CN103801697B - A kind of metal paste 3D prints without mould gel forming method - Google Patents
A kind of metal paste 3D prints without mould gel forming method Download PDFInfo
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- CN103801697B CN103801697B CN201410047534.XA CN201410047534A CN103801697B CN 103801697 B CN103801697 B CN 103801697B CN 201410047534 A CN201410047534 A CN 201410047534A CN 103801697 B CN103801697 B CN 103801697B
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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 35
- 239000000843 powder Substances 0.000 claims abstract description 23
- 238000010146 3D printing Methods 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 238000013499 data model Methods 0.000 claims abstract description 8
- 238000009825 accumulation Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000007712 rapid solidification Methods 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 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
- 239000002245 particle Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 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
- 239000000428 dust Substances 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
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000005266 casting Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000000087 stabilizing 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
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- 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
- 238000001746 injection moulding 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
- 229920000642 polymer Polymers 0.000 description 1
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- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Powder Metallurgy (AREA)
Abstract
The invention provides a kind of metal slip 3D to print without mould gel forming method, 3D printing technique is combined with gel shaped technology, gel shaped technique is utilized to prepare metal slip, the raw material printed using this slip as 3D, then 3D printing device is utilized to print according to data model layering, make metal slip rapid solidification by the addition controlling initator and catalyst, successively accumulation forms metal body, and drying, sintering obtain large scale, complicated shape metal parts product.The method can prepare the part comprising the conventional gel such as enclosed cavity, complicated inner cavity casting and cannot prepare, utilize 3D printing technique direct forming base substrate, without mould development expense, single-piece, small lot batch manufacture are with the obvious advantage, and require low to powder stock, and process stabilizing is reliable, strong operability, fugitive rate consuming time is high, and cost is low, is conducive to the industrialization that 3D printing technique prepares large scale, complicated shape metal parts.
Description
Technical field
The present invention relates to a kind of Metal Powder Forming Technology, belong to metallic element preparing technical field, in particular, provide a kind of metal slip 3D and print without the gel shaped method preparing large scale, complicated shape metal parts of mould.
Background technology
3D prints, i.e. the one of Quick-forming is based on three-dimensional data model, and applying powder powder can jointing material, is carried out the technology of constructed object by the mode successively printed.3D prints and normally adopts digital technology file printing machine to realize, the field such as Making mold, industrial design of being everlasting for the manufacture of model, now gradually for the direct manufacture of product.Its basic process is: in a computer 3D model is divided into some layers, 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, a final formation 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, directly can obtain almost arbitrary shape, there is the metal parts of metallurgical binding.But, existing 3D printing technique cost is very high, on the one hand because 3D printing device is expensive, need to be equipped with the heating system such as laser, electron beam by powder smelting, being that the cost of raw material is high on the other hand, in order to ensure the uniformity be shaped, needing good sphericity, mobility excellence, particle diameter thin and uniform powder, and whole forming process length consuming time, efficiency are low, thus the production cost of single products is remained high.
Gel casting is a kind of Wetting forming technology, mainly through the slurry of preparation low viscosity, high solid loading, then makes the polymerization of the organic monomer in slurry make slurry solidify in place, thus obtains the base substrate of high strength, high density, excellent in uniformity.Its basic procedure is: organic monomer and solvent are mixed with certain density premixed liquid, add the slurry that powder is configured to 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 bond and solidify to form base substrate, drying, to come unstuck and sintering obtains part product.Compared with traditional forming technology, the advantages such as gel casting has the large scale that is easily shaped, complicated shape part, blank strength is high, content of organics is few, have broad application prospects in iron-based, stainless steel, titanium base, aluminum base powder metallurgy part.But first gel casting technology needs to prepare mould, and 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 are restricted.
The invention provides a kind of large scale, the complicated shape metal parts preparation method that are combined with gel shaped technology by 3D printing technique, utilize gel shaped technique to prepare adherent metal slip, this slip can by controlling the addition quick solidification of initator and catalyst.The raw material printed using this slurry as 3D, utilizes 3D printing device to print according to data model layering, and metal slip rapid solidification also successively accumulates formation metal body, then obtains metallic element product by dry, sintering.Compared with printing technique with metal 3D cost low, low to metal dust requirement, consuming time short, efficiency is high.Compared with conventional gel casting, without the need to mould, and size, the shape strong adaptability to parts.Yet there are no the relevant report utilizing metal slip 3D printing without the gel shaped preparation large scale of mould, complicated shape metal parts method.
Summary of the invention
A kind of metal slip 3D is the object of the present invention is to provide to print without the gel shaped method preparing large scale, complicated shape metal parts of mould, gel shaped technique is utilized to prepare the raw material of metal slip as 3D printing, 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 as follows:
1) premixed liquid is configured: 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 by controlling the rapid polymeric gel of addition of initator and catalyst;
2) prepare metal slip: the metal dust adding particle mean size 5 ~ 50 μm in above-mentioned premixed liquid, is prepared into the slip of solid concentration 40vol.% ~ 60vol.%, the oleic acid then adding powder quality 0.01wt ~ 0.2wt% improves 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 hierarchy slicing process, and 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 of powder quality 0.1 ~ 1wt.%, 0.5 ~ 3mmol/L(relative to the volume of premixed liquid) catalyst dimethylaniline, print according to three-dimensional data model after Homogeneous phase mixing, the organic monomer that layering prints in disposed slurry forms three-dimensional network polymer gel by chemical crosslinking, thus making metal paste rapid solidification, successively accumulation forms base substrate;
5) body drying and coming unstuck: metal body is vacuum drying 2 ~ 8h under 60 DEG C ~ 100 DEG C conditions, subsequently under argon gas stream moves atmospheric condition, carries out degumming process by part blanks at 300 DEG C ~ 600 DEG C insulation 3 ~ 6h;
6) blank sintering: under vacuum, sinters 2 ~ 4h and namely obtains required complicated shape metal parts in 600 ~ 1500 DEG C of temperature ranges by base substrate.
Compared with prior art, the present invention has following characteristics:
1) part shape strong adaptability: 3D prints and can prepare the big-size complicated shape part comprising the conventional gel such as enclosed cavity, complicated inner cavity casting and cannot prepare;
2) without mould: when utilizing conventional gel injection molding techniques 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 good sphericity, mobility excellence, particle diameter thin and uniform powder, and because the fusing-cooling procedure time is short when preparing alloy, in order to ensure that part uniformity must select alloyed powder; And the requirement of the present invention to powder stock is low, and element powders can be used;
4) industrialization is easy to: 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.
Detailed description of the invention
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) premixed liquid is configured: 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 by controlling the rapid polymeric gel of addition of initator and catalyst;
2) prepare powder of stainless steel slip: the powder of stainless steel adding particle mean size 20 μm in above-mentioned premixed liquid, is prepared into the slip of solid concentration 60vol.%, the oleic acid then adding powder quality 0.1wt% improves 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 hierarchy slicing process, 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 of powder of stainless steel quality 1wt.%, 0.5mmol/L(relative to the volume of premixed liquid) catalyst dimethylaniline, print according to three-dimensional data model after Homogeneous phase mixing, the organic monomer that layering prints in disposed slurry forms three-dimensional network polymer gel by chemical crosslinking, thus making metal paste rapid solidification, successively accumulation forms base substrate;
5) body drying and coming unstuck: metal body is vacuum drying 8h under 60 DEG C of conditions, subsequently under flowing atmospheric condition, carries out degumming process by part blanks at 600 DEG C of insulation 3h;
6) blank sintering: under vacuum, sinters 2h and namely obtains required large scale, complicated shape stainless steel parts in 1350 DEG C of temperature ranges by base substrate.
embodiment 2: utilize titanium valve slip 3D to print without mould gel shaped preparation large scale, the pure titanium parts of complicated shape
1) premixed liquid is configured: 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 by controlling the rapid polymeric gel of addition of initator and catalyst;
2) prepare metal slip: the titanium valve adding particle mean size 50 μm in above-mentioned premixed liquid, is prepared into the slip of solid concentration 40vol.%, the oleic acid then adding powder quality 0.2wt% improves 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 hierarchy slicing process, 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 of powder quality 0.1wt.%, 3mmol/L(relative to the volume of premixed liquid) catalyst dimethylaniline, print according to three-dimensional data model after Homogeneous phase mixing, the organic monomer that layering prints in disposed slurry forms three-dimensional network polymer gel by chemical crosslinking, thus making metal paste rapid solidification, successively accumulation forms base substrate;
5) body drying and coming unstuck: metal body is vacuum drying 2h under 100 DEG C of conditions, subsequently under argon gas stream moves atmospheric condition, carries out degumming process by part blanks at 300 DEG C of insulation 6h;
6) blank sintering: under vacuum, namely obtains required large scale, the pure titanium parts of complicated shape by base substrate at 1200 DEG C of sintering 4h.
Claims (1)
1. metal slip 3D prints without a mould gel forming method, it is characterized in that:
Step one, configuration premixed liquid: organic monomer hydroxyethyl methacrylate and solvent toluene are mixed by a certain percentage and be configured to premixed liquid, the concentration of organic monomer hydroxyethyl methacrylate is 30vol.%-50vol.%;
Step 2, prepare metal slip: the metal dust adding particle mean size 5-50 μm in above-mentioned premixed liquid, be prepared into the slip of solid concentration 40vol.%-60vol.%, the oleic acid then adding metal dust quality 0.01wt-0.2wt% improves slip mobility;
Step 3, data modeling: use 3D sculpting software to design the large-scale part model of enclosed cavity, complicated inner cavity, part model is carried out hierarchy slicing process, and 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, the initator benzoyl peroxide of powder quality 0.01-1wt.% and the catalyst dimethylaniline relative to premixed liquid volume 0.1-3mmol/L is added in metal paste, print according to three-dimensional data model after Homogeneous phase mixing, the organic monomer that layering prints in disposed slurry forms three-dimensional network polymer gel by chemical crosslinking, thus making metal paste rapid solidification, successively accumulation forms base substrate;
Step 5, body drying and come unstuck: metal body is vacuum drying 2-8h under 60 DEG C of-100 DEG C of conditions, subsequently under argon gas stream moves atmospheric condition, carry out degumming process by part blanks at 300 DEG C-600 DEG C insulation 3-6h;
Step 6, blank sintering: under vacuum, sinter 2-4h by the base substrate carrying out degumming process and obtain required metallic element in 600-1500 DEG C of temperature range.
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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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| CN103801697B true CN103801697B (en) | 2015-12-09 |
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| JP2013116045A (en) * | 2010-03-08 | 2013-06-13 | Osaka Univ | Method for creating three-dimensional cell aggregate, three-dimensional gel carrier for cell cultivation used in the same, and three-dimensional cell aggregate |
| CN102093646B (en) * | 2010-10-29 | 2012-07-18 | 华南理工大学 | Material for rapid three dimensional printing forming and preparation method thereof |
| CN102407332A (en) * | 2011-12-05 | 2012-04-11 | 烟台工程职业技术学院 | Preparation method for porous titanium |
| CN102755199A (en) * | 2012-08-06 | 2012-10-31 | 上海上远齿科技术有限公司 | Method for producing zirconia denture through rapid prototype of gel-casting |
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