CN1765548A - Method for preparing prills and apparatus thereof - Google Patents
Method for preparing prills and apparatus thereof Download PDFInfo
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- CN1765548A CN1765548A CN 200510086998 CN200510086998A CN1765548A CN 1765548 A CN1765548 A CN 1765548A CN 200510086998 CN200510086998 CN 200510086998 CN 200510086998 A CN200510086998 A CN 200510086998A CN 1765548 A CN1765548 A CN 1765548A
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Abstract
The invention provides a method for producing metal ball and relative device, belonging to the metal paste mould technique area. The method comprises: firstly, selecting a gel system and confirming the kinds and contents of monomer and cross linker; selecting the solvent to preparing the premixed solution according to the oxidizing property of metal powder; adding dispersant and metal powder to ball mill for a certain time to prepare\e the paste with high solid content and the viscosity less than 1Pa.s; then mixing the paste and adding initiator and catalyst, dropping said paste into the medium exclusive to selected solvent. Since the ball is formed by boundary tension, the inner part of ball drop has chemical reaction to be solidified when dropped into said medium. The invention comprises following advantages: smooth surface, tight structure, uniform, high strength, better abrasion-resistance, molded without mould, and lower cost.
Description
Technical field
The invention belongs to metal colloidal state field shaping technique, a kind of method and device thereof for preparing prill particularly is provided.Flexibly the thought of organic monomer generation radical polymerization is incorporated in the metal balling technique, metal forming technology and producing high-molecular gained knowledge organically combine, relate to quick colloidal formation technical field, belong to the category that colloidal formation prepares different purposes, difform metal material and parts, be applicable to the preparation prill, especially millimeter level prill.
Technical background
High-quality Metal Ball has extremely important purposes in daily production and life, usually be used as the abrasive media in the ball mill, be used for the grinding and the batch mixing process of some metal powder materials, though be that a kind of auxiliary material is indispensable, and be one of key factor of decision grinding efficiency.For different purposes, powder and grinding machinery, raw material, the sphere diameter of Metal Ball also all there is different requirements.In addition, the Metal Ball of high-wearing feature is also as the rolling element in the bearing, perhaps parts of firearms aspect and high precision instrument etc.
At present, the method for preparing Metal Ball mainly contains injection, isostatic pressing method, mould pressing etc.These methods respectively have characteristics.Yet, for preparation high strength, high-wearing feature Metal Ball cheaply, particularly millimetre-sized metal microbead, present technology of preparing all is difficult to reach requirement.
Technology contents
The object of the present invention is to provide a kind of method and device thereof for preparing prill, it can prepare any surface finish, compact structure, evenly zero defect, high strength, high-wearing feature, prill cheaply, particularly millimeter level prill also provides a kind of easy implement device.
General thought of the present invention is: by (promptly dissolving each other anything but in the medium that water base or non-water base slip is splashed into a kind of and the mutual exclusion of slip solvent for use, such as using oil medium) for water-based slurry, drop is after entering this medium, according to the minimum principle of interface energy, under the effect of interfacial tension, form smooth spherical particle, spherical particle is in the process that this medium falls, solidify powder maintenance sphere owing to inner generation chemical reaction generates three-dimensional netted macromolecular compound, finally do not have mould and obtain high-quality prill.
The present invention selects a kind of gel rubber system, determines monomer and crosslinking agent kind and content, again according to the solvent of the oxidisability selective system of institute's forming metal powder with the preparation premixed liquid; Add dispersant and metal-powder then, the ball milling certain hour prepares the slip of the viscosity of high solid loading less than 1Pas; After adding initator and catalyst while stirring, more this slip is splashed in the medium with selected solvent mutual exclusion with splashing into device.Because interfacial tension effect balling-up, when spherical drop fell in medium, chemical change took place and solidifies in inside.Concrete processing step is as follows:
1, selects a kind of gel rubber system, organic monomer and crosslinking agent and water or other organic solvent mixed dissolution of Raolical polymerizable can take place, make premixed liquid, the total concentration that can produce the organic monomer of free radical and crosslinking agent should be 1%～50%, and organic monomer is 10: 1～120: 1 with the ratio of the quality of crosslinking agent.
2, metal powder material is added in the above-mentioned premixed liquid while stirring, the percent by volume of the metal powder material that adds accounts for and adds 50%～100% of overall solution volume after the metal powder material, ball milling is prepared the slip of viscosity less than 1Pas after 1～48 hour, carry out defoaming treatment then.
The percent by volume of metal powder should be 50%～100%, otherwise sintering shrinkage is big, influences the balling-up quality.When metal powder is added above-mentioned solution, in order to improve dispersiveness, reduce viscosity, also can add dispersant, dispersant can be polyacrylic acid, polyacrylamide, poly amic acid, ammonium citrate 1～4 kind, also can be other dispersant, consumption is 0.1%～3.0% of a metal powder quality.
Described ball milling can carry out in planetary ball mill or homemade ball mill.Described defoaming treatment was by froth in vacuum, 40 ℃～90 ℃ de-bubbles 5～30 minutes.Described defoaming treatment also can be by adding defoamer, and available defoamer has isooctanol, aliphatic acid, tbp 1～3 kind, and consumption is 0.05%～3% of a metal powder material quality.
3, initator and catalyst are added while stirring in the slip after the above-mentioned defoaming treatment, the consumption of initator is that per 100 milliliters of suspended substances add 0.1%～20% initator 20～300 microlitres, and catalyst consumption is that per 100 milliliters of suspended substances add 20～600 microlitres; Described catalyst is a tetramethylethylenediamine.Monomer can also can if heat causes, can not add initator by thermal-initiated polymerization by the initator initiated polymerization.
4, the slip that will add initator and catalyst with diameter optionally splash into device splash into heating, with the medium of slip solvent for use mutual exclusion in (promptly dissolving each other anything but), drop enters after the medium, form coccoid, solidify conformal in the process that descends, collection bead, washing, drying, sintering are made prill.
In the step 1, the gel rubber system of selecting has many kinds, the organic monomer that can produce free radical can be 1～4 kind in acrylamide, N hydroxymethyl acrylamide, hydroxyethyl methacrylate, the hydroxy propyl methacrylate, also can for other can polymerization reaction take place organic matter.Described crosslinking agent can be methylene-bisacrylamide, and perhaps other can play the organic matter of crosslinked action.The mass ratio of monomer and crosslinking agent and total concentration with directly influencing the intensity and the shrinkage of molding blank, promptly influence green body quality.
Metal powder material described in the step 2 is 1～4 kind in carbonyl iron dust, iron-nickel alloy powder, stainless steel powder, the cemented carbide powder, also can be other metal powder material.
Device of the present invention is the uprise 1 that the medium 2 of certain and the mutual exclusion of slip solvent is housed below splashing into device 8, the bottom of uprise 1 is connected on the conical flask 5 with rubber stopper, conical flask 5 is placed on above the little retort stand 6, whole uprise 1 is placed in the water-bath heater 3, heat with heating furnace 7 bottom of this heater 3, be that cryosel bathes 10 in the large beaker 9, the small beaker 12 that fills slip 11 is placed on cryosel and bathes in 10.Splashing into below the device is the uprise that is equipped with the medium of slip solvent for use mutual exclusion, one conical flask is arranged at the bottom of uprise, conical flask is placed on the little brandreth, the latter half of whole uprise is placed on carries out the water-bath heating in the container of a heating, just solidified before splashing in order to prevent in addition, the carrying out that influence is operated below also has a cryosel bath apparatus, comes " passivation " initator.
The invention has the advantages that:
1, the combination of the three-dimensional netted polymerization macromolecule of formation and metallic particles is very strong because inner monomer and crosslinking agent react, intensity height, the good toughness of the back base substrate that is shaped;
2, owing to utilize interfacial tension balling-up, sphericity height, smooth surface, the good uniformity of institute's balling-up;
3, solid concentration is generally all greater than 50% in the slurry, and content of organics is few, and solvent is few, so the drying and sintering after-contraction is less, and ball big or small easy to control, intensity height;
4, utilization of the present invention is the minimum principle of interface energy glomeration under the effect of interfacial tension, and inside chemical reaction takes place and solidifies conformal in the process that descends, and whole forming process is not used spherical mould, so cost is lower;
5, according to different requirements, select the device that splashes into of different-diameter, can prepare the different ball of diameter, technology is flexible;
6, ball is more little, and decrease speed is slow more, and polymerization time is abundant more, and sphericity is high more, so the inventive method is suitable for preparing bead more, and particularly millimetre-sized bead;
Description of drawings
Fig. 1 is the structural representation of preparation prill device of the present invention.Wherein, uprise 1, medium 2, heater 3, water 4, conical flask 5, retort stand 6, heating furnace 7, splash into that device 8, large beaker 9, cryosel bathe 10, metal slip 11, small beaker 12.
The specific embodiment
Embodiment 1: the preparation of iron-based bead
1, selects the acrylamide gel system, wherein acrylamide is an organic monomer, and methylene-bisacrylamide is a crosslinking agent, and the selection chloroform is a solvent, the total concentration of monomer and crosslinking agent accounts for 20% of solution, and organic monomer is 50: 1 with the ratio of the quality of crosslinking agent;
2, iron powder material is commercially available 500 order carbonyl iron dusts, and purity is 99.3%, adds iron powder in premixed liquid, the volumn concentration of iron powder is 50%, add the dispersant ammonium citrate, consumption is 0.5% of an iron powder quality, makes the slurry that viscosity is 0.6Pas in 3 hours through ball milling.0.1% the isooctanol that adds the metal-powder quality then carries out de-bubble;
3, will fill the small beaker of slip, putting into cryosel bathes, cool off after 30 minutes, initator and catalyst are added in the above-mentioned slip while stirring, initator is an ammonium persulfate, consumption is that per 100 milliliters of slips add 1.0% initator 20 microlitres, adds the catalyst tetramethylethylenediamine, and its consumption is per 100 milliliters and adds 40 microlitres;
4, the slip of above-mentioned adding initator and catalyst being splashed into temperature rapidly is in 60 ℃ the polymethylphenyl siloxane fluid medium;
5, falling the bottom when bead just in time solidifies fully.Through collection, washing, dry, sintering, make 2.5 millimeters iron-based bead again.
Embodiment 2: the preparation of carbide alloy bead
1, selects the N hydroxymethyl acrylamide gel rubber system, wherein N hydroxymethyl acrylamide is an organic monomer, and methylene-bisacrylamide is a crosslinking agent, and the selection absolute ethyl alcohol is a solvent, the total concentration of monomer and crosslinking agent accounts for 18% of solution, and organic monomer is 90: 1 with the ratio of the quality of crosslinking agent;
2, cemented carbide powder is for being commercially available powder, in above-mentioned premixed liquid, add cemented carbide powder, its volume fraction is 55%, the polyacrylamide that adds powder quality 1% is a dispersant, cemented carbide powder is for being commercially available powder, and polyacrylamide is a dispersant, makes the slurry that viscosity is 0.8Pas in 5 hours through ball milling.0.2% the aliphatic acid that adds the metal-powder quality then carries out de-bubble;
3, will fill the small beaker of slip, putting into cryosel bathes, cool off after 30 minutes, initator and catalyst are added in the above-mentioned slip while stirring, initator is an ammonium persulfate, consumption is that per 100 milliliters of slips add 5% initator 50 microlitres, adds the catalyst tetramethylethylenediamine, and its consumption is per 100 milliliters and adds 70 microlitres;
4, the slip of above-mentioned adding initator and catalyst being splashed into temperature rapidly is in 90 ℃ the methyl-silicone oil medium;
5, with example 1;
Embodiment 3: the preparation of stainless steel bead
1, selects the hydroxyethyl methacrylate gel rubber system, wherein hydroxyethyl methacrylate is an organic monomer, and methylene-bisacrylamide is a crosslinking agent, and the selection deionized water is a solvent, the total concentration of monomer and crosslinking agent accounts for 22% of solution, and organic monomer is 30: 1 with the ratio of the quality of crosslinking agent;
2, powder is that 400 commercially available purpose stainless steel powders add in the above-mentioned premixed liquid, and its volume fraction is 53%, and the polyacrylic acid that adds powder quality 1% is a dispersant, makes the slurry that viscosity is 0.9Pas in 20 hours through ball milling.0.6% the tbp that adds the metal-powder quality then carries out de-bubble;
3, in cryosel is bathed, cool off after 20 minutes, initator and catalyst are added in the above-mentioned slip while stirring, and initator is a potassium peroxydisulfate, and consumption is that per 100 milliliters of slips add 15% initator 10 microlitres, add the catalyst tetramethylethylenediamine, its consumption is per 100 milliliters and adds 30 microlitres;
4, the slip of above-mentioned adding initator and catalyst being splashed into temperature rapidly is in 95 ℃ the dimethicone medium;
5, with example 1;
Embodiment 4: the preparation of iron-nickel alloy bead
1, selects the hydroxy propyl methacrylate gel rubber system, wherein hydroxy propyl methacrylate is an organic monomer, and methylene-bisacrylamide is a crosslinking agent, and the selection deionized water is a solvent, the total concentration of monomer and crosslinking agent accounts for 15% of solution, and organic monomer is 10: 1 with the ratio of the quality of crosslinking agent;
2, the iron-nickel alloy powder adds in the above-mentioned premixed liquid, and its volume fraction is 57%, and the poly amic acid that adds powder quality 2% is a dispersant, makes the slurry that viscosity is 0.5Pas in 12 hours through ball milling.Froth in vacuum is 15 minutes then;
3, slurry cools off after 30 minutes in cryosel is bathed, initator and catalyst are added in the above-mentioned slip while stirring, and initator is a potassium peroxydisulfate, and consumption is that per 100 milliliters of slips add 0.5% initator 50 microlitres, add the catalyst tetramethylethylenediamine, its consumption is per 100 milliliters and adds 100 microlitres;
4, the slip of above-mentioned adding initator and catalyst being splashed into temperature rapidly is 80 ℃ silicone oil medium;
5, with example 1;
More than prepared bead, any surface finish, the high compact structure of sphericity, even zero defect, intensity is higher, wearability is good, sphere diameter is easy to control, mould-free forming, cost is low.
Claims (8)
1, a kind of method for preparing prill is characterized in that: concrete processing step is:
A, select a kind of gel rubber system, organic monomer and crosslinking agent and water or other organic solvent mixed dissolution of Raolical polymerizable can take place, make premixed liquid, can produce the organic monomer of free radical and the total concentration of crosslinking agent and should be controlled between 1%～50%, organic monomer is 10: 1～120: 1 with the ratio of the quality of crosslinking agent;
B, metal powder material is added in the above-mentioned premixed liquid while stirring, the percent by volume of the metal powder material that adds accounts for and adds 50%～100% of overall solution volume after the metal powder material, ball milling is prepared the slip of viscosity less than 1Pas after 1～48 hour, carry out defoaming treatment then; Described ball milling carries out in planetary ball mill or homemade ball mill;
C, initator and catalyst are added in the slip after the above-mentioned defoaming treatment while stirring, the consumption of initator is that per 100 milliliters of suspended substances add 0.1%～20% initator 20～300 microlitres, and catalyst consumption is that per 100 milliliters of suspended substances add 20～600 microlitres; Described catalyst is a tetramethylethylenediamine;
D, will add initator and catalyst slip with diameter optionally splash into device splash into heating, with the medium of slip solvent for use mutual exclusion in, drop enters after the medium, form orbicule, solidify conformal in the process of decline, collection bead, washing, drying, sintering are made prill;
2, method according to claim 1, it is characterized in that: the organic monomer of the produced free radical described in a step is 1～4 kind in acrylamide, N hydroxymethyl acrylamide, hydroxyethyl methacrylate, the hydroxy propyl methacrylate, or organic matter that can polymerization reaction take place; Crosslinking agent is a methylene-bisacrylamide, perhaps can play the organic matter of crosslinked action.
3, method according to claim 1 is characterized in that: the metal powder material described in the b step is in carbonyl iron dust, iron-nickel alloy powder, stainless steel powder, the cemented carbide powder 1～4 kind;
4, method according to claim 1, it is characterized in that: in the b step, when metal powder is added above-mentioned solution, add dispersant, dispersant is polyacrylic acid, polyacrylamide, poly amic acid, ammonium citrate 1～4 kind, and consumption is 0.1%～3.0% of a metal powder quality.
5, method according to claim 1 is characterized in that: in the b step, described defoaming treatment was by froth in vacuum, 40 ℃～90 ℃ de-bubbles 5～30 minutes.
6, method according to claim 1, it is characterized in that: in the b step, described defoaming treatment is by adding defoamer, and described defoamer is isooctanol, aliphatic acid, tbp 1～3 kind, and consumption is 0.05%～3% of a metal powder material quality.
7, method according to claim 1 is characterized in that: in the c step, monomer uses heat to cause by thermal-initiated polymerization, does not add initator.
8, a kind of device of realizing claim 1 preparation prill method, it is characterized in that: this device is the uprise (1) that the medium (2) of certain and the mutual exclusion of slip solvent is housed below splashing into device (8), the bottom of uprise (1) is connected on the conical flask (5) with rubber stopper, conical flask (5) is placed on above the little retort stand (6), whole uprise (1) is placed in the water-bath heater (3), heat with heating furnace (7) bottom of this heater (3), be that cryosel is bathed (10) in the large beaker (9), the small beaker (12) that fills slip (11) is placed on cryosel and bathes in (10).
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100869982A CN100363133C (en) | 2005-11-25 | 2005-11-25 | Method for preparing prills and apparatus thereof |
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| CNB2005100869982A CN100363133C (en) | 2005-11-25 | 2005-11-25 | Method for preparing prills and apparatus thereof |
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| CN1765548A true CN1765548A (en) | 2006-05-03 |
| CN100363133C CN100363133C (en) | 2008-01-23 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101645475B (en) * | 2008-08-07 | 2013-01-02 | 晶元光电股份有限公司 | Luminous element and manufacturing method thereof |
| CN105140750A (en) * | 2015-06-25 | 2015-12-09 | 合肥蓝科新材料有限公司 | Low-noise motor carbon brush material blended with iron-nickel alloy powder and preparation method of material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| SG86995A1 (en) * | 1997-12-15 | 2002-03-19 | Ceramet Composition And Proces | Mouldable composition and process |
| CN1233699C (en) * | 2002-11-22 | 2005-12-28 | 陕西科技大学 | Method for synthesizing starch microsphere |
| US20050115658A1 (en) * | 2003-11-04 | 2005-06-02 | Daga Amit K. | Joining of ceramic powder pressed components in the green or sintered state with a gelcast joint |
| EP1730224A4 (en) * | 2004-03-23 | 2009-03-25 | Commw Scient Ind Res Org | Polymer beads incorporating iron oxide particles |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101645475B (en) * | 2008-08-07 | 2013-01-02 | 晶元光电股份有限公司 | Luminous element and manufacturing method thereof |
| CN105140750A (en) * | 2015-06-25 | 2015-12-09 | 合肥蓝科新材料有限公司 | Low-noise motor carbon brush material blended with iron-nickel alloy powder and preparation method of material |
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| CN100363133C (en) | 2008-01-23 |
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Granted publication date: 20080123 Termination date: 20101125 |