CN1263519C - Method for preparing artificial head bones made from composite material and for modifying surface - Google Patents
Method for preparing artificial head bones made from composite material and for modifying surface Download PDFInfo
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- CN1263519C CN1263519C CN 200410012852 CN200410012852A CN1263519C CN 1263519 C CN1263519 C CN 1263519C CN 200410012852 CN200410012852 CN 200410012852 CN 200410012852 A CN200410012852 A CN 200410012852A CN 1263519 C CN1263519 C CN 1263519C
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- polymethyl methacrylate
- micropowder
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Abstract
The present invention provides a method for preparing an artificial skull made from composite material and for modifying the surface of the skull, which aims at providing the artificial skull of composite material and enhancing the bioactivity of the surface of the artificial skull, and the artificial skull is used for repairing the skull defects of a human body. The present invention has the preparing method that polymethylmethacrylate, biological carbon fiber or glass fiber, and hydroxyapatite micropowder or beta-tricalcium phosphate micropowder are compounded to utilize multi-layer compounding and hot pressing technology to prepare the artificial skull. The present invention has the surface modifying method that the prepared artificial skull is soaked in simulated body fluid so as to form bone-like apatite, thereby, the bioactivity and the synosteosis of the material are enhanced.
Description
Technical field
The present invention relates to be used to repair the preparation and the surface modifying method thereof of the damaged composite artificial skull of human skull.
Background technology
Owing to reasons such as traffic and industrial accident and disease of brain, need the patient who implements the skull repairing urethroptasty to rise year by year, ten thousand examples surplus the annual head injury patient of China reaches 50 suddenly wait to study a kind of ideal skull substitution material.
The material that has been used for repair of cranial defects mainly is metal material and macromolecular material.Metal material wherein since patient head temperature difference reaction is responsive to external world, make patient that uncomfortable sensation be arranged, and long-term difference variation can injured brain tissue.Macromolecular material such as widely used polymethyl methacrylate, have good biocompatibility, characteristics such as plastotype is easy to process, but some mechanical property is poorer than the human skull, mainly be fragility, shock resistance is relatively poor, biological activity is undesirable etc., is not ideal artificial skull material.
The biological medical polymer composite, owing to have the characteristics of medical macromolecular materials (as polylactic acid, poly-methylpropanoic acid methyl ester, polyglycolic acid etc.) and medical inorganic material (as hydroxyapatite, calcium phosphate etc.) concurrently, be widely used in repairing, replacing tissue and organ.Studies show that of Kokubo etc. (Kokubo T.MaterialsScience Forum, 1999,293:65-82), new osseous tissue has only the bone like apatite layer by generating at material surface to form.Bruijn etc. think (de Bruijn JD, Yuan H, Dekker R, et al.In:Davies ed.Bone Engineering, em squared incorporated, Toronto, Canada, 2000:421-431), the formation of biomaterial surface bone like apatite layer is the prerequisite that it has osteoinductive.
Also there is not bibliographical information at present, polymethyl methacrylate and biologic inorganic fiber and hydroxyapatite micropowder or bata-tricalcium phosphate micropowder composite are used for the skull reparation, and this material surface carried out modification, improve the biological activity and the synosteosis of material surface.
Summary of the invention
The objective of the invention is to draw the characteristics of biological medical polymer composite, and modification is carried out on its surface, make its surface generate osteoid apatite, improve the biological activity of material, be used for repair of cranial defects.The present invention is that (composite of β-TCP) is a bulk material with biologic inorganic fiber reinforcement polymethyl methacrylate (PMMA) and hydroxyapatite micropowder (HA) or bata-tricalcium phosphate micropowder, utilize MULTILAYER COMPOSITE technology and hot-pressing technique, prepare the composite artificial skull.Product is made its modification in simulated body fluid (SBF solution), form osteoid apatite, improve the biological activity and the synosteosis of material surface.
The composite that is used for the skull reparation of the present invention is multiple structure.Its material is formed and is comprised polymethyl methacrylate, biological carbon fiber or glass fibre, hydroxyapatite micropowder or bata-tricalcium phosphate micropowder, inner each layer is the homogeneous body of biological carbon fiber or glass fibre and polymethyl methacrylate, and upper and lower surface is for applying the composite layer of hydroxyapatite micropowder or bata-tricalcium phosphate micropowder and polymethyl methacrylate.
The composite that is used for the skull reparation of the present invention, product thickness is 1.8～2.0mm.It is 0.35-0.45mm that there is the layer thickness of coat on upper and lower surface.
The preparation method that is used for the composite of skull reparation of the present invention, undertaken by following step:
(1) methyl methacrylate and polymethyl methacrylate are carried out polymerisation in bulk by 5: 3 mass ratioes, need not add other initiators;
(2) adopt MULTILAYER COMPOSITE fabrication techniques composite plate, inner each layer shop one deck biological carbon fiber or glass fibre, just be coated with one deck polymethyl methacrylate, become the homogeneous body layer of biological carbon fiber or glass fibre and polymethyl methacrylate, upper and lower surface is for applying hydroxyapatite micropowder or bata-tricalcium phosphate micropowder and polymethyl methacrylate composite layer, wherein polymethyl methacrylate be set by step (1) described methyl methacrylate and polymethyl methacrylate by the bulk polymeric material of 5: 3 mass ratioes, it is 1.8～2.0mm that its composite plate number of plies and coating thickness satisfy product thickness, on, it is the requirement of 0.35-0.45mm that lower surface has the layer thickness of coat, the coating thickness of described hydroxyapatite micropowder or bata-tricalcium phosphate micropowder is not strict with, and applies evenly to get final product;
(3) composite plate that step (2) is obtained more than 3 hours, makes its preliminary polymerization 55-65 ℃ of insulation;
(4) the preliminary polymerization plate hot moulding that step (3) is obtained, mold pressing parameter is: mold temperature 120-130 ℃, pressure 14-20MPa, insulation be more than 2.5 hours, treats that mould reduces to the demoulding after the room temperature;
(5) composite plate that obtains of step (4) is carried out surface finish, punching, deburring, cleaning, oven dry and is promptly obtained composite products.
The method of modifying of described composite: at first composite products is placed simulated body fluid to carry out dynamic soaking and handle, treatment temperature is 37 ± 0.5 ℃, and soak time is no less than 5 days, behind the natural drying, place that heat treatment is more than 1 hour under the 80-90 ℃ of condition, natural cooling gets final product.
The simulated body fluid step preparation as follows that composite modification is used, by being made into total amount 500ml solution:
(1) takes by weighing 3.997g NaCl, 0.1764g NaHCO
3, 0.1118g KCl, 0.1141g K
2HPO
43H
2O, 0.1525g MgCl
26H
2O, 0.0355g Na
2SO
4, placing container, the adding deionized water fully dissolves, mixing;
(2) take by weighing 0.1387g CaCl
2After adding deionized water dissolving, dropwise add in the solution that step (1) obtains it and auxiliary the stirring, be made into total amount 500ml solution, shake up;
(3) weighing 1.5143g Tris, the trometamol of preparation 250ml, pH value to 7.25 ± 0.05 of the solution that the hydrochloric acid solution regulating step (2) of trometamol and 1M is obtained promptly obtains simulated body fluid solution.
The composite artificial skull of the inventive method preparation and surface modification, it is damaged to be used to repair the human skull, biologically active height, the characteristics that synosteosis is good.
Description of drawings
Fig. 1 composite artificial skull preparation were established figure
Fig. 2 composite artificial skull product photo
Fig. 3 a, 3b are respectively material surface and handle forward and backward X-ray diffractogram
Fig. 4 material surface infrared spectrogram
Fig. 5 a, 5b, 5c be respectively material surface handle before, handle 3 days, handle 15 days sem photograph
Process route shown in Figure 1: glass fibre mat and methyl methacrylate (MMA) are combined into composite plate with polymethyl methacrylate (PMMA) and hydroxyapatite micropowder, after the drying, be loaded on hot pressing making sheet in the mould that scribbles one deck releasing agent, after the demoulding, carry out surface finish, punching, deburring, cleaning, dry the artificial skull product.Place simulated body fluid to carry out surface treatment the artificial skull product.Carry out the material surface structure after the surface treatment and morphology observation, performance test, qualified products are applied to clinical.
The specific embodiment
Embodiment 1
1, composite artificial skull preparation
Preparation method is that methyl methacrylate (MMA) and polymethyl methacrylate (PMMA) are carried out polymerisation in bulk with 5: 3 (mass ratio), does not add other initiators.Take MULTILAYER COMPOSITE technology system composite plate, inner each layer shop one deck biological glass fiber (or carbon fiber) just is coated with one deck methyl methacrylate and polymethyl methacrylate bulk polymeric material, makes biological carbon fiber or glass fibre and MMA and PMMA homogeneous body; Upper and lower surface is for applying hydroxyapatite (HA) and MMA and PMMA complex, and way is at methyl methacrylate and polymethyl methacrylate bulk polymeric material surface-coated hydroxyapatite (or bata-tricalcium phosphate); The composite plate of doing is put into baking oven, and temperature is controlled at 55-65 ℃, and insulation 3h makes its preliminary polymerization.Adopt the compacting of hot moulding technology then, the temperature that mould is set is 120-130 ℃, is coated with one deck releasing agent, and pressure is 14-20MPa, and insulation 2.5h makes the material full solidification.The demoulding when treating that mold temperature drops to room temperature is carried out surface finish, punching, deburring, cleaning, oven dry and is obtained the artificial skull product, and the product photo is seen Fig. 2.
2, the preparation of simulated body fluid (preparation 500ml)
With the following component of the accurate weighing of electronic balance, to insert in the beaker of 250ml, the adding deionized water fully dissolves, mixing, wherein CaCl
2Be made into aqueous solution separately, and it is dropwise added and auxiliary the stirring.At last solution is inserted in the volumetric flask of 500ml and shake up;
| Composition | NaCl | NaHCO 3 | KCl | K 2HPO 4·3H 2O | MgCl 2·6H 2O | CaCl 2 | Na 2SO 4 |
| Quality (g) | 3.997 | 0.1764 | 0.1118 | 0.1141 | 0.1525 | 0.1387 | 0.0355 |
Weighing 1.5143g Tris, the trometamol of preparation 250ml.The hydrochloric acid solution of trometamol and 1M is regulated pH value to 7.25 ± 0.05 of simulated body fluid, monitor with precision acidity meter.
3, the surface treatment of sample
The artificial skull product is placed simulated body fluid, utilize constant flow pump that system for handling is in dynamically, temperature is controlled at 37 ± 0.5 ℃, soaks more than 5 days natural drying.Again product is placed baking oven, heat treatment is 1 hour under 80-90 ℃ of condition, behind the natural cooling, gets the artificial skull product of modification.
4, the material surface morphology observation is analyzed and is characterized
Material surface structure after the surface treatment and pattern utilize scanning electron microscopic observation, the phase composition of material surface thing to utilize the chemical composition of X-ray diffractometer and determination of infrared spectroscopy, material surface to utilize energy spectrum analysis.
Material surface is handled forward and backward X-ray diffraction test result and is shown in Fig. 3 a, 3b respectively.Material is amorphous before handling as seen from the figure, and handling the back is osteoid apatite.
Sample soaks after 15 days its surperficial infrared spectrogram with simulated body fluid and sees Fig. 4.[PO among the figure
4 3-] absorption line at 1063cm
-1The place, [OH
-] spectral line of group (hydrogen bond association hydroxyl) then appears at 1635cm
-1, 3428cm
-1The place, the surface deposits that proves this sample is an osteoid apatite.
Before sample is handled with simulated body fluid, handle 3 days, the sem test result that handled 15 days and be shown in Fig. 5 a, 5b, 5c respectively, as seen from the figure, material surface has only finely dispersed hydroapatite particles before handling, handle the bone-like apatite stone granulate that 3 days material surfaces are covered with subglobular, particle size is about about 300nm, handle 15 days osteoid apatite particle sizes and become big, be dense distribution.
With power spectrum table 1 is listed in Ca, P, the O quantitative analysis of treatment surface, it can be seen from the table, the content of Cl is maximum in the time of 3 days, secondly is the content of Ca and P; After 9 days, the content of P increases, and secondly is Cl and Ca; The content of P constantly increases after 15 days, the peak value of Ca secondly, its content also constantly increases, and the content of Cl constantly descends, the testimonial material surface forms osteoid apatite.
The main component of the material surface that table 1 is treated and content
| Element(Wt％)(Day) | 3d | 9d | 15d |
| O Na Mg P Cl K Ca | 16.59 26.34 0.92 7.76 38.42 0.94 9.02 | 28.74 9.90 2.29 15.09 23.27 1.12 19.58 | 40.69 5.52 3.54 18.94 7.55 1.15 22.61 |
Claims (3)
1. one kind is used for the composite that skull is repaired, be multiple structure, it is characterized in that the material composition comprises polymethyl methacrylate, biological carbon fiber or glass fibre, hydroxyapatite micropowder or bata-tricalcium phosphate micropowder, inner each layer is the homogeneous body of biological carbon fiber or glass fibre and polymethyl methacrylate, upper and lower surface is for applying the composite layer of hydroxyapatite micropowder or bata-tricalcium phosphate micropowder and polymethyl methacrylate, product thickness is 1.8～2.0mm, on, it is 0.35-0.45mm that lower surface has the layer thickness of coat, and wherein said polymethyl methacrylate is that methyl methacrylate and polymethyl methacrylate are 5: 3 bulk polymeric material by mass ratio.
2. the preparation method of the described composite of claim 1 is characterized in that being undertaken by following step:
(1) methyl methacrylate and polymethyl methacrylate are carried out polymerisation in bulk by 5: 3 mass ratioes, need not add other initiators;
(2) adopt MULTILAYER COMPOSITE fabrication techniques composite plate, inner each layer Shop one deck biological carbon fiber or glass fibre, just be coated with one deck polymethyl methacrylate, become the homogeneous body layer of biological carbon fiber or glass fibre and polymethyl methacrylate, upper and lower surface is for applying hydroxyapatite micropowder or bata-tricalcium phosphate micropowder and polymethyl methacrylate composite layer, wherein polymethyl methacrylate be set by step (1) described methyl methacrylate and polymethyl methacrylate by the bulk polymeric material of 5: 3 mass ratioes, it is 1.8～2.0mm that its composite plate number of plies and coating thickness satisfy product thickness, on, it is the requirement of 0.35-0.45mm that lower surface has the layer thickness of coat, the coating thickness of described hydroxyapatite micropowder or bata-tricalcium phosphate micropowder is not strict with, and applies evenly to get final product;
(3) will go on foot the composite plate that poly-(2) obtain and more than 3 hours, make its preliminary polymerization 55-65 ℃ of insulation;
(4) the preliminary polymerization plate hot moulding that step (3) is obtained, mold pressing parameter is: mold temperature 120-130 ℃, pressure 14-20MPa, insulation be more than 2.5 hours, treats that mould reduces to the demoulding after the room temperature;
(5) composite plate that step (4) is obtained is carried out surface finish, punching, deburring, cleaning, oven dry and is promptly obtained composite products.
3. the described method of modifying that is used for the composite that skull repairs of claim 1, it is characterized in that at first composite products being placed simulated body fluid to carry out dynamic soaking handles, treatment temperature is 37 ± 0.5 ℃, soak time is no less than 5 days, behind the natural drying, place that heat treatment is more than 1 hour under the 80-90 ℃ of condition, natural cooling gets final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410012852 CN1263519C (en) | 2004-03-17 | 2004-03-17 | Method for preparing artificial head bones made from composite material and for modifying surface |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410012852 CN1263519C (en) | 2004-03-17 | 2004-03-17 | Method for preparing artificial head bones made from composite material and for modifying surface |
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|---|---|
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| CN1263519C true CN1263519C (en) | 2006-07-12 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2120745B1 (en) * | 2006-11-30 | 2010-12-29 | Smith & Nephew, Inc. | Fiber reinforced composite material |
| CN101249282B (en) * | 2008-03-31 | 2011-05-18 | 陕西科技大学 | Preparation of biological compound material for bone repairing |
| CN101757686A (en) * | 2010-01-22 | 2010-06-30 | 吴琼 | Preparation method of medical compound glass fiber calcium-containing reinforced bone cement product |
| CN101757685A (en) * | 2010-01-22 | 2010-06-30 | 孙桂森 | Preparation method of medical glass fiber magnesium-containing hydroxyapatite bone cement product |
| CN101791429A (en) * | 2010-04-01 | 2010-08-04 | 李胜 | Preparation method of medical composite glass fiber strontium containing enhanced bone cement product |
| CN102641522B (en) * | 2012-04-13 | 2013-09-18 | 辽宁工业大学 | Method for preparing medical three-dimensional gradient netlike carbon fiber/ hydroxyapatite (HA)/ medical stone composite material |
| CN106310379A (en) * | 2016-08-30 | 2017-01-11 | 谢秋艳 | Modified bionic nanocomposite and application thereof |
| CN106267362A (en) * | 2016-08-31 | 2017-01-04 | 阮丽丽 | A kind of bionical medical composite material and application thereof |
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