CN101530918B - Method for preparing composite component with strengthened TiB based on titanium alloy via powder metallurgy method - Google Patents
Method for preparing composite component with strengthened TiB based on titanium alloy via powder metallurgy method Download PDFInfo
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- CN101530918B CN101530918B CN2008102338553A CN200810233855A CN101530918B CN 101530918 B CN101530918 B CN 101530918B CN 2008102338553 A CN2008102338553 A CN 2008102338553A CN 200810233855 A CN200810233855 A CN 200810233855A CN 101530918 B CN101530918 B CN 101530918B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1084—Alloys containing non-metals by mechanical alloying (blending, milling)
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1089—Alloys containing non-metals by partial reduction or decomposition of a solid metal compound
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0073—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only borides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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Abstract
This invention relates to a method for preparing composite component with strengthened TiB based on titanium alloy via powder metallurgy method, especially a method for preparing composite material of Ti-based metal substrate. In one mode, a titanium hydride can be added into a basically pure titanium, alloyization material and boron source so as to compact and sinter the mixture of these materials via the powder metallurgy method and to prepare a component that is composed of titanium alloy and having strengthened titanium boride. In the other mode, the basically pure titanium, alloyization material and boron source can be tempestuously mixed (having the titanium hydride or not) to the following degree: removing an oxide film that may be formed on the titanium precursor so as to manufacture the component in which the oxygen content is minimum.
Description
Technical field
The present invention relates generally to the metal alloy of ceramic reinforced, especially titanium alloy of titanium boride reinforcement and preparation method thereof.
Background technology
Prepared in the element by wide range of materials, powder metallurgic method (PM) is a kind of very popular method, the many employings in these materials more generally for example casting, forming process or machining and so on conventional method be very difficult or impossible.Powder metallurgic method is particularly suitable for preparing element by refractory material and the material that can't form real alloy in other technique, and because its repeatable and non-waste characteristics are very suitable for the large-scale manufacturing (for example manufacturing of automotive components).
In typical powder metallurgical technique, metal dust is mixed with alloying material, lubricant, binding agent or analog, then adopt suitable process unit to be pressed into nearly clean shape (near-netshape), in controlled atmosphere, carry out subsequently sintering the powder of compacting is bonded together in metallurgical mode.Usually, may carry out one or more minor actions, comprise and deburr and relevant surface treatment, press again, flood and reduce hole.
Titanium has excellent corrosion resistance, relatively high heat resistance and high specific strength, during therefore the engineering through being usually used in weight sensitive is used.Transport service, especially relevant with aerospace applications, especially have benefited from the use of titanium and titanium alloy, thereby created efficient platform on the structure.Yet its limited rigidity makes the advantage of the homologue higher with respect to its refractoriness that must present of abundant exploitation titanium become very difficult up to now.For example, half of the elastic modelling quantity of titanium-base alloy the chances are base steel material and nickel-base material.The material that adopts additional amount has reduced the odds for effectiveness of the relatively Ni-based and iron-based alternative of titanium to remedy these relatively low stiffness values.
A kind of method that improves the rigidity of titanium-base alloy is exactly that they are carried out combination with the ceramic material with relative high-modulus.This combination with bulk metal (a bulk metal) and continuous or discrete reinforcement body is the part of a relatively new class material, this material is referred to as and is metal-matrix composite (MMC), and wherein structural property can customize by next the application for concrete engineering of suitable selection component material.Common MMC's, especially titanium base MMC, the variant of discontinuous structure can bear powder metallurgic method, this be because compound formative ceramic material (compound-forming ceramic material) thus in the process of sintering, can improve the performance of whole composite with the react body that strengthened of titanium basis.Particularly, except improving the rigidity of titanium, strengthening material (typically being the graininess form) also brings other structural benefits, comprises that hardness is higher for relevant wearing and tearing, and multiple to improve fracture toughness.
In the PM technique for the preparation of titanium base MMC, the titanium precursor can with another kind of combination of materials, described another kind of material forms ceramic reinforced material sclerosis, rigidity under suitable temperature and pressure condition, simply enumerate some such as titanium boride (TiB), titanium carbide (TiC) or titanium nitride (TiN).Wherein, TiB is proved to be the hardening constituent that is particularly suitable as titanium MMC, because TiB shows high intensity, hardness, heat resistance and elastic modelling quantity, Thermodynamically stable in whole titanium alloy PM treatment conditions, be insoluble in the titanium alloy, have similar thermal coefficient of expansion to titanium alloy, and between itself and titanium matrix, form stable crystal boundary.But, TiB itself is also unstable, therefore must original position obtain, for example by titanium diboride (TiB
2) react acquisition with the Ti powder in sintering process.
Produce titanium base MMC by powder metallurgy and face a lot of challenges.Most important factor is exactly to the control such as the dvielement of carbon, hydrogen, oxygen or nitrogen for high-quality titanium base MMC (perhaps having improved fracture toughness and fatigue resistance).And it also is very important avoiding forming magnesium compound and sodium compound.In these elements, oxygen is the most important element that needs restriction.For example, remaining oxygen may form on the surface of titanium precursor with the form of oxidation film.By having limited the more desirably for example generation of diboride above-mentioned of hardening constituent, the existence of this oxygen can reduce density and the mechanical performance of final products.It is also very crucial to the microstructure and the prevention reinforcement composition chaining that obtain homogeneous that powder is carried out suitable mixing.
Exist demand to having excellent toughness, corrosion resistance, high rigidity, wearability and stable on heating high strength titanium sill.Further also exist in the effective mode of cost and produce these materials to satisfy the demand of high yield part making method.
Summary of the invention
The present invention satisfies these demands, wherein the method and apparatus that combines following characteristics is disclosed.The preparation method of composite component (composite component) is disclosed according to a first aspect of the invention.This element is by titanium alloy matrix and the TiB that is distributed in this matrix
2The composite that reinforcing particle is made, wherein the method comprises multiple precursor (that is, composition) material mixed and obtains mixture, then described mixture is carried out the mixture of compacting and the described compacting of sintering with the element of preparation form of composite.These precursor materials comprise basically pure titanium (for example simple substance titanium), titantium hydride (TiH
2), alloying material (alloying material) and boron source material.The heat that produces in sintering process reacts boron source material and titanium and forms titanium diboride (for example, as the compound of particle form), simultaneously TiH
2Become activation and with mixture in any oxygen of existing react (helping thus to remove).TiB in the sintering process
2Obtain TiB with the reaction of simple substance titanium, TiB only is thermodynamically stable in titanium alloy.TiB in MMC as reinforcing particle.On basis, be that obvious difference is arranged for the sintering of middle use should be appreciated that with other high-temperature operation that relates to fusing now, the difference be sintering relate to material be heated to be lower than slightly its fusing point temperature (typically near fusing point, but do not limit, fusing point 80%), the particle of the dispersion of precursor material is adhered to mutually by solid-state diffusion.Similarly, term " compacting (compact) " and its variant are the synonyms of compacting (pressing), wherein adopt the machine tools of rigidity to apply large pressure at mixture and make this mixture obtain preferred geometry.For example non-limiting, this compacting or compacting operation can relate to the pressure of 5-100 ton/square inch.
Choose wantonly, precursor material is pulverous.In this case, can use basically pure titanium powder.In the present context, term " basic " refers to the arrangement of key element or feature, accurate uniformity or the behavior of demonstrating can embody in practice the accurate state that is weaker than although described arrangement can be expected in theory.Same, this term representative degree that quantitative numerical value, measurement result or other relevant expression can be different with the reference value of claiming in the situation that the basic function of the theme that does not cause paying close attention to changes.For example, be easy to obtain purity and be 99.9% commercially available titanium, can be considered to substantially pure titanium like this.In addition, the substantially pure metal oxidation of titanium its substantially pure essence that do not detract for example.Therefore, be exposed to the substantially pure titanium that forms oxidation film, layer or analog after the ambiance in the metal surface and still be considered in the present context substantially pure titanium.
Point more specifically, the diameter of composition titanium powder is the 9-75 micron, more typical scope is the 18-28 micron.The typical range of alloying material powder is the 5-75 micron.Similarly, the TiB that makes
2The typical range of powder is the 5-75 micron.Although those of ordinary skills know many titanium matrix and can use, some alloy shows as the structural detail special adaptability of the structural detail used of aviation and automobile for example.These comprise β titanium, α-2 titanium, γ titanium and their combination.The example that can be used for the β titanium among the present invention comprise the aluminium that contains about 6wt% and approximately the titanium of the vanadium of 4wt% (also be, Ti 6-4), and contain the tin of the aluminium of the 6wt% that has an appointment, about 2wt%, approximately zirconium and the about titanium (that is, Ti 6-2-4-2) of the molybdenum of 2wt% of 4wt%.The inventor finds that Ti 6-4 is particularly suitable for preparing the automotive components that composite is strengthened, and this is because Ti 6-4 alloy relatively enriches, has preferably chemical compatibility and easily processing.The example of α-2 titanium and γ titanium comprises intermetallic compound, comprises TiAl and Ti
3Al.Alloying material discussed above can be aluminium vanadium powder end, and it can comprise various approximate ratios, is not defined as on 60% the aluminum ratio 40% vanadium, 60% vanadium on 50% vanadium and 40% aluminum ratio on 50% the aluminum ratio.
In specific form, the boron source material is by TiB
2Form.In another kind is selected, can comprise at the most the approximately TiH of 10wt% in the mixture
2, more specific scope is the TiH of about 3-7wt%
2Firing rate in sintering process preferably is defined as the highest 5 ℃/minute, and more special scope is 2-5 ℃/minute.Sintering process of the present invention can preferably be carried out in controlled atmosphere, thereby avoids oxidation and relevant pollution.The example of this control can comprise emptying environment or at inert environments.
In another option, mixed process can have two purposes.Except main make powder or other component are carried out the equally distributed benefit, the inventor determines that also more violent mixed method assists in removing oxide layer, this oxide layer may since metal exposed to be accumulated in titanium in atmosphere or relevant aerobic environment lip-deep.In this way, mixing also comprises this oxygen sill of removing at least a portion.More particularly, the removal process comprises that precursor material being placed in the inert environments (argon gas after the oxygen of for example finding time) then is rotated precursor material and mixes until the time that described mixed material has predetermined characteristic, described predetermined characteristic is the evidence of alloying and the tap density (tap density) that improved before maximum powder size, surface flatness, the sintering for example, latter's correspondence rock or compacting with the bulk density (bulk density) of composite material after promoting precipitation.Rotation mixes can more specifically comprise the rotary speed that adopts mixer, and mixing drum or other hydrid component carry out High Rotation Speed in long-time.The inventor finds, produces or both necessary mixabilities that realize in above-mentioned predetermined properties, the removal oxide-film under about 3600 rev/mins rotary speed in about 4-12 hour.
The present invention is fit to produce a large amount of titanium based structures elements very much, but the inventor finds that they are particularly suitable for the element of auto industry and relevant means of transport.In the present context, term " automobile " not merely refers to car, also comprises the motor vehicles of truck, motorcycle, bus and relevant means of transportation.In automobile was used, the inventor found that the element that oily material disclosed by the invention and method obtain especially is fit to the application relevant with engine, and mechanical load and the condition of high temperature high in this application exist simultaneously.The example of automotive components comprises valve (valve), retention tab (retainer), valve spring (valve spring), connecting rod, bolt, securing member, spiral bearing spring (coil suspension spring) and gas extraction system (exhaust system).
Except above-mentioned mixing, compacting and sintering operation, also may carry out other optional step.For example, the surface modification operation of one or many, for example deburr (deburring), surface-pressure shot-peening (surface compressive peening), (the latter is with in the lubricant injection element to reduce hole or dipping, such as can be used in bearing, axle journal or the relevant anti-attrition parts), can be used for improving the function of final element.
Another aspect of the present invention is the method that discloses for the preparation of the material of powder metallurgy processing.The method comprises a large amount of precursor powder materials, comprise that substantially pure titanium, titantium hydride, alloying material and boron source material put the mixer of titanium base into, ambiance in the mixer is replaced substantially with inert fluid, and powder size reduces 20% at least until mixture shows with the rotation of predefined minimum speed and predefined shortest time, the tap density of mixture improves 30% or basically removed the oxide-film of titanium powder at least with agitator.After mixing is finished, mixture is carried out sintering.
Choose wantonly, the structure of agitator (agitator) can be various forms of.In one form, agitator is comprised of numerous titanium base spheroids or sphere, and these spheroids or sphere can rotate in mixer, such as motion or the similar mode by container.In another form, agitator can be from the radial oar that stretches out of elongated rotating shaft, rod or associated components, so that stir powder when rotating shaft rotates.In preferred option, the minimum predetermined rotating speed of spheroid or parts is about 3600 rev/mins (RPM), and the shortest Preset Time is about 4 hours.
According to a further aspect in the invention, the method for preparing titanium boride reinforcement titanium-based metal matrix composite elements is disclosed.The method comprises mixes at least substantially pure titanium powder with alloying material and boron source material.The degree of mixing and the record of front are similar, wherein said mixing is more violent with respect to only the composition material being carried out basically the mixing that even distributions needs, because remove most of or whole any oxide skin(coating) that may form in titanium powder by the rubbing of Powdered collision storeroom.Except mixing, mixture must be compacted into the shape of element, afterwards with the mixture sintering of the compacting degree to the hardening constituent that is enough to that boron source material and titanium are reacted and obtains be comprised of titanium boride.
In a kind of optional form, this method further comprises adds titantium hydride in titanium powder, alloying material and boron source material composition, thereby it can be mixed with them.Behind the element sintering, can also comprise the one or more other step in forging and the annealing operation.
Description of drawings
Can understand better as detailed below of the present invention by accompanying drawing, structure identical among the figure represents with identical Reference numeral, wherein: the process chart for preparing according to aspects of the present invention titanium base MMC element shown in Figure 1; Shown in Figure 2 is the change curve that hydrogen content changes with sintering temperature in titanium base MMC; Shown in Figure 3 is the sketch of the equipment that uses in the composition material for the preparation of titanium base MMC mixes; Shown in Fig. 4 A-4C is various precursor materials after violent mixed process according to aspects of the present invention; Fig. 5 and shown in Figure 6 be respectively that exemplary dimensions for the titanium powder of TP325 and TP250 distributes; Shown in Figure 7 is from TiB behind sintering
2Result to the X-ray diffraction analysis of the transformation of TiB; Shown in Figure 8 is ESEM (SEM) photo of Al-V alloying powder; Shown in Figure 9 is the distribution of sizes of Al-V alloying powder among Fig. 8; Shown in Figure 10 A-10D is the microstructure of the Ti MMC behind the sintering according to aspects of the present invention; Shown in Figure 11 A-11F is the microstructure that adopts according to aspects of the present invention the Ti MMC behind the sintering of different process; Shown in Figure 12 A-12B is that Ti MMC microstructure behind the sintering is to the dependence of various forging temperatures; Shown in Figure 13 A-13B is different TiB
2Addition is on the impact of Ti MMC microstructure.
The specific embodiment
At first referring to Fig. 1, schematically show step behind mixing, compacting and sintering step and the optional sintering.The first step comprises mixes 100.As shown in the figure, use at least four kinds of different composition materials, comprise the titanium 110 of the substantially pure form of simple substance titanium or other, titantium hydride 120, alloying material 130 and boron source material 140.To those skilled in the art, a variety of known method blending constituent materials are arranged here; Some such methods comprise that ball milling mixes, vibromill mixes and V-type is mixed.These conventional methods are the suitable purpose that will reach generally, that is, precursor material is evenly distributed relatively in the mixture of these materials.
Next with reference to Fig. 3, the present inventor finds that the modification that these conventional hybrid modes are carried out can be for the performance that improves the precursor that mixes, especially because it relates to the raising of reduction, the smoothness on surface, the front alloying of sintering a little and the mixture tap density of powder size.(latter can analogize to and only realize required the comparing of above-mentioned even mixing with the combination that mixes severity by improving significantly incorporation time, composition is shaken more fiercely), the inventor finds not only to realize some above-mentioned attributes, and because the mechanical friction of being stirred between powder can be removed potential undesirable oxide layer that may form on the titanium powder surface.Activation step (activationstep) is also served as in violent like this mixing (for example process of lapping by revising), because the removal of this oxide layer may be favourable, because reduce porosity, corrosion susceptibility and may be to the follow-up pollution of expection TiB hardening constituent.In addition, the inventor has confirmed high-speed stirred, especially adopt in the situation that different size titanium ball carries out, be good at the sort of areal deformation that produces the composition material that causes the high surface energy level, this causes forming dislocation and unordered (disorder) in the final crystal structure, thereby Crack Extension mechanism (crack propagation mechanic) is minimized.
The inventor finds that also amended mechanical disintegration processing (MPT) is conducive to improve tap density and final densities.An example of the inventor adopted the simplification series processing conditions relevant with MPT comprises: (1) finds time then to provide the argon shield to powder (pressure is higher than atmospheric pressure) indoor; (2) the described chamber of cooling is not so that the temperature of powder is higher than 35 ℃; (3) providing ball and dusty material point other weight ratio is 1: 12; (4) providing bulb diameter is respectively that the ratio of the ball amount of 20mm, 10mm and 8mm is 3: 3: 1; (5) described powder is ground; time is 4-12 hour, and speed is 3600RPM.These steps should be so that the size reduction 20-60% of (1) powder, (2) cause more smooth powder surface, (3) promotion is pre-alloyed, and (4) tap density improves 30-40%, and the raising of sintered density is corresponding with the MPT processing time.
Shown in the figure is the operation of the mixing apparatus that uses in the present invention.Mixing apparatus comprises and mixes rotating cylinder or similarly container 150, the precursor feeds pipeline 160 with pump 170, rotating shaft 180 and be installed in rigidly agitator 190 on the rotating shaft 180.In the present invention, the inventor finds that the mechanical disintegration processing method revised and precursor material work well especially in the preparation preferred mixture.In a concrete form, mixed process (referring to adopt the process of the MPT of modification) is selected substantially pure titanium ball or the sphere 195 of different size, and wherein the diameter of sphere can be 20 millimeters, and other is 10 millimeters and 8 millimeters.Mix in the rotating cylinder 150 in case precursor material is placed on, then this container can bleed to get rid of remaining oxygen.Subsequently argon gas (being higher than 99.999%) or relevant inert fluid pumping are entered in this container to the pressure (for example reaching about 1.2 atmospheric pressure) that slightly raises thus prevent Powder Oxidation.In order to prevent polluting, the inside of container all is to be made by substantially pure titanium, and the cooling medium of pumping by cooling medium loop 155 for example cooling water can not be higher than 35 ℃ in order to guarantee room temperature.The weight ratio of titanium ball and technique powder is 1: 12.Mixing was carried out 4-12 hour with 3600 rev/mins rotating speed, and every batch of precursor material is 5-10Kg.
The existence of titantium hydride 120 further reduces the existence of the oxygen in the element of sintering in mixture.And the decomposition of titantium hydride produces tiny titanium valve, thereby it fills up the density of the space raising element between other mixed-powder.The inventor has found TiH
2Interpolation have preferred scope, very little possibly can't play fully additional oxygen remove, may cause too much in sintering process, occurring inhomogeneous cracking.
As previously mentioned, existed many ceramic base titanium compounds can be used as the hardening constituent of titanium matrix.But, the inventor has determined some the suitable Ti of production MMC elements than other.For example, than TiC and TiB, TiN is weak hardening constituent, and the latter is better among TiC and the TiB.Thermodynamically stable ceramic particle (for example TiB and TiB
2) concentration selected according to using.Concerning many automobiles were used, the inventor found that the upper limit can be about 18wt%, and lower limit can be low to moderate 1wt%.From phasor, the inventor expects Ti and TiB
2Reaction meeting in sintering process forms the thermodynamically stable phase of TiB in titanium alloy.
The second step that adopts in the preparation material comprises that compacting, compacting or alternate manner form described mixture.This is shown in step 200.Blend step as described above has a lot of methods this element can be formed its green state (namely before the sintering).The quiet moulding such as these methods comprise or compression molding etc.In compacting 200, be enough to make parts to keep being essentially nearly clean shape to the added pressure of mixture, and wait for simultaneously sintering step 300 (below discuss).
The 3rd step was sintering step 300.In sintering process, thereby the green compact element of compacting is heated and makes titanium (for example Ti simple substance) and alloying material carry out alloying, thereby obtains the titanium based substrate.As previously mentioned, thus can adopt controlled environment to fall oligosaprobic possibility.The temperature that sintering step 300 can carry out is preferably between 1200 ℃-1450 ℃.Sintering step 300 can comprise the heat protocol with gradient, such as being between 2 ℃/minute-5 ℃/minute.Particularly, sintering temperature on an example of the impact of hydrogen amount among the Ti-MMC as shown in Figure 2.
Can use cooling scheme subsequently, wherein the element of sintering cooled off in 7 hours.In this case, cooldown rate can be about 200 ℃/hour.And in sintering step 300, form TiB thereby react between boron source material 140 and the titanium 110, and titanium alloy (for example Ti6Al4V).Same, described step also may comprise closed die forging (closed die forging) or densified (the phase-transformation densification) 400 of phase transformation, and the aperture that stays in the sintering process here can forge by hot pressing (hot-press forging) and removes.This step is preferably carried out at high temperature.Be applied to coating on these parts in room temperature and help to stop at high temperature partial oxidation.In one form, coating contains Al
2O
3, SiO
2And B
2O
3And organic bond.For some coatings, be to utilize brush to apply when parts are heated to 70 ℃, the described parts of subsequent drying.Typical forging range is 900-1400 ℃, more particularly 1200-1350 ℃, specifically depends on TiB
2Content, more the forging temperature used of high request is higher for content.Typical minimizing is more wide in range than (ratio of cross-sectional area before and after forging sometimes is called thickness and reduces percentage, and is relevant with the size of processed MMC material) should to be between the 300%-800%, and special scope is 500%-700%.In this scope, sintering temperature can be 1350 ℃.Typical annealing temperature should be in the wide region between 550-950 ℃, especially between 650-740 ℃.Time should be 0.5-2 hour.
Still as shown in Figure 1, also can adopt closed die forging or relevant phase transformation densified.In this case, the hot pressing in mold closing can be used for additionally removing hole and carrying out subsequently densified.In this case, sintering temperature is 1350 ℃.Typical annealing temperature should be 650-740 ℃, and scope is 550-950 ℃.Time should be 0.5-2 hour.The inventive method can obtain to be higher than 99% high sintered density.
Especially referring to Fig. 4 A-4D, the typical hybrid powder image that shown is before and after MPT, wherein Fig. 4 A is corresponding is titanium valve before the MPT, Fig. 4 B is corresponding is TiB before the MPT
2Powder, Fig. 4 C is corresponding be alloying powder (concrete is the Al-V powder) before the MPT and Fig. 4 D corresponding be mixed-powder behind the MPT.Than the powder that does not carry out the MPT processing, the performance of the powder that MPT processed under above-mentioned MPT condition shows the powder size 20%-60% that descended, the surface flatness of powder is improved, and it is slight pre-alloyed that some powder are carried out, and improves tap density 30%-40%.MPT is as shown in the table on the impact of sintered density:
| Process time (hour) | Density (g/cc) |
| 0 | 3.06 |
| 4 | 3.97 |
| 8 | 4.05 |
| 12 | 4.12 |
Compacting before the sintering and relevant tap density can be by multiple vibrations, rock or relevant stirring means obtains.A kind of method that improves the front compacting of sintering is real by cold forming.In one form, this can carry out 3 minutes under the condition of room temperature, 190-360MPa (that is, being approximately 28000-52000psi), and typical time range is 1-6 minute, and typical pressure range is 230-270MPa.The inventor has been found that the preferred size of titanium particle should be the 22-34 micron in the wide region of 5-75 micron in order to obtain best green density (green density) and green strength (green strength).Sintering process comprises that the speed with 2-5 ℃/minute heats these green component until they reach desirable sintering temperature, be approximately 1300 ℃, typical temperature range (as mentioned above) is 1200-1450 ℃, is incubated 3 hours, and typical time range is 2-8 hour.In sintering process, advantageously keep 10
3The vacuum 2-8 of Pa hour, more specifically time range be 3-6 hour to reach 99% solid density.Sintering time is more long more further to improve sintered density.
The size variable of precursor material, but be between the 9-75 micron extensively for the preparation of the typical size range of the titanium powder of Ti6Al4V MMC, and narrower range is at the 18-28 micron.There is multiple possible method to carry out the preparation of titanium valve.A kind of is with hydride-dehydrogenation compound titanium valve preparation method (ahydride-dehydride titanium powder making process), obtains different powder sizes by the rotary speed that changes in the jet grinding process.Referring to Fig. 5 and Fig. 6, show distribution of sizes and the pattern of two kinds of typical Ti6Al4V particles especially, what wherein Fig. 5 was corresponding is 325 purpose titanium valves, and Fig. 6 corresponding be 250 purpose titanium valves.
Typical TiB
2Particle size is at the 5-75 micron, can obtain by the self propagating high temperature synthetic method, such as following reaction equation: Ti+2B → TiB
2+ Q (324KJ/mol).TiB
2The physical property of powder is as shown in the table; Fig. 7 shows before the difference sintering X-ray diffraction analysis of sample behind sample (namely green compact) and the sintering, shows how by TiB
2Obtain TiB with the Ti sintering reaction.Comprise titanium, TiH for the precursor that obtains result shown in Figure 7
2, Al-V 40 alloys and TiB
2Powder.TiB
2Average particle size particle size be 9.2 microns, be about 99% TiB
2
| Physical property | Value |
| Density, g/cm 3 | 4.25 |
| Fusing point, ℃ | 2850-2980 |
| Thermal expansion, m/m.k | 8.1×10 -6 |
| Pyroconductivity, W/m ℃ | 60-120 (at 25 ℃) 55-125 (at 2300 ℃) |
| Bending strength, MPa | 350-500 |
| Knoop hardness, GPa | 30-34 |
| Resistivity, p 0.cm | 14.4 |
| Elastic modelling quantity, GPa | 550 |
TiB
2Has close density with Ti6Al4V.This is conducive to they are mixed.Yet, have been found that TiB
2Greatly reduce the sintered density of titanium MMC.Work as TiB
2Content surpass 7wt%, the density after the forging also begins greatly to reduce.A kind of possible explanation may be that the relative density of boron (being approximately 2.34 g/ccs) and titanium (about 4.5 g/ccs) differs greatly.
The typical particle size of Al-V alloying material is the 5-75 micron.When being Powdered, these alloying materials also obtain by commercially available self propagating high temperature synthetic method, and the simple form of described method is according to following reaction: Al+V
2O
5→ AlV
X+ Al
2O
3+ Q.
For preparation Ti6Al4V MMC, prepared three kinds of different Al-V alloy powders, the ratio of Al and V is respectively 60/40,50/50 and 40/60.Chemical composition mainly is O, C, Fe and the Si that Al and V also have trace.Shown in Fig. 8 and Fig. 9 are special is exactly ESEM (SEM) pattern and the particle size distribution of 60/40Al-V powder.
Referring to Figure 10-Figure 13, that shown is the TiB of various sintering steps and different weight percentage
2The result who obtains.Referring to Figure 10 A-10D, shown is to have different Ti B especially
2Microstructure behind the sintering of the Ti6Al4V MMC of level.Sintering temperature is 1300 ℃ and TiB
2Content be respectively 7%, 10%, 15% and 20%.Referring to Figure 11 A-11H, shown is because different Ti B especially
2The microstructure of concentration and processing conditions.Especially, TiB
2Concentration is changed to 5% (Figure 11 C and 11D) from 3% (Figure 11 A and 11B), and 7% (Figure 11 E-11H), and comprise the impact (Figure 11 B, 11D, 11F and 11H) of other treatment step, comprise forging (at 950 ℃) and annealing (at 930 ℃).Referring to Figure 10, shown is to have different Ti B especially
2Microstructure behind the sintering of the MMC of content.Especially referring to Figure 11, be depicted as and have different Ti B
2The MMC of content is microstructure after the annealing after the forging.Can find out that from the comparison of Figure 10-Figure 11 10%TiB MMC has densification and microstructure (dense and cleanmicrostructure) clearly.Shown in Figure 12 A and 12B, the variable effect of forging temperature the microstructure of Ti6Al4V/TiBMMC.Same, provided TiB in various degree among Figure 13 A and the 13B
2The impact of the microstructure of boron source material after on sintering, that forge and annealing.Particularly, they have shown that forging temperature and annealing temperature are on the impact of hole.For example, can be seen from the foregoing, concerning tearing tendency and porosity level, carry out forging ratio at 1150 ℃ and under 950 ℃, forge far better.Especially with reference to Figure 13, the microstructure that shown is after the annealing.
Referring to Fig. 1, operation numerous examples of 500 are feasible behind the sintering at this, for example machining (comprising deburring), surface-pressure shot-peening or press etc. again.Another example comprises the step of anti-oxidation.In this case, can at room temperature apply coating at final parts, this coating comprises various oxides, for example Al
2O
3, SiO
2And B
2O
3And organic binder bond.In one form, be heated to a little the temperature that raises at parts, for example about 70 ℃ the time, can apply coating with brush to some coatings, the described parts of subsequent drying.
Than the Ti6Al4V alloy of not strengthening, described Ti6Al4V MMC has higher intensity and elastic modelling quantity.Like this, TiB
2Excellent strengthening material for the Ti6Al4V titanium alloy.For example, the elastic modelling quantity of the Ti6Al4V after the reinforcement is higher than 140GPa, on average is 155GPa, and the mean value of the Ti6Al4V that does not strengthen is 100GPa.Ultimate tensile strength is higher than 1350MPa (on average being 1450MPa), is significantly higher than the mean value 1140MPa of the Ti6Al4V that does not strengthen; 0.2% yield strength is higher than 1250MPa (on average being 1300MPa), compares, and the mean value of the Ti6Al4V that does not strengthen is 980MPa.Rockwell hardness is higher than 43.Be connecting rod (connecting rod) for automobile engine according to the structural detail example of one aspect of the invention preparation, but those skilled in the art should understand that and also can prepare many other elements.
Although purpose has in order to demonstrate the invention provided some representative embodiment and details, obviously can in the situation that does not depart from the category of the present invention that appended claim limits, carry out various changes for the ordinary skill in the art.
Claims (21)
1. preparation comprises the method for the composite component of titanium alloy matrix and titanium diboride reinforcement body, and the method comprises:
Use amended mechanical disintegration to process, the multiple precursor material that will comprise basically pure titanium, titantium hydride, alloying material and boron source material mixes;
The described mixture of compacting; With
The mixture of the described compacting of sintering; so that in described sintering process; described boron source material and described basically pure titanium react to prepare titanium boride and described titantium hydride become activation with described mixture in any oxygen of existing react; wherein said amended mechanical disintegration is processed and comprised: (1) is in the indoor argon shield of finding time then to provide to powder; (2) the described chamber of cooling is not so that the temperature of powder is higher than 35 ℃; (3) providing ball and dusty material point other weight ratio is 1: 12; (4) providing bulb diameter is respectively 20mm; the ratio of the ball amount of 10mm and 8mm is 3: 3: 1; (5) described powder is ground; time is 4-12 hour, and speed is 3600RPM.
2. the method for claim 1, wherein said precursor material is powder type.
3. method as claimed in claim 2, wherein said mixing further comprise at least a portion of removing any material based on oxygen that forms on the described basically surface of pure titanium.
4. method as claimed in claim 3, wherein said removing comprises being placed on described multiple precursor material in the inert environments and they being rotated and mixes until described mixed material had till the time of predetermined characteristic.
5. method as claimed in claim 4, wherein said rotation mixes and comprises that rotating speed is 3600 rpms, continues 4 hours.
6. the method for claim 1, wherein said matrix is selected from β titanium, α-2 titanium, γ titanium and its combination.
7. method as claimed in claim 6, wherein said mixture comprises the titantium hydride of 3-7wt%.
8. the method for claim 1, the heating in the wherein said sintering process is carried out with 5 ℃/minute speed at the most.
9. the method for claim 1, wherein said alloying material comprises aluminium and vanadium.
10. the method for claim 1, wherein said boron source material comprises titanium diboride.
11. the method for claim 1, wherein said element comprises automotive components.
12. method as claimed in claim 11, wherein said automotive components are selected from valve, retention tab, valve spring, connecting rod, securing member, spiral bearing spring and gas extraction system.
13. method as claimed in claim 11, wherein said automotive components is bolt.
14. the method for claim 1 further comprises at least one sintering rear surface modification operation.
15. method as claimed in claim 14, wherein said at least one sintering rear surface modification operation is selected from deburrs, reduces hole and lubricant impregnation.
16. be used for the preparation method of the titanium base material of powder metallurgy processing, described method comprises:
Multiple precursor powder materials is positioned in the titanium base mixer, and described precursor powder materials comprises basically pure titanium, titantium hydride, alloying material and boron source material;
Basically substitute ambiance in the described mixer with inert fluid;
Use amended mechanical disintegration to process, with the minimum scheduled time of the predetermined speed rotating spoon of minimum, until obtain to have one of following at least mixture: (1) powder size reduces 20% at least; (2) tap density of described mixture increases by 30% at least; (3) basically from described titanium powder, removed oxidation film; With
With described mixture sintering; wherein said amended mechanical disintegration is processed and comprised: (1) is in the indoor argon shield of finding time then to provide to powder; (2) the described chamber of cooling is not so that the temperature of powder is higher than 35 ℃; (3) providing ball and dusty material point other weight ratio is 1: 12; (4) providing bulb diameter is respectively that the ratio of the ball amount of 20mm, 10mm and 8mm is 3: 3: 1; (5) described powder is ground; time is 4-12 hour, and speed is 3600RPM.
17. method as claimed in claim 16, wherein said agitator comprise through a plurality of balls based on titanium of structure to rotate in described mixer.
18. method as claimed in claim 16, the predetermined speed of wherein said minimum are 3600 rev/mins, the described minimum scheduled time is 4 hours.
19. the method for the titanium-based metal matrix composite element that the preparation titanium boride is strengthened, described method comprises:
Use amended mechanical disintegration to process, at least basically pure titanium powder is mixed with alloying material and boron source material, so that the basically major part of any oxide that forms in described basically pure titanium powder is therefrom removed;
Described mixture compacted is become the shape of described element; With
The mixture of the described compacting of sintering; so that in described sintering process; described boron source material and described basically pure titanium react; with the hardening constituent that obtains being consisted of by described titanium boride; wherein said amended mechanical disintegration is processed and comprised: (1) is in the indoor argon shield of finding time then to provide to powder; (2) the described chamber of cooling is not so that the temperature of powder is higher than 35 ℃; (3) providing ball and dusty material point other weight ratio is 1: 12; (4) providing bulb diameter is respectively 20mm; the ratio of the ball amount of 10mm and 8mm is 3: 3: 1; (5) described powder is ground; time is 4-12 hour, and speed is 3600RPM.
20. method as claimed in claim 19 also is included in before the described mixing, adds titantium hydride in described basically pure titanium powder, alloying material and boron source material.
21. method as claimed in claim 19, further comprise in case described sintering finish, to described element forge and anneal at least a.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/955,673 US20100040500A1 (en) | 2007-12-13 | 2007-12-13 | METHOD OF MAKING TITANIUM ALLOY BASED AND TiB REINFORCED COMPOSITE PARTS BY POWDER METALLURGY PROCESS |
| US11/955,673 | 2007-12-13 | ||
| US11/955673 | 2007-12-13 |
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| Publication Number | Publication Date |
|---|---|
| CN101530918A CN101530918A (en) | 2009-09-16 |
| CN101530918B true CN101530918B (en) | 2013-03-27 |
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| CN2008102338553A Active CN101530918B (en) | 2007-12-13 | 2008-12-12 | Method for preparing composite component with strengthened TiB based on titanium alloy via powder metallurgy method |
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| Country | Link |
|---|---|
| US (1) | US20100040500A1 (en) |
| CN (1) | CN101530918B (en) |
| DE (1) | DE102008061024B4 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103506625A (en) * | 2013-10-15 | 2014-01-15 | 攀枝花学院 | Manufacturing method for abrasion-resistant titanium basic bearing bush |
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| US20130084190A1 (en) * | 2011-09-30 | 2013-04-04 | General Electric Company | Titanium aluminide articles with improved surface finish and methods for their manufacture |
| CN102363214B (en) * | 2011-11-14 | 2013-11-13 | 宁波江丰电子材料有限公司 | Method for mixing tungsten powder and titanium powder |
| CN102672187B (en) * | 2012-05-08 | 2013-08-14 | 哈尔滨工业大学 | Preparation methods of layered titanium matrix composite material |
| US9447484B2 (en) | 2013-10-02 | 2016-09-20 | Honeywell International Inc. | Methods for forming oxide dispersion-strengthened alloys |
| US9399257B2 (en) | 2014-04-16 | 2016-07-26 | Honeywell International Inc. | Methods for forming ceramic reinforced titanium alloys |
| US20170067137A1 (en) * | 2015-09-07 | 2017-03-09 | Seiko Epson Corporation | Titanium sintered body and ornament |
| CN107584129B (en) * | 2017-08-03 | 2019-07-23 | 西安理工大学 | A kind of copper-titantium hydride-boron composite powder method after reduction ball milling |
| EP3663019A1 (en) * | 2018-12-07 | 2020-06-10 | The Swatch Group Research and Development Ltd | Method of manufacturing precious metal alloys and precious metal alloys thus obtained |
| RU2711699C1 (en) * | 2019-08-21 | 2020-01-21 | Федеральное государственное автономное образовательное учреждение высшего образования "Белгородский государственный национальный исследовательский университет" (НИУ "БелГУ") | METHOD OF PRODUCING COMPOSITE MATERIAL Ti/TiB |
| CN111644615B (en) * | 2020-06-16 | 2022-03-01 | 西安稀有金属材料研究院有限公司 | Preparation method for realizing high strength and toughness of TC4 titanium alloy by co-strengthening method |
| CN113102752A (en) * | 2021-03-11 | 2021-07-13 | 华南理工大学 | High-performance powder metallurgy titanium metal and preparation method thereof |
| CN113957288B (en) * | 2021-09-18 | 2022-05-24 | 华南理工大学 | Low-cost high-performance TiBw/Ti composite material and preparation method and application thereof |
| CN114182127B (en) * | 2021-12-09 | 2022-08-12 | 吉林大学 | High-performance in-situ reinforced titanium-based composite material and preparation process thereof |
| CN115595653B (en) * | 2022-10-27 | 2024-02-02 | 哈尔滨工业大学 | Titanium boride whisker and preparation method thereof |
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| US6010661A (en) * | 1999-03-11 | 2000-01-04 | Japan As Represented By Director General Of Agency Of Industrial Science And Technology | Method for producing hydrogen-containing sponge titanium, a hydrogen containing titanium-aluminum-based alloy powder and its method of production, and a titanium-aluminum-based alloy sinter and its method of production |
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| CN101530918A (en) | 2009-09-16 |
| DE102008061024B4 (en) | 2012-03-08 |
| DE102008061024A1 (en) | 2009-07-30 |
| US20100040500A1 (en) | 2010-02-18 |
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