Method of preparing porous ceramic calcium phosphate granules

FIELD: medical-destination materials and products.

SUBSTANCE: preparation of hydroxyapatite-based porous ceramic granules, which can be used to fill bone defects in traumatology, orthopedics, maxillofacial surgery, and surgical stomatology, comprises preliminary synthesis of calcium phosphate powder with Ca/P ratio 1.5-1.67 and preparing suspension with 10% gelatin solution in proportion of 0.5-3 mL solution per 1 g powder at solution temperature 10 to 39° C. Suspension of hydroxyapatite in aqueous gelatin solution is then dispersed in neutral liquid vegetable oil, resulting mixture is stirred by blade stirrer at rotation speed 100 to 1500 rpm. Under effect of surface tension, spherical granules are formed, which are washed, dried, and subjected to heat treatment at 900-1250° C.

EFFECT: enabled preparation of granules with controlled size and open porosity occupying 20 to 80% of the volume.

1 tbl, 4 ex

 

The invention relates to the field of ceramic materials for medicine, namely to traumatology and orthopedics, maxillofacial surgery and dental surgery, and can be used for the manufacture of materials for filling bone defects.

Ceramic granules can be manufactured by various methods, including crushing blocks, followed by running, spray drying, quenching fluids, hydrothermal synthesis, obtaining granules of irregular or close to spherical geometry (1-4). The latter is preferable as to prevent inflammatory reactions of the body, and to the process of osseointegration (5, 6).

A known method based on the spheroidizing of liquid droplets due to surface tension forces, which is realized with the use of mixtures of suspension of hydroxyapatite in solution of the binder (chitosan) and liquid paraffin (5). The method allows to obtain porous granules of spherical shape, the open pores which are formed by burning bundles. However, the disadvantages of the method involve the use of molten paraffin and low porosity of the material obtained.

The closest technical solution is a method for granules based on hydroxyapatite, which consists in mixing calcium hydroxide and monosubstituted phosphate feces is tion, monohydrate in a molar ratio CA/P=1,67, adding to this mixture an aqueous solution containing hydrogel with a polymer concentration of 0.01-10.0 wt.%, the mixing of these substances at a temperature 20-41°when neutral is rn,8-7,2, followed by filtration and drying precipitated the final product in the form of granules at a temperature of 105-160°With (7).

The technical result of the invention is a method of manufacturing a spherical porous ceramic granules with adjustable size and open porosity of 20 to 80 vol.%, ranging in size from 50 to more than 2000 μm, the composition from tricalcium phosphate (CA/P=1,5) to hydroxyapatite (CA/P=1,67).

To achieve a technical result of the proposed suspension technology, based on the principle of immiscible fluids with subsequent thermal treatment. Powder of calcium phosphate from tricalcium phosphate to hydroxyapatite mixed with a solution of gelatin in distilled water, which promotes the adhesion of the powder particles, when the temperature of the solution in the range from 15 to 39°C. suspension Concentration ranges from 0.5 to 3.0 ml of a 10%aqueous solution of gelatin, 1 g of powder of calcium phosphate. After that, the suspension is introduced into the dispersing medium, which is used vegetable oil, stirring paddle stirrer. Speed peremeshivajutsa ranging from 100 to 1500 rpm, the duration of mixing is from 5 to 60 minutes After settling for 5 min the precipitate in the form of spherical granules is filtered off, washed off the oil with ethyl alcohol, dried and subjected to heat treatment at temperatures from 900 to 1250°with exposure at these temperatures from 30 to 300 minutes

The invention is illustrated by the following examples.

Example 1. 5 g of powder of calcium phosphate with a CA/P=1,67 mixed with 10%solution of gelatin in distilled water at a temperature of 20°With the ratio of the powder-liquid 1 g/1.5 ml of the Suspension is placed in a vegetable oil at room temperature, which was stirred paddle stirrer speed of 200 rpm for 15 minutes After sedimentation, filtration, washing and drying the granules are subjected to heat treatment at a temperature of 1200°aged 60 min Annealed samples have a porous structure with the contents of the open pores 39-41%, size then, from 1 to 10 μm. The size of the granules is in the range from 1000 to 10000 microns.

Example 2. 5 g of powder of calcium phosphate with a CA/P=1,60 mixed with 10%solution of gelatin in distilled water at a temperature of 25°With the ratio of the powder-liquid 1 g/2 ml Suspension is placed in a vegetable oil at room temperature, which was stirred paddle stirrer at 500 rpm for 15 minutes After sedimentation,filtration, washing and drying the granules are subjected to heat treatment at a temperature of 1200°aged 60 min Annealed samples have a porous structure with the contents of the open pores 53-55%, a pore size of from 1 to 10 μm. The size of the granules is in the range from 600 to 7000 microns.

Example 3. 5 g of powder of calcium phosphate with a CA/P=1,58 mixed with 10%solution of gelatin in distilled water at a temperature of 35°With the ratio of the powder-liquid 1 g/2,5 ml of the Suspension is placed in a vegetable oil at room temperature, which was stirred paddle stirrer with a speed of 1000 rpm for 30 minutes After sedimentation, filtration, washing and drying the granules are subjected to heat treatment at a temperature of 1000°aged 60 min Annealed samples have a porous structure with the contents of the open pores 70-72%, size then, from 0.5 to 15 μm. The size of the granules is in the range from 50 to 900 μm.

Example 4. 5 g of powder of calcium phosphate with a CA/P=1.50 is mixed with 10%solution of gelatin in distilled water at a temperature of 39°With the ratio of the powder-liquid 1 g/3 ml, the Suspension is placed in a vegetable oil at room temperature, which was stirred paddle stirrer with a speed of 1500 rpm for 60 minutes After sedimentation, filtration, washing and drying the granules are subjected to heat treatment is ri a temperature of 900° With aged 60 min Annealed samples have a porous structure with the contents of the open pores 79-81%, a pore size of 0.5 to 15 μm. The size of the granules is in the range from 50 to 400 microns.

The table shows the characteristics of the granules of calcium phosphates obtained by various modes of carrying out the process. When the temperature of the suspension and the dispersion medium of less than 15°With the process of granulation is not realizable due to the rapid hardening of the suspension, and at temperatures above 39° - the average size of the granules is less than 50 μm. If the stirring speed is less than 100 rpm is agglomerating granules, and at speeds above 1500 rpm - granules have an average size less than 50 microns. When the temperature of heat treatment below 900°With no sintering powder of calcium phosphate, and at a temperature above 1250°With sharply reduced porosity.

400-800
Table

Characteristics of the granules of calcium phosphates obtained by various modes of carrying out the process.
No.The temperature of the solution, °The suspension concentration, ml/gThe stirring speed, rpmThe duration of mixing, minThe temperature of the heat treatment, °The exposure time, minthe size of the granules, mcmThe open porosity, %
110120020----
210250040----
3103150060----
415120020950301500-190036
5152500401100120900-130053
61531500601250300500-90084
720120020950301200-160036
82025040----
9203150060125030087
102512002095030800-120039
11252500401100120400-80055
122531500601250300200-50083
133012002095030800-120033
14302500401100120300-70054
153031500601250300100-50084
163512002095030300-70033
17352500401100120100-50052
183531500601250 300100-20087
1939120040950120200-60037
20393150040125012050-10085
21451500601000120less than 5037
2225250040850120--
23252500401300120400-80023

Sources of information taken into account

1. Williams D.F. The science and applications of biomaterials // Advances in Materials Technology Monitor. 1994. V.1, N2. P.1-38.

2. Orlovsky VP, G. Sukhanov, Ezhova ZH.A., rodicheva GV Hydroxyapatite ceramics // J. Union chem. of the society to them. Mendeleev. 1991. T.36, No. 6. S.

3. Hench L.L. Bioceramics and the future // Ceramics and Society. Ed. P.Vincenzini. Techna, Faenza, 1995. P.101-120.

4. De Bruijn J.D. Calcium phosphate biomaterials: bone-bonding and biodegradation properties. Thesis Leiden. - Haveka B.V., Alblasserdam, 1993. - 172 p.

5. Paul W., Sharma C.P. Development of porous spherical hydroxyapatite granules: application towards protein delivery // J.Mater. ScL: Mater. Med. 1999. V.10, N7. P.383-388./p>

6. Weinlander M, H. Plenk, Jr., Adar F. and Holmes R. In: Bioceramics and the human body, Eds. A.Ravaglioli and A.Krajewski. Elsevier, London, 1992. P.317.

7. Krylov E.A. Way to obtain hydroxiapatite polysaccharide granules. Patent RU 2235061, 2004.

A method of manufacturing a porous spherical granules of calcium phosphate, which consists in the preparation of suspensions of pre-synthesized powder of calcium phosphate with a ratio of CA/P of 1.5 to 1.67 with 10%solution of gelatin in a ratio of from 0.5 to 3.0 ml solution of gelatin per 1 g of the powder at the temperature of the solution from 10 to 39°obtaining a suspension of powder in a solution of gelatin, add this suspension in vegetable oil, stirring the mixture paddle stirrer with speed from 100 to 1500 rpm with subsequent washing of the pellets and their heat treatment at a temperature of from 900 up to 1250°C.



 

Same patents:

FIELD: ceramic industry; metallurgy; method of production of the industrial ceramics and refractories.

SUBSTANCE: the invention is pertaining to the field of industrial ceramics and refractories and may be used for manufacture of the details working under the mechanical loadings. The technical result of the invention is creation of the strong ceramics containing zirconium dioxide with the structure having the various size of the grain resulting in the high viscosity of destruction. The invention presents the method of manufacture of the strong ceramics including molding of the billets out of the ultradispersible powder containing zirconium dioxide, sintering with the subsequent quenching. At that the sintering of the billets conduct in the vacuum with the residual pressure of no less than (2-3)·10-5 mmHg with the isothermal aging in the temperature field of existence of the of zirconium dioxide cubical phase at 1750-1800°C within 2-12 hours. The heating speed up to the sintering temperature is changed a stage-by-stage: up to the temperature of 1200°C it makes 350-500° C per hour, and further up to the sintering temperature - 300-320°C/hour. For molding of the billets use the ultradispersible powder containing zirconium dioxide of not less than 20 mass % with the additives of the metals oxides from the group consisting of yttrium oxide, calcium oxide, magnesium oxide, ceric oxide and their mixtures and in addition - aluminum oxide.

EFFECT: the invention ensures creation of the strong ceramics containing zirconium dioxide with the structure having the various size of the grain resulting in the high viscosity of destruction.

5 cl, 1 tbl, 2 ex

FIELD: electrical industry; metallurgy; methods of production of the solid electrolyte.

SUBSTANCE: the invention is pertaining to production of the refractory products, in particular, to the method of production of the solid electrolytes from the powders of the refractory compounds and may be used in electrical industry and metallurgical branches of industry. The technical result of the invention is production of the solid electrolytes having the improved technological and operational properties. The method provides for production of the solid electrolyte from the nano-dispersive powders of the preset composition produced by the plasma-chemical method. The produced powders are preliminary subjected to the preliminary sequential thermal treatment at the temperature of 800-1400°C within 0.5-1 h. Then conduct the mechanical activation in the ball grinder with addition of the surface-active substance for 25-100 hours, mix it with the organic binder and fritting in the furnace within 10 hours at the temperature of 1200±20°C, and for 12 hours at increasing the temperature from 1200 up to 1600°C. Cool the mass for 0.5 hour from 1600 down to 1200°C, keep it for 10 hours. At the temperature of 1200°C with the subsequent chilling down to the room temperature together with the furnace. In the capacity of the surface-active substance use oleinic acid in amount of 1-2 mass %, and as the organic binder they use paraffin in amount of 16-20 mass %.

EFFECT: the invention ensures production of the solid electrolytes having the improved technological and operational properties.

2 cl, 1 tbl, 2 ex

The invention relates to the field of technical ceramics and refractories and can be used for the manufacture of products used in electrical engineering, mechanical engineering, chemical and metallurgical industries and other industries
The invention relates to the production of ceramic materials and concerns a method for obtaining sintered semi-finished products, which, after sintering can be used, for example, as components of ceramic materials

The invention relates to the technology of ceramics and can be used in chemical, nuclear, electrical industry

FIELD: medical technologies; production of the carbonate hydroxyapatite ceramics.

SUBSTANCE: the invention is pertaining to the charge for the carbonate hydroxyapatite ceramics. The charge for production of the ceramic material on the basis of the carbonate of hydroxyapatite may be used for filling-up the osteal defects in traumatology and orthopedics, the maxillofacial surgery and the surgical stomatology. The charge of the carbonate hydroxyapatite additionally contains 2-20 mass % of the potassium carbonate. The technical result of the invention is production of the dense ceramic material and reduction of the temperature of its sintering. At that its kilning may be conducted in the air medium in the ordinary kilns without application of the special cost intensive inventory maintaining the set humidity and the gas medium.

EFFECT: the invention ensures production of the dense ceramic material and reduction of the temperature of its sintering.

1 ex, 1 tbl

The invention relates to the field of synthesis of new chemically pure caesium containing compounds which can be used as substances-matrices for the manufacture of the active part radionuclide sources, in particular ionizing radiation sources on the basis of cesium-137

FIELD: medicine.

SUBSTANCE: mixture has lyophilized allogenic bone tissue and additionally has allogenic hydroxyapatite and patient autoplasma enriched in blood platelets. The components are taken in ratio in %: lyophilized allogenic bone tissue - 60; allogenic hydroxyapatite - 20; patient autoplasma enriched in blood platelets - 20.

EFFECT: provided increase in transplantation mixture plasticity; usability for modeling transplant from the given mixture of required form; tightly closed bone tissue defect.

4 dwg

FIELD: medical technologies; production of the carbonate hydroxyapatite ceramics.

SUBSTANCE: the invention is pertaining to the charge for the carbonate hydroxyapatite ceramics. The charge for production of the ceramic material on the basis of the carbonate of hydroxyapatite may be used for filling-up the osteal defects in traumatology and orthopedics, the maxillofacial surgery and the surgical stomatology. The charge of the carbonate hydroxyapatite additionally contains 2-20 mass % of the potassium carbonate. The technical result of the invention is production of the dense ceramic material and reduction of the temperature of its sintering. At that its kilning may be conducted in the air medium in the ordinary kilns without application of the special cost intensive inventory maintaining the set humidity and the gas medium.

EFFECT: the invention ensures production of the dense ceramic material and reduction of the temperature of its sintering.

1 ex, 1 tbl

FIELD: medicine.

SUBSTANCE: method involves applying hydroxyapatite collagen material plate so that plate size is selected to be by 5-8 mm greater than trepanation opening.

EFFECT: enhanced effectiveness in making plastic repair of maxillary sinus; excluded allergic responses.

The invention relates to the field of medicine and relates to a method of forming a bone implant, which can be used for plastic bone as in the treatment and prosthetics areas of bone affected by degeneration, when bone defects resulting from congenital or acquired diseases

The invention relates to medicine, namely to orthopedics and traumatology, and can be used for bone grafting
The invention relates to medicine, namely to traumatology in the treatment of hip fractures

FIELD: medicine.

SUBSTANCE: method involves applying hydroxyapatite collagen material plate so that plate size is selected to be by 5-8 mm greater than trepanation opening.

EFFECT: enhanced effectiveness in making plastic repair of maxillary sinus; excluded allergic responses.

FIELD: medical technologies; production of the carbonate hydroxyapatite ceramics.

SUBSTANCE: the invention is pertaining to the charge for the carbonate hydroxyapatite ceramics. The charge for production of the ceramic material on the basis of the carbonate of hydroxyapatite may be used for filling-up the osteal defects in traumatology and orthopedics, the maxillofacial surgery and the surgical stomatology. The charge of the carbonate hydroxyapatite additionally contains 2-20 mass % of the potassium carbonate. The technical result of the invention is production of the dense ceramic material and reduction of the temperature of its sintering. At that its kilning may be conducted in the air medium in the ordinary kilns without application of the special cost intensive inventory maintaining the set humidity and the gas medium.

EFFECT: the invention ensures production of the dense ceramic material and reduction of the temperature of its sintering.

1 ex, 1 tbl

FIELD: medicine.

SUBSTANCE: mixture has lyophilized allogenic bone tissue and additionally has allogenic hydroxyapatite and patient autoplasma enriched in blood platelets. The components are taken in ratio in %: lyophilized allogenic bone tissue - 60; allogenic hydroxyapatite - 20; patient autoplasma enriched in blood platelets - 20.

EFFECT: provided increase in transplantation mixture plasticity; usability for modeling transplant from the given mixture of required form; tightly closed bone tissue defect.

4 dwg

FIELD: medical-destination materials and products.

SUBSTANCE: preparation of hydroxyapatite-based porous ceramic granules, which can be used to fill bone defects in traumatology, orthopedics, maxillofacial surgery, and surgical stomatology, comprises preliminary synthesis of calcium phosphate powder with Ca/P ratio 1.5-1.67 and preparing suspension with 10% gelatin solution in proportion of 0.5-3 mL solution per 1 g powder at solution temperature 10 to 39° C. Suspension of hydroxyapatite in aqueous gelatin solution is then dispersed in neutral liquid vegetable oil, resulting mixture is stirred by blade stirrer at rotation speed 100 to 1500 rpm. Under effect of surface tension, spherical granules are formed, which are washed, dried, and subjected to heat treatment at 900-1250° C.

EFFECT: enabled preparation of granules with controlled size and open porosity occupying 20 to 80% of the volume.

1 tbl, 4 ex

Transplant mixture // 2301684

FIELD: medicine.

SUBSTANCE: transplant mixture has liophylized allogenic bone tissue and allogenic hydroxyapatite and patient autoblood platelets gel with Metronidazole, taken in the following components proportions (%): liophylized allogenic bone tissue - 65; allogenic hydroxyapatite - 10; patient autoblood platelets gel - 20; Metronidazole - 5.

EFFECT: enhanced effectiveness of treatment; no clamps required; reliably and tightly closed bone tissue defect; accelerated regenerate reorganization; improved antiseptic and immunomodulating action.

FIELD: medicine, orthopedics, oral surgery, surgical stomatology.

SUBSTANCE: the present innovation refers to the system of delivering medicinal preparations and could be applied for filling in osseous defects or as a matrix for cell cultures. Porous hydroxyapatite ceramics with bimodal distribution of pores contains thin intragranular (under 10 mcm diameter) and large-scale interpenetrating intergranular pores, the size being above 100 mcm, at total quantity of about 41-70 rot.%. The method deals with manufacturing spherical granules of about 400-600 mcm diameter that contain hydroxyapatite powder and gelatin, pressing these spherical granules under 10-100 MPa pressure and thermal treatment at about 900-1250°C at keeping from 30 to 300 min. The innovation enables to create ceramics with bimodal distribution of pores.

EFFECT: higher efficiency of manufacturing.

2 cl, 1 tbl

FIELD: medicine.

SUBSTANCE: described are implants based on biodegradable thixotropic compound with pseudo-plastic properties and implant injected under skin or into skin in fibrous tissue. Containing microparticles of at least one biocompatible ceramic compound in suspension, in at least one liquid carrier containing at least one compound based hyaluronic acid and at least one biodegradable thixotropic compound with pseudo-plastic properties. Also disclosed is kit for preparation such implants directly before application, as well as implant production and using for filling of crinkles, and/or skin cavity, and/or cicatrices.

EFFECT: implants of simplified injection.

14 cl, 4 ex

Up!