CN108379671A - A kind of C/C-SiC composite material bones plate and preparation method thereof with BMP controlled-release coatings - Google Patents
A kind of C/C-SiC composite material bones plate and preparation method thereof with BMP controlled-release coatings Download PDFInfo
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- CN108379671A CN108379671A CN201810196425.2A CN201810196425A CN108379671A CN 108379671 A CN108379671 A CN 108379671A CN 201810196425 A CN201810196425 A CN 201810196425A CN 108379671 A CN108379671 A CN 108379671A
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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Abstract
The invention discloses a kind of C/C SiC ceramic matrix composite material bones plate and preparation method thereof with BMP controlled-release coatings, which includes by 0 ° of non-woven fabrics, carbon fibre web tire and 90 ° of non-woven fabrics C/C composite material bases that alternative stacked is formed successively；The C/C composite material bases interlayer fills needle-punched carbon fiber, and SiC is filled in the hole of C/C composite material bases；The surface of C/C composite material bases is coated with pyrolysis layer of charcoal；The surface of the pyrolysis layer of charcoal is coated with SiC layer；And the surface recombination of the SiC layer has BMP controlled-release coatings.The bone plate has good biocompatibility, and fatigue behaviour is good, and mechanical property is close with people's bone, and will not be to generations interference or barrier effects such as MRI, CT, x-ray inspections.
Description
Technical field
The present invention relates to biomedical material technologies, and in particular to a kind of C/C-SiC with BMP controlled-release coatings is multiple
Condensation material bone plate and preparation method thereof.
Background technology
Traditional bone plate is mostly metal material, predominantly stainless steel and titanium alloy.But the bone plate of metal material exists
Problems with is primarily present in clinical application：(1) there are stress shieldings, are easily destroyed fracture blood fortune；(2) it is also easy to produce in vivo
Electrochemical reaction is corroded；(3) healing of fracture cannot be directly facilitated, easily occur delayed union or disunion, bone plate fracture,
The postoperative complications such as screw loosening falls off, rejection；(4) patient's x-ray, CT and MRI inspection results are frequently subjected to metal synthetism
Plate seriously affects, and causes inspection result inaccurate.
Patent document CN1296013C discloses a kind of carbon fiber reinforced polyetheretherketonecomposite composite material bone plate, by carbon fiber
It is injection moulded and obtains after particle and polyether-ether-ketone mixing granulation, due to being injection moulding, it is continuous more than 2cm that length not can be used
Carbon fiber can not obtain and continuously sprawl structure, and therefore, the humidification that carbon fiber is played does not play a role completely.
Therefore, there is an urgent need for developing a kind of good biocompatibility, mechanical property is more adapted to people's bone, and will not be to the inspection of patient
The bone plate that the fruit that comes to an end impacts, to replace existing bone plate.
Invention content
It is an object of the present invention to overcome the shortcomings of to mention in background above technology and defect, providing a kind of having BMP
C/C-SiC composite material bones plate of (bone morphogenetic protein) controlled-release coating and preparation method thereof, the bone plate bio-compatible
Property it is good, mechanical property and people's bone are close, and interference or blocking will not be generated to medical inspection.
In order to solve the above technical problems, technical solution proposed by the present invention is：
A kind of C/C-SiC composite material bones plate with BMP controlled-release coatings,
Include by 0 ° of non-woven fabrics, carbon fibre web tire and 90 ° of non-woven fabrics C/C composite material bases that alternative stacked is formed successively
Material；
The C/C composite material bases interlayer fills needle-punched carbon fiber, is filled in the hole of C/C composite material bases
SiC；
The surface of C/C composite material bases is coated with pyrolysis layer of charcoal；
The surface of the pyrolysis layer of charcoal is coated with SiC layer；And
The surface recombination of the SiC layer has BMP controlled-release coatings.
As a preferred option, the simple substance Si for accounting for SiC layer gross mass 0.1%~0.5% is contained in the SiC layer.
As a preferred option, the BMP controlled-release coatings are the slow-release gelatin microspheres coating of the molecule of activated protein containing BMP.
Further preferred scheme, in the BMP controlled-release coatings, the grain size of BMP sustained-release micro-spheres is 10 μm~100 μm, packet
Envelope rate >=80%, carrying drug ratio are 20 μ of μ g/mg~50 g/mg.
As a preferred option, the loading of the needle-punched carbon fiber be C/C composite material base quality 10%~
15%, a diameter of 5 μm~7 μm of needle-punched carbon fiber.
As a preferred option, the pyrolysis layer of charcoal is multilayer, and the thickness of each layer of pyrolytic carbon is 2mm~5mm, pyrolysis
Total covering amount of charcoal is the 5%~10% of C/C composite material base quality.
As a preferred option, the elasticity modulus of the bone plate is 10GPa~30GPa, and compression strength >=200MPa resists
Curved intensity >=220MPa, shear strength >=16MPa, tensile strength are 110MPa~130MPa, elongation percentage≤2%.
A kind of preparation method of the above-mentioned C/C-SiC composite material bones plate with BMP controlled-release coatings, including following step
Suddenly：
(1) 0 ° of non-woven fabrics, carbon fibre web tire and 90 ° of non-woven fabrics are cut by design size, then by cut 0 ° of nonwoven
Cloth, carbon fibre web tire and 90 ° of non-woven fabrics alternative stacked successively are filled needle-punched carbon fiber as reinforced phase in interlayer, and are passed through
SiC is filled in the hole of product of the chemical vapor infiltration after alternative stacked；
(2) product of alternative stacked obtained by step (1) is placed on warm table and is preheated, on the product of alternative stacked
Pyrolytic carbon is coated, discharge interlayer gas is then squeezed in pyrolysis layer of charcoal outer cladding SiC by chemical vapour deposition technique, then will
Product is placed in preliminary mould, the shape pre-shaped designed by preliminary mould；
(3) the good product of step (2) pre-shaped is put into preheating in preheating oven, then takes out and is put into progress in molding die
It is hot-forming, obtain C/C-SiC composite materials；
(4) mold of the step (3) after hot-forming is cooled, takes out product, product is cleaned and is dried, so
CNC processing is carried out according to the design drawing of bone plate afterwards, obtains C/C-SiC composite material bone plate precast bodies；
(5) slow-release gelatin microspheres of the molecule of activated protein containing BMP are prepared by emulsification and cross linked solidification method；
(6) carbon-carbon composite bone plate precast body surface modification shell obtained by as electrostatic self-assembled method in step (4) is poly-
Sugar；
(7) use dip-coating method that the slow-release gelatin microspheres of the molecule of activated protein containing BMP obtained by step (5) are compounded in step
Suddenly the surface of the C/C-SiC composite material bone plate precast bodies of chitosan is modified with obtained by (6) to get with BMP controlled-release coatings
C/C-SiC composite material bones plate.
Above-mentioned preparation method, it is preferred that in the step (5), the slow-release gelatin microspheres of the molecule of activated protein containing BMP have
Body is prepared by the following method to obtain：
(5.1) configuration gelatin solution, which is placed in water-bath, preheats, and the gelatin solution of preheating is added drop-wise in atoleine dropwise,
It is stirred when being added dropwise, continues to stir evenly after dripping, be then transferred in ice-water bath rapidly and handled, add crosslinking agent friendship
Connection, is washed with cleaning solution after the completion of crosslinking, obtains faint yellow microballoon；Be placed in again under low temperature environment continue solidification one section when
Between, it is finally fully washed, is sieved again with cleaning solution, packing, gelatin microballoon of having leisure；
(5.2) the blank gelatine microsphere that step (5.1) is prepared is as raw material, and system is mixed with sodium alginate soln
Standby gelatin/sodium alginate blank nucleocapsid structure sustained-release micro-spheres；
(5.3) the gelatin/sodium alginate blank nucleocapsid structure sustained-release micro-spheres that step (5.2) is prepared are added to bone
It is slow to get the gelatin-sodium alginate nucleocapsid structure for being loaded with BMP after fully shaking in the PBS buffer solutions of morphogenetic proteins
Release microballoon.
Above-mentioned preparation method, it is preferred that in the step (3), the temperature of preheating is 45 DEG C~75 DEG C, the time of preheating
For 40min~60min.
Above-mentioned preparation method, it is preferred that in the step (3), hot-forming temperature is 100 DEG C~250 DEG C, pressurization
Time is 60min~120min, external pressure 100kg/cm2~120kg/cm2。
Above-mentioned preparation method, it is preferred that in the step (3), the volume content of carbon fiber in C/C-SiC composite materials
Density >=1.75g/cm of >=35%, C/C-SiC composite material3。
Above-mentioned preparation method, it is preferred that in the step (4), cooling temperature is 35 DEG C~45 in the operation that cools
DEG C, cooling time is 5min~10min, and cooling external pressure is 110kg/cm2~120kg/cm2。
Above-mentioned preparation method, it is preferred that in the step (4), dry temperature is 155 DEG C~165 DEG C.
Compared with the prior art, the advantages of the present invention are as follows：The present invention passes through 0 ° of non-woven fabrics, carbon fibre web tire and 90 ° of nothings
Alternative stacked forms carbon-carbon composite matrix to woven fabric successively, SiC is filled in the hole of C/C composite material bases, in interlayer
Fill needle-punched carbon fiber as reinforced phase, pyrolytic carbon is coated on product, pyrolysis layer of charcoal surface coated Si/C, through pre-shaped with
Hot-forming obtained C/C-SiC composite materials, then by C/C-SiC composite processings at bone plate precast body, then in synthetism
Compound BMP controlled-release coatings on plate precast body obtain the C/C-SiC composite material bones plate with BMP controlled-release coatings.Gained synthetism
Plate has good biocompatibility, and fatigue behaviour is good, and mechanical property is close with people's bone, and will not be examined to MRI, CT, x-ray
Generations interference or the barrier effect such as look into.
Description of the drawings
Fig. 1 is that the compressed pattern of people's bone and 1 gained C/C-SiC composite materials of the embodiment of the present invention compares photo, in Fig. 1
Left figure is people's bone, and right figure is C/C-SiC composite materials.
Fig. 2 is the photo of 1 gained C/C-SiC composite material bones plate of the embodiment of the present invention.
Fig. 3 is the microscopic appearance (SEM) of people's bone and 1 gained C/C-SiC composite material bones plate of the embodiment of the present invention.
Fig. 4 is the SEM figures for the C/C-SiC composite materials for not impregnating simulated body fluid.
Fig. 5 is the SEM figures for impregnating C/C-SiC composite material of the simulated body fluid after 70 days.
Fig. 6 is the interpolation energy spectrum diagram of Fig. 5.
Fig. 7 is remaining bending strength-displacement curve after 1 gained C/C-SiC Composites Fatigues of the embodiment of the present invention.
Fig. 8 is that the SEM of 1 hollow gelatin microballoon of the embodiment of the present invention schemes.
Fig. 9 is the SEM figures of gelatin-sodium alginate nucleocapsid structure sustained-release micro-spheres in the embodiment of the present invention 1.
Figure 10 is the In-vitro release curves that BMP controlled-release coatings load gentamicin sulphate in the embodiment of the present invention 1.
Specific implementation mode
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1：
A kind of preparation method of the C/C-SiC composite material bones plate with BMP controlled-release coatings of the present invention, including it is following
Step：
The size that 0 ° of non-woven fabrics, carbon fibre web tire and 90 ° of non-woven fabrics are cut into design block, is designed according to mechanical structure
It is required that by cut 0 ° of non-woven fabrics, carbon fibre web tire and 90 ° of non-woven fabrics successively alternative stacked, needle-punched carbon fiber is filled in interlayer
As reinforced phase, and SiC is filled in the hole of the product by chemical vapor infiltration after alternative stacked.
The product of gained alternative stacked is placed on warm table and is preheated, two layers of heat is coated on the product of alternative stacked
Charcoal is solved, the thickness of every layer of pyrolytic carbon is 3mm, and total covering amount of the pyrolytic carbon on product is the 5% of quality of item；Then pass through
Chemical vapour deposition technique squeezes discharge interlayer gas, pressing is suitable, and product is then placed on pre-shaped in pyrolysis layer of charcoal outer cladding SiC
In mould, by the shape pre-shaped of preliminary mould design.
The good product of pre-shaped is put into preheating oven and is preheated, preheating temperature is 45 DEG C, preheating time 40min, then
Taking-up is put into molding die, and molding covers tightly, and mold is sent into hot-forming progress is hot-forming, and hot-forming temperature is
100 DEG C, pressing time 60min, external pressure 100kg/cm2, C/C-SiC composite materials are obtained, gained C/C-SiC is compound
The volume content of carbon fiber is 38% in material, and the density of carbon-carbon composite is 1.85g/cm3。
Mold after will be hot-forming is sent into cooling bench and cools, and cooling temperature is 35 DEG C, and cooling time, 5min, cold
But external pressure is 110kg/cm2, it is re-fed into stripping station, product is taken out in die sinking, then product is cleaned and dried, dry
Temperature is 155 DEG C, then carries out CNC processing according to the design drawing of bone plate, it is prefabricated to obtain C/C-SiC composite material bones plate
Body.
Configuration gelatin solution, which is placed in water-bath, to be preheated, and the gelatin solution of preheating is added drop-wise in atoleine dropwise, side drop
Edged stirs, and continues to stir evenly after dripping, is then transferred in ice-water bath rapidly and is handled, add cross-linking agents,
It is washed with cleaning solution after the completion of crosslinking, obtains faint yellow microballoon；It is placed in again under low temperature environment and continues solidification a period of time, most
It is fully washed, is sieved again with cleaning solution afterwards, packing, gelatin microballoon of having leisure；Using blank gelatine microsphere as raw material, and with sea
Solution of sodium alginate is mixed with gelatin/sodium alginate blank nucleocapsid structure sustained-release micro-spheres；By gelatin/sodium alginate blank core-shell structure copolymer
Structure slow-releasing microballoon is added in the PBS buffer solutions of bone morphogenetic protein, to get being loaded with the gelatin-of BMP after fully shaking
Sodium alginate nucleocapsid structure sustained-release micro-spheres.
Chitosan is modified as electrostatic self-assembled method C/C-SiC composite materials bone plate precast body surface obtained by；Using
The slow-release gelatin microspheres of the gained molecule of activated protein containing BMP are compounded in by dip-coating method to be modified with the C/C-SiC of chitosan and answers
The surface of condensation material bone plate precast body is to get the C/C-SiC composite material bones plate with BMP controlled-release coatings.
People's bone with the compressed pattern comparison photo of gained C/C-SiC composite materials (behave in Fig. 1 as shown in Figure 1 by left figure
Bone, right figure are C/C-SiC composite materials).The photo of gained C/C-SiC composite material bones plate is as shown in Figure 2.
People's bone and the microscopic appearance of C/C-SiC composite material bones plate obtained by the present embodiment are as shown in Figure 3.As seen from Figure 3,
The bone plate (h in Fig. 3) of people's bone (b in Fig. 3) and the present embodiment is porous structure, this porous structure can be cell adherence and
The offer smoothly channel of growing up of bone tissue, can reinforce the interface cohesion degree between implant and bone tissue.
Pass through the biocompatibility of simulated body fluid immersion test research material.The C/C-SiC for not impregnating simulated body fluid is compound
The SEM of material schemes as shown in figure 4, the SEM for impregnating C/C-SiC composite material of the simulated body fluid after 70 days schemes as shown in figure 5, Fig. 6
For the interpolation energy spectrum diagram of Fig. 5.Known by gamma-spectrometric data analysis, the surface of C/C-SiC composite materials after simulated body fluid impregnates
A surface sediments are deposited, which is made of Ca, P and O element, and wherein the atomic ratio of calcium phosphorus is 1.6, is shown in C/C-
There is osteoid apatite generation on SiC ceramic matrix composite material surface, illustrates that gained C/C-SiC composite materials can promote the healing of bone.
The fatigue behaviour of gained C/C-SiC composite materials is studied, C/C-SiC composite materials respectively 60%,
70%, remaining bending strength-displacement curve after the load of 80%, 90% stress fatigue is as shown in Figure 7.As seen from Figure 7, work as fatigue
When stress level is relatively low in the process (60% and 70%), remaining bending strength is equal to or slightly higher than static buckling intensity, from figure
As can be seen that curve table sample residue bending strength-displacement curve under both stress levels reveals longer displacement, reflection
Sample is in plasticity after fatigue；After horizontal (the 80% and 90%) fatigue loading of higher stress, the remaining bending strength of sample is aobvious
It writes higher than under static buckling intensity, such as 90% stress level, the bending strength of sample is promoted up to 42.94%.But with
The raising material plasticity of intensity is declined, material catastrophic failure.In addition, occurring subtle on curve after high stress level load
Rank, i.e. the Second bearing face of material, these Second bearing faces are the main reason for causing remaining bending strength to be promoted.Known by Fig. 7,
The C/C-SiC composite materials have good fatigue behaviour.
Fig. 8 is that the SEM of blank gelatine microsphere schemes, and Fig. 9 is that the SEM of gelatin-sodium alginate nucleocapsid structure sustained-release micro-spheres schemes,
Figure 10 is the In-vitro release curves that BMP controlled-release coatings load gentamicin sulphate, wherein lower curve is that nucleocapsid structure carries medicine
Gelatin/sodium alginate microballoon, top curve are the gelatin drug bearing microsphere of not core-shell structure.As seen from Figure 10, there is core-shell structure copolymer knot
The load medicine gelatin/sodium alginate microballoon of structure has better medicament slow release performance, nothing compared with the gelatin drug bearing microsphere of not core-shell structure
Phenomenon of burst release effectively extends pharmaceutical release time.
The mechanical property of gained C/C-SiC composite material bones plate is tested, C/C-SiC composite material bones plate
Mechanical property parameters are as shown in table 1.
Embodiment 2：
A kind of preparation method of the C/C-SiC composite material bones plate with BMP controlled-release coatings of the present invention, including it is following
Step：
The size that 0 ° of non-woven fabrics, carbon fibre web tire and 90 ° of non-woven fabrics are cut into design block, is designed according to mechanical structure
It is required that by cut 0 ° of non-woven fabrics, carbon fibre web tire and 90 ° of non-woven fabrics successively alternative stacked, needle-punched carbon fiber is filled in interlayer
As reinforced phase.
The product of gained alternative stacked is placed on warm table and is preheated, two layers of heat is coated on the product of alternative stacked
Charcoal is solved, the thickness of every layer of pyrolytic carbon is 2mm, and total covering amount of the pyrolytic carbon on product is the 6% of quality of item, squeezes discharge
Interlayer gas, pressing is suitable, and then product is placed in preliminary mould, the shape pre-shaped designed by preliminary mould.
The good product of pre-shaped is put into preheating oven and is preheated, preheating temperature is 55 DEG C, preheating time 50min, then
Taking-up is put into molding die, and molding covers tightly, and mold is sent into hot-forming progress is hot-forming, and hot-forming temperature is
150 DEG C, pressing time 80min, external pressure 105kg/cm2, C/C-SiC composite materials are obtained, gained C/C-SiC is compound
It is 1.90g/cm that the volume content of carbon fiber, which is the density of 40%, C/C-SiC composite materials, in material3。
Mold after will be hot-forming is sent into cooling bench and cools, and cooling temperature is 38 DEG C, and cooling time, 6min, cold
But external pressure is 112kg/cm2, it is re-fed into stripping station, product is taken out in die sinking, then product is cleaned and dried, dry
Temperature is 158 DEG C, then carries out CNC processing according to the design drawing of bone plate, it is prefabricated to obtain C/C-SiC composite material bones plate
Body.
Configuration gelatin solution, which is placed in water-bath, to be preheated, and the gelatin solution of preheating is added drop-wise in atoleine dropwise, side drop
Edged stirs, and continues to stir evenly after dripping, is then transferred in ice-water bath rapidly and is handled, add cross-linking agents,
It is washed with cleaning solution after the completion of crosslinking, obtains faint yellow microballoon；It is placed in again under low temperature environment and continues solidification a period of time, most
It is fully washed, is sieved again with cleaning solution afterwards, packing, gelatin microballoon of having leisure；Using blank gelatine microsphere as raw material, and with sea
Solution of sodium alginate is mixed with gelatin/sodium alginate blank nucleocapsid structure sustained-release micro-spheres；By gelatin/sodium alginate blank core-shell structure copolymer
Structure slow-releasing microballoon is added in the PBS buffer solutions of bone morphogenetic protein, to get being loaded with the gelatin-of BMP after fully shaking
Sodium alginate nucleocapsid structure sustained-release micro-spheres.
Chitosan is modified as electrostatic self-assembled method C/C-SiC composite materials bone plate precast body surface obtained by；Using
The slow-release gelatin microspheres of the gained molecule of activated protein containing BMP are compounded in by dip-coating method to be modified with the C/C-SiC of chitosan and answers
The surface of condensation material bone plate precast body is to get the C/C-SiC composite material bones plate with BMP controlled-release coatings.
The mechanical property of gained C/C-SiC composite material bones plate is tested, C/C-SiC composite material bones plate
Mechanical property parameters are as shown in table 1.
Embodiment 3：
A kind of preparation method of the C/C-SiC composite material bones plate with BMP controlled-release coatings of the present invention, including it is following
Step：
The size that 0 ° of non-woven fabrics, carbon fibre web tire and 90 ° of non-woven fabrics are cut into design block, is designed according to mechanical structure
It is required that by cut 0 ° of non-woven fabrics, carbon fibre web tire and 90 ° of non-woven fabrics successively alternative stacked, needle-punched carbon fiber is filled in interlayer
As reinforced phase.
The product of gained alternative stacked is placed on warm table and is preheated, two layers of heat is coated on the product of alternative stacked
Charcoal is solved, the thickness of every layer of pyrolytic carbon is 4mm, and total covering amount of the pyrolytic carbon on product is the 8% of quality of item, squeezes discharge
Interlayer gas, pressing is suitable, and then product is placed in preliminary mould, the shape pre-shaped designed by preliminary mould.
The good product of pre-shaped is put into preheating oven and is preheated, preheating temperature is 65 DEG C, preheating time 55min, then
Taking-up is put into molding die, and molding covers tightly, and mold is sent into hot-forming progress is hot-forming, and hot-forming temperature is
200 DEG C, pressing time 100min, external pressure 110kg/cm2, C/C-SiC composite materials are obtained, gained C/C-SiC is multiple
It is 1.95g/cm that the volume content of carbon fiber, which is the density of 42%, C/C-SiC composite materials, in condensation material3。
Mold after will be hot-forming is sent into cooling bench and cools, and cooling temperature is 40 DEG C, and cooling time, 8min, cold
But external pressure is 115kg/cm2, it is re-fed into stripping station, product is taken out in die sinking, then product is cleaned and dried, dry
Temperature is 160 DEG C, then carries out CNC processing according to the design drawing of bone plate, it is prefabricated to obtain C/C-SiC composite material bones plate
Body.
Configuration gelatin solution, which is placed in water-bath, to be preheated, and the gelatin solution of preheating is added drop-wise in atoleine dropwise, side drop
Edged stirs, and continues to stir evenly after dripping, is then transferred in ice-water bath rapidly and is handled, add cross-linking agents,
It is washed with cleaning solution after the completion of crosslinking, obtains faint yellow microballoon；It is placed in again under low temperature environment and continues solidification a period of time, most
It is fully washed, is sieved again with cleaning solution afterwards, packing, gelatin microballoon of having leisure；Using blank gelatine microsphere as raw material, and with sea
Solution of sodium alginate is mixed with gelatin/sodium alginate blank nucleocapsid structure sustained-release micro-spheres；By gelatin/sodium alginate blank core-shell structure copolymer
Structure slow-releasing microballoon is added in the PBS buffer solutions of bone morphogenetic protein, to get being loaded with the gelatin-of BMP after fully shaking
Sodium alginate nucleocapsid structure sustained-release micro-spheres.
Chitosan is modified as electrostatic self-assembled method C/C-SiC composite materials bone plate precast body surface obtained by；Using
The slow-release gelatin microspheres of the gained molecule of activated protein containing BMP are compounded in by dip-coating method to be modified with the C/C-SiC of chitosan and answers
The surface of condensation material bone plate precast body is to get the C/C-SiC composite material bones plate with BMP controlled-release coatings.
The mechanical property of gained C/C-SiC composite material bones plate is tested, C/C-SiC composite material bones plate
Mechanical property parameters are as shown in table 1.
Embodiment 4：
A kind of preparation method of the C/C-SiC composite material bones plate with BMP controlled-release coatings of the present invention, including it is following
Step：
The size that 0 ° of non-woven fabrics, carbon fibre web tire and 90 ° of non-woven fabrics are cut into design block, is designed according to mechanical structure
It is required that by cut 0 ° of non-woven fabrics, carbon fibre web tire and 90 ° of non-woven fabrics successively alternative stacked, needle-punched carbon fiber is filled in interlayer
As reinforced phase.
The product of gained alternative stacked is placed on warm table and is preheated, two layers of heat is coated on the product of alternative stacked
Charcoal is solved, the thickness of every layer of pyrolytic carbon is 5mm, and total covering amount of the pyrolytic carbon on product is the 10% of quality of item, the row of extruding
Go out interlayer gas, pressing is suitable, and then product is placed in preliminary mould, the shape pre-shaped designed by preliminary mould.
The good product of pre-shaped is put into preheating oven and is preheated, preheating temperature is 75 DEG C, preheating time 60min, then
Taking-up is put into molding die, and molding covers tightly, and mold is sent into hot-forming progress is hot-forming, and hot-forming temperature is
250 DEG C, pressing time 120min, external pressure 120kg/cm2, C/C-SiC composite materials are obtained, gained C/C-SiC is multiple
It is 1.98g/cm that the volume content of carbon fiber, which is the density of 45%, C/C-SiC composite materials, in condensation material3。
Mold after will be hot-forming is sent into cooling bench and cools, and cooling temperature is 45 DEG C, cooling time 10min,
Cooling external pressure is 120kg/cm2, it is re-fed into stripping station, product is taken out in die sinking, then product is cleaned and dried, dry
Temperature be 165 DEG C, then according to the design drawing of bone plate carry out CNC processing, it is pre- to obtain C/C-SiC composite material bones plate
Body processed.
Configuration gelatin solution, which is placed in water-bath, to be preheated, and the gelatin solution of preheating is added drop-wise in atoleine dropwise, side drop
Edged stirs, and continues to stir evenly after dripping, is then transferred in ice-water bath rapidly and is handled, add cross-linking agents,
It is washed with cleaning solution after the completion of crosslinking, obtains faint yellow microballoon；It is placed in again under low temperature environment and continues solidification a period of time, most
It is fully washed, is sieved again with cleaning solution afterwards, packing, gelatin microballoon of having leisure；Using blank gelatine microsphere as raw material, and with sea
Solution of sodium alginate is mixed with gelatin/sodium alginate blank nucleocapsid structure sustained-release micro-spheres；By gelatin/sodium alginate blank core-shell structure copolymer
Structure slow-releasing microballoon is added in the PBS buffer solutions of bone morphogenetic protein, to get being loaded with the gelatin-of BMP after fully shaking
Sodium alginate nucleocapsid structure sustained-release micro-spheres.
Chitosan is modified as electrostatic self-assembled method C/C-SiC composite materials bone plate precast body surface obtained by；Using
The slow-release gelatin microspheres of the gained molecule of activated protein containing BMP are compounded in by dip-coating method to be modified with the C/C-SiC of chitosan and answers
The surface of condensation material bone plate precast body is to get the C/C-SiC composite material bones plate with BMP controlled-release coatings.
The mechanical property of gained C/C-SiC composite material bones plate is tested, C/C-SiC composite material bones plate
Mechanical property parameters are as shown in table 1.
The mechanical property correction data of the bone plate of 1 each embodiment of table and existing common synthetism plate material and people's bone
| Synthetism plate material | Tensile strength MPa | Elastic modulus G Pa | Elongation percentage % |
| Embodiment 1 | 113-136 | 12-29 | 1.6 |
| Embodiment 2 | 99-139 | 10-30 | 1.5 |
| Embodiment 3 | 90-138 | 9-31 | 1.4 |
| Embodiment 4 | 110-128 | 12-29 | 1.5 |
| People's bone | 80-150 | 1-30 | 1.5 |
| 317 stainless steels | 670-710 | 192-230 | 12 |
| Titanium alloy | 770-810 | 95-129 | 10 |
| Co-Cr-Mo alloys | 428-470 | 190-230 | 18 |
| C/ nylon | 230-270 | 6-14 | 5.4 |
By table 1 as it can be seen that having the C/C-SiC composite material bones plate of BMP controlled-release coatings obtained by 1-4 of the embodiment of the present invention
Tensile strength, elasticity modulus and elongation percentage are close with people's bone, and 317 stainless steels, titanium alloy, Co-Cr-Mo alloys and C/ nylon
There are larger gaps for the mechanical property of composite material and the mechanical property of people's bone.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of C/C-SiC composite material bones plate with BMP controlled-release coatings, it is characterised in that：
Include by 0 ° of non-woven fabrics, carbon fibre web tire and 90 ° of non-woven fabrics C/C composite material bases that alternative stacked is formed successively；
The C/C composite material bases interlayer fills needle-punched carbon fiber, and SiC is filled in the hole of C/C composite material bases；
The surface of C/C composite material bases is coated with pyrolysis layer of charcoal；
The surface of the pyrolysis layer of charcoal is coated with SiC layer；And
The surface recombination of the SiC layer has BMP controlled-release coatings.
2. the C/C-SiC composite material bones plate according to claim 1 with BMP controlled-release coatings, it is characterised in that：Institute
It states in SiC layer containing the simple substance Si for accounting for SiC layer gross mass 0.1%~0.5%.
3. the C/C-SiC composite material bones plate according to claim 1 with BMP controlled-release coatings, it is characterised in that：Institute
State the slow-release gelatin microspheres coating that BMP controlled-release coatings are the molecule of activated protein containing BMP.
4. the C/C-SiC composite material bones plate according to claim 3 with BMP controlled-release coatings, it is characterised in that：Institute
State in BMP controlled-release coatings, the grain sizes of BMP sustained-release micro-spheres is 10 μm~100 μm, encapsulation rate >=80%, carrying drug ratio be 20 μ g/mg~
50μg/mg。
5. the C/C-SiC composite material bones plate according to claim 1 with BMP controlled-release coatings, it is characterised in that：Institute
The loading for stating needle-punched carbon fiber is the 10%~15% of C/C composite material base quality, a diameter of 5 μm of needle-punched carbon fiber~
7μm。
6. the C/C-SiC composite material bones plate according to claim 1 with BMP controlled-release coatings, it is characterised in that：Institute
It is multilayer to state pyrolysis layer of charcoal, and the thickness of each layer of pyrolytic carbon is 2mm~5mm, and total covering amount of pyrolytic carbon is C/C composite materials
The 5%~10% of substrate mass.
7. the C/C-SiC composite material bones plate according to claim 1 with BMP controlled-release coatings, it is characterised in that：Institute
State bone plate elasticity modulus be 10GPa~30GPa, compression strength >=200MPa, bending strength >=220MPa, shear strength >=
16MPa, tensile strength are 110MPa~130MPa, elongation percentage≤2%.
8. such as the system of the C/C-SiC composite material bones plate according to any one of claims 1 to 7 with BMP controlled-release coatings
Preparation Method includes the following steps：
(1) 0 ° of non-woven fabrics, carbon fibre web tire and 90 ° of non-woven fabrics are cut by design size, then by cut 0 ° of non-woven fabrics, carbon
Web tire and 90 ° of non-woven fabrics alternative stacked successively, fill needle-punched carbon fiber as reinforced phase, and pass through chemical gas in interlayer
SiC is filled in the hole of product of the phase osmosis after alternative stacked；
(2) product of alternative stacked obtained by step (1) is placed on warm table and is preheated, coated on the product of alternative stacked
Then pyrolytic carbon squeezes discharge interlayer gas, then by product by chemical vapour deposition technique in pyrolysis layer of charcoal outer cladding SiC
It is placed in preliminary mould, the shape pre-shaped designed by preliminary mould；
(3) the good product of step (2) pre-shaped is put into preheating in preheating oven, then takes out and is put into progress hot pressing in molding die
Molding, obtains C/C-SiC composite materials；
(4) mold of the step (3) after hot-forming is cooled, takes out product, product is cleaned and is dried, is then pressed
CNC processing is carried out according to the design drawing of bone plate, obtains C/C-SiC composite material bone plate precast bodies；
(5) slow-release gelatin microspheres of the molecule of activated protein containing BMP are prepared by emulsification and cross linked solidification method；
(6) carbon-carbon composite bone plate precast body surface obtained by as electrostatic self-assembled method in step (4) modifies chitosan；
(7) use dip-coating method that the slow-release gelatin microspheres of the molecule of activated protein containing BMP obtained by step (5) are compounded in step
(6) gained is modified with the surface of the C/C-SiC composite material bone plate precast bodies of chitosan to get with BMP controlled-release coatings
C/C-SiC composite material bones plate.
9. preparation method according to claim 8, it is characterised in that：In the step (5), the molecule of activated protein containing BMP
Slow-release gelatin microspheres be prepared especially by following methods：
(5.1) configuration gelatin solution, which is placed in water-bath, preheats, and the gelatin solution of preheating is added drop-wise in atoleine dropwise, side drop
Edged stirs, and continues to stir evenly after dripping, is then transferred in ice-water bath rapidly and is handled, add cross-linking agents,
It is washed with cleaning solution after the completion of crosslinking, obtains faint yellow microballoon；It is placed in again under low temperature environment and continues solidification a period of time, most
It is fully washed, is sieved again with cleaning solution afterwards, packing, gelatin microballoon of having leisure；
(5.2) the blank gelatine microsphere that step (5.1) is prepared is as raw material, and is mixed with sodium alginate soln bright
Glue/sodium alginate blank nucleocapsid structure sustained-release micro-spheres；
(5.3) the gelatin/sodium alginate blank nucleocapsid structure sustained-release micro-spheres that step (5.2) is prepared are added to Bones morphology
It is micro- to get the gelatin-sodium alginate nucleocapsid structure sustained release for being loaded with BMP after fully shaking in the PBS buffer solutions that albumen occurs
Ball.
10. preparation method according to claim 8, it is characterised in that：
In the step (3), the temperature of preheating is 45 DEG C~75 DEG C, and the time of preheating is 40min~60min；
In the step (3), hot-forming temperature is 100 DEG C~250 DEG C, and pressing time is 60min~120min, outside pressure
Power is 100kg/cm2~120kg/cm2；
In the step (3), volume content >=35%, C/C-SiC composite material of carbon fiber is close in C/C-SiC composite materials
Degree >=1.75g/cm3；
In the step (4), cooling temperature is 35 DEG C~45 DEG C in the operation that cools, and cooling time is 5min~10min, cold
But external pressure is 110kg/cm2~120kg/cm2；
In the step (4), dry temperature is 155 DEG C~165 DEG C.
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| CN110585491A (en) * | 2019-09-27 | 2019-12-20 | 长沙晟天新材料有限公司 | Carbon fiber composite bone fracture plate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106580417A (en) * | 2016-12-16 | 2017-04-26 | 厦门市豪尔新材料股份有限公司 | Carbon fiber composite material bone plate and preparation method thereof |
| CN107670119A (en) * | 2017-09-12 | 2018-02-09 | 中南大学 | A kind of self-bone grafting C-base composte material bone plate and preparation method thereof |
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2018
- 2018-03-09 CN CN201810196425.2A patent/CN108379671A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106580417A (en) * | 2016-12-16 | 2017-04-26 | 厦门市豪尔新材料股份有限公司 | Carbon fiber composite material bone plate and preparation method thereof |
| CN107670119A (en) * | 2017-09-12 | 2018-02-09 | 中南大学 | A kind of self-bone grafting C-base composte material bone plate and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110585491A (en) * | 2019-09-27 | 2019-12-20 | 长沙晟天新材料有限公司 | Carbon fiber composite bone fracture plate and preparation method thereof |
| CN110585491B (en) * | 2019-09-27 | 2021-12-14 | 长沙晟天新材料有限公司 | Carbon fiber composite bone fracture plate and preparation method thereof |
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