湖南碳康生物科技有限公司 | Carbon fiber composite material artificial rib with adjustable length and preparation method thereof |
| US11980548B2 (en) | 2017-08-23 | 2024-05-14 | Hunan Tankang Biotech Co., Ltd. | Carbon fiber composite artificial bone and preparation method thereof |
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| CN103920186A (en) * | 2014-04-17 | 2014-07-16 | 倪昕晔 | Magnesium-containing hydroxyapatite coating on surface of medical material and preparation method of coating |
| CN104587527A (en) * | 2015-01-16 | 2015-05-06 | 中国石油大学(华东) | Bio-functionalized carbon/carbon composite material and preparation method thereof |
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| CN110841114B (en) * | 2019-09-27 | 2021-12-14 | 长沙晟天新材料有限公司 | Carbon fiber composite material artificial bone and preparation method thereof |
| CN110680559A (en) * | 2019-09-27 | 2020-01-14 | 长沙晟天新材料有限公司 | Chest lock integrated piece and preparation method thereof |
| CN110841114A (en) * | 2019-09-27 | 2020-02-28 | 长沙晟天新材料有限公司 | Carbon fiber composite material artificial bone and preparation method thereof |
| CN111925226A (en) * | 2020-01-19 | 2020-11-13 | 湖南碳康生物科技有限公司 | Carbon fiber composite skull patch and preparation method thereof |
| CN111925226B (en) * | 2020-01-19 | 2022-04-08 | 湖南碳康生物科技有限公司 | Carbon fiber composite skull patch and preparation method thereof |
| CN112370569A (en) * | 2021-01-15 | 2021-02-19 | 湖南碳康生物科技有限公司 | Carbon fiber composite material artificial rib and preparation method thereof |
| CN112876269A (en) * | 2021-01-18 | 2021-06-01 | 湖南碳康生物科技有限公司 | Carbon fiber composite material artificial rib with adjustable length and preparation method thereof |
| CN112843340A (en) * | 2021-01-18 | 2021-05-28 | 湖南碳康生物科技有限公司 | Carbon-based composite material artificial rib and preparation method thereof |
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