CN107041968A - One kind prepares ZrO2The HA dip-coating slurries of Bone Defect Repari bioceramic scaffold material - Google Patents

One kind prepares ZrO2The HA dip-coating slurries of Bone Defect Repari bioceramic scaffold material Download PDF

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CN107041968A
CN107041968A CN201611148187.5A CN201611148187A CN107041968A CN 107041968 A CN107041968 A CN 107041968A CN 201611148187 A CN201611148187 A CN 201611148187A CN 107041968 A CN107041968 A CN 107041968A
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zro
powder
bone
slurry
scaffold material
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全仁夫
王拓
谢尚举
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HANGZHOU CITY XIAOSHAN DISTRICT TRADITIONAL CHINESE MEDICAL HOSPITAL
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HANGZHOU CITY XIAOSHAN DISTRICT TRADITIONAL CHINESE MEDICAL HOSPITAL
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
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Abstract

The present invention relates to the preparation method of bioceramic scaffold material.One kind prepares ZrO2The HA dip-coating slurries of Bone Defect Repari bioceramic scaffold material, the slurry is made up of following component by mass percentage：ZrO2Powder 2 ~ 35%, HA powder 10 ~ 40%, distilled water 50 ~ 65%, etherophosphoric acid 1.0 ~ 2.5%, ethyl cellulose 0.1 ~ 0.5%.The Bone Defect Repari bioceramic scaffold material porosity prepared using the slurry is high, and pore size is suitable, not only makes hydroxyapatite be easy to be degraded and absorbed, and bone tissue is easy to grow into, fusion speed is fast, with host bone strong bonded, obvious foreign body reaction, good biocompatibility will not be produced.

Description

One kind prepares ZrO2The HA dip-coating slurries of Bone Defect Repari bioceramic scaffold material
Technical field
The present invention relates to the preparation of bioceramic scaffold material.
Background technology
At present, become very universal clinically by the method for transplanting artificial bone to treat Cranial defect patient.No matter Which kind of material artificial bone derives from, and can it transplant successful key and be in postoperative bone graft there is normal freshman bone tissue head Enter.It is mainly reflected in：1st, enough area of new bone whether are produced at bone collection；2nd, it is in bone graft and normal bone tissues junction No generation is firm to be combined.It is worth noting that, clinically most bone collection can only all play a part of bone replacement at present, Area of new bone can not be also allowed to grow into well in graft and be allowed to combine together.This also means that bone graft exists in patient's body The risk of consume, aging.And the healing fractured after big section bone collection is a complicated process, the extension of its healing time increases Add implant to cause the probability of foreign body rejection, then cause larger range of Periprosthetic bone to dissolve after infection.So, people is improved The bone formation performance and bone fusion rate of work bone graft, also imply that the success rate for improving whole bone collection operation.Therefore, how Improve the bone formation performance of artificial bone organization material and of great interest with bone fusion rate.HA/ZrO2Composite is in body Complete biocompatibility is shown in inside and outside experiment, does not have adverse reaction, cytotoxicity at bone tissue, musculature interface Experiment is faint, acceptable with the reaction of hemolytic test.Therefore, ZrO2Graded composite HA tissue engineered bones carry for bone collection For good alternative materials.Research shows HA/ZrO2Densified composite, average bending strength is up to 898.67 MPa, and highest can Up to 1112.4MPa, the C of K I are up to 7.3-11.4 MPa.m1/2, exceed well over human body natural's bone strength.And dense body intensity is excessive simultaneously Also the problem of stress covers is brought.And by HA/ZrO2Dense body is made after foam ceramic material by changing voidage to adjust Its intensity, obtains mechanical property and most gets close to nature the high emulated artificial bone material of bone structure, this is also HA/ZrO2Foamed ceramics material Where the sharpest edges of material.
HA has after the chemical composition structure similar to human body hard tissue, HA materials implantation human body, under the infiltration of body fluid, Can be by Partial digestion and calcium, P elements necessary to discharging human body, and be absorbed by tissue, utilize, new tissue is incorporated into, from And HA and body bone tissue is obtained good combination.There is low intensity, poor toughness, threshing etc. as timbering material and lack in simple HA Fall into.Zirconium dioxide（ZrO2）Ceramic material just has higher bending strength, fracture toughness and relatively low modulus of elasticity, and ZrO2Also there is certain biocompatibility.Use ZrO2As mechanical property can be obtained after HA reinforcements and biocompatibility is all good Biocomposite material.And dense body intensity is excessive while also bringing the problem of stress covers.
The content of the invention
The present invention it is an object of the invention to provide one kind in view of the above-mentioned problems, prepare ZrO2Bone Defect Repari bioceramic scaffold material HA dip-coating slurries, the Bone Defect Repari bioceramic scaffold material porosity prepared using the slurry is high, and pore size is suitable, not only Hydroxyapatite is set to be easy to be degraded and absorbed, and bone tissue is easy to grow into, fusion speed is fast, and host bone strong bonded, no Obvious foreign body reaction, good biocompatibility can be produced.
In order to realize above-mentioned purpose, present invention employs following technical scheme：
One kind prepares ZrO2The HA dip-coating slurries of Bone Defect Repari bioceramic scaffold material, the slurry is by mass percentage by following Component constitute：
ZrO2Powder 2 ~ 35%
HA powder 10 ~ 40%
Distilled water 50 ~ 65%
Etherophosphoric acid 1.0 ~ 2.5%
Ethyl cellulose 0.1 ~ 0.5%.
Preferably, the slurry is made up of following component by mass percentage：
ZrO2Powder 25 ~ 35%
HA powder 10 ~ 18%
Distilled water 50 ~ 60%
Etherophosphoric acid 1.0 ~ 2.5%
Ethyl cellulose 0.1 ~ 0.5%.
As further preferably, the slurry is made up of following component by mass percentage：
ZrO2Powder 30 ~ 32%
HA powder 12 ~ 15%
Distilled water 50 ~ 60%
Etherophosphoric acid 1.0 ~ 2.5%
Ethyl cellulose 0.1 ~ 0.5%.
Preferably, the slurry is made up of following component by mass percentage：
ZrO2Powder 2 ~ 5%
HA powder 30 ~ 40%
Distilled water 55 ~ 65%
Etherophosphoric acid 1.0 ~ 2.5%
Ethyl cellulose 0.1 ~ 0.5%.
As further preferably, step 1）Middle second layer slurry is made up of following component by mass percentage：
ZrO2Powder 3 ~ 4%
HA powder 32 ~ 36%
Distilled water 56 ~ 60%
Etherophosphoric acid 1.0 ~ 2.5%
Ethyl cellulose 0.1 ~ 0.5%.
The present invention for existing bioceramic material be difficult to once porosity increases meet to artificial bone compression strength with This defect of toughness reguirements, adds nanometer ZrO in HA2Particle is to strengthen the compression strength and toughness of timbering material, so as to be Bone defect healing provides a kind of porosity height, the Bone Defect Repari bioceramic scaffold that compression strength is big, toughness is strong.Bone Defect Repari of the present invention Bioceramic scaffold material is a nanometer ZrO2Slurry is mixed into appropriate proportions with HA, then is applied to the poly- of appropriate aperture and porosity Ammoniacum sponge sintering is formed.Because porosity is high, pore size is suitable, not only makes hydroxyapatite be easy to be degraded and absorbed, and And bone tissue is easy to grow into, fusion speed is fast, with host bone strong bonded, will not produce obvious foreign body reaction, bio-compatible Property is good, and bioceramic of the present invention can be not only used for bone tissue injury repair, can be also used for Cell culture invitro.
Brief description of the drawings
Fig. 1 is the foamed ceramics artificial vertebral body dimensional drawing of embodiment 1.
Fig. 2 is the super depth of field picture of the foamed ceramics artificial vertebral body of embodiment 1.
Fig. 3 is the 12 weeks after operation centrum sample of embodiment 1 and X pieces.
Fig. 4 embodiment 2Micro CT are unenhanced and 3-D view.
The material three-dimensional structure that the data post processing of Fig. 5 embodiments 2 is formed.
The Stereolithography of Fig. 6 embodiments 2 and later stage degreasing sintered prepared HA/ZrO2Bioceramic material.
Fig. 7 embodiments 2HA/ZrO2Bioceramic material scanning electron microscope (SEM) photograph.
Fig. 8 embodiments 2HA/ZrO2Bioceramic material powder XRD analysis figure.
Fig. 9 embodiments 2HA/ZrO2Bioceramic material MTT tests OD values.
Figure 10 embodiments 2HA/ZrO2Area of new bone two, CT-3D Reconstruction after bioceramic material implant materials.
Embodiment
Below with dog lumbar vertebra HA/ZrO2Bioceramic scaffold material is carried out specifically as example to the present invention It is bright.
Embodiment 1
1.1 model organic foam materials are pre-processed
Using polyurethane as bubbles model material, because polyurethane material has film between network, and the presence of a film makes slurry Hardly enter inside foam body Model, by cause plug-hole, slurry can not be uniformly distributed, sinter after foamed ceramics voidage and Mechanical property is poor.Therefore need first to get through film, make organism formation of foam tridimensional network.In addition, organic foam model is deposited Hydrophily is poor, angle of wetting is small thus slurry is difficult absorption.To improve the hanging performance of foams cast material, it is necessary to carry out pre- Processing.Organic polyurethane foamed material is cut into high 24cm, radius 9cm semicircle column type sizes, using 60 DEG C, 15wt% hydrogen-oxygens Change sodium solution and soak 3.5 h, rubbed 3 times, dried standby repeatedly with clear water.Organic polyurethane foamed material after processing due to Lit up by alkali lye corruption, surface roughness substantially increases, therefore its hydrophily and adhesion property is made moderate progress.Again with surfactant after It is continuous that organic polyurethane foam material is surface-treated, finally soaked and dried after 24h with 5% PVA.
1.2 ZrO2The preparation of powder, slurry
Preheating is carried out to powder using chamber type electric resistance furnace, treatment temperature programming rate when between 30 DEG C to 800 DEG C is 2 DEG C/min, programming rate is 4 DEG C/min when between 800 DEG C to 1250 DEG C, is warming up to after 1250 DEG C to be incubated 4h and complete powder and locates in advance Reason.Slurry prepares and uses additive formula：Polyvinyl alcohol（PVA）, carboxymethyl cellulose（CMC）Content be 0.5%, add 10% Ludox, polypropylene acid ammonium (PAA-NH4) content be 0.6%.Hanging first adds ZrO2Mass fraction be 60%, therefore Entire slurry solid rate is about 60%.Raw material is carried out to be thoroughly mixed after grinding, using sphere of powder mass ratio 1：2, rotating speed 300r/min High speed ball mill grind 3h to produce slurry, a certain amount of deionized water and Ludox are first then stirred into 10 min, CMC is added With defoamer octanol, ZrO2Powder, is stirred for 3 h, waits hanging.Additional size inside organic foam during hanging is passed through Extrusion is removed, it is ensured that its through-hole rate.Spontaneously dried after sample is placed in into the h of 18h ~ 24 at room temperature again.It is then placed in baking oven, 12 h are dried under the conditions of 110 DEG C, moisture content is down to less than 1%.Then second grinding, hanging are carried out, is used Same additive formula, but add ZrO2The mass fraction of powder is down to 57%, entire slurry solid rate is down to 57%.Second Rise using centrifugation grout coating process, i.e., untreated organic foam material is first put into centrifugation bottom of the tube, in order to isolate the slurry thrown away, Soaked organic foam containing slurry is put into again, 1500r/min centrifugations 1min.The 3rd extension of row after same process is dried Slurry, the 3rd same additive formula, but ZrO twice before2Powder quality fraction be 54%, entire slurry solid rate adjust to 54%。
1.3 ZrO2The sintering of ceramics
Three-stage sintering process is employed to precast body sample after above-mentioned hanging to be sintered, and is respectively（1）Baking stage：In room When temperature is to 100 DEG C, programming rate is 2 DEG C/min, and purpose makes moisture evaporation remaining in precast body sample.（2）Volatilization period： At 100 DEG C to 200 DEG C, it is 1 DEG C/min to control programming rate, at 200 to 500 DEG C, and control programming rate rises in 1 DEG C/2min When temperature is to 500 DEG C, be incubated 1h, after when being warming up to 500 to 750 DEG C, control programming rate for 2 DEG C/3min, is warming up to after 750 DEG C, Be incubated 1h, after when being warming up to 750 to 1200 DEG C, control programming rate for 2 DEG C/min.（3）The high-temperature roasting stage：Persistently sinter afterwards Temperature is maintained at 3 DEG C/min, after the maximum sintering temperature for reaching 1550 DEG C, then is incubated 3h and furnace cooling.Obtain high 24cm, half The footpath pure ZrO of 9cm semicircle column types2Artificial vertebral body.
1.4 in pure ZrO2Foamed ceramics artificial vertebral body surface dip-coating HA gradient coatings
Two-step method dip coating is taken to coat gradient HA coatings.First time dip-coating wet end furnish is：ZrO2Powder 31.1%, HA powders 13.3%, etherophosphoric acid 1.4%, ethyl cellulose 0.2%, distilled water 53%.HA powders first are heated into insulation 2h after 800 DEG C in advance to locate Reason, then above-mentioned raw materials are mixed in 50 DEG C of hot water, and stir 5h.By the pure ZrO sintered out2Foamed ceramics artificial vertebral body immerses Slurry, waits and is taken out after being impregnated with completely, get rid of additional size.100 DEG C of drying 5h, are heated to 900 DEG C and are incubated 5h, finally heated to arrive 1250 DEG C of holding 1h.Second of dip-coating wet end furnish be：ZrO2Powder 3.9%, HA powders 35.5%, etherophosphoric acid 1.4%, ethyl Cellulose 0.2%, distilled water 58% has been configured and repeated the above steps after slurry.Obtain HA/ZrO2Graded composite foamed ceramics is artificial Centrum.
The HA/ZrO of above-mentioned2The specific data of graded composite foamed ceramics artificial vertebral body are mean porosities 77.47%, The MPa of mean compressive strength 10.25, vitro cytotoxicity test（MTT）（—）.
Embodiment 2
1.1 femoral shaft Cranial defect animal models
Experiment uses male adult beasle dog, the kg of body weight 7.3 ± 1.2, according to the mm of dog femoral shaft Cranial defect critical value 15, experiment In clip the mm of dog femur stage casing 15, set up femoral shaft defect model.Modus operandi：Preoperative 12 h fasting, with 3% amobarbital Sodium (1 m1/kg) is through Intravenous Anesthesia, and anesthesia is finished, promoting the circulation of qi cannula, and surgical procedure continues oxygen uptake.It is field of operation skin depilatory, clear Clean, sterilization, drape, take the cm of right lower extremity thigh lateral median incision about 8, successively cut skin, hypodermis, and electric coagulation hemostasis appears Leg muscle, from row blunt separation in fascial space between muscle, exposure femur measures after length, clips the mm of femur stage casing 15 (complete Layer includes periosteum) it is made under Cranial defect model, row Limited contact Plate internal fixiation, C- arm shape X-ray machines to have an X-rayed and sees that screw length is closed Suitable, Interal fixation is safe, is rinsed repeatedly with physiological saline, confirms to close otch without layer-by-layer suture after the residual such as apparatus gauze.Art The U intramuscular injection of Benzylpenicillin sodium salt 1,600,000 afterwards, once a day, continues 3 d, to prevent infection, conventinal breeding.
1.2 Micro-CT data acquisitions
Dog femoral shaft Cranial defect model is put into animal specific Micro CT, volume scan is carried out, voltage 90 is appraised and decided in CT scannings KV, the uA of electric current 278, the um of surface sweeping thickness 34.92.All images reach graphics workstation through digital interface, with DICOM data lattice Formula is exported.
1.3 Micro-CT data are converted and post-processing
The Micro CT DICOM data exported are converted by MAGICS softwares, concrete operations are as follows：By beasle dog stock Key stage casing CT medical images source three-dimensional data imports MAGICS softwares by original size, sets Picture Coordinate, Usage profile line Instrument measures the Density Distribution at the position, and order threshold value is increased using region（Thresh Holding）, to density where it Scope is chosen, and filters out skeletal tissue.The femur cross section of generation forms cavity sometimes, and empty generation is due to doctor What the difference of image threshold value itself was caused, therefore to enter edlin by adjusting threshold range or editor's mask instrument, this Sample processing does not influence follow-up calculating.After repairing, appropriate accuracy is chosen, three-dimensional reconstruction is carried out to gray value where femoral shaft, Export the stl file used in 3 D-printing.
Required according to the porosity of required composite, STL formatted files are further processed.Transfer image, Take dog femoral shaft stage casing average diameter, including the mm of race diameter 14, the mm of inner ring diameter 8.Hollow circuit cylinder is stretched, Design of length is 15 cm, array, makees SPL along its length, then draws a ball excision entity, along rotation array, is cut with hemisphere entity Upper plane, using filling array.Cylinder cuts the whole entity of insertion, and cylinder intersects for 90 °, then elongatedness carries out array.Preserve Result is changed, stl file is exported.
1.4 Stereolithographies print ZrO2Ceramics
Dog femoral shaft CT scan data is converted into after stl file and further working process, the light of CeraFab 7500 is directed into Solidify in three-dimensional printer.It is 40 μm to set flat resolution（635 dpi）, pixel（X,Y）1920*1080, workbench size （X,Y,Z）76 mm*43 mm*150 mm, 25 μm of thickness, the time for exposure is 1 s, starts printing thickness parameter and is set to 10 μ m.Preparation of nano level ZrO2Mud, adds photosensitive resin, makes ZrO2It is 15% with resin quality ratio, imports charging basket.According to setting ginseng Number starts print routines, resin is caused polymerisation by LED ultraviolet sources, material successively curing molding, forms complex light Quick resin germule.After first embryogenesis, to its further degreasing sintered processing, degreasing is carried out simultaneously with sintering during this.Specifically Step is as follows：（1）Drying and volatilization period：From 25 DEG C to 75 DEG C, the h of heating-up time 4, programming rate is 0.208 K/min, is protected The warm h of time 6, evaporates excessive moisture.And then continue ascending temperature up to 500 DEG C, wherein it heats up when rising to rated temperature Time, programming rate and soaking time are variant.（2）Degreasing and high temperature sintering stage：During from 500 DEG C to 1 250 DEG C, control The h of heating-up time 7.5, speed is 1.677 K/min, and temperature is to without insulation, continuing ascending temperature after 1 250 DEG C to 1 450 DEG C, control programming rate takes 1 h in 3.333 K/min, is incubated 2 h.（3）Cooling stage：Reach 1 450 DEG C of most high fever After junction temperature, then 2 h are incubated, are cooled down afterwards with -0.660 K/min, take 36 h to 25 DEG C.Whole degreasing sintered process 120.5 h are taken altogether.
1.5 dip coating prepares HA/ZrO2Gradient composites
Dip coating is taken to prepare HA/ZrO2Gradient composites.Comprise the following steps that：First layer wet end furnish, 31.1% nanoscale ZrO2Powder, 13.3% nanoscale HA powder, 53% distilled water, 1.4% etherophosphoric acid, 0.2% ethyl cellulose.HA is heated to 800 2 h are incubated after DEG C, standby, distilled water is heated to 50 DEG C, above-mentioned material is mixed and imported in distilled water, is sufficiently stirred for.Light is consolidated The pure ZrO of chemical conversion type2It is fully permeated in ceramics immersion slurry, take out, get rid of additional size.2 are dried in 100 DEG C of electric furnaces H, is heated to 900 DEG C, is incubated 5 h, finally heated to 1 250 DEG C, is incubated 1 h.Second layer wet end furnish, 3.9% nanoscale ZrO2Powder, 35.5% nanoscale HA powder, 58% distilled water, etherophosphoric acid matches constant, the above-mentioned step of repetition with ethyl cellulose Suddenly.HA/ZrO is obtained after cooling2Gradient composites.

Claims (5)

1. one kind prepares ZrO2The HA dip-coating slurries of Bone Defect Repari bioceramic scaffold material, it is characterised in that slurry presses quality percentage It is made up of than counting following component：
ZrO2Powder 2 ~ 35%
HA powder 10 ~ 40%
Distilled water 50 ~ 65%
Etherophosphoric acid 1.0 ~ 2.5%
Ethyl cellulose 0.1 ~ 0.5%.
2. one kind according to claim 1 prepares ZrO2The HA dip-coating slurries of Bone Defect Repari bioceramic scaffold material, its feature It is that slurry is made up of following component by mass percentage：
ZrO2Powder 25 ~ 35%
HA powder 10 ~ 18%
Distilled water 50 ~ 60%
Etherophosphoric acid 1.0 ~ 2.5%
Ethyl cellulose 0.1 ~ 0.5%.
3. one kind according to claim 2 prepares ZrO2The HA dip-coating slurries of Bone Defect Repari bioceramic scaffold material, its feature It is that slurry is made up of following component by mass percentage：
ZrO2Powder 30 ~ 32%
HA powder 12 ~ 15%
Distilled water 50 ~ 60%
Etherophosphoric acid 1.0 ~ 2.5%
Ethyl cellulose 0.1 ~ 0.5%.
4. one kind according to claim 1 prepares ZrO2The HA dip-coating slurries of Bone Defect Repari bioceramic scaffold material, its feature It is that slurry is made up of following component by mass percentage：
ZrO2Powder 2 ~ 5%
HA powder 30 ~ 40%
Distilled water 55 ~ 65%
Etherophosphoric acid 1.0 ~ 2.5%
Ethyl cellulose 0.1 ~ 0.5%.
5. one kind according to claim 4 prepares ZrO2The HA dip-coating slurries of Bone Defect Repari bioceramic scaffold material, its feature It is that slurry is made up of following component by mass percentage：
ZrO2Powder 3 ~ 4%
HA powder 32 ~ 36%
Distilled water 56 ~ 60%
Etherophosphoric acid 1.0 ~ 2.5%
Ethyl cellulose 0.1 ~ 0.5%.
CN201611148187.5A 2016-12-13 2016-12-13 One kind prepares ZrO2The HA dip-coating slurries of Bone Defect Repari bioceramic scaffold material Pending CN107041968A (en)

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Application publication date: 20170815