TW201114415A - Method and equipment of forming porous bio-ceramic bone scaffold - Google Patents

Abstract

The invention provides a forming method and a forming apparatus of forming a porous bio-ceramic bone scaffold. A ceramic green body of the porous bio-ceramic bone scaffold is constituted by a plurality of successive ceramic solid films. The invention is to uniformly mix one kind of bio-compatible ceramic powders with a ceramic sol in a ratio, and to stir the mixture into a slurry; next, to pave a plurality of layers of slurry in sequence on or above a working platform; after paving of each layer of slurry, to proceed irradiation of a laser beam on said layer of slurry according to a corresponding sectional pattern to form said ceramic solid film where the ceramic sol in said layer of slurry generates a chemical gelation reaction when irradiated by the laser beam; and eventually, to remove the retained slurry on the plurality of ceramic solid films to obtain the ceramic green body.

Description

201114415 VI. Description of the invention: [Technical field to which the invention pertains] 丨rous The present invention relates to a method for forming a porous biomedical ceramic skeleton scaffold (f〇nning meth〇d^^ device (forming Equipment) Rapid Prototyping (RP) forming technology uses layered processing technology to automatically create 3D solid objects in accordance with CAD geometry. Rapid prototyping technology can overcome tooling The unfinished geometric corners of the machine can be automated, and the prototypes are shaped without the shape constraints. Therefore, the rapid prototyping technology is particularly suitable for forming porous ceramic skeleton supports. The molding tools used in the rapid prototyping equipment are divided into two major systems: the laser system and the nozzle system. The rapid prototyping equipment that uses the nozzle system generally has the disadvantages of slow speed, easy material blockage, etc. , is a melting deposition method of the ^ nozzle system (Fused Dep〇siti n M〇deling, FDM) device ^ heats the strand-shaped raw material into a semi-melted state, and then extrudes the material through the nozzle. The stacking process requires a longer time and less efficiency. The same is true for the system. Multi-Jet M〇dding, MJM device. Multi-nozzle sprays the binder on the powdered material. The binder can bond the granular powder, but the binder is easy to block. Shot energy can be adjusted in a larger range 'generally' as long as it is a powdery original two: rapid prototyping equipment can be sintered or sintered using laser light.

4 6Lunghwa/200903TW 201114415 Up to now, the lamination processing technology using biomedical materials and laser light as heating tools to make biomedical tissue engineering scaffolds can be divided into three major ^: 〇 ') stereo lithography methods (Stereolithography Apparatus) , SLA): mixing biomedical materials with UV resin, UV laser (formed by υγ ray curing; (2) Selective Laser sintefing (SLS): using thunder The light is a heat source for selective 'scanning of the powdered state of the biomedical material to cause sintering between the powder particles; and (3) Fused Deposition Molding (FDM): using a nozzle to extrude the biomedical material According to the specific path stacking, a structure having pores can be produced. In the above technique, the SLA uses ultraviolet light-sensitive resin as a bond to generate a gas harmful to the human body when it is subjected to post-sintering treatment to remove the photosensitive resin. SLS uses a laser light pair. The biomedical materials are sintered or directly sintered to form pottery pieces. Therefore, the material is subjected to a large density of laser energy, which is easy to be formed, shrunk and deformed. The staggered type of mesh-like crust-like cylindrical structure has a small contact area between the upper and lower layers, resulting in poor strength. The prior art technique of forming a bribe with f-lighting is a micro-mirror (galVan) 〇meter mirror scan) Let the laser beam, i high and small in the range of the laser, can only be scanned in the laser beam. When the working mode is large, the f-beam of the above device has a large angle of refraction. Defocusing occurs at the sintering site, causing insufficient + shot and reducing the sintering effect. Therefore, one of the aspects of the present invention is to provide a molding method and a fine device for forming a ^^ phase t* bracket to avoid The above-mentioned problem [Summary of the Invention] 5 6LunghWa/20〇9〇3TW [201114415] According to a preferred embodiment of the present invention, the molding method is used to form a porous biomedical ceramic skeleton scaffold. One of the ceramic green body of the biomedical ceramic skeletal support is composed of: N [layer continuous ceramic solid fllm, wherein N is a natural number. The forming method is first Biological phase The ceramic powder (bi〇_c〇mpatibl'e ceramic powder) is uniformly mixed with a ceramic sol in a ratio and stirred into a slurry. Then, the molding method is applied to the first slurry. The forming method is followed by irradiating the first layer with a laser beam according to a cross-sectional pattern corresponding to the first solid layer of the solid layer, wherein the first layer of pulp A portion of the slurry that is irradiated with the laser beam is heated to cause a chemicai geation reaction to form the first layer of ceramic solid layer. Next, the molding method is to apply the first layer of the slurry to the first layer of the slurry, and the / system ranges from 2 to 纽. Next, the method irradiates a portion of the slurry of the first layer with the laser beam according to a cross-sectional pattern corresponding to the solid/thin layer of the second/second ceramic layer, wherein the cerium layer slurry is subjected to the laser When the beam is irradiated, the slurry is heated to cause the ceramic sol to generate the chemical gel reaction, thereby forming a layer of ceramics. Next, the molding method is a step of repeatedly coating the first layer of the slurry and irradiating the f-th layer slurry with the laser beam until the N-layer ceramic solid layer is completed. Next, the molding method removes the residual slurry attached to the N-layer ceramic solid layer to obtain the ceramic green body. Finally, the molding method is to dry the ceramic green body and complete the porous biomedical ceramic skeleton support by sintering the ceramic green body. According to the molding apparatus of the preferred embodiment of the present invention, the molding apparatus is used for molding a biomedical shouting bracket. The porpoise of the medicinal medicinal genus: 路 架 — 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶 陶The molding apparatus includes a work table, a coating device, a layer forming device, and a removing device. The table has a plane and is actuated to move up and down along one of the axes perpendicular to the plane. The coating is loaded

6Lunghwa/200903TW 6 201114415 Slurry. The slurry is mixed with __---Tao powder and -H-capacity. The (4) device is heterozygous and is controlled to cooperate with the lifting of the table to sequentially apply the N layer slurry to the upper layer forming device of the table, including a light beam generating device and a light guiding mechanism. The laser beam produces an I-set to produce a laser beam. The guiding mechanism and the focusing mirror are actuated in parallel with the plane according to a cross-sectional pattern corresponding to one of the solid layers of the ceramic layer, wherein the system ranges from 丨 to Ν. The guide is configured to direct (10) a laser beam to the focusing mirror. ~...' See the focus of the laser beam to the i-th layer of the slurry, wherein the portion of the seventh layer of the material irradiated by the laser beam is heated to cause a gel reaction, and then a shape Lai m fine thin layer. This removal = its lion fit cooperates to remove the residual polymer attached to the N layer __ thin layer to obtain the Taman chain. The advantages and spirit of the present invention will be further understood from the following detailed description of the invention. [Embodiment] = Referring to the drawings - and Figs. 2A to 2c, the drawings show the flow of the fine method according to the present invention. The invention of root age, method 1 is used for forming-porous biomedical research and bone support. In particular, the ceramic green body of one of the ceramic bio-skeleton scaffolds is composed of a continuous ceramic solid layer of N layers, wherein N is a natural number 1 a to 2 c, and is used according to the present invention. The molding device 2 of the preferred embodiment is used to form a ceramic green body of the porphyritic ceramic skeleton support. As shown in the figure, the molding method according to the present invention first performs step S10 to prepare a biocompatible ceramic powder and a ceramic sol.

In a specific embodiment, the biocompatible ceramic powder may be a Sanma fill 6Lunghwa/200903TW 7 201114415 r〇:TMi^:r; ca〇'P2〇5'si〇-diameter visible forming work: ruler; In a specific embodiment, the ceramic sol can be stored in the same manner as the above-mentioned rubber or oxygen, and the like. The molding method according to the present invention is a biocompatible ceramic powder and the ceramic pot. The slurry is formed into a slurry. Adjust the glue to the ratio - evenly mixed, and the stirring weight of the 中 中 ' 'bio-compatible ceramic powder and the pottery sol granules ratio of 60wt / o: 40wt% ~ 30wt%: 70wt% 〇中' the pulp The composition of the material is 30~ biocompatible ceramics, 10~15wt% solvent, and 35~55wt% water. The suspending agent is sodium hexametaphosphate (03) 6], 30 〇 ^ % 3 1 ()). The viscosity of the slurry is about 1200 cP to 3000 俜 = = = = = ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' It has a plane and is actuated along the plane perpendicular to the plane 5 to raise and lower the axis of the shaft. According to the present invention, the funnel 222 containing the granules SL can be contained and the funnel = 224 (or cylindrical drum) can be used. Sl' is coated into a thin layer of homogenous particles. Each layer can be controlled at about 〇.imm. However, the invention is not limited thereto, and is required

6Lunghwa/200903TW 8 201114415 The coating thickness can be varied according to the curve and the grain (four) of the product section curve. For example, when the cross-section curvature of the product is larger, the thickness of the material becomes smaller. And the present invention is not coated with a horizontal or equal thickness, and then as shown in FIG. 3 and FIG. 3B, the molding method according to the present invention performs step S16 according to the corresponding layer-layer ceramic: thin layer %, One section of the pattern 卩 solid film forming device% of the kilon emission of the laser beam of the first layer of the SL, the part of the secret SL, the first to find the first SI SI ^, the beam of the light of the Secretary SL' The heating is caused to cause a chemical gel reaction to form the first layer of the ceramic layer SL, (the dark portion in Fig. 2B). That is to say, the ceramic sol is dehydrated to form a chain-like molecular structure (ϋ, 'Si_0_Si, A1-0-A1), and further developed into a network structure, although the growth touches the biocompatible ceramic powder, it is about to be biocompatible. The ceramic powder is tight, and the wire-bonded knot is also produced by the X-ray glue in the adjacent state of H, and the gel reacts and sticks. After the completion of the chemical gel reaction, a two-dimensional porous ceramic green body is formed. Since no organic binder is used, no harmful gases are generated during the removal of the remainder and subsequent sintering processes. Since the energy required to cause the chemical sol reaction of the ceramic sol is much smaller than that required for sintering the ceramic powder, the influence of shrinkage and deformation of the ceramic workpiece can be greatly reduced. As shown in Fig. 2B, the solid film forming device 26 includes a laser beam generating device 262, a light guiding mechanism 264, and a focusing mirror 266. The laser beam generating means 262 is for generating a laser beam, for example, a c〇2 laser, an Nd:YAG laser, a He-Cd laser, an Ar laser or a UV laser. In a specific embodiment, the smart laser beam generating device 262 can add a temperature sensing device. When the temperature sensor detects that the cooling water temperature for cooling the laser beam generating device 262 exceeds 25 ° C. The laser beam generating means 262 stops the excitation of the light. t

6Lunghwa/200903TW 201114415 Unlike the prior art, which uses galvanometer scanning to focus the laser beam on each layer of the slurry SL', the light guiding mechanism 264 and the focusing mirror 266 are in accordance with the cross-sectional pattern of each layer of ceramic solid thin layer SL" The XY plane is moved parallel as shown in Figure 2B. The light guiding mechanism 264 is configured to guide the laser beam to the focusing mirror 266. The focusing mirror 266 is used to focus the laser beam to each layer of slurry SL'. In one embodiment, the scanning rate of the laser beam is 85 mm/s, the scanning pitch is 〇.imm, and the laser power is i〇w. In a specific embodiment, a jet tube can be added to the focusing mirror 266. The ejector tube is used to introduce low-pressure air and is quickly ejected through its nozzle, which prevents the ceramic slurry from splashing and attaching to the focusing lens during laser beam scanning, which affects the accuracy of laser beam scanning. - Also shown in Figure 2B, the light directing mechanism 264 in accordance with the present invention includes a plurality of fixed mirrors and mirrors that can be actuated in parallel with the Χ γ plane as shown in Figure 2B. For example, reference numerals 264a and 264b in FIG. 2 denote fixed mirrors, and reference numeral 264c denotes a mirror that can be actuated to move along an axis of the X-axis shown in parallel with FIG. 2B, and numeral 264d denotes a follow-up mirror 264c. A mirror that is actuated and movable along one of the axes of the gamma axis shown in Figure 2B. The focusing mirror 266 moves along with the mirror 264d. In a specific embodiment, the solid-state film forming apparatus 26 according to the present invention has a laser beam scanning red for a 45G surface χ 25G wrist, a maximum speed of more than 3000 mm/min, and an XY-axis repeatability design of the soil 0.02. The ground's and the bristle mirror scan allow the laser beam to be concentrated. The prior art f 2 solid film forming device 26 is designed to improve the shortcomings of the first working small and the laser light f, and the energy is insufficient. The system is in accordance with the present invention. Subsequent coating of new -

6Lunghwa/200903TW 201114415 After the layer of slurry, it is not necessary to re-adjust the __ standard. In addition, it should be emphasized that in Wei application, it is necessary to not use the same thickness. Next, as shown in the figure, an integer index in the molding method 'z ^ according to the present invention. Subsequently, according to the step S22' of the present invention, the laser is irradiated by the laser beam by the laser beam irradiated by the laser beam, which is emitted by the laser beam, which is emitted by the laser beam. The gel reaction, heating into the pottery SL,,. In practice, through the CAM ^ = formation of 5 Haidi 7-layer ceramic solid-state thin layer connection, according to the calculation of 牯-哉 &;; solid t surgery, the computer and the molding equipment 2 thin 臈 may be formed by (10) The solid-state Si-forming device 26 is controlled to heat the mother-layer slurry, and then enters the slurry layer SL which is automatically judged by the cut-off 1 = two-step S24. Heating and coating on the table 14 of the present invention, the result of the determination of the method of 丨 勃 〜 〜 24 is negative, according to the distance (a thin layer of production exquisite S18, actuating the table 24 down and 'continuously Step S20 and step S22 are performed.

6Lunghwa/200903TW 11 1 is a confirmer, according to the molding method of the present invention, FIG. 2C) removal removal device (not shown in FIG. 2A, FIG. 2, SL, to obtain a solid layer SL of the layer of ceramics) The residual slurry 3 has a ceramic transformation chain 3 having an inner communication hole 3^2. In the specific embodiment of the ceramic spray liquid (for example, water) shown in Fig. 3, the removal device can be left with the residue SL. The water is removed from the N-layer ceramic solid-state thin layer SL, 201114415. In practical applications, 'because of the use of ceramics: the light paste itself as a supporting structure' uses the suspension force generated by the viscosity of the ceramic slurry itself as i=irif (rerhanging) part of the building power. Therefore, the ceramic green body of the biomedical ceramic skeleton scaffold having the convex suspension structure supporting hole can be produced without the need of ί ΐ 。 。. Finally, the molding method according to the present invention is performed. Step S26, supplying dry = 3 ' and performing the shouting, and completing the porous-porcelain skeleton scaffold. The porous biomedical ceramic skeleton branch according to the present invention has a sinusoidal structure, which can be different 3D model map, made ^ special The shape and size of the bone path support. Generally suitable for cell size f, the growth of the biomedical tissue pore size is between the deletion ~ just (four). ^ Kang Ben invention of the porous her stent can make a porosity of 100 /rni biomedical tissue to facilitate cell attachment and growth. In one embodiment, the biocompatible ceramic powder is a tricalcium phosphate (eg, phosphoric acid dance) or |>2〇5, in a sintering process The ceramic green body 3 can be heated to 1200 〇C or higher and sintered by infiltration. Thereby, the mechanical properties of the porous biomedical ceramic skeleton support can be improved, and the bending strength can be increased from 3 MPa to 16 MPa or more. At the same time, the bioactivity is increased. In another embodiment, the biocompatible ceramic powder can be made of Ai2^ powder, and the porous biomedical ceramic skeleton scaffold can be heated and infiltrated after the hydroxyapatite is completed. To the surface of the porous biomedical ceramic skeleton scaffold, the cells adhere and proliferate. - In summary, the material used in the present invention is in a slurry state, has a turbulent fluidity, and has a solid material. The advantages of the material and the liquid material can uniformly mix the ceramic sol and the biocompatible ceramic powder, and facilitate the uniform laying of the thin layer of the mass. The material bonding principle applied by the invention is the gel original.

12 6Lunghwa/200903TW 201114415 The chemical gel reaction that can be triggered by the cleaning of the property is used, and the molding equipment of the smaller invention can be used, and the laser sweeps the impact. According to the shortcomings of the small and the laser beam focusing energy is insufficient. . The function and spirit of the present invention will be apparent from the above-described preferred embodiments, and the invention will be limited. Phase 3

Arrangement of GiJS variational a. According to the present invention, the patent application scope of the above-mentioned two ft (four) should be rooted and scaled, so that it covers the possible change of the financial

13 6Lunghwa/200903TW 201114415 [Simplified illustration of the drawings] The flow chart of the molding method according to a preferred embodiment of the present invention is used in the application of the thinning device to form the finer device according to the present invention. Shouting a sketch of the process of scanning and heating the process. The C system uses the molding apparatus according to the present invention to form a schematic diagram of a ceramic buried in a pile of multi-layer ceramics (four). Fig. 2 is a schematic view of a ceramic green body completed according to the molding method of the present invention. [Main component symbol description] 1: molding method 2: molding apparatus 222: funnel 24: table 262: laser beam generating devices 264a, 264b, 264c, 264d: 266 = focusing mirrors S10 to S28: method step 22: coating device 224: squeegee 26: solid film forming device 264: light guiding mechanism mirror 264: light guiding mechanism SL: slurry SL': slurry Floor

14 6Lunghwa/200903TW 201114415 3: Ceramic green body SL’': ceramic solid layer 32: inner communication hole

15 6Lunghwa/200903TW

Claims (1)

201114415 VII. Patent application scope: 1. The molding method of the hole-supporting bracket, the self-employed, the shaft® (8); the New Zealand and the sol-proportional mixing (b) coating the first layer of slurry on a workbench (c) = should be a cross-sectional pattern of the first layer of ceramic solid layer, a part of the slurry of the first layer of slurry is irradiated with a light, and the material of the first sound is added New ^ biochemical gel reaction to form the first layer of solid layer; (d) coating slurry on the (four) layer of slurry, Huai range from 2 to an integer index; (4) according to the corresponding layer / layer of pottery a solid-state thin layer-section pattern, the part of the slurry is irradiated by the ti-t beam, wherein the portion of the layer/polymer is irradiated with a beam of light, and the material is heated to produce the sol The chemical rubberization reaction further forms the solid layer of the first layer of ceramics; (f) repeating the step (6) and the step (8) until the completion of the solid layer τ».L · (g) removal of the layer a residual slurry of a ceramic solid layer, a ceramic green body; and (h) drying the ceramic green body, and performing the ceramic green body The porous biomedical ceramic skeleton scaffold is completed by sintering. 2. The molding method according to claim 1, wherein the biocompatible ceramic powder is selected from the group consisting of tricalcium phosphate, hydroxyapatite, chitin, %0, Ca0, ί> , Si〇2, Mg0, and a combination of the powders of the group 6 Lunghwa/200903TW 16 201114415 into one of the groups t. 3. The molding method according to claim 2, wherein the biocompatible ceramics is a catechin or a P2〇5' in the step (h), the Tauman is heated to 1200°. C or more is sintered by infiltration. 4. The molding method according to claim 1, wherein the ceramic sol is selected from the group consisting of cerium oxide sol, titanium oxide sol, alumina sol, cerium oxide sol, and a mixture thereof. one. 5. The molding method according to claim 1, wherein the weight ratio of the biocompatible ceramic powder to the ceramic sol is 60 wt%: 40 wt% to 30 wto/〇: 70 wt%. The molding method according to claim 1, wherein the composition of the slurry is 30 to 50 wt / 〇 biocompatible ceramic powder, i 〜 15 wt% solvent, 35 to 55 wt% terracotta sol and 2 to 5 wt. % suspending agent. 7. The molding method according to claim 6, wherein the solvent is water, and the suspension is sodium hexametaphosphate [(NaP03)6], sodium tripolyphosphate (Na5P3O10). Φ 8. The molding method of claim 1, wherein the laser beam is selected from the group consisting of a C02 laser, a Nd..YAG laser, a He-Cd laser, an Ar laser, and a One of the groups consisting of UV lasers. 9. The molding method according to claim 1, wherein the biocompatible ceramic powder is Al2〇3 powder, and after the porous biomedical ceramic skeleton support is completed, the hydrogen oxyapatite is heated and infiltrated. To the surface of the porous biomedical ceramic skeleton scaffold. 10. A molding apparatus for forming a porous biomedical ceramic skeleton support, wherein the ceramic green body of the porous biomedical ceramic skeleton support is composed of a N-layer continuous ceramic solid 17 6Lunghwa/200903TW 201114415 thin layer. 'N is a natural number, the molding apparatus comprises: a work σ, the workbench has a plane and is actuated to move up and down along an axis perpendicular to the plane; a coating is applied, the coating is placed in a slurry, The Lai system is uniformly mixed with and rang, and the coating device is matched and controlled to match the lifting and lowering of the working table to the working table. Above or above; - state thin layer forming device 'the sound riding forming device comprises - a laser light generating device, a light guiding mechanism and a focusing mirror, the laser beam is used for producing a laser beam The light guiding mechanism and the focusing mirror are moved parallel to the plane according to the section corresponding to the yth layer, the light guiding mechanism is configured to guide the laser beam to the focusing, the focusing mirror For focusing the laser beam to the 7th layer Material, the system, from the 1 to N - integer index, wherein the first layer of material is affected by the lightning, part of the slurry irradiated by the beam is heated to cause the ceramic sol to generate the chemical gel reaction to form the yth layer a ceramic solid layer; and a removal device configured to cooperate to remove residual slurry adhering to the ceramic solid layer to obtain the ceramic green body. 11. The molding apparatus of claim 1, wherein the laser beam is selected from the group consisting of a C02 laser, a Nd:YAG laser, a He-Cd laser, an Ar laser, and a UV. One of the groups consisting of lasers. 12. The molding apparatus of claim 1, wherein the light guiding mechanism comprises a plurality of fixed mirrors and a mirror that can be actuated to move parallel to the plane. 13. The molding apparatus of claim 1, wherein the removing device sprays a liquid to remove residual pulp adhering to the N-layer ceramic solid layer. 6Lunghwa/200903TW 18