CN102151832B - Extrusion forming agent and preparation and use thereof - Google Patents
Extrusion forming agent and preparation and use thereof Download PDFInfo
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- CN102151832B CN102151832B CN 201110047568 CN201110047568A CN102151832B CN 102151832 B CN102151832 B CN 102151832B CN 201110047568 CN201110047568 CN 201110047568 CN 201110047568 A CN201110047568 A CN 201110047568A CN 102151832 B CN102151832 B CN 102151832B
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Abstract
The invention discloses an extrusion forming agent, and preparation and use thereof, in particular to a forming agent for a tungsten-based alloy or hard alloy or ceramic powder extrusion forming process, and preparation and use thereof. The forming agent comprises 60 to 80 percent of solid and liquid paraffin wax, 3 to 8 percent of carnauba wax, 10 to 20 percent of high density polyethylene and ethylene-vinylacetate copolymer, 1 to 8 percent of plasticizer, 1 to 5 percent of stearic acid and the balance of modifier. In the invention, the drawbacks of long degreasing time, low degreasing conformality and more degreasing defects of extrusion blanks, particularly large-size extrusion blanks, are overcome, the raw materials are cheap and easy to purchase, the component compatibility of the prepared forming agent is high, the forming agent is used in a powder extrusion forming process, the micro structure of the forming agent is uniform, the forming agent has strong interaction force with powder, the formability is high, the quick and flawless degreasing of blanks with a thickness of 40 millimeters can be realize, the production efficiency is improved, and the development of extrusion forming industry is promoted greatly.
Description
Technical field
The invention belongs to the powder metallurgy formation technical field, relate to a kind of extrusion forming agent and preparation thereof and the application in powder extrusion forming technique.
Background technology
Along with the development of society, the demand of sintered metal product is constantly increased.Powder extrusion forming is the novel forming technique of a kind of powder metallurgy that develops rapidly in recent years, have that product length is unrestricted, density relatively evenly, the efficient advantages of higher, now become one of effective method of the products such as preparation big L/D ratio powder metallurgy pipe, rod, bar, band.
In PEM technique, restricting large thickness, complex-shaped large scale, changes of section parts, to develop main factor be binder and removing process thereof, especially the design of binder and preparation are directly determining quality and the applicable cases of extruded product, are the keys of extrusion forming technology success or failure.
Traditional binder is two constituent elements or three constituent elements in the cemented carbide extrusion molding technique, such as external PE (polyethylene)/SA (stearic acid), and PP (polypropylene)/SA (stearic acid); Domestic 20/SBS (s-B-S block polymer)+75/PW (paraffin)+5/SA (stearic acid) etc., its constituent element is comparatively single, and the shape holding of shaping base is relatively poor, and degreasing time is long, and the degreasing defective is many.Bai Jiasheng etc. comprise that in the disclosed a kind of cemented carbide extrusion molding agent of CN1788889A (21,6,2006) paraffin, high molecular polymer and polarity hangs down the molecular activity material, exist feedstock preparation complicated, the problem of degreasing time long (72h).Lu Pingshu etc. are at CN101372556A (25,2,2009) disclose a kind of cemented carbide extrusion molding agent, its constituent element is by weight percentage: paraffin 65～80%, butadiene-styrene rubber 10～20%, dibutyl phthalate 3～5%, rapeseed oil 3～5%, stearic acid 3～5%, surplus is organic solvent, the feeding useful load lower (binder quality percentage composition is 8%) of this binder preparation, and have a certain amount of extruding base that gives up.Sun Dan is in PM technique (2010,28 (4): 262-265) the novel binder of upper employing prepares ultra-fine cemented carbide rod base, its binder constituent element is calculated by mass percentage and is comprised solid paraffin (SPW)+atoleine (LPW): 60～80%, high density polyethylene (HDPE) (HDPE)+ethylene-vinyl acetate copolymer (EVA): 10～30%, stearic acid (SA): 5～10%, prepared feeding lack of homogeneity, the easy segregation of binding agent, and excellent base is easy to produce cracking in the solvent degreasing process, and the yield rate of product is lower.T.Jardiel etc. are at Ceramics International (2009,35:2329-2335) upper report: adopt paraffin-polyolefin binding agent to prepare the zirconia light-wall pipe, its binding agent constituent element by volume percentage is counted 46%PW+50%PP+4%SA, and the big L/D ratio tube wall thickness that makes is less than 200 μ m.Fan Jinglian etc. are in PM technique (2003,3 (21): 131-134) upper report: adopt a kind of multicomponent oil+wax sculpture material System Modification binding agent, the injection base that has prepared tungsten bar bullet core material, but this feeding useful load is 51%, only just show good flowability at 120～180 ℃, be not suitable for preparing low temperature (60-80 ℃) extrusion forming process of big L/D ratio powder metallurgy exemplar.Zhao Hongmei etc. are at Arms Material scientific and engineering (2006,29 (5): 59-64) upper report: adopt respectively polypropylene (PP)-polystyrene (PS)-vegetable oil (Oil)-stearic acid (SA) and polypropylene (PP)-paraffin (PW)-vegetable oil (Oil)-stearic acid (SA)-two kinds of binder systems of plasticizer (DOP), utilize power injection molding to obtain the fragile tungsten heavy alloy bullet core of Φ 22.5mm, its injection temperature is 180～200 ℃, be not suitable for preparing low temperature (60-80 ℃) extrusion forming technology of big L/D ratio powder metallurgy sample, and it is high to inject base degreasing rate in the solvent degreasing process.
Summary of the invention
The present invention is intended to develop the novel binder of a kind of powder extrusion forming that is applicable to large scale, complicated exemplar, its performance requirement comprises that binder constituent element compatibility is good, good with powder adherence, powder loading is high, formability good, particularly can satisfy the quick zero defect degreasing of large scale base substrate.
A kind of extrusion forming agent, it is that composition by following mass percent is prepared from: the gross mass 60～80% of solid paraffin (PW) and atoleine (LPW), the gross mass 10～20% of high density polyethylene (HDPE) (HDPE) and ethylene-vinyl acetate copolymer (EVA), plasticizer (DOP) 1～8%, stearic acid (SA) 1～5%, Brazil wax (CW) 3～8%, surplus are modifier (PEW).
Described plasticizer comprises: down ketone, two butyl benzene diacid, dimethyl benzene diacid, dioctyl sebacate, o-phthalic acid dibutyl ester or dibutyl phthalate.
Described modifier is Tissuemat E.
The preparation method of described extrusion forming agent is as follows:
1) kneading device is warming up to 150～170 ℃, and is incubated;
2) load weighted high density polyethylene (HDPE) is put into the kneading device heating and melting, after complete melting, slowly add ethylene-vinyl acetate copolymer, constantly stir, until both form the homogeneous molten mixture;
3) the melting mixing temperature is reduced to 100～120 ℃, adds load weighted modifier in the molten mixture that obtains to step (2), constantly stir, make and combine together;
4) solid paraffin, atoleine and Brazil wax are added successively in the melt blended material that step (3) obtains, constantly stir, mixing time is 20～60min;
5) again plasticizer and stearic acid are added in the kneading device, stir 10～30min, make required binder.
Described extrusion forming agent can be applied to tungsten-bast alloy or carbide alloy or ceramic powders extrusion molding.
Advantage and the good effect of invention
A kind of novel multicomponent compound mixture has improved single paraffin binder degreasing difficulty, degreasing time length and the poor shortcoming of shape holding.Raw material is inexpensive, and preparation technology is simple, has improved the compatibility between the binder constituent element, has strengthened the interaction of binder and powder, has reduced binder segregation defective, has improved the feeding uniformity.Reduce the viscosity of feeding, improved the rheological property of feeding, improved powder loading.Reduced the base substrate residual stress, shape holding is good, can comprehensively adopt solvent degreasing and hot degreasing process, and degreasing efficient is high, can realize the quick zero defect degreasing of large exemplar.
Single paraffin binder softening point in skimming processes is more concentrated, softening transform very easily is heated, and it is more concentrated owing to decomposition temperature in decomposing subtractive process, very easily produce the defectives such as cracking and distortion, skimming processes is difficult to control, cause degreasing time long, and the paraffinic base green strength is low, during degreasing internal stress large, discharge slower, need at high temperature long-time degreasing, degreasing efficient is low, and green compact are prone to foaming, ftracture, subside and distortion etc. in skimming processes, are only suitable in the product of producing smallclothes.
The interpolation of modifier has improved compatibility between the binder constituent element among the present invention, and the interpolation of polar waxes CW, EVA and surfactant SA has strengthened the interaction of binder and powder, has reduced binder segregation defective, has improved the feeding uniformity.Add modifier when improving compatibility, reduced the fusing point of whole binder, improved flowability, also be added with LPW, reduced the viscosity of feeding, improved the rheological behavior of feeding, be conducive to the raising of powder loading.The PW coarse grains, the condensation shrinkage factor can be up to 20%, easily produce larger internal stress in extruded stock and cause shaping, degreasing defective, adopt CW to allocate PW, the CW grain graininess is little, good toughness, be difficult for fragmentation, good plasticity is arranged, tend under pressure flow, reduce residual stress in the base substrate, improved the base substrate degreasing quality.Owing to added and being easy to dissolve the LPW that removes, the Quick solvent degreasing of the base of both can having realized being shaped also can guarantee the degreasing zero defect, and degreasing rate is high, is conducive to carrying out fast of subsequent thermal degreasing, is fit to the degreasing of large exemplar.
Description of drawings
Fig. 1 is embodiment 1 sample photo
(a) binder fracture SEM photo wherein; (b) binder fracture petrographic microscope photo; (c) extruded rod base photo (Φ 24mm);
Fig. 2 is embodiment 2 sample photos
(a) binder fracture SEM photo wherein; (b) binder fracture petrographic microscope photo; (c) excellent base fracture SEM photo after the degreasing; (d) excellent base photo (Φ 38mm) after the degreasing.
The specific embodiment
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1
(1) takes by weighing respectively 60% solid paraffin with mass percent, 10% atoleine, 8% high density polyethylene (HDPE), 8% ethylene-vinyl acetate copolymer, 4% plasticizer (dioctyl phthalate), 1% stearic acid, 6% Brazil wax, 3% modifier (Tissuemat E).
(2) kneading device is warming up to 160 ℃, and is incubated.
(3) load weighted 8% high density polyethylene (HDPE) is put into the kneading device heating and melting, after complete melting, slowly add 8% ethylene-vinyl acetate copolymer, constantly stir, until both form the homogeneous molten mixture.
(4) the melting mixing temperature is reduced to 100 ℃, adds 3% modifier (Tissuemat E) in the above-mentioned melt blended material, constantly stir, make and combine together.
(5) solid paraffin, atoleine and the Brazil wax of getting ready added in the above-mentioned melt blended material in order together, constantly stir, mixing time is 30min.
(6) again plasticizer and the stearic acid of getting ready added in the kneading device, stir 10min, make required binder (such as Fig. 1 a, b).
(7) gained binder and W-Ni-Fe ball milling powder are carried out mixing, melting temperature is 160 ℃, and mixing time is 3h, make feeding, pressing material is put into extruder, extrusion temperature is 70 ℃, with the medium speed, extrude Φ 24mm big L/D ratio rod base (such as Fig. 1 c) under the certain pressure.
Embodiment 2
(1) takes by weighing respectively 55% solid paraffin with mass percent, 15% atoleine, 10% high density polyethylene (HDPE), 10% ethylene-vinyl acetate copolymer, 5% plasticizer (dioctyl phthalate), 1% stearic acid, 3% Brazil wax, 1% modifier (Tissuemat E).
(2) kneading device is warming up to 170 ℃, and is incubated.
(3) load weighted 10% high density polyethylene (HDPE) is put into the kneading device heating and melting, after complete melting, slowly add 10% ethylene-vinyl acetate copolymer, constantly stir, until both form the homogeneous molten mixture.
(4) the melting mixing temperature is reduced to 110 ℃, in above-mentioned melt blended material, adds 1% modifier (Tissuemat E), constantly stir, make and combine together.
(5) solid paraffin, atoleine and the Brazil wax of getting ready added in the above-mentioned melt blended material in order together, constantly stir, mixing time is 60min.
(6) again plasticizer and the stearic acid of getting ready added in the kneading device, stir 15min, make required binder (such as Fig. 2 a, b).
(7) gained binder and tungsten, nickel, iron powder are carried out mixing, melting temperature is 160 ℃, and mixing time is 3h, make feeding, pressing material is put into extruder, extrusion temperature is 75 ℃, with the medium speed, extrude Φ 38mm big L/D ratio rod base under the certain pressure.
(8) adopt two step defatting technologies to the ungrease treatment of extruded rod base, can obtain at short notice flawless large scale degreasing rod base (Fig. 2 c, d).
Claims (4)
1. extrusion forming agent, it is characterized in that, that composition by following mass percent is prepared from: the gross mass 60 ~ 80% of solid paraffin and atoleine, the gross mass 10 ~ 20% of high density polyethylene (HDPE) and ethene-vinyl acetate co-polymer, plasticizer 1 ~ 8%, stearic acid 1 ~ 5%, Brazil wax 3 ~ 8%, surplus is modifier.
2. extrusion forming agent according to claim 1 is characterized in that, described plasticizer comprises: down ketone, two butyl benzene diacid, dimethyl benzene diacid, dioctyl sebacate, o-phthalic acid dibutyl ester or dibutyl phthalate.
3. extrusion forming agent according to claim 1 is characterized in that, described modifier is Tissuemat E.
4. the preparation method of claim 1 or 2 or 3 described extrusion forming agents is characterized in that, and is specific as follows:
1) kneading device is warming up to 150 ~ 170 ℃, and is incubated;
2) load weighted high density polyethylene (HDPE) is put into the kneading device heating and melting, after complete melting, slowly add ethene-vinyl acetate co-polymer, constantly stir, until both form the homogeneous molten mixture;
3) the melting mixing temperature is reduced to 100 ~ 120 ℃, adds load weighted modifier in the molten mixture that obtains to step (2), constantly stir, make and combine together;
4) solid paraffin, atoleine and Brazil wax are added successively in the melt blended material that step (3) obtains, constantly stir, mixing time is 20 ~ 60min;
5) again plasticizer and stearic acid are added in the kneading device, stir 10 ~ 30min, make required binder.
5, the application process of claim 1 or 2 or 3 described extrusion forming agents is characterized in that, is applied to tungsten-bast alloy or carbide alloy or ceramic powders extrusion molding.
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| CN105884341A (en) * | 2016-04-05 | 2016-08-24 | 安徽省含山民生瓷业有限责任公司 | Domestic ceramic steaming tool processing pug |
| WO2018059473A1 (en) * | 2016-09-30 | 2018-04-05 | 珠海天威飞马打印耗材有限公司 | Three-dimensional forming filament, manufacturing method, and forming method |
| CN106735240B (en) * | 2016-12-23 | 2019-12-24 | 株洲硬质合金集团有限公司 | Preparation method of PCB bar |
| CN107243628B (en) * | 2017-06-08 | 2019-04-16 | 重庆文理学院 | A kind of binder for titanium hydride powders injection moulding |
| CN107243636B (en) * | 2017-06-08 | 2019-02-22 | 重庆文理学院 | A kind of ejection forming method of metal titanium products |
| CN107214332B (en) * | 2017-06-08 | 2019-04-12 | 重庆文理学院 | A kind of titanium hydride powders injection moulding feeding product and preparation method thereof |
| CN111468735A (en) * | 2020-04-16 | 2020-07-31 | 上海钨睿新材料科技有限公司 | Hard alloy extrusion molding agent based on paraffin base and extrusion feeding preparation process thereof |
| CN111940720A (en) * | 2020-08-18 | 2020-11-17 | 厦门金鹭硬质合金有限公司 | Forming agent for hard alloy extrusion rod blank and mixing process thereof |
| CN113695575A (en) * | 2021-07-15 | 2021-11-26 | 武晓峰 | Injection molding method of locknut |
| CN113699454B (en) * | 2021-08-30 | 2022-07-15 | 江苏科技大学 | 3D printing product and preparation method thereof |
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