阅读说明：本技术 一种碳纤维复合材料人工骨及其制备方法 (Carbon fiber composite material artificial bone and preparation method thereof ) 是由 谭周建 于 2019-09-27 设计创作，主要内容包括：本发明提供了一种碳纤维复合材料人工骨及其制备方法,人工骨垂直于长度方向的截面为U形,人工骨由连续碳纤维编织物复合材料层和碳纤维非织造布复合材料层叠加构成；连续碳纤维编织物复合材料层和碳纤维非织造布复合材料层的碳纤维间均填充有碳基体。该复合材料具有质量轻、生物相容性好、化学稳定性好、力学性能与人体骨相近、疲劳性好、可设计性强、无伪影等特点,且表层孔隙和表面稳定粘附有羟基磷灰石,以提高复合材料的生物活性,促进骨生长和诱导骨增殖。(The invention provides a carbon fiber composite artificial bone and a preparation method thereof, wherein the section of the artificial bone perpendicular to the length direction is U-shaped, and the artificial bone is formed by overlapping a continuous carbon fiber braided fabric composite material layer and a carbon fiber non-woven fabric composite material layer; and carbon matrixes are filled between the carbon fibers of the continuous carbon fiber braided fabric composite material layer and the carbon fiber non-woven fabric composite material layer. The composite material has the characteristics of light weight, good biocompatibility, good chemical stability, mechanical property similar to human bone, good fatigue, strong designability, no artifact and the like, and hydroxyapatite is stably adhered to surface pores and surfaces of the composite material, so that the biological activity of the composite material is improved, the bone growth is promoted and the bone proliferation is induced.)

1. The utility model provides a carbon-fibre composite artificial bone which characterized in that: the cross section of the artificial bone perpendicular to the length direction is U-shaped, and the artificial bone is formed by overlapping a continuous carbon fiber braided fabric composite material layer and a carbon fiber non-woven fabric composite material layer; and carbon matrixes are filled between the carbon fibers of the continuous carbon fiber braided fabric composite material layer and the carbon fiber non-woven fabric composite material layer.

2. The artificial bone made of carbon fiber composite material according to claim 1, wherein: the continuous carbon fiber braid composite layer comprises a cloth, tape or strip woven from carbon fiber bundles.

3. The artificial bone made of carbon fiber composite material according to claim 2, wherein: the twist of the carbon fiber bundle is 10-500 twists/m, and the single carbon fiber bundle comprises 1k, 3k, 6k, 12k or 24k carbon fibers.

4. The artificial bone made of carbon fiber composite material according to claim 1, wherein: hydroxyapatite is adhered to the inner and the surface of the pores of the artificial bone made of the carbon fiber composite material.

5. The artificial bone made of carbon fiber composite material according to claim 4, wherein: the mass of the hydroxyapatite accounts for 5-15% of the mass of the carbon fiber composite material artificial bone.

6. The artificial bone made of carbon fiber composite material according to claim 1, wherein: the artificial bone made of the carbon fiber composite material comprises one or two carbon fiber non-woven fabric composite material layers, and when the artificial bone made of the carbon fiber composite material comprises the two carbon fiber non-woven fabric composite material layers, the continuous carbon fiber braided fabric composite material layer is arranged between the two carbon fiber non-woven fabric composite material layers.

7. The artificial bone made of carbon fiber composite material according to claim 1, wherein: the carbon fiber non-woven fabric composite material layer comprises the following components with the surface density of 10g/m²～60g/m²A carbon fiber nonwoven fabric.

8. The artificial bone made of carbon fiber composite material according to claim 1, wherein: the continuous carbon fiber braided fabric composite material layer and the carbon fiber non-woven fabric composite material layer are riveted by adopting carbon fibers in a needling mode, and the areal density of riveting points is 5 points/cm²25 dots/cm²。

9. The method for preparing the artificial bone made of the carbon fiber composite material according to any one of claims 1 to 8, wherein the method comprises the following steps: the method comprises the following steps:

1) twisting the carbon fiber bundle into a carbon fiber rope, then weaving into a continuous fiber braided fabric, riveting carbon fiber non-woven fabric on the surface of the continuous fiber braided fabric, and then preparing into a U-shaped carbon fiber prefabricated body by adopting a mold;

2) the carbon fiber preform is subjected to chemical vapor infiltration and/or impregnation-pyrolysis to generate a carbon matrix, a blank is obtained, and the blank is machined to obtain the carbon fiber preform;

or generating hydroxyapatite in the pores and on the surface of the blank, and then machining to obtain the material.

10. The method for preparing the artificial bone made of the carbon fiber composite material according to claim 9, wherein the method comprises the following steps:

hydroxyapatite is produced by plasma spraying, electrochemical deposition or sol-gel methods.

Technical Field

The invention relates to an artificial bone material, in particular to a carbon fiber reinforced carbon composite artificial bone and a preparation method thereof, belonging to the field of biomedical materials.

Background

The traditional artificial bone is mainly made of metal materials, and has many clinical application problems, such as osteoporosis, fracture, rejection reaction and other postoperative complications caused by stress shielding due to mismatch of mechanical properties, toxicity of corrosion-dissolved ions, metal artifacts which are not favorable for postoperative diagnosis, necessary secondary operations and the like. The nonmetallization of bone-knitting materials has become a trend, and carbon materials have good biocompatibility. Wherein the carbon fiber, pyrolytic carbon, carbon nanotube and its compound are applied in biomedical fields. The carbon fiber composite material is a carbon-based material which is composed of carbon fibers and fabrics thereof as reinforcements, has the characteristics of light weight, strong designability, no artifact and the like compared with other materials, and has certain improvement on biocompatibility, chemical stability and mechanical property. However, the carbon fiber reinforced carbon composite bone-knitting material designed in the prior art has some obvious technical problems: for example, in the carbon-ceramic composite bone fracture plate disclosed in chinese patent (CN108171798A), the chopped carbon fibers are distributed in the structural frame in an evenly distributed or unevenly distributed manner, and the surface of the bone fracture plate is coated with resin carbon, so that the mechanical properties of the bone fracture plate are poor. Chinese patent (CN 108577957 a) discloses a carbon/carbon-silicon carbide composite bone plate, which comprises a carbon/carbon composite base material formed by sequentially and alternately laminating 0-degree non-woven fabric, a carbon fiber mesh blank and 90-degree non-woven fabric, wherein the cloth mesh lamination has large damage to continuous fibers by needling. In addition, the connection strength between the hydroxyapatite on the surface layer of the carbon fiber reinforced carbon composite material bone-knitting material in the prior art and a matrix is weak, and the bone-knitting material is easy to crack or delaminate due to large difference of thermal expansion coefficients in direct contact.

Disclosure of Invention

Aiming at the defects in the prior art, the first purpose of the invention is to provide the carbon fiber composite material artificial bone taking carbon fibers and carbon fiber fabrics as reinforcing phases, which has the characteristics of light weight, good biocompatibility, good chemical stability, mechanical property similar to human bone, good fatigue, strong designability, no artifact and the like, and hydroxyapatite is stably adhered to surface pores and surfaces, so that the biological activity of the composite material can be improved, the bone growth can be promoted, and the bone proliferation can be induced.

The invention also aims to provide a method for preparing the carbon fiber composite material artificial bone, which has simple steps and easily obtained raw materials.

In order to achieve the technical purpose, the invention provides an artificial bone made of a carbon fiber composite material, wherein the section of the artificial bone perpendicular to the length direction is U-shaped, and the artificial bone is formed by riveting and superposing a continuous carbon fiber braided fabric composite material layer and a carbon fiber non-woven fabric composite material layer; and carbon matrixes are filled between the carbon fibers of the continuous carbon fiber braided fabric composite material layer and the carbon fiber non-woven fabric composite material layer.

The continuous carbon fiber braided fabric in the carbon fiber composite material is composed of long carbon fibers, the carbon fiber content is high, the strength support is mainly provided, the carbon fiber non-woven fabric is composed of short fibers, the short fibers are arranged on the surface layer, the characteristic of high porosity of the carbon fiber non-woven fabric is utilized, a large number of surfaces can be provided for attaching hydroxyapatite, meanwhile, the short fibers penetrate into the continuous carbon fiber braided fabric to play a riveting role, the hydroxyapatite can penetrate into the carbon fibers, tissue cells can grow into the interior, and the binding capacity with tissues is improved.

The cross section of the artificial bone made of the carbon fiber composite material, which is vertical to the length direction, is in a U shape, so that the artificial bone can be conveniently butted with an autologous bone, dislocation is avoided, the connection strength is improved, and the rigidity of the artificial bone structure can be improved.

Preferably, the continuous carbon fiber braid composite material layer comprises a cloth, tape or strip woven from carbon fiber bundles.

Preferably, the carbon fiber non-woven fabric composite material layer comprises an areal density of 10g/m²～60g/m²A carbon fiber nonwoven fabric.

Preferably, the twist of the carbon fiber bundle is 10 to 500 twists/m, and the single carbon fiber bundle includes 1k, 3k, 6k, 12k or 24k carbon fibers (1k represents 1 thousand carbon fibers). The carbon fiber bundles are twisted and then woven into a continuous woven structure such as cloth, a belt or a strip, so that the rigidity can be greatly improved, and the flexural modulus can be improved.

In a preferable scheme, hydroxyapatite is adhered to the inner and surface of the pores of the carbon fiber composite material artificial bone. The hydroxyapatite is introduced to guide the growth of tissue cells and improve the binding capacity of biocompatibility and tissues.

In a more preferable scheme, the mass of the hydroxyapatite accounts for 5% -15% of the mass of the carbon fiber composite material artificial bone.

According to the preferable scheme, the continuous carbon fiber braided fabric composite material layer and the carbon fiber non-woven fabric composite material layer are riveted by adopting carbon fibers in a needling mode, and the areal density of riveting points is 5 points/cm²25 dots/cm². The bonding strength between the carbon fiber knitted fabric and the carbon fiber cloth and between the carbon fiber woven fabric and the carbon fiber non-woven fabric can be improved by adopting proper riveting point surface density.

Preferably, the carbon fiber composite artificial bone comprises one or two carbon fiber non-woven fabric composite material layers, and when the carbon fiber composite artificial bone comprises the two carbon fiber non-woven fabric composite material layers, the continuous carbon fiber braided fabric composite material layer is arranged between the two carbon fiber non-woven fabric composite material layers. The carbon fiber composite artificial bone has a double-layer structure or a sandwich structure.

The riveting of the invention is that the continuous carbon fiber braided fabric composite material layer and the carbon fiber non-woven fabric composite material layer are riveted and formed by carbon fibers through needling.

The invention also discloses a preparation method of the carbon fiber composite material artificial bone, which comprises the following steps:

1) twisting the carbon fiber bundles into carbon fiber ropes, then weaving into continuous carbon fiber braided fabrics, riveting carbon fiber non-woven fabrics on the surfaces of the continuous carbon fiber braided fabrics, and then preparing into a U-shaped carbon fiber prefabricated body by adopting a mold for assistance;

2) the carbon fiber preform is subjected to chemical vapor infiltration and/or impregnation-pyrolysis to generate a carbon matrix, a blank is obtained, and the blank is machined to obtain the carbon fiber preform; or generating hydroxyapatite in the pores and on the surface of the blank, and then machining to obtain the material.

Preferably, the hydroxyapatite is formed by plasma spraying, electrochemical deposition or sol-gel method.

In the preparation method, the blank body can be subjected to a high-temperature impurity removal or thermal refining treatment step or is not subjected to treatment.

The carbon fiber bundle of the present invention is twisted into one or more bundles.

The surface density of the carbon fiber nonwoven fabric of the present invention was 10g/m²～60g/m²。

The riveting is carried out by adopting carbon fibers in a needling manner, and the areal density of the riveting points is 5 points/cm²25 dots/cm²。

The mold can be a carbon material mold, the shape of which can be designed according to the needs, for example, the mold with the U-shaped cavity can be designed according to the needs.

The machining of the invention includes trimming, polishing, punching and the like.

The chemical vapor infiltration process of the invention comprises the following steps: and (2) putting the carbon fiber preform into a vacuum furnace, cracking an introduced gas source (natural gas, methane or propylene and the like are used as a carbon source, nitrogen or hydrogen is used as a diluent gas, and the flow ratio of the carbon source gas to the diluent gas is 1: 0-2) at the temperature of 850-1300 ℃, then, permeating a chemical vapor into the carbon fiber blank, and preparing the carbon fiber composite blank after 10-100 hours.

The liquid impregnation-cracking densification process comprises the following steps: the carbon fiber preform is subjected to densification processes such as resin (furan, phenolic aldehyde, copper foil and the like) or asphalt (graphite asphalt, coal asphalt) vacuum pressurization impregnation, curing treatment (resin), cracking (resin: 900-1050 ℃, normal pressure; asphalt: 750-850 ℃, 50-200 MPa) and the like. The dipping pressure is 1.0MPa to 5.0MPa, and the dipping time is 2 hours to 10 hours; the curing temperature is 160-230 ℃, and the curing time is 10-50 hours; the cracking time is 2-20 hours.

The blank can also be subjected to high-temperature impurity removal treatment, and the treatment process conditions are as follows: the temperature is 1500-2300 ℃, and the holding time is 1-10 hours.

The preparation process of the hydroxyapatite coating comprises the following steps:

(1) plasma spraying method:

1) the granularity of the hydroxyapatite powder is 20-150 mu m; 2) the plasma spraying power is 20 kW-40 kW; 3) The heat treatment temperature is 600-800 ℃, and the time is 1-5 hours.

(2) Electrochemical deposition:

1) the ratio of Ca ions to P ions in the phosphorus-containing and calcium-containing solution is 1.67; 2) the current density is 0.5mA/cm 2-3 mA/cm 2; 3) the deposition time is 20min to 150 min; 4) the temperature of the electrolyte is 25-90 ℃; 5) the heat treatment temperature is 700-1000 ℃ and the time is 1-5 hours.

(3) Sol-gel method:

1) the sol is prepared by mixing and reacting phosphoric acid triethanol and calcium nitrate, wherein the ratio of Ca ions to P ions is 1.67; 2) the gel temperature is 80-120 ℃, and the time is 3-20 hours; 3) the heat treatment temperature is 400-800 ℃, and the time is 1-5 hours.

The carbon fiber composite material artificial bone provided by the invention takes carbon as a base material, takes a continuous fiber braided fabric and a carbon fiber non-woven fabric as reinforcing phases, the two layers form an integral structure through riveting, and fibers in the carbon fiber non-woven fabric penetrate into the continuous fiber braided fabric to form a porous layer, so that hydroxyapatite with biological activity is filled into the gap layer, the falling of matrix particles can be avoided, and meanwhile, the bone growth and the induced bone proliferation are promoted.

The carbon fiber continuous fiber braided fabric can adopt single-bundle carbon fibers or multiple-bundle carbon fibers twisted into ropes and then braided strips, cloth or belts and the like.

Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:

the artificial bone of the invention adopts the carbon fiber composite material, has the characteristics of light weight, good biocompatibility, good chemical stability, mechanical property similar to that of human bone, good fatigue property, strong designability, no artifact and the like, and hydroxyapatite is stably adhered to surface pores and surfaces, thus improving the bioactivity of the composite material, promoting bone growth and inducing bone proliferation.

The artificial bone made of the carbon fiber composite material has a laminated structure of the continuous carbon fiber braided fabric and the carbon fiber non-woven fabric, the continuous carbon fiber is mainly composed of long fibers, the carbon fiber content is high, the strength support is mainly provided, the carbon fiber non-woven fabric is composed of short fibers, the carbon fiber non-woven fabric is arranged on the surface layer, a large number of surfaces can be provided for attaching hydroxyapatite by utilizing the characteristic of high porosity of the carbon fiber non-woven fabric, meanwhile, the short fibers penetrate into the continuous carbon fiber braided fabric to play a riveting role, the penetration of the hydroxyapatite into the carbon fiber and the growth of tissue cells to the inside are facilitated, and the binding capacity with tissues is.

The carbon fiber composite material artificial bone has good mechanical properties: the tensile strength is 120 MPa-220 MPa, the tensile modulus is 10 GPa-30 GPa, and the bending strength is more than or equal to 180 MPa.

Drawings

Fig. 1 is a structural view of a twisted continuous carbon fiber braid.

FIG. 2 is an SEM photograph of a two-layer structure carbon fiber composite prepared in example 1; wherein (a) is a cross-section; (b) is a surface; (a) the upper layer is non-woven fabric (short fiber layer), and the lower layer is twisted carbon fiber continuous braided strips, and has a two-layer structure.

Fig. 3 is a schematic view of the shape of the artificial bone made of the carbon fiber composite material, the left view is a top view, and the right side is a schematic view of a section in the length direction.

Detailed Description

The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.