CN103801697A - Method for forming mould-free gel with metal sizing agents through 3D printing - Google Patents
Method for forming mould-free gel with metal sizing agents through 3D printing Download PDFInfo
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- CN103801697A CN103801697A CN201410047534.XA CN201410047534A CN103801697A CN 103801697 A CN103801697 A CN 103801697A CN 201410047534 A CN201410047534 A CN 201410047534A CN 103801697 A CN103801697 A CN 103801697A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 52
- 239000002184 metal Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000010146 3D printing Methods 0.000 title claims abstract description 20
- 238000004513 sizing Methods 0.000 title abstract 5
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000013499 data model Methods 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 11
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000009825 accumulation Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000013461 design Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 238000010382 chemical cross-linking Methods 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000005266 casting Methods 0.000 abstract description 8
- 238000007639 printing Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 6
- 230000000977 initiatory effect Effects 0.000 abstract 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000010935 stainless steel Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000007630 basic procedure Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
The invention provides a method for forming mould-free gel with metal sizing agents through 3D printing. A 3D printing technology is combined with a gel forming technology, the metal sizing agents are prepared through a gel forming process, the sizing agents are adopted as the raw materials of 3D printing, then layered printing is carried out through 3D printing equipment according to a data model, the metal sizing agents are solidified fast by controlling the additive number of initiating agents and catalysts, the initiating agents and the catalysts are accumulated layer by layer to form a metal blank, and the metal blank is dried and sintered to obtain a metal part product with a large size and in a complex shape. The method can be used for manufacturing a part including a sealed cavity and a complex inner cavity, the part cannot be manufactured through a traditional gel casting forming mode, the blank is directly formed through the 3D printing technology, mould development cost is saved, the method has obvious advantages in single part production and small scale production, requirements for powder materials are low, the process is stable and reliable, the operability is strong, consumed time is short, efficiency is high, cost is low, and the industrialization of manufacturing the metal part with the large size and in the complex shape through the 3D printing technology is facilitated.
Description
Technical field
The present invention relates to a kind of Metal Powder Forming Technology, belong to metallic element preparing technical field, particularly provide a kind of metal slip 3D to print without the gel shaped method of preparing large scale, complicated shape metal parts of mould.
Background technology
3D prints, i.e. the one of Quick-forming is that applying powder powder can jointing material take three-dimensional data model as basis, carrys out the technology of constructed object by the mode of successively printing.3D prints and normally adopts digital technology file printing machine to realize, and the fields such as mould manufacture, industrial design of being everlasting are for the manufacture of model, now gradually for the direct manufacture of product.Its basic process is: 3D model is divided into some layers in computer, by 3D printing device in one plane according to data model layered graph, by the material such as plastics, metal sintering or stick together, and then stacking up in layer.By the accumulation of every one deck different graphic, finally form a three-dimensional body.
Metal parts 3D printing technique, as forward position and most potential technology the most in whole 3D printing system, is the important development direction of advanced manufacturing technology.At present, utilize 3D printing technique to prepare stainless steel, titanium base, nickel-base alloy, can directly obtain arbitrary shape almost, there is the metal parts of metallurgical binding.But, existing 3D printing technique cost is very high, on the one hand due to 3D printing device costliness, need to be equipped with the heating system such as laser, electron beam by powder smelting, be that the cost of raw material is high on the other hand, for the uniformity that guarantees to be shaped, need the thin and uniform powder of good sphericity, mobility excellence, particle diameter, and whole forming process length consuming time, efficiency are low, thereby make the production cost of single products high.
Gel casting is a kind of Wetting forming technology, main by the slurry of preparation low viscosity, high solid loading, then makes the organic monomer polymerization in slurry that slurry original position is solidified, thereby obtains the base substrate of high strength, high density, excellent in uniformity.Its basic procedure is: organic monomer and solvent are mixed with to certain density premixed liquid, add powder to be configured to the slurry of low viscosity, high solid loading, after adding initator and catalyst, slip is injected in non-porous mould, organic monomer cross-linked polymeric in slurry forms three-dimensional network shaped polymer gel, make slurry original position bonding and solidify to form base substrate, drying, come unstuck and sintering obtains part product.Compared with traditional forming technology, the advantage such as gel casting has easy shaping large scale, complicated shape part, blank strength is high, content of organics is few, is having broad application prospects aspect iron-based, stainless steel, titanium base, aluminium base powdered metal parts.But first gel casting technology needs to prepare mould, the cost of single-piece and small lot batch manufacture is high, and some complicated shape parts cannot prepare mould, as enclosed cavity, complicated inner cavity etc., the application of gel casting is restricted.
The invention provides a kind of large scale that 3D printing technique is combined with gel shaped technology, complicated shape metal parts preparation method, utilize gel shaped technique to prepare adherent metal slip, this slip can solidify rapidly by the addition of controlling initator and catalyst.The raw material of printing using this slurry as 3D, utilizes 3D printing device to print according to data model layering, and metal slip solidifies rapidly and successively accumulation forms metal body, then obtains metallic element product by dry, sintering.With metal 3D print compared with technique cost low, to metal dust requirement low, consuming time short, efficiency is high.Compared with conventional gel casting, without mould, and size, shape strong adaptability to parts.Yet there are no and utilize metal slip 3D to print the relevant report without the gel shaped preparation large scale of mould, complicated shape metal parts method.
Summary of the invention
The object of the present invention is to provide a kind of metal slip 3D to print without the gel shaped method of preparing large scale, complicated shape metal parts of mould, utilize gel shaped technique to prepare the raw material that metal slip is printed as 3D, then utilize 3D printing technique to prepare metal body, obtain large scale, complicated shape metal parts through super-dry, sintering.Its concrete technology flow process and parameter are as follows:
1) configuration premixed liquid: organic monomer hydroxyethyl methacrylate (HEMA) and solvent toluene are mixed by a certain percentage and be configured to premixed liquid, the concentration of organic monomer HEMA is 30vol.% ~ 50vol.%, and this monomer can be by controlling the rapid polymeric gel of addition of initator and catalyst;
2) prepare metal slip: in above-mentioned premixed liquid, add the metal dust of particle mean size 5 ~ 50 μ m, be prepared into the slip of solid concentration 40vol.% ~ 60vol.%, then add the oleic acid of powder quality 0.01wt ~ 0.2wt% to improve slip mobility;
3) data modeling: use 3D sculpting software to design the part model of desired structure shape, particularly there is the large-scale part model of enclosed cavity, complicated inner cavity, part model is carried out to hierarchy slicing processing, synusia thickness is 0.05mm ~ 0.25mm, obtains the three-dimensional modeling data of part;
4) 3D prints: the three-dimensional modeling data of part is imported in 3D printing device, in metal paste, add the initator benzoyl peroxide, 0.5 ~ 3mmol/L(of powder quality 0.1 ~ 1wt.% with respect to the volume of premixed liquid) catalyst dimethylaniline, after evenly mixing, print according to three-dimensional data model, the organic monomer that layering is printed in disposed slurry forms three-dimensional netted polymer gel by chemical crosslinking, thereby metal paste is solidified rapidly, and successively accumulation forms base substrate;
5) body drying and coming unstuck: metal body is vacuum drying 2 ~ 8h under 60 ℃ ~ 100 ℃ conditions, under the moving atmospheric condition of argon gas stream, carries out degumming process by part base substrate at 300 ℃ ~ 600 ℃ insulation 3 ~ 6h subsequently;
6) blank sintering: under vacuum condition, base substrate sintering 2 ~ 4h in 600 ~ 1500 ℃ of temperature ranges is obtained to required complicated shape metal parts.
Compared with prior art, the present invention has following characteristics:
1) part shape strong adaptability: 3D prints to prepare and comprises the big-size complicated shape part that the conventional gel such as enclosed cavity, complicated inner cavity casting cannot be prepared;
2) without mould: while utilizing conventional gel casting technique to prepare part, first need to prepare mould, then prepare slurry and inject die forming and go out base substrate, and the present invention utilizes metal slip 3D to print direct forming base substrate, without mould development expense, single-piece, small lot batch manufacture are with the obvious advantage;
3) powder stock requires low: the direct 3D of metal prints and requires high to powder stock, need the thin and uniform powder of good sphericity, mobility excellence, particle diameter, and while preparing alloy because the fusing-cooling procedure time is short, in order to guarantee that part uniformity must select alloyed powder; And the present invention to powder stock require lowly, and can use element powders;
4) be easy to industrialization: compared with the direct 3D printing-forming of metal, cost of the present invention is low, reliability is high, strong operability, is convenient to realize suitability for industrialized production.
The specific embodiment
embodiment 1: utilize powder of stainless steel slip 3D to print without the gel shaped preparation large scale of mould, complicated shape stainless steel parts
1) configuration premixed liquid: organic monomer hydroxyethyl methacrylate (HEMA) and solvent toluene are mixed by a certain percentage and be configured to premixed liquid, the concentration of organic monomer HEMA is 50vol.%, and this monomer can be by controlling the rapid polymeric gel of addition of initator and catalyst;
2) prepare powder of stainless steel slip: in above-mentioned premixed liquid, add the powder of stainless steel of particle mean size 20 μ m, be prepared into the slip of solid concentration 60vol.%, then add the oleic acid of powder quality 0.1wt% to improve slip mobility;
3) data modeling: use 3D sculpting software to design the large-scale part model of desired structure shape, particularly there is the large-scale part model of enclosed cavity, complicated inner cavity, part model is carried out to hierarchy slicing processing, and synusia thickness is 0.05mm, obtains the three-dimensional modeling data of part;
4) 3D prints: the three-dimensional modeling data of part is imported in 3D printing device, in slip, add the initator benzoyl peroxide, 0.5mmol/L(of powder of stainless steel quality 1wt.% with respect to the volume of premixed liquid) catalyst dimethylaniline, after evenly mixing, print according to three-dimensional data model, the organic monomer that layering is printed in disposed slurry forms three-dimensional netted polymer gel by chemical crosslinking, thereby metal paste is solidified rapidly, and successively accumulation forms base substrate;
5) body drying and coming unstuck: metal body is vacuum drying 8h under 60 ℃ of conditions, is flowing under atmospheric condition subsequently, and part base substrate is carried out to degumming process at 600 ℃ of insulation 3h;
6) blank sintering: under vacuum condition, base substrate sintering 2h in 1350 ℃ of temperature ranges is obtained to required large scale, complicated shape stainless steel parts.
embodiment 2: utilize titanium valve slip 3D to print without the gel shaped preparation large scale of mould, the pure titanium parts of complicated shape
1) configuration premixed liquid: organic monomer hydroxyethyl methacrylate (HEMA) and solvent toluene are mixed by a certain percentage and be configured to premixed liquid, the concentration of organic monomer HEMA is 30vol.%, and this monomer can be by controlling the rapid polymeric gel of addition of initator and catalyst;
2) prepare metal slip: in above-mentioned premixed liquid, add the titanium valve of particle mean size 50 μ m, be prepared into the slip of solid concentration 40vol.%, then add the oleic acid of powder quality 0.2wt% to improve slip mobility;
3) data modeling: use 3D sculpting software to design the large-scale part model of desired structure shape, particularly there is the large-scale part model of enclosed cavity, complicated inner cavity, part model is carried out to hierarchy slicing processing, and synusia thickness is 0.25mm, obtains the three-dimensional modeling data of part;
4) 3D prints: the three-dimensional modeling data of part is imported in 3D printing device, in metal paste, add the initator benzoyl peroxide, 3mmol/L(of powder quality 0.1wt.% with respect to the volume of premixed liquid) catalyst dimethylaniline, after evenly mixing, print according to three-dimensional data model, the organic monomer that layering is printed in disposed slurry forms three-dimensional netted polymer gel by chemical crosslinking, thereby metal paste is solidified rapidly, and successively accumulation forms base substrate;
5) body drying and coming unstuck: metal body is vacuum drying 2h under 100 ℃ of conditions, under the moving atmospheric condition of argon gas stream, carries out degumming process by part base substrate at 300 ℃ of insulation 6h subsequently;
6) blank sintering: under vacuum condition, base substrate is obtained to required large scale, the pure titanium parts of complicated shape at 1200 ℃ of sintering 4h.
Claims (1)
1. metal slip 3D prints without a mould gel forming method, it is characterized in that:
Step 1, configuration premixed liquid: organic monomer hydroxyethyl methacrylate and solvent toluene are mixed by a certain percentage and be configured to premixed liquid, and the concentration of organic monomer hydroxyethyl methacrylate is 30vol.% ~ 50vol.%;
Step 2, prepare metal slip: in above-mentioned premixed liquid, add the metal dust of particle mean size 5 ~ 50 μ m, be prepared into the slip of solid concentration 40vol.% ~ 60vol.%, then add the oleic acid of powder quality 0.01wt ~ 0.2wt% to improve slip mobility;
Step 3, data modeling: use 3D sculpting software to design the part model of desired structure shape, particularly there is the large-scale part model of enclosed cavity, complicated inner cavity, part model is carried out to hierarchy slicing processing, synusia thickness is 0.05mm ~ 0.25mm, obtains the three-dimensional modeling data of part;
Step 4,3D print: the three-dimensional modeling data of part is imported in 3D printing device, in metal paste, add the initator benzoyl peroxide of powder quality 0.01 ~ 1wt.% and the catalyst dimethylaniline with respect to premixed liquid volume 0.1 ~ 3mmol/L, after evenly mixing, print according to three-dimensional data model, the organic monomer that layering is printed in disposed slurry forms three-dimensional netted polymer gel by chemical crosslinking, thereby metal paste is solidified rapidly, and successively accumulation forms base substrate;
Step 5, body drying and come unstuck: metal body is vacuum drying 2 ~ 8h under 60 ℃ ~ 100 ℃ conditions, under the moving atmospheric condition of argon gas stream, carry out degumming process by part base substrate at 300 ℃ ~ 600 ℃ insulation 3 ~ 6h subsequently;
Step 6, blank sintering: under vacuum condition, the base substrate sintering 2 ~ 4h in 600 ~ 1500 ℃ of temperature ranges that carries out degumming process is obtained to required metallic element.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410047534.XA CN103801697B (en) | 2014-02-11 | 2014-02-11 | A kind of metal paste 3D prints without mould gel forming method |
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| CN201410047534.XA CN103801697B (en) | 2014-02-11 | 2014-02-11 | A kind of metal paste 3D prints without mould gel forming method |
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| CN103801697A true CN103801697A (en) | 2014-05-21 |
| CN103801697B CN103801697B (en) | 2015-12-09 |
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