CN1029349C - Production technology for W-alloy bar materials - Google Patents
Production technology for W-alloy bar materials Download PDFInfo
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- CN1029349C CN1029349C CN91103266A CN91103266A CN1029349C CN 1029349 C CN1029349 C CN 1029349C CN 91103266 A CN91103266 A CN 91103266A CN 91103266 A CN91103266 A CN 91103266A CN 1029349 C CN1029349 C CN 1029349C
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Abstract
The present invention relates to technology for producing tungalloy bar materials by using an extrusion method. White paraffin is used as a plasticizer. At specific extrusion temperature and extruding speed, an extruded blank is dewaxed and presintered in flowing hydrogen stream. Finally, liquid-phase sintering and vacuum heat-treatment are performed to obtain a blank with high strength, high toughness and stability. The technology is suitable for continuous mass production and has the advantages of high production efficiency, high material using rate, stable quality and low cost.
Description
The present invention relates to the production technique of a kind of powder metallurgy rod-shaped material, especially high-gravity tungsten-Ni-Fe (W-Ni-Fe) alloy rod-shaped material, wherein the moulding of material is to adopt improved Powder Extrusion Molding technology, and it belongs to powder metallurgical technology.
Usually, high specific gravity alloy material, as the tungsten-nickel-ferro-alloy material is to produce with powder metallurgy process, its production process mainly comprises technological processs such as powder batch mixing, compression moulding, liquid phase sintering, vacuum heat treatment, and experiment shows: the performance of high-density alloy and the composition of alloy and preparation technology have confidential relation.
The briquetting process of traditional high-specific gravity tungsten alloy blank mainly adopts two kinds of compression molding and isostatic cool pressing compression mouldings, utilize then and mill, the tungstenalloy blank is made in machinings such as car, or use pressure processing method, make the alloy plastic deformation, produce required blank, still, it is little to think directly to produce diameter in enormous quantities with these two kinds of methods, the rod-shaped material that slenderness ratio is big is very difficult, and the first, because softening agent is difficult for removing totally, so material property instability, the second, the size of blank can not be near the size of finished product, so amount of machining is big, the utilization ratio of material is low, the 3rd, production efficiency is low, is not suitable for producing in enormous quantities.
The Japanese documentation spy opens the preparation method that flat 2-122027 has introduced a kind of tungsten sintered alloy, this preparation method is that the nickel of the tungsten powder of 85-97% and surplus and iron powder are mixed the formation powder mix, powder mix is paused/the square centimeter hydrostatic forming in 1-4, this compacting thing is under 〉=1430 ℃ condition, in hydrogen gas stream, carry out liquid phase sintering, through in vacuum, heat-treating again after the liquid phase sintering.
Main purpose of the present invention is traditional high-specific gravity tungsten alloy production technique by selecting for use of softening agent in the extruding shaping technique improved.
The technology that the present invention proposes has with respect to traditional high-specific gravity tungsten alloy blank complete processing that processing is easy, material use efficiency is high, the blank density height of being processed, toughness is strong, good mechanical property, advantage such as can produce in enormous quantities, this method be particularly useful for producing diameter less than 6 millimeters, slenderness ratio greater than 15 the pole stock and the pole stock of special crosssection.
The high-density alloy powder extrusion process route synoptic diagram that Fig. 1 proposes for the present invention.
Fig. 2 is dewaxing back high-density alloy X ray diffracting spectrum.
Fig. 3 is the relation curve of paraffin add-on and diameter shrinking percentage, and wherein X-coordinate is add-on (weight %), and ordinate zou is diameter shrinking percentage (%).
It is little below in conjunction with accompanying drawing the present invention to be produced diameter, and the technology of the shaft-like tungsten alloy that slenderness ratio is big is done concrete description.
Process route of the present invention is: will carry out batch mixing through the tungsten (W) of selecting to have certain per distribution ratio composition-nickel (Ni)-iron (Fe) metal dust; Add plasticizer; Carry out Powder Extrusion Molding; Become parison to remove plasticizer, presintering; Liquid-phase sintering; Vacuum heat.
The manufacturing process of a kind of high-specific gravity tungsten alloy pole stock of the present invention, mainly be that the softening agent that will melt joins in the mixed powder in this technology, this softening agent is that fusing point is 48-56 ℃ a white paraffin, add-on is a 4-7%(weight), also have aviation spirit in the softening agent of said fusing as thinner, per 100 gram white paraffins are joined 150 milliliters of aviation spirit; Powder Extrusion Molding, extrusion temperature are 30-50 ℃; Remove softening agent and presintering; Furnace atmosphere is a flowing hydrogen when removing softening agent and presintering, heat up with stove when removing softening agent, carry out presintering after reaching more than 950 ℃, insulation is more than 1 hour, control respectively by different warm areas with the heat-up rate that stove heats up, when being lower than 300 ℃ heat-up rate be the 35-45 degree/hour, in the time of 300-450 ℃ heat-up rate be the 60-70 degree/hour, in the time of more than 450 ℃ heat-up rate be the 70-100 degree/hour.
As seen from Figure 1, in order to realize extrusion molding, need be before extruding, in the batch mixing of W-Ni-Fe, add a certain amount of softening agent, after extrusion molding, then will adopt appropriate means that softening agent is removed away, need the problem of primary study in the powder extrusion process that these several steps are high-density alloys, also be the feature whereabouts that the present invention is different from conventional powder extrusion process.
In the shaft-like blank production technique of high-specific gravity tungsten alloy of the present invention,
(1) softening agent selects for use
For realizing the powder extruding, must in the metal-powder raw material, add some other materials, make it have certain fluidity and formability, this class material is called softening agent, softening agent needs that plasticising performance is preferably arranged in certain temperature range, be easy to remove low price, characteristics such as obtain easily, the softening agent that the present invention selects for use is that fusing point is 48-56 ℃ a white paraffin.
(2) add-on of softening agent
According to weight percent, the add-on of paraffin was at 4% o'clock, and initial squeeze pressure is up to 8.1 * 10
5Newton/A °, (A °=1.96 * 10
-5m
2) and need repeatedly push in advance, extrusion temperature is required harsh, finally extruding the finished product blank has the add-on of transverse crack, poor toughness, paraffin big more, extrusion pressure is more little, but add-on was at 7% o'clock, the volume ratio of paraffin is up to 63.6%, the add-on that increases paraffin is unfavorable for later dewaxing and sintering process, and therefore, the paraffin add-on that the present invention selects for use is 4-7%, add-on is 5% o'clock, comparatively speaking, the transverse crack of extruding finished product is few, the toughness height, and the relative density of finished powder base is higher, and dewaxing and sintering also carry out easily.
(3) the adding method of softening agent
The simplest method is that heating paraffin is melted, pour into then in the blended metal-powder, for the powder extrusion process is carried out smoothly, softening agent can be coated on the metal-powder surface equably, also can select following adding method for use: at first heating paraffin is melted, adding a certain amount of aviation spirit then dilutes as thinner, at last this paraffin-gasoline blended solution is poured in the metal-powder that has mixed, and stir, after treating that gasoline volatilizees substantially, can carry out the powder extruding.
(4) powder extrusion process
The powder extrusion process comprises pre-extruding and finished product two stages of extruding, and wherein the purpose of pre-extruding is that paraffin is mixed more equably with metal-powder.
Extrusion temperature is controlled between 30-50 ℃, when temperature is hanged down, the paraffin powder mixture is mobile poor, and the powder base toughness of extruding is little, hard and crisp, fracture easily, when temperature was too high, paraffin was in a liquid state in the compound, with metal separation, paraffin flows out from die gap easily during extruding, can not push smoothly.
Extrusion speed remains between the 5-7 mm/second, because extrusion speed is too fast, makes extrusion process wayward; Extrusion speed is too slow, and the pressed compact of extruding is hard and crisp, and there is transverse crack on the surface, poor toughness, frangibility.
(5) remove softening agent and presintering
Remove softening agent, i.e. dewaxing, paraffin produces carbon when being subjected to thermo-cracking, if remove not exclusively, this residual carbon will produce serious influence to the alloy property of last formation.
Dewaxing is adopted the blank that squeezes out is carried out carrying out with the method for stove intensification heating, because in dewaxing process and after the dewaxing, powder base intensity is very low, can't move at all, so making dewaxing and presintering in the present invention carries out simultaneously, the blank that is about to squeeze out removes softening agent (dewaxing) and presintering with the pre-freezing of a furnace of small-sized dewaxing, diameter and batch according to blank are adjusted the dewaxing effect that can obtain with the stove heat-up rate, presintering is one hour more than 950 ℃, can make the pressed compact material obtain enough intensity.
Dewaxing to high-specific gravity tungsten alloy extruding powder base can or be filled under the nitrogen atmosphere and carry out at vacuum atmosphere, adopt the vacuum dewaxing to need strict control process parameters, otherwise cause powder base cracking easily, this is because the volume percent of paraffin can be up to 50% in extruding powder base, dewaxing in a vacuum, the inner paraffin gas of powder base increases the pressure on powder base surface, speeding up of paraffin effusion powder base, cause powder base surface to be subjected to bigger tension force and to produce cracking, adopt hydrogen as dewaxing atmosphere, hydrogen flowing quantity is about 0.1～0.3 meter
3/ hour.
The finishing operation of production high-specific gravity tungsten alloy rod-shaped material technology of the present invention is liquid phase sintering and vacuum heat treatment operation, when adopting the powder extrusion process to produce high-specific gravity tungsten alloy, its liquid sintering technology is identical with conventional high-specific gravity tungsten alloy sintering process, for preventing thin diameter, the shaft-like blank deformation of high-fineness ratio should be noted strict control sintering temperature when sintering, usually the liquid phase sintering temperature is at 1480-1540 ℃, sintering time is about 90 minutes, the purpose of vacuum heat treatment is to improve the performance of high-specific gravity tungsten alloy, because its cross section of shaft-like high specific gravity tungsten alloy material is than blocky little, so the condition of vacuum heat treatment is also corresponding low, usually, the condition of vacuum heat treatment is in 0.13pa(1 * 10
-9Torr) under the vacuum condition, got final product in about 90 minutes in about 1100 ℃ of processing.
To adopt that complete processing of the present invention produces by W mutually and Ni, the high-specific gravity tungsten alloy that the Fe solid solution matrix constitutes is mutually observed mutually and is shown: under normal circumstances, high-specific gravity tungsten alloy with the production of powder extrusion process, its metallographic structure is basic identical with the metallographic structure of the high-density alloy of producing with ordinary method, still, and the nodularization of W phase particle, homogeneous microstructure, densification, so the mechanical property of material, intensity and toughness all are significantly increased, and the stable performance of alloy.
The advantage of this technology is to be applicable to the production in enormous quantities W-alloy bar materials, high-level efficiency, low cost.
Embodiment:
With explained hereafter diameter of the present invention is 4 millimeters, and slenderness ratio is respectively 22,20.5,15 high-specific gravity tungsten alloy bar.
Alloy ingredient adopts the W232 alloy, it is the alloy of 95%W-3.5%Ni-1.5%Fe component, purity＞99% of tungsten (W) wherein, mean particle size (Fei Shi) 3.30 μ m, (the purity 99.8% of Ni, mean particle size (Fei Shi) 4.18 μ m, purity＞99.5% of iron (Fe), mean particle size (Fei Shi) 5.22 μ m, metal-powder passes through batch mixing, in the metal-powder that mixes, add 4 respectively, 5,6,7 weight %, fusing point is that 48-56 ℃ white paraffin is as softening agent, mix, the adding method of softening agent is to pour in the mixed metal-powder after the heating paraffin fusing, for softening agent is coated on the metal-powder surface equably, can add thinner, use aviation spirit as thinner, earlier heating paraffin is melted, then with the ratio adding aviation spirit of per 100 gram paraffin with 150 milliliters aviation spirit, again this paraffin-gasoline mixed solution is poured in the metal-powder that has mixed, fully stir, the compound that has stirred pushed in advance with finished product push, extrusion temperature is controlled between 30-50 ℃, the extruded velocity of powder base remains on the 5-7 mm/second, experiment shows that the powder base that adds aviation spirit can more successfully push, the blank defective of extruding is less, as required the powder base is machined to certain-length and shape after the extruding, adorning three stoves then dewaxes respectively and presintering, when dewaxing, adopt and heat up with stove, heat-up rate to the differing temps district can be controlled to be respectively: in the time of 0-300 ℃ heat-up rate be the 435-45 degree/hour, in the time of 300-450 ℃ heat-up rate be the 60-70 degree/hour, when 450 degree are above, heat-up rate be the 70-100 degree/hour, three stoves reach 900 respectively, 950, presintering is one hour in the time of 1000 ℃, when sintering, make filler with aluminum oxide in the stove, and employing vacuum and two kinds of atmosphere of hydrogen, when adopting hydrogen gas hydrogen, initial stage and later stage in dewaxing feed hydrogen with different flow, and amount is about 0.15 meter during the initial stage
3/ hour, when furnace temperature was 400-700 ℃, hydrogen flowing quantity was 0.3 meter
3/ hour, the experiment surface, blank under the vacuum atmosphere is prone to cracking, seldom occurs cracking phenomena under the nitrogen atmosphere and fill, and can make blank obtain better intensity when pre-sintering temperature is 950 ℃, at last blank is carried out liquid phase sintering and thermal treatment to obtain the finished product, in this technological process, the control sintering temperature is 1480 ± 10 ℃, and sintering time is 90 minutes, used alumina packing should be the powder of 80 mesh sieves, and the condition of vacuum heat treatment is: in 0.13pa(1 * 10
-9Torr) under the vacuum condition, handled 90 minutes at 1100 ℃, the powder base of different paraffin add-ons and the alloy behind the sintering various performance measurements have been carried out, the paraffin that can see adding from table 1 is many more, the density of powder base is more little, this is owing to increase after the paraffin add-on, squeeze reduces, and residual hole is increased, and measures the density of alloy, hardness and diameter shrinkage results (table 2, Fig. 3) show, paraffinicity is big more, and the shrinking percentage during sintering is big more, but the density and hardness of final alloy and the congruent alloy of producing with existing method is basic identical, metallographicobservation shows that sintering structure is that globular tungsten phase particle wraps in matrix centre mutually, homogeneous microstructure, defectives such as hole and crackle are arranged are not seen in densification, and X ray diffracting spectrum shows, have only W phase and Ni in the alloy, Fe matrix phase does not have Ni
11W
4The C phase, this explanation dewaxing is completely, and when using other softening agent, often is difficult for making softening agent to remove fully, very easily has the Ni that can obviously influence alloy property
11W
4Phases such as C, table 3 are density and hardnesses of the alloy after the different sintering temperatures, and table 4 is the performance with the bar base of the identical composition of powder extrusion process and compression molding production and same size.(table 1,2,3,4 is seen the literary composition back)
Stable with the up to a hundred kilograms of shaft-like blank performances of plurality of specifications W232 high-specific gravity tungsten alloy that the described processing method of the foregoing description is produced, the diameter made from it has good armor-piercing action less than 6 millimeters bullet, weigh 20 the gram about at bullet when flight velocity is the 800-900 meter per second, high pressure 5 armor platings of penetrable 10 mm thick, this performance is better than high-quality steel bomb ball greatly, therefore as seen, it is feasible adopting the powder extrusion process to produce the shaft-like base of tungstenalloy, it has overcome the shortcoming of common drawing method, can make size near finished product, diameter is less, the extruding powder base that slenderness ratio is bigger, can directly obtain the finished product base after sintering and the thermal treatment, not only can save great machining of workload (mold pressing-process for machining) or complicated press working operation, enhance productivity, the utilization ratio height of bar base material, be applicable to serialization production in enormous quantities, the production efficiency height, steady quality, and cost is low, wherein material use efficiency is compared with pressure processing craft with common pressing process, be respectively 70,45,60%, can see that the material use efficiency of using explained hereafter bar base of the present invention is apparently higher than prior art.
Table 1
Paraffin add-on (%) 4567
Actual density (g/cm
3) 9.76 8.91 7.93 7.3
Theoretical density (g/cm
3) 10.4 9.45 8.67 8.03
Table 2
Paraffin add-on (%) 4567
Alloy density (g/cm
3) 18.03 18.04 18.02 18.01
Alloy rigidity (HRC) 28.3 29.5 30.5 30.2
Table 3
Sintering temperature (℃) 1,480 1,500 1520
Alloy density (g/cm
3) 18.02 18.03 18.02
Alloy rigidity (HRC) 29.2 30.0 30.5
Table 4
Processing performance σ b δ hardness density
System Mpa % HRc gram per centimeter
3
Powder worker mean value 1,007 17.5 29.7 18.03
Minimum value 983.5 10.7 28.7 18.01
Squeeze maximum value 1,027 25.3 30.8 18.05
Press skill experiment quantity 20 20 14 14
Mould mean value 982.9 20.3 29.1＞18
Pressure minimum value 933.9 10.0--
Worker's maximum value 1,010 26.4--
Claims (1)
1, a kind of manufacturing process of high-specific gravity tungsten alloy pole stock, this technology mainly comprises the powder batch mixing, liquid phase sintering, vacuum-treat, sintering temperature is 1480-1540 ℃, it is characterized in that:
(1) softening agent with fusing joins in the mixed powder, this softening agent is that fusing point is 48-56 ℃ a white paraffin, add-on is 4-7 (weight %), also has aviation spirit in the softening agent of described fusing as thinner, and per 100 gram white paraffins are joined 150 milliliters of aviation spirit;
(2) Powder Extrusion Molding, extrusion temperature are 30-50 ℃;
(3) remove softening agent and presintering, furnace atmosphere is a flowing hydrogen when removing softening agent and presintering, heat up with stove when removing softening agent, carry out presintering after reaching more than 950 ℃, insulation is more than 1 hour, and the said heat-up rate that heats up with stove is controlled respectively by different warm areas, when being lower than 300 ℃ heat-up rate be the 35-45 degree/hour, in the time of 300-450 ℃ heat-up rate be the 60-70 degree/hour, in the time of more than 450 ℃ heat-up rate be the 70-100 degree/hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91103266A CN1029349C (en) | 1991-05-22 | 1991-05-22 | Production technology for W-alloy bar materials |
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|---|---|---|---|
| CN91103266A CN1029349C (en) | 1991-05-22 | 1991-05-22 | Production technology for W-alloy bar materials |
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| CN1029349C true CN1029349C (en) | 1995-07-19 |
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| CN91103266A Expired - Fee Related CN1029349C (en) | 1991-05-22 | 1991-05-22 | Production technology for W-alloy bar materials |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067615C (en) * | 1996-01-19 | 2001-06-27 | 冶金工业部钢铁研究总院 | Method for producing high-gravity alloy manufactured product |
| CN100460143C (en) * | 2006-05-12 | 2009-02-11 | 上海六晶金属科技有限公司 | Method for preparing tungsten base high-specific-gravity alloy thin-sheet |
| CN203501764U (en) * | 2012-08-31 | 2014-03-26 | 北京天龙钨钼科技有限公司 | Partition plate assembly used for tungsten sintering furnace |
| CN106148745B (en) * | 2015-04-14 | 2018-06-12 | 上海六晶科技股份有限公司 | The method that tungsten nickel iron alloy is prepared using zone sintering method |
| CN110834093A (en) * | 2019-11-06 | 2020-02-25 | 南通冠达粉末冶金有限公司 | Energy-saving powder metallurgy process |
| CN112413023B (en) * | 2020-11-20 | 2022-11-08 | 贵州新安航空机械有限责任公司 | Processing method of thin sheet powder metallurgy brake disc |
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