CN101148360A - Customized forming method for gradient porous structure ceramic - Google Patents

Customized forming method for gradient porous structure ceramic Download PDF

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Publication number
CN101148360A
CN101148360A CNA2007100184664A CN200710018466A CN101148360A CN 101148360 A CN101148360 A CN 101148360A CN A2007100184664 A CNA2007100184664 A CN A2007100184664A CN 200710018466 A CN200710018466 A CN 200710018466A CN 101148360 A CN101148360 A CN 101148360A
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China
Prior art keywords
paraffin
ceramic
minus
microballoon
hours
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CNA2007100184664A
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Chinese (zh)
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CN101148360B (en
Inventor
李涤尘
连芩
李翔
郭宏强
靳忠民
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西安交通大学
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Abstract

The present invention discloses the customized forming process of gradient porous structural ceramic. By means of the combined fast light solidifying and gel molding formation technology, porous ceramic product in spherical pore and micro tube combining structure and complicated profile may be obtained. The technological process of the present invention is simple and has low cost, high precision and high forming efficiency.

Description

A kind of customized forming method of gradient porous structure ceramic
Technical field
The present invention relates to a kind of manufacturing novel process with porous microstructure ceramics bracket of gradient variation, particularly have on its profile and customize complex profile and the dimensional precision height that requires, inside has by ball hole and microtubule mixes the porous microstructure that forms, and has the feature of porosity and bore diameter gradient variation.
Background technology
The vesicular structure customized forming is the manufacturing difficult point of porous ceramics, and its product is widely used and urgent demand in fields such as biomedicine, petrochemical complex, aerospace, defence and militaries.Research at present mostly concentrates on the preparation of the ceramic objects of single aperture, porosity, but can't satisfy the demand to the ceramic objects of vesicular structure with mutability aperture and porosity and complicated customization profile profile structure.For example, the osseous tissue ecto-entad is the microstructure of a graded in the natural bone, therefore, for the ceramic objects that is used for big section osseous tissue defect repair, then there are two difficult points in the development of its ceramics bracket, i.e. the customized forming of ceramics bracket coupling defect area macrostructure and the customized forming technology of inner vesicular structure.Can support have coupling bone defect area macrostructure will be the oriented growth of following area of new bone form and the important factor in order that bone is rebuild, and inner uniform distribution and the hole that is interconnected or pore passage structure are fixed cells and the place are provided, guarantee that the support deep can obtain the key of the sustainable supply of nutrient for the cell Growth and Differentiation.The porous ceramics that exists mainly adds polymer microballoon the process of making base substrate from powder stock at present, and high temperature sintering is made porous ceramics then.The support of this method preparation, connectivity structure and communication aperture between its ball hole are difficult to controlled.And the microtubule resin minus mould that passes through that proposes at present prepares microtubule connectivity structure ceramics bracket, yet is difficult to satisfy organizational project and assembles in different bones or chondrocyte and the osseous tissue defect repair process requirement to aperture and porosity.
Summary of the invention
In order to satisfy multi-functional requirement to the ceramic objects external and internal compositions, overcome defective or deficiency that porous ceramics is difficult to precise forming and known processes existence, the objective of the invention is to, propose a kind of customized forming processing method of utilizing photocureable rapid shaping and gel casting forming technology to make the porous ceramics product of ball hole and microtubule mixed structure.This processing method can produce need not that the later stage goes to expect to process, customize and make complicated macroscopical profile profile structure, and size accurately, the inner mixing with microtubule form porous ceramics product with aperture and porosity gradient variation by the ball hole.
In order to realize above-mentioned task, the present invention adopts following technical solution:
A kind of customized forming method of gradient porous structure ceramic is characterized in that, this method prepares the porous ceramics product of ball hole and microtubule mixed structure with photocureable rapid shaping and attached gel casting technology, specifically comprises the following steps:
Step 1 at first according to actual requirement, on the basis of the three-dimensional model of the coupling macroscopic view complex profile structure of structure, is finished the three-dimensional model design that customizes ceramic objects support minus mould, and its inside has the microtubule of connection minus structure; And this mould three-dimensional model is converted into the data file that can directly process;
Step 2 is done layering with the delamination software in the rapidform machine and is handled, and processing data is imported in the manufacturing course, utilizes accurate rapidform machine moulding to make support minus resin die;
Step 3 in support minus resin die, makes that paraffin microballoon and support minus resin die are bonding with the priming by vacuum of paraffin microballoon under the pressurized, heated condition, and makes mutual little contact between the paraffin microballoon;
Step 4, prepare ceramic slurry, according to mass ratio with ceramic powder: water solvent: organic monomer: dispersion agent: linking agent=(100~150): (40~70): (5~10): (1~2): the ratio uniform mixing of (1~2), put into the vacuum machine and remove bubble, slurry through strong aqua adjustment formation PH=(7~9) adds an amount of initiator and catalyzer again and forms ceramic slurry;
Step 5 is gone into to be bonded with the ceramic slurry vacuum impregnating that configures in the support minus resin die of paraffin microballoon, at room temperature dry 72 hours;
Step 6 is put into electric furnace with exsiccant support minus resin die, can form the porous ceramics product with ball hole and microtubule mixed structure through sintering process.
Sintering process parameter is: heat-up rate is 5 ℃/hour.Rise to 340 ℃ from room temperature, be incubated 5 hours; Rise to 660 ℃ with 10 ℃/h again, be incubated 5 hours; Rise to 1200 ℃ with 60 ℃/hour then, be incubated 5 hours; Close furnace power after the insulation, reduced to the room temperature taking-up through 48 hours naturally and get final product.
Method of the present invention is on the preparation technology's of traditional ceramics basis, proposition utilizes the technology of paraffin microballoon and photocuring moulding micro-tubular structure minus mould, can produce by ball hole and microtubule to mix the ceramic objects that forms the vesicular structure with aperture and porosity gradient variation.New cost is low, precision is high, shaping efficiency is high, technology simple process method for the realization of the porous ceramics of complex construction provides.
Description of drawings
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is the three-dimensional model diagram with the customization ceramic objects minus mould that is communicated with microtubule system;
Fig. 3 is preparation technology's schema of paraffin microballoon;
Fig. 4 is preparation technology's schema of ceramic slurry;
The present invention is described in further detail below in conjunction with accompanying drawing.
Embodiment
Referring to Fig. 1, make customized forming method according to utilize photocureable rapid shaping and gel casting forming technology that the present invention proposes with gradient porous structure ceramic, its concrete steps comprise:
1.3D the pattern layout step according to actual requirement, is set up the three-dimensional data model that customizes ceramic objects minus mould with Pro/E software, its inside has the microtubule of connection minus structure, as shown in Figure 2; And model shown in Figure 2 is stored as the data file that can directly process, STL formatted file for example.
2. the delamination software that carries with rapidform machine is done the layering processing, and processing data is imported in the manufacturing course, utilizes the precise light curing formation machine to make the negative shape resin die of support.Its concrete processing parameter is: LASER Light Source: solid statelaser (355nm wavelength); Spot diameter: 0.2mm; Lift height: 0.10mm; Fill sweep velocity: 5000mm/s; Fill vectorial spacing: 0.10mm; Support sweep velocity: 2000mm/s; Speed is striden in jumping: 8000mm/s; Profile scan speed: 3000mm/s; Compensation diameter: 0.12mm; Worktable lifting speed: 4.00mm/s; Point supports sweep time: 0.50ms; Line structure sweep time: 0.50ms.Above-mentioned steps all is mature technologies of the routine of this area.
3. as shown in Figure 3, follow these steps to prepare the paraffin microballoon:
1) with paraffin: gelatin: water solvent=(10~20): 1: the mass ratio of (150~500) is at the beaker mixed raw material, is heated to 90 ℃ and paraffin is melted fully and forms mixture with gelatin;
2) this mixture is placed on the magnetic stirring apparatus stirs, under 90 ℃ of heat-retaining conditions, stirred 1 hour, make to form the outstanding liquid that mixes of homodisperse small droplets in this mixture;
3) this liquor is poured in the container of 0 ℃ of frozen water, in frozen water, formed the paraffin microballoon;
4) filtering net by 50~1000 μ m apertures, screening paraffin microballoon, and under vacuum drying for standby.
4. under vacuum condition, the paraffin microballoon for preparing is inserted in the resin die.Then, under 1.5 normal atmosphere, 50 ℃ are incubated 1 hour, and the wax ball is bondd in advance, and cooling rapidly makes paraffin microballoon and resin mould adhesion-molded then.
5. as shown in Figure 4, follow these steps to prepare ceramic slurry:
1) gets 60g ceramic powder (for example β-TCP, hydroxyapatite, aluminum oxide etc.), add in the 35g water solvent (for example deionized water or distilled water etc.), add 4g organic monomer (for example acrylamide or methyl-acyl-oxygen ethyl-trimethyl salmiac or adipic dihydrazide etc.), 0.5g linking agent (N for example more respectively, N-dimethylene diacrylamine or N, N-two acetonyl acrylamides, dibenzalacetone base acrylamide etc.), 0.6g dispersion agent (for example sodium polyacrylate or ammonium polyacrylate etc.) forms mixture.
2), put into the bubble that the vacuum machine is removed slurry through this mixture of ultra-sonic dispersion 5 hours.Regulate pH value of slurry with strong aqua, its pH value is maintained about 7~9.
3) in this slurry, add 0.2g initiator (for example ammonium persulphate or Sodium Persulfate, Potassium Persulphate) and 0.1g catalyzer (N, N, N ' N '-Tetramethyl Ethylene Diamine or N again, N-dimethylcyclohexylamine, N, N, N ', N ", N " pentamethyl-diethylenetriamine etc.) make ceramic slurry.The slurry curing time that configures is 5-10 minute.
6. the ceramic size vacuum that configures is injected the resin mold mould of bonding paraffin microballoon.At room temperature dry 72 hours.
7. this mould is put into electric furnace and carry out sintering.Sintering process parameter is: heat-up rate is 5 ℃/hour.Rise to 340 ℃ from room temperature, be incubated 5 hours; Rise to 660 ℃ with 10 ℃/h again, be incubated 5 hours; Rise to 1200 ℃ with 60 ℃/h then, be incubated 5 hours; Close furnace power after the insulation, reduced to room temperature through 48 hours naturally.
8. after surface-conditioning, can obtain having the ceramic objects of gradient porous structure.

Claims (8)

1. the customized forming method of a gradient porous structure ceramic is characterized in that, this method prepares the porous ceramics product of ball hole and microtubule mixed structure with photocureable rapid shaping and attached gel casting technology, specifically comprises the following steps:
Step 1 at first according to actual requirement, on the basis of the three-dimensional model of the coupling macroscopic view complex profile structure of structure, is finished the three-dimensional model design that customizes ceramic objects support minus mould, and its inside has the microtubule of connection minus structure; And this mould three-dimensional model is converted into the data file that can directly process;
Step 2 is done layering with the delamination software in the rapidform machine and is handled, and processing data is imported in the manufacturing course, utilizes accurate rapidform machine moulding to make support minus resin die;
Step 3 in support minus resin die, makes that paraffin microballoon and support minus resin die are bonding with the priming by vacuum of paraffin microballoon under the pressurized, heated condition, and makes mutual little contact between the paraffin microballoon;
Step 4, prepare ceramic slurry, according to mass ratio with ceramic powder: water solvent: organic monomer: dispersion agent: linking agent=(100~150): (40~70): (5~10): (1~2): the ratio uniform mixing of (1~2), put into the vacuum machine and remove bubble, slurry through strong aqua adjustment formation PH=(7~9) adds an amount of initiator and catalyzer again and forms ceramic slurry;
Step 5 is gone into to be bonded with the ceramic slurry vacuum impregnating that configures in the support minus resin die of paraffin microballoon, at room temperature dry 72 hours;
Step 6 is together put into electric furnace with dried ceramic body and support minus resin die thereof, can form the porous ceramics product with ball hole and microtubule mixed structure through sintering process.
2. the method for claim 1 is characterized in that, described support minus mould is the micro-tubular structure minus and customizes profile shell minus integrated mould.
3. the method for claim 1, it is characterized in that, described paraffin microballoon selects paraffin, gelatin and water solvent with (10~20): 1: the mass ratio preparation of (150~500) also mixes, and mixes post-heating to 90 and ℃ forms mixture, can form the paraffin microballoon through 0 ℃ of frozen water condensation.
4. the method for claim 1 is characterized in that, described pressurized, heated condition is to be heated to 50 ℃ under 1.5 normal atmosphere, makes that paraffin microballoon and resin mould are bonding.
5. the method for claim 1 is characterized in that, described sintering process parameter is: making heat-up rate earlier is 5 ℃/hour, rises to 340 ℃ from room temperature, is incubated 5 hours then; Rise to 660 ℃ with 10 ℃/hour again, be incubated 5 hours; Rise to 1200 ℃ with 60 ℃/hour then, be incubated 5 hours; Close furnace power after the insulation, reduced to the room temperature taking-up through 48 hours naturally and get final product.
6. the method for claim 1 is characterized in that, described initiator is ammonium persulphate or Sodium Persulfate, Potassium Persulphate, and described catalyzer is N, N, N ' N '-Tetramethyl Ethylene Diamine or N, N-dimethylcyclohexylamine, N, N, N ', N ", N " pentamethyl-diethylenetriamine.
7. as claim 1 or 3 described methods, it is characterized in that the preparation method of described paraffin microballoon is:
With paraffin: gelatin: water solvent=(10~20): 1: the mass ratio of (150~500) is at the beaker mixed raw material, is heated to 90 ℃ and paraffin is melted fully and forms mixture with gelatin;
Mixture is placed on the magnetic stirring apparatus stirs, under 90 ℃ of heat-retaining conditions, stirred 1 hour, make and form the outstanding liquid that mixes of homodisperse small droplets in the mixture;
Mixture after being mixed liquor is poured in the container of 0 ℃ of frozen water, in frozen water, can be formed the paraffin microballoon;
4) by the filtering net in 50~1000 μ m apertures, screen the paraffin microballoon, and dry under vacuum.
8. the method for claim 1, it is characterized in that, described linking agent is N, N-dimethylene diacrylamine or N, N-two acetonyl acrylamides, dibenzalacetone base acrylamide, described organic monomer is acrylamide, methyl-acyl-oxygen ethyl-trimethyl salmiac or adipic dihydrazide, and described dispersion agent is sodium polyacrylate or ammonium polyacrylate.
CN200710018466A 2007-08-14 2007-08-14 Customized forming method for gradient porous structure ceramic CN101148360B (en)

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CN101306950B (en) * 2008-06-23 2011-01-05 西安交通大学 Direct light-curing fabrication method of hollow blade ceramic cast
CN101954446A (en) * 2010-09-29 2011-01-26 西安交通大学 Photocuring die and method for manufacturing waxy template for precise casting
CN102430151A (en) * 2011-09-05 2012-05-02 西安交通大学 Tissue engineering bone cartilage composite bracket and integrated photocuringable forming method thereof
CN101397209B (en) * 2008-10-28 2012-05-23 西安交通大学 Fusible pattern moulding method of silicon carbide with complicated shape
CN101660202B (en) * 2009-09-15 2012-07-04 西安交通大学 Method for preparing ceramic-based three-dimensional photonic crystals with photo-curing direct molding
CN103989541A (en) * 2014-05-19 2014-08-20 西安交通大学 Method for manufacturing high-strength composite bone and cartilage support with complex molded surface
CN104493952A (en) * 2015-01-06 2015-04-08 彭晓领 Gel-casting 3D printing preparation method for ceramic gradient material
CN105382928A (en) * 2015-11-04 2016-03-09 合肥丰德科技股份有限公司 Molding die for ceramic fiber filtering pipe
CN105801108A (en) * 2016-03-11 2016-07-27 北京科技大学 Preparation method of three-dimensional open-framework structure lithium base block tritium value-added agent material
WO2017045191A1 (en) * 2015-09-16 2017-03-23 广东工业大学 Method for preparing photocuring-formed high-density ceramic
CN107032824A (en) * 2017-05-11 2017-08-11 西安交通大学 A kind of manufacture method of directed tissue ceramic matric composite part
CN107320220A (en) * 2017-06-14 2017-11-07 西安交通大学 A kind of preparation method of the porous implant based on ceramic increasing material manufacturing

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CN101306950B (en) * 2008-06-23 2011-01-05 西安交通大学 Direct light-curing fabrication method of hollow blade ceramic cast
CN101397209B (en) * 2008-10-28 2012-05-23 西安交通大学 Fusible pattern moulding method of silicon carbide with complicated shape
CN101660202B (en) * 2009-09-15 2012-07-04 西安交通大学 Method for preparing ceramic-based three-dimensional photonic crystals with photo-curing direct molding
CN101954446A (en) * 2010-09-29 2011-01-26 西安交通大学 Photocuring die and method for manufacturing waxy template for precise casting
CN102430151B (en) * 2011-09-05 2013-12-04 西安交通大学 Tissue engineering bone cartilage composite bracket and integrated photocuringable forming method thereof
CN102430151A (en) * 2011-09-05 2012-05-02 西安交通大学 Tissue engineering bone cartilage composite bracket and integrated photocuringable forming method thereof
CN103989541A (en) * 2014-05-19 2014-08-20 西安交通大学 Method for manufacturing high-strength composite bone and cartilage support with complex molded surface
CN103989541B (en) * 2014-05-19 2016-04-27 西安交通大学 There is the preparation method of the high strength composite bone cartilage frame of complex profile
CN104493952A (en) * 2015-01-06 2015-04-08 彭晓领 Gel-casting 3D printing preparation method for ceramic gradient material
WO2017045191A1 (en) * 2015-09-16 2017-03-23 广东工业大学 Method for preparing photocuring-formed high-density ceramic
CN105382928A (en) * 2015-11-04 2016-03-09 合肥丰德科技股份有限公司 Molding die for ceramic fiber filtering pipe
CN105801108A (en) * 2016-03-11 2016-07-27 北京科技大学 Preparation method of three-dimensional open-framework structure lithium base block tritium value-added agent material
CN105801108B (en) * 2016-03-11 2018-09-14 北京科技大学 A kind of preparation method of three-dimensional open-framework lithium matrix body tritium increment agent material
CN107032824A (en) * 2017-05-11 2017-08-11 西安交通大学 A kind of manufacture method of directed tissue ceramic matric composite part
CN107032824B (en) * 2017-05-11 2020-04-28 西安交通大学 Manufacturing method of ceramic matrix composite part with oriented structure
CN107320220A (en) * 2017-06-14 2017-11-07 西安交通大学 A kind of preparation method of the porous implant based on ceramic increasing material manufacturing
CN107320220B (en) * 2017-06-14 2019-12-24 西安交通大学 Preparation method of porous implant based on ceramic additive manufacturing

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