CN104387105A - Method for preparing porous alumina ceramic material through combination of 3D printing and reactive sintering - Google Patents
Method for preparing porous alumina ceramic material through combination of 3D printing and reactive sintering Download PDFInfo
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- CN104387105A CN104387105A CN201410562321.0A CN201410562321A CN104387105A CN 104387105 A CN104387105 A CN 104387105A CN 201410562321 A CN201410562321 A CN 201410562321A CN 104387105 A CN104387105 A CN 104387105A
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Abstract
The invention relates to a method for preparing a porous alumina ceramic material through combination of 3D printing and reactive sintering. The method comprises the following steps: 1) adding aluminium powder or aluminium alloy powder into a feeding box of a three-dimensional printer, and printing porous biscuit through the three-dimensional printer; 2) performing processes of solidification, debonding, oxidation and sintering in sequence on the porous biscuit prepared in the step 1) so as to obtain the porous alumina ceramic material.
Description
Technical field
The present invention relates to a kind of preparation method of porous alumina ceramic material, belong to porous ceramic film material preparing technical field.
Background technology
Porous alumina ceramic has lightweight, high permeability, resistance to chemical attack, rub resistance, low-expansion coefficient and good high-temperature stability, is with a wide range of applications in fields such as High Temperature Gas, liquid filtration, support of the catalyst, lagging materials.According to the embody rule demand of different field, can design the void content of porous alumina ceramic, pore size, relevant preparation method also has a lot of report.As using aluminum oxide as aggregate, carbon dust and ethyl cellulose composite pore-forming agent prepare the porous alumina ceramic (Chinese patent, patent No. CN101734909A) of porosity >50%.Mix according to a certain percentage with aluminum nitrate, citric acid and water, 150-200 DEG C of reaction, foamed alumina pottery (Chinese patent, patent No. CN101717105A) is prepared in high-temperature calcination.Using aluminum isopropylate as presoma, using gelatin wrapping-freeze drying process prepares porous alumina ceramic, and void content 30-97% is adjustable, pore size 1-100 μm adjustable (Chinese patent, patent No. CN196257A).Above report is all the control measures of microtexture, does not relate to complex configuration, the especially inner preparation with complicated macroscopic pores structure.
Three-dimensional printing technology (3DP) is as the one of quick shaping process, automatically the prototype or direct finished parts (mould) with certain function can, fast, directly, accurately by design philosophy be converted into, effectively shorten the R&D cycle of product, improve the one-pass finished rate of product design, manufacture, reduce product development cost.3DP technology have employed the ink ejecting method in printing technique, and binding agent, when directly not contacting powder surface, is sprayed onto on the position of needs by shower nozzle selectively, is successively bondd by the lamella of part.This technology can realize the design preparation of three-D pore structure.But conventional 3DP prepares the method for porous alumina, that thin alumina powder jointed (~ 0.5 μm), dextrin are mixed in distilled water, then lyophilize obtains loose granulation powder, size distribution 50 ~ 200 μm, facilitate 3DP successively powder sprawl (MelcherR, Mater Lett 2006; 60:572-75).But sample shrinking percentage in rear sintering process is about 20%, is difficult to realize the manipulation from prototype to accurately preparation, thus greatly reduces the using value of 3DP.
Therefore, how to prepare the low porous ceramic film material of shrinking percentage in conjunction with 3DP technology, remain an important research direction of these those skilled in the art.
Summary of the invention
The present invention is intended to overcome the high defect of the existing porous ceramic film material shrinking percentage adopting 3DP technology to prepare, and the invention provides the method that a kind of 3D printing association reaction sintering prepares porous alumina ceramic material.
The invention provides a kind of method preparing porous alumina ceramic material, described method comprises:
1) aluminium powder or Al alloy powder are added in the box for feeding odd of three-dimensional printer, print porous biscuit by three-dimensional printer;
2) by step 1) the porous biscuit prepared successively through overcuring, unsticking, oxidation, sintering circuit, obtain described porous alumina ceramic material.
Preferably, described Al alloy powder comprises AlSi5 powder and/or AlSi12 powder.
Preferably, in described aluminium powder or Al alloy powder, particle is 10-25 μm of spheroidal particle.
Preferably, step 1) in, the parameter of 3 D-printing is: the thickness in monolayer of porous biscuit is 50-200 μm, and binding agent saturation ratio is 60-150%, binding agent comprises the mixture of ethylene glycol, ethylene glycol monobutyl ether and these two kinds of binding agents, and time of drying is 60-120s.
Preferably, step 2) in, the parameter of curing process is: at 100 ~ 120 DEG C, is incubated 24 ~ 96 hours.
Preferably, step 2) in, be warming up to 200-600 DEG C with the heat-up rate of 0.2-2 DEG C/min in debinding process, soaking time is 2-12 hours.
Preferably, step 2), be warming up to 550-1400 DEG C with the heat-up rate of 0.2-2 DEG C/min in oxidation operation, soaking time is 2-24 hours.
Preferably, step 2) in, be warming up to 1550-1600 DEG C with the heat-up rate of 5-10 DEG C/min in sintering circuit, soaking time is 2-8 hours.
Beneficial effect of the present invention:
(1) 3DP can prepare complex-shaped goods without the need to mould, and goods surround and watch homogeneity and hole connectedness is good, aperture and controlled porosity;
(2) before and after reaction sintering, the shape and size of sample are substantially constant, effectively realize from the accurate realization being designed into the finished product.
Accompanying drawing explanation
Fig. 1 shows the scanning electron microscope (SEM) photograph of material powder Al (a) and the AlSi12 (b) used in two embodiments of the present invention;
Fig. 2 shows the XRD figure of Al base substrate and the porous alumina ceramic prepared in two embodiments of the present invention;
Fig. 3 shows the profile scanning electron microscopic picture of Al base substrate (a) and the porous alumina ceramic (b) prepared in an embodiment of the invention;
Fig. 4 shows the photo in kind of Al base substrate (grey) and the porous alumina ceramic (white) prepared in an embodiment of the invention.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
The object of the invention is to print technique by 3D provides a kind of technique simple, method with low cost prepares the porous aluminum of complicated shape and excellent performance, porous alumina ceramic material is prepared by further reaction sintering, realize nearly size shaping, sintering, to overcome prior art Problems existing and deficiency.Choose AlSi alloy, oxidation generates Al simultaneously
2o
3, SiO
2, sintering generates porous mullite combined aluminum oxide.
The invention discloses a kind of preparation method of porous alumina ceramic material, comprise the steps, choose ball-type metal aluminium powder body prepared by atomization, prepare porous aluminum base substrate by 3D printer quick shaping process, obtain porous alumina ceramic material by being oxidized under air atmosphere and sintering.The invention provides a kind of technique simple, method with low cost prepares the porous alumina ceramic of complicated shape and excellent properties, has the advantage that nearly size is shaping, sinter.
The invention provides a kind of method preparing porous alumina ceramic material, specifically comprise the steps:
A aluminium powder adds in commercial three-dimensional printer box for feeding odd by ();
B () loads the three-dimensional image needing to print in computer, start to print after regulating print parameters;
C porous body that () is printed solidifies in an oven;
D the sample after () solidification is put into retort furnace and is carried out de-binding agent, oxidation, sintering, finally obtain porous alumina ceramic.
Metal-powder described in step (a) is that Al and alloy thereof are as AlSi5, AlSi12 etc.
In step (a), metal-powder is the spheroidal particle of size 10-25 μm.
Print parameters described in step (b) is thickness 50-200 μm, and binding agent saturation ratio is 60-150%, and time of drying is 60-120s.
Condition of cure described in step (c) is 100 ~ 120 DEG C of insulations 24 ~ 96 hours.
De-binder temperature described in step (d) is 200-600 DEG C, and heat-up rate is 0.2-2 DEG C/min; Oxidizing temperature is 550-1400 DEG C, and heat-up rate is 0.2-2 DEG C/min; Sintering temperature is 1550-1600 DEG C, and heat-up rate is 5-10 DEG C/min.
Compared to the prior art comparatively, the present invention has following beneficial effect:
(1) 3DP can prepare complex-shaped goods without the need to mould, and goods surround and watch homogeneity and hole connectedness is good, aperture and controlled porosity;
(2) before and after reaction sintering, the shape and size of sample are substantially constant, effectively realize from the accurate realization being designed into the finished product.
Below some exemplary embodiments are listed further better the present invention to be described.Should understand; the above-mentioned embodiment that the present invention describes in detail; and following examples are only not used in for illustration of the present invention and limit the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.In addition, concrete proportioning, time, temperature etc. in following processing parameter are also only exemplary, and those skilled in the art can select suitable value in the scope of above-mentioned restriction.
Embodiment 1
(1) 10 ~ 25 μm of Al powder (as shown in a in Fig. 1) are added in commercial three-dimensional printer box for feeding odd;
(2) adopt print parameters to be thickness 50 μm, binding agent saturation ratio is 80%, and binding agent is 15% ethylene glycol and 85% ethylene glycol monobutyl ether mixture, and time of drying is 60s;
(3) printed porous body is 120 DEG C of solidification 24h in an oven;
(4) sample after solidification is put into retort furnace and is carried out 2 DEG C/min and rise to 600 DEG C to de-binding agents (being incubated 2 hours), 1 DEG C/min rises to 1400 DEG C of oxidations (being incubated 6 hours), 5 DEG C/min rises to 1600 DEG C of sintering (being incubated 4 hours), finally obtain porous alumina ceramic, bending strength 74.8Mpa, porosity 45%, sample size increases 0.6%;
As can be seen from Figure 2, aluminium powder complete oxidation, final product is alumina ceramic material; As can be seen from Fig. 4, photo is also, porous alumina ceramic size prepared by the present embodiment and base substrate size very close, there is not much changes.
Embodiment 2
(1) 10 ~ 25 μm of Al powder are added in commercial three-dimensional printer box for feeding odd;
(2) adopt print parameters to be thickness 100 μm, binding agent saturation ratio is 120%, and binding agent is 15% ethylene glycol and 85% ethylene glycol monobutyl ether mixture, and time of drying is 90s;
(3) printed porous body is 120 DEG C of solidification 24h in an oven;
(4) sample after solidification is put into retort furnace and is carried out 1 DEG C/min and rise to 600 DEG C to de-binding agents (being incubated 2 hours), 1 DEG C/min rises to 1400 DEG C of oxidations (being incubated 12 hours), 5 DEG C/min rises to 1600 DEG C of sintering (being incubated 2 hours), finally obtain porous alumina ceramic, bending strength 71.3Mpa, porosity 44%, sample size increases 0.8%;
As can be seen from Figure 2, aluminium powder complete oxidation, final product is alumina ceramic material; As can be seen from Figure 3, biscuit particle packing is closely knit, presents good sintering neck and connect after sintering between particle.
Embodiment 3
(1) 20-25 μm of AlSi5 powder is added in commercial three-dimensional printer box for feeding odd;
(2) adopt print parameters to be thickness 75 μm, binding agent saturation ratio is 80%, and binding agent is 15% ethylene glycol and 85% ethylene glycol monobutyl ether mixture, and time of drying is 120s;
(3) printed porous body is 120 DEG C of solidification 24h in an oven;
(4) sample after solidification is put into retort furnace and is carried out 2 DEG C/min and rise 600 DEG C to de-binding agents (being incubated 4 hours), 0.5 DEG C/min rises to 1400 DEG C of oxidations (being incubated 24 hours), 5 DEG C/min rises to 1600 DEG C of sintering (being incubated 4 hours), finally obtain porous mullite combined aluminum oxide pottery, bending strength 63.4Mpa, porosity 48%, sample size increases 1.2%.
Embodiment 4
(1) 20-25 μm of AlSi12 powder (as shown in b in Fig. 1) is added in commercial three-dimensional printer box for feeding odd;
(2) adopt print parameters to be thickness 150 μm, binding agent saturation ratio is 120%, and binding agent is 15% ethylene glycol and 85% ethylene glycol monobutyl ether mixture, and time of drying is 90s;
(3) printed porous body is 120 DEG C of solidification 24h in an oven;
(4) sample after solidification is put into retort furnace and is carried out 2 DEG C/min and rise to 600 DEG C to de-binding agents (being incubated 2 hours), 0.3 DEG C/min rises to 1100 DEG C (being incubated 8 hours), 0.5 DEG C/min rises to 1400 DEG C of oxidations (being incubated 4 hours), 5 DEG C/min rises to 1600 DEG C of sintering (being incubated 4 hours), finally obtain porous mullite combined aluminum oxide pottery, bending strength 60.2Mpa, porosity 47.5%, sample size increases 1.1%.
Claims (8)
1. prepare a method for porous alumina ceramic material, it is characterized in that, described method comprises:
1) aluminium powder or Al alloy powder are added in the box for feeding odd of three-dimensional printer, print porous biscuit by three-dimensional printer;
2) porous biscuit step 1) prepared, successively through overcuring, unsticking, oxidation, sintering circuit, obtains described porous alumina ceramic material.
2. method according to claim 1, is characterized in that, described Al alloy powder comprises AlSi5 powder and/or AlSi12 powder.
3. method according to claim 1 and 2, is characterized in that, in described aluminium powder or Al alloy powder, particle is the spheroidal particle of 10-25 μm.
4., according to described method arbitrary in claim 1-3, it is characterized in that, in step 1), the parameter of 3 D-printing is: the thickness in monolayer of porous biscuit is 50-200 μm, binding agent saturation ratio is 60-150%, and binding agent comprises ethylene glycol and/or ethylene glycol monobutyl ether, and time of drying is 60-120s.
5., according to described method arbitrary in claim 1-4, it is characterized in that, step 2) in, the parameter of curing process is: at 100 ~ 120 DEG C, is incubated 24 ~ 96 hours.
6., according to described method arbitrary in claim 1-5, it is characterized in that, step 2) in, be warming up to 200-600 DEG C with the heat-up rate of 0.2-2 DEG C/min in debinding process, soaking time is 2-12 hours.
7., according to described method arbitrary in claim 1-6, it is characterized in that, step 2), be warming up to 550-1400 DEG C with the heat-up rate of 0.2-2 DEG C/min in oxidation operation, soaking time is 2-24 hours.
8., according to described method arbitrary in claim 1-7, it is characterized in that, step 2) in, be warming up to 1550-1600 DEG C with the heat-up rate of 5-10 DEG C/min in sintering circuit, soaking time is 2-8 hours.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105196545A (en) * | 2015-10-20 | 2015-12-30 | 江苏科技大学 | Method for improving adhesion quality of polymer three-dimensional printed product by using instant adhesive |
| CN105645840A (en) * | 2015-12-30 | 2016-06-08 | 成都新柯力化工科技有限公司 | Ceramic material for 3D printing and manufacturing method thereof |
| CN105777180A (en) * | 2016-03-01 | 2016-07-20 | 贵州师范大学 | Method for preparing porous silicon nitride through three-dimensional printing |
| CN106036999A (en) * | 2016-08-08 | 2016-10-26 | 普瑞特机械制造股份有限公司 | Compound cigarette filter tip |
| CN106179520A (en) * | 2016-07-08 | 2016-12-07 | 江西应陶康顺实业有限公司 | The preparation method of alumina catalyst carrier |
| CN108585886A (en) * | 2018-06-11 | 2018-09-28 | 哈尔滨工业大学 | A kind of porous ceramic film material and preparation method thereof that porosity change is controllable |
| CN109527657A (en) * | 2018-12-21 | 2019-03-29 | 深圳市合元科技有限公司 | The preparation method and electronic smoke atomizer of atomizing component |
| CN112207288A (en) * | 2020-09-16 | 2021-01-12 | 山东工业陶瓷研究设计院有限公司 | Metal ceramic composite part and preparation method thereof |
| CN112430103A (en) * | 2020-11-19 | 2021-03-02 | 中国科学院金属研究所 | Photocuring 3D printing hierarchical pore ceramic material and preparation method thereof |
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| WO2019045733A1 (en) * | 2017-08-31 | 2019-03-07 | Desktop Metal, Inc. | Particle agglomeration for additive metal manufacturing |
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| CN105196545A (en) * | 2015-10-20 | 2015-12-30 | 江苏科技大学 | Method for improving adhesion quality of polymer three-dimensional printed product by using instant adhesive |
| CN105645840A (en) * | 2015-12-30 | 2016-06-08 | 成都新柯力化工科技有限公司 | Ceramic material for 3D printing and manufacturing method thereof |
| CN105645840B (en) * | 2015-12-30 | 2018-03-23 | 安徽长朗三维科技有限公司 | A kind of ceramic material and its manufacture method for 3D printing |
| CN105777180A (en) * | 2016-03-01 | 2016-07-20 | 贵州师范大学 | Method for preparing porous silicon nitride through three-dimensional printing |
| CN106179520B (en) * | 2016-07-08 | 2018-09-11 | 江西应陶康顺实业有限公司 | The preparation method of alumina catalyst carrier |
| CN106179520A (en) * | 2016-07-08 | 2016-12-07 | 江西应陶康顺实业有限公司 | The preparation method of alumina catalyst carrier |
| CN106036999A (en) * | 2016-08-08 | 2016-10-26 | 普瑞特机械制造股份有限公司 | Compound cigarette filter tip |
| CN108585886A (en) * | 2018-06-11 | 2018-09-28 | 哈尔滨工业大学 | A kind of porous ceramic film material and preparation method thereof that porosity change is controllable |
| CN108585886B (en) * | 2018-06-11 | 2020-07-21 | 哈尔滨工业大学 | Porous ceramic material with controllable porosity change and preparation method thereof |
| CN109527657A (en) * | 2018-12-21 | 2019-03-29 | 深圳市合元科技有限公司 | The preparation method and electronic smoke atomizer of atomizing component |
| CN112207288A (en) * | 2020-09-16 | 2021-01-12 | 山东工业陶瓷研究设计院有限公司 | Metal ceramic composite part and preparation method thereof |
| CN112430103A (en) * | 2020-11-19 | 2021-03-02 | 中国科学院金属研究所 | Photocuring 3D printing hierarchical pore ceramic material and preparation method thereof |
| CN112430103B (en) * | 2020-11-19 | 2022-01-25 | 中国科学院金属研究所 | Photocuring 3D printing hierarchical pore ceramic material and preparation method thereof |
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