CN104057089A - Metal, ceramic powder and polymer mixture used for manufacturing metal and ceramic products and method for removing polymer from moldings by acid catalysis - Google Patents
Metal, ceramic powder and polymer mixture used for manufacturing metal and ceramic products and method for removing polymer from moldings by acid catalysis Download PDFInfo
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- CN104057089A CN104057089A CN201310089837.3A CN201310089837A CN104057089A CN 104057089 A CN104057089 A CN 104057089A CN 201310089837 A CN201310089837 A CN 201310089837A CN 104057089 A CN104057089 A CN 104057089A
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Abstract
The invention discloses a metal, ceramic powder and polymer material mixture used for manufacturing metal, ceramic and compound (mixed) material (material component) products and a method for removing polymer materials from moldings by acid catalysis. The mixture comprises the following materials in volume ratio: 40-70% of material components and 60-30% of polymer material adhesives (being composed of the following materials in mass ratio: 50-95% of main materials that can be removed by acid catalysis at a relatively low temperature, 46-4.5% of ancillary materials that can be thermally removed at a relatively high temperature and 4-0.5% of additives); the mixture is used for molding by mixing, banburying, squeezing and granulating; main polymer materials are removed by acid catalysis from molded green bodies at a relatively low temperature, auxiliary polymer materials and additives are thermally melted, resolved and removed at a relatively high temperature, and the green bodies are sintered to obtain target products. The mixture and the method have the advantages that adhesive removing is low in temperature and short in time; removed materials are reusable by recycling, condensing and separating, and are environment-friendly; after molding, pouring gate and flow passage rejecting materials can be repeatedly recycled; the product cost is lowered.
Description
Technical field
The present invention relates to a kind of metal, ceramic powders and macromolecular material mixing thing for the manufacture of metal, pottery and multiple (mixing) condensation material goods thereof.This mixing thing is suitable for use as powder injection (mold pressing, die casting) moulding, and products formed removes macromolecular material through acid catalysis, obtains metal, ceramic composite materials goods.
Background technology
Powder injection-molded is novel near-net-shape manufacturing technology with respect to classical production process, is especially applicable to manufacturing microminiature, planform complexity, goods in enormous quantities.
To the research and development of the powder injection-molded technology history of existing two more than ten years, some binder systems that formed by macromolecular material and corresponding viscidity-removing method and equipment thereof are formed both at home and abroad.Such as: exploitation is morning, domestic at present popular cerul bonding system and unsticking technology thereof, equipment; Application number 200810143137.7 patent disclosed polyformaldehyde base bonding system and acid catalysis viscidity-removing methods thereof; The disclosed polyformaldehyde base of application number 200780026523.1 patent bonding system, and the disclosed Continuous Heat viscidity-removing method to polyformaldehyde base bonding system of application number 201080028060.4 patents.In fact, any bonding system has its debonding proces corresponding to adopted macromolecular material performance (temperature, time); The variation of the arbitrary component of bonding system conversely speaking,, the variation that all can bring debonding proces.The differentiation of its quality is its material, process costs, and whether environmental protection, circulation low-carbon (LC).
With regard to the cerul of current trend, carboxaldehyde radicals binder system, all cannot recycle the macromolecular material after removing.Wax-based binder is in the time of unsticking, even if reclaim, the composition reclaiming also cannot regeneration, sometimes or even in line; No matter polyformaldehyde system is Continuous Heat unsticking, or acid catalysis unsticking, is to be all depolymerized to gaseous formaldehyde as prerequisite taking polyformaldehyde, thereafter formaldehyde is burnt, and has both wasted resource, again environment has been increased to carbon row.
Moreover, injection moulding is mainly for the manufacture of microminiature goods, per injection because of the rejecting material of cast gate, runner be all heavy several times even tens times of goods base, due to the character of polyformaldehyde heat depolymerization, the rejecting material of sprue channel is mixing through the circulation of certain number of times, after injection, there is depolymerization more, can not mix again use, cause a large amount of wastes.
So, develop bonding system and the corresponding unsticking technology thereof of efficient, energy-conservation, circulation, low-carbon (LC), can be related to this new technology of injection moulding healthy, sustainable development.
Summary of the invention
Macromolecular material of the present invention and metal, pottery and mixed (answer) thereof are closed powder mixing thing, by metal, pottery and mix (answering) and close powder and combine two class materials with the bonding system adopting and form.
In any mixing thing, adopt which kind of metal, pottery and mixed (answer) thereof to close powder, the material decision (hereinafter referred to as material component) being specified by the target product of manufacturing.Comprise: the mixture of a kind of metal dust or various metals powder, such as the mixture of iron powder, cobalt powder, molybdenum powder, chromium powder, niobium powder, nickel powder, manganese powder, tungsten powder, copper powder, aluminium powder etc. and two or more different proportion powder thereof; The alloy powder of various metals, such as powder of stainless steel, the low-alloy powder of the different trades mark; Ceramic powders, comprising: oxide ceramics, and such as zirconia, aluminium oxide etc., nitride ceramics, such as silicon nitride, aluminium nitride etc., carbide ceramics, such as carborundum etc.; Multiple (mixing) condensation material of cermet, such as iron plating aluminium oxide, iron plating zirconia, nickel plating aluminium oxide, nickel plating zirconia etc.
Binding agent combines the macromolecular material that adopts by main macromolecular material that at a lower temperature can acid catalyzed decomposition unsticking, and heat fusing decomposes the assistant high molecular material and the auxiliary agent composition that remove.
The main macromolecular material of described acid catalyzed decomposition unsticking comprises: PETG, ethyl cellulose, hydroxypropyl cellulose, ethene-butylene cellulose, acetate fiber, the sub-acid imide of O-phthalic etc.
It is TPO material that described heat fusing decomposes the assistant high molecular material removing, as polyethylene (PE), polypropylene (PP) etc.
Described auxiliary agent is mainly dispersant, plasticizer class material, the preferred PIBA of the present invention, polyisobutenyl succimide.
The volume of material component and binder component composition in mixing thing of the present invention: material component accounts for 40-70%, and binder component accounts for 60-30%.
In binder component of the present invention, by mass percentage, the main macromolecular material that acid catalyzed decomposition removes accounts for 50-95%; Heat fusing decomposes the assistant high molecular material removing and accounts for 46-4.5%; Dispersant, plasticizer analog assistant account for 4-0.5%.
The mixing method of mixing thing of the present invention is: first by auxiliary agent, TPO assistant high molecular material and the mixing of material component are extremely even, then adds primary binder mixing to even.
Mixing equipment is common on the market mixer, kneader, banbury, screw extruder, granule-forming machine etc.
The preparation method of a kind of macromolecular material for metal, ceramic base moulding and metal, ceramic powders mixing thing, it is characterized in that, processing step comprises as follows: 1. first by binder component mass ratio, the heat fusing that accounts for 46-4.5% is decomposed and removes assistant high molecular material, account for 4-0.5% and help class, mix with the material component that accounts for volume ratio 40-70%, 110-275 DEG C of banburying to evenly; 2. by binder component mass ratio, during 1. the main macromolecular material that the acid catalyzed decomposition that accounts for 50-95% is removed adds, 100-250 DEG C of banburying extremely evenly; 3. uniform banburying mixing thing is extruded in screw extruder; 4. by extruded stock granulation in granule-forming machine, so that the moulding of next procedure.
The invention is characterized in, the macromolecular material in described mixing thing, the removal methods after moulding, comprises the steps:
1. the goods after moulding are put into and removed stove, between 100 DEG C-250 DEG C, pass into acid mist, remove the macromolecular material that acid catalyzed decomposition removes at a lower temperature, the time of removing is 2-6 hour;
2. remove heat fusing decomposes under higher temperature assistant high molecular material and auxiliary agent.This temperature range is 250 DEG C-500 DEG C, and the time of removing is 2-10 hour.
The clean base removing after macromolecular material enters sintering circuit, and sintering process determines according to the material component of goods, can with remove operation and carry out continuously in same equipment, also can separately in distinct device, carry out.
Advantage of the present invention: remove that temperature is low, the time is short, catalytic eliminating product used extracts through water-ring vacuum pump, through condensation, separation, recovery, can realize most of resource regeneration recycles, environment facies are to close friend, after injection, cast gate, runner are rejected in the mixing thing reuse process of getting off and are seldom degraded, and have reduced goods cost.
Embodiment
Embodiment mono-
Manufacture stainless steel products.Material material 304 powder of stainless steel and acid catalyzed decomposition remove the macromolecular material system combinations mixing thing of main component.304 powder of stainless steel of volume ratio 62%, macromolecular material system combinations volume accounts for 38%.First by the LLDPE of mass ratio 5%, 3% stearic acid matter and 304 powder of stainless steel premix 1 hour in mixer, puts into kneader and mediates 1 hour at 220 DEG C; Evenly put into macromolecular material system combinations mass ratio 92% PETG again, mediate 1 hour at 250 DEG C, discharging proceeds to banbury banburying 1 hour at 250 DEG C, obtains mixing thing; Again mixing thing is proceeded to extruder, extrude, oven dry, granulation; Obtain green article by injector injection moulding; Green article is put into vacuum drying oven and at 260 DEG C, pass into acid mist, remove 4 hours, remove the main component macromolecular material PETG of acid catalyzed decomposition at a lower temperature, at 500 DEG C, remove 8 hours, remove the auxiliary element macromolecular material LLDPE that heat fusing decomposes under higher temperature; The goods that remove after macromolecular material are sent into sintering in continuous fritting furnace, and at 1350 DEG C, sintering 8 hours, obtains 316L stainless steel products.
Embodiment bis-
Manufacture ceramic.Material material oxidation zirconium powder end and acid catalyzed decomposition remove the macromolecular material system combinations mixing thing of main component.The Zirconium oxide powder of volume ratio 59%, macromolecular material system combinations volume accounts for 41%.First by the low density polyethylene (LDPE) of mass ratio 7%, 3% polyisobutene and material material oxidation zirconium powder end premix 1 hour in mixer, puts into kneader and mediates 1 hour at 220 DEG C; Evenly put into the hydroxypropyl cellulose of macromolecular material system combinations mass ratio 90% again, mediate 1 hour at 175 DEG C, discharging proceeds to banbury banburying 0.5 hour at 200 DEG C, obtains mixing thing; Again mixing thing is proceeded to extruder, extrude, granulation, oven dry; Obtain green article by injector injection moulding; Green article is put into acid catalyzed decomposition and remove stove, import acid mist at 170 DEG C and remove 4 hours, remove the main component macromolecular material hydroxypropyl cellulose of acid catalyzed decomposition, at 500 DEG C, remove 6 hours, remove the auxiliary element macromolecular material low density polyethylene (LDPE) that heat fusing decomposes under higher temperature; The goods that remove after macromolecular material are sent into sintering in push pedal sintering furnace, and at 1510 DEG C, sintering 6 hours, obtains zircite product.
Embodiment tri-
Manufacture iron nickel low-alloy goods.The macromolecular material system combinations mixing thing of material material carbonyl iron dust and carbonyl nickel powder mixture (Fe:Ni=96:4) and acid catalyzed decomposition.The carbonyl iron of volume ratio 59%, nickel powder, macromolecular material system combinations volume 41%.First by the high density polyethylene (HDPE) of mass ratio 7%, 3% PIBA, with material material carbonyl iron dust and carbonyl nickel powder mixture (Fe:Ni=96:4) premix 1 hour in mixer, puts into kneader and mediates 1 hour at 150 DEG C; Evenly put into ethene-butylene cellulose of macromolecular material system combinations mass ratio 90% again, mediate 1 hour at 110 DEG C, discharging proceeds to banbury banburying 0.5 hour at 150 DEG C, obtains mixing thing; Again mixing thing is proceeded to extruder, extrude, oven dry, granulation; Obtain green article by injector injection moulding; Green article is put into vacuum sintering furnace, at 170 DEG C, pass into acid mist, remove 4 hours, remove main component macromolecular material ethene-butylene cellulose of acid catalyzed decomposition at a lower temperature, at 500 DEG C, remove 6 hours, remove the auxiliary element macromolecular material high density polyethylene (HDPE) that heat fusing decomposes under higher temperature; The sintering that heats up in vacuum sintering furnace is incubated 6 hours at 1230 DEG C, is cooled to normal temperature, obtains Fe4Ni goods.
Claims (10)
1. one kind is closed powder and is removed taking acid catalysis the mixing thing forming as the high polymer binder two class materials of main component by metal, pottery and multiple (mix) thereof, it is characterized in that the macromolecular material main component in mixing thing, after the moulding of mixing thing, acid catalysis removes at a lower temperature.
2. mixing thing described in claim 1, metal, pottery and multiple (mixing) thereof are closed powder (material material) volume ratio and are accounted for 40-70%, remove as the high polymer binder volume of main component and account for 60-30% taking acid catalysis.
3. described in claim 2, volume ratio accounts for 40-70% metal, pottery and multiple (mixing) thereof are closed powder kind, and the material being specified by the target product of manufacturing determines.
4. described in claim 2, volume ratio accounts for the binding agent of 60-30%, remove macromolecular material as main component at lower temperature taking acid catalysis by accounting for binding agent mass percent 50-95%, account for the assistant high molecular material that binding agent mass percent 46-4.5% removes in higher temperature fusion and decomposition; Account for binding agent mass percent 4-0.5% dispersant, plasticizer auxiliary material composition.
5. described in claim 4, accounting for the binding agent mass percent 50-95% main component macromolecular material that acid catalysis removes at a lower temperature comprises: one or more compositions of PETG, ethyl cellulose, hydroxypropyl cellulose, ethene-butylene cellulose, acetate fiber, the sub-acid imide of O-phthalic etc.
6. described in claim 4, account for polyethylene (PE), polypropylene (PP) etc. that assistant high molecular material that binding agent mass percent 46-4.5% removes in higher temperature fusion and decomposition mainly refers to TPO.
7. described in claim 4, account for binding agent mass percent 4-0.5% dispersant, plasticizer auxiliary material comprise: PIBA, polyisobutenyl succimide etc.
8. a kind of by metal described in claim 1, pottery and multiple (mixing) thereof are closed powder and are removed taking acid catalysis as the mixing thing of the high polymer binder two class material compositions of main component, be characterised in that for make injection green compact the later stage remove processing procedure in do not collapse because removing of macromolecular material is inhomogeneous, ensure the complete and even intensity of goods, in the time producing mixing thing, first by the assistant high molecular material that fusion and decomposition removes under higher temperature, auxiliary agent mixes with material material, mediate and banburying, add again the main macromolecular material banburying that acid catalysis removes at a lower temperature, extrude, granulation.
9. the macromolecular material main component in mixing thing described in claim 1, becomes green compact in the injection moulding of mixing thing, and when green compact are removed to macromolecular material, acid catalysis removes at a lower temperature; Remove thing recoverable, environment facies are to close friend.
10. mixing thing described in claim 1, is characterised in that cast gate, runner that injection produces when green compact reject material, has good stability, can be repeatedly mixing, extrude, granulation, injection, reduce costs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201310089837.3A CN104057089A (en) | 2013-03-20 | 2013-03-20 | Metal, ceramic powder and polymer mixture used for manufacturing metal and ceramic products and method for removing polymer from moldings by acid catalysis |
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| CN201310089837.3A CN104057089A (en) | 2013-03-20 | 2013-03-20 | Metal, ceramic powder and polymer mixture used for manufacturing metal and ceramic products and method for removing polymer from moldings by acid catalysis |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104325144A (en) * | 2014-10-27 | 2015-02-04 | 福立旺精密机电(中国)有限公司 | Metal injecting molding catalytic debinding method and catalytic debinding furnace |
| CN106399875A (en) * | 2016-12-16 | 2017-02-15 | 苏州耐思特塑胶有限公司 | Preparing method and application of high-strength metal composite |
| CN106591677A (en) * | 2016-12-16 | 2017-04-26 | 苏州耐思特塑胶有限公司 | Preparing technology and application for antibacterial composite metal material |
| CN108620579A (en) * | 2018-07-13 | 2018-10-09 | 江苏新达科技有限公司 | A kind of powdered metallurgical material process equipment and its processing technology |
| WO2020245645A1 (en) | 2019-06-05 | 2020-12-10 | Indian Institute of Technology Kharagpur | A green body composition and functional gradient materials prepared thereof |
| CN108620579B (en) * | 2018-07-13 | 2024-04-26 | 江苏新达科技有限公司 | Powder metallurgy material processing equipment and processing technology thereof |
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| US5977230A (en) * | 1998-01-13 | 1999-11-02 | Planet Polymer Technologies, Inc. | Powder and binder systems for use in metal and ceramic powder injection molding |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104325144A (en) * | 2014-10-27 | 2015-02-04 | 福立旺精密机电(中国)有限公司 | Metal injecting molding catalytic debinding method and catalytic debinding furnace |
| CN106399875A (en) * | 2016-12-16 | 2017-02-15 | 苏州耐思特塑胶有限公司 | Preparing method and application of high-strength metal composite |
| CN106591677A (en) * | 2016-12-16 | 2017-04-26 | 苏州耐思特塑胶有限公司 | Preparing technology and application for antibacterial composite metal material |
| CN108620579A (en) * | 2018-07-13 | 2018-10-09 | 江苏新达科技有限公司 | A kind of powdered metallurgical material process equipment and its processing technology |
| CN108620579B (en) * | 2018-07-13 | 2024-04-26 | 江苏新达科技有限公司 | Powder metallurgy material processing equipment and processing technology thereof |
| WO2020245645A1 (en) | 2019-06-05 | 2020-12-10 | Indian Institute of Technology Kharagpur | A green body composition and functional gradient materials prepared thereof |
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