CN101530918A - 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 PDF

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CN101530918A
CN101530918A CN200810233855A CN200810233855A CN101530918A CN 101530918 A CN101530918 A CN 101530918A CN 200810233855 A CN200810233855 A CN 200810233855A CN 200810233855 A CN200810233855 A CN 200810233855A CN 101530918 A CN101530918 A CN 101530918A
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titanium
powder
sintering
mixture
boron source
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CN101530918B (en
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Y·王
R·D·里基
L·周
Y·吴
Q·段
T·杨
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Northwest Institute for Non Ferrous Metal Research
GM Global Technology Operations LLC
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Northwest Institute for Non Ferrous Metal Research
GM Global Technology Operations LLC
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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)
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Ceramic Products (AREA)

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

Prepare based on titanium alloy and the method composite component that TiB strengthens by powder metallurgic method
Technical field
[0001] the present invention relates generally to the metal alloy of ceramic reinforced, especially titanium alloy of strengthening of titanium boride and preparation method thereof.
Background technology
[0002] 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 by refractory material and can't forms the material preparation element of real alloy in other technology, and because its repeatable and non-waste characteristics are very suitable for the large-scale manufacturing (for example manufacturing of automotive components).
[0003] in typical powder metallurgical technique, metal dust is mixed with alloying material, lubricant, binding agent or analog, adopt suitable process unit to be pressed into nearly clean shape (near-netshape) then, in controlled atmosphere, carry out sintering subsequently 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.
[0004] titanium has excellent corrosion resistance, high relatively hear 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 on the structure platform efficiently.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 is to remedy the odds for effectiveness that these relatively low stiffness values have reduced the Ni-based relatively and iron-based alternative of titanium.
[0005] a kind of method of the rigidity of raising titanium-base alloy is exactly that they are carried out combination with the ceramic material with relative high-modulus.This is the part of a relative newer class material with the bulk metal (a bulk metal) and the combination of continuous or discrete reinforcement body, this material is referred to as and is metal-matrix composite (MMC), and wherein structural property can come to customize at concrete engineering application by suitable selection component material.Common MMC's, especially titanium base MMC, the variant of discontinuous structure can bear powder metallurgic method, and this is can improve whole performance of composites because compound forms property ceramic material (compound-forming ceramic material) with the react body that strengthened of titanium basis in the process of sintering.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.
[0006] in the PM technology that is used for preparing 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 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, hear 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, and for example reacts acquisition by titanium diboride (TiB2) and Ti powder in sintering process.
[0007] produces 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, Can Yu 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 the 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.
[0008] exists demand to having excellent toughness, corrosion resistance, high rigidity, wearability and stable on heating high strength titanium sill.Further also exist with the cost effective and efficient manner and produce these materials to satisfy the demand of high yield part making method.
Summary of the invention
[0009] 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 this method comprises multiple precursor (that is, composition) material mixed and obtains mixture, then described mixture is carried out the element of the mixture of compacting and the described compacting of sintering with the preparation form of composite.These precursor materials comprise pure basically 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), TiH simultaneously 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 tangible difference is arranged now for the sintering of middle use should be appreciated that with other high-temperature operation that relates to fusing, the difference be sintering relate to material be heated to be lower than its fusing point slightly temperature (typically near fusing point, but do not limit, fusing point 80%), the dispersed particles 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 big pressure on 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.
[0010] choose wantonly, precursor material is pulverous.In this case, can use pure basically titanium powder.In the present context, term " basic " is meant the arrangement of key element or feature, accurate uniformity or the behavior of demonstrating can embody the accurate state that is weaker than in practice 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 under the situation that the basic function of the theme that does not cause being paid close attention to changes.For example, be easy to obtain purity and be 99.9% commercially available titanium, can be considered to pure substantially titanium like this.In addition, the pure substantially metal oxidation of titanium its pure substantially essence that do not detract for example.Therefore, be exposed to the pure substantially titanium that on the metal surface, forms oxidation film, layer or analog after the ambiance and still be considered to pure substantially titanium in the present context.
[0011] 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, Ti6-4), and contain the tin of the aluminium of the 6wt% that has an appointment, about 2wt%, approximately 4wt% zirconium and approximately the molybdenum of 2wt% titanium (that is, Ti6-2-4-2).The inventor finds that Ti6-4 is particularly suitable for preparing the automotive components that composite is strengthened, and this is because the Ti6-4 alloy relatively enriches, has better chemical compatibility and processing easily.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.
[0012] in specific forms, 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 the environment of emptying or at inert environments.
[0013] 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) is rotated precursor material mixing then till described mixed material has the time of predetermined characteristic, the evidence of alloying and the tap density (tap density) that improved before for example maximum powder size of described predetermined characteristic, surface flatness, the sintering, latter's correspondence rock or compacting to promote the bulk density (bulk density) of post precipitation composite material.Rotation mixes can more specifically comprise the rotary speed that adopts mixer, and mixing drum or other hydrid component carry out the high speed rotation 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.
[0014] the present invention is fit to be used for producing 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 is meant 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 the 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).
[00015] 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 pressurization 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 to improve the function of final element.
[0016] another aspect of the present invention is to disclose to prepare the method that is used for the powder metallurgy material processed.This method comprises a large amount of precursor powder materials, comprise that pure substantially 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, with agitator with the rotation of predefined minimum speed and predefined shortest time until mixture show that powder size reduces 20% at least, the tap density of mixture improves 30% or removed the oxide-film of titanium powder basically at least.After mixing is finished, mixture is carried out sintering.
[0017] choose wantonly, the structure of agitator (agitator) can be various forms of.In one form, agitator is made up 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, makes to 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.
[0018] according to a further aspect in the invention, the method for preparing titanium boride reinforcement titanium-based metal matrix composite elements is disclosed.This method comprises mixes pure at least substantially 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 the required mixing of only the composition material being carried out basically evenly distributing, because remove most of or whole any oxide skin(coating) that may form on 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 made up of titanium boride.
[0019] 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
[0020] can understand identical structure among the figure better to as detailed below of the present invention by accompanying drawing
Represent with identical Reference numeral, wherein:
The process chart for preparing titanium base MMC element according to aspects of the present invention 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 mixes institute at the composition material that is used for preparing titanium base MMC and uses the sketch of equipping;
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 the exemplary dimensions that is used 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 Size Distribution of Al-V alloying powder among Fig. 8;
Shown in Figure 10 A-10D is the microstructure of the TiMMC behind the sintering according to aspects of the present invention;
Shown in Figure 11 A-11F is the microstructure that adopts the TiMMC behind the sintering of different process according to aspects of the present invention;
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 to the influence of TiMMC microstructure.
The specific embodiment
[0021], schematically shows step behind mixing, compacting and sintering step and the optional sintering at first referring to Fig. 1.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 pure substantially 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.The generally suitable purpose that will reach of these conventional methods, that is, precursor material is evenly distributed relatively in these mixtures of material.
[0022] next with reference to Fig. 3, the present inventor finds can be used to improve to the modification that these conventional hybrid modes are carried out the performance of the precursor of mixing, especially because it relates to the raising of alloying before the smoothness, sintering a little on reduction, the surface of powder size and mixture tap density.(latter can analogize to and only realize required the comparing of above-mentioned even mixing with the combination that mixes severity by improving incorporation time significantly, 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 under 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 crackle extension mechanism (crack propagation mechanic) is minimized.
[0023] inventor finds that also amended mechanical crushing processing (MPT) helps improving tap density and final densities.An example of the inventor adopted the simplification series processing conditions relevant with MPT comprises: (1) finds time to provide then 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 make the size of (1) powder reduce 20-60%, and (2) cause more smooth powder surface, and (3) promote pre-alloyed, and (4) tap density improves 30-40%, and the raising of sintered density is corresponding with the MPT processing time.
[0024] be the operation of the mixing apparatus that uses in the present invention shown in the figure.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 agitator 190 on the rotating shaft 180 rigidly.In the present invention, the inventor finds that the mechanical crushing processing method revised and precursor material work well especially in the preparation preferred mixture.In a concrete form, mixed process (being meant the process that adopts the MPT that revises) is selected the pure substantially titanium ball or the sphere 195 of different size for use, 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 be bled 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 elevated pressure (for example reaching about 1.2 atmospheric pressure) slightly thus prevent the powder oxidation.In order to prevent to pollute, the inside of container all is to be made by pure substantially titanium, and the cooling medium of pumping by cooling medium loop 155 for example cooling water can be in order to guarantee that room temperature is not higher than 35 ℃.The weight ratio of titanium ball and technology 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.
[0025] 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 range, very little possibly can't play fully additional oxygen remove, may cause in sintering process, occurring inhomogeneous cracking too much.
[0026] 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.
Second step of [0027] adopting 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 (just before the sintering).Quiet moulding such as these methods comprise or compression molding or the like.In compacting 200, be enough to make parts to keep being essentially nearly clean shape, and wait for sintering step 300 (below discuss) simultaneously the added pressure of mixture.
[0028] the 3rd step was a 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 reduce contamination of heavy.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 to an example of the influence of hydrogen amount among the Ti-MMC as shown in Figure 2.
[0029] 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, and titanium alloy (for example Ti6Al4V) thereby react between boron source material 140 and the titanium 110.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 can forge (hot-press forging) removal by hot pressing here.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, the forging temperature used of high request is high more more for content.Typical minimizing is more wide in range than (ratio of cross-sectional area before and after forging is called thickness sometimes and reduces percentage, and is relevant with the size of processed MMC material) should to be between 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.
[0030] 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 carry out densified subsequently.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.
[0031] especially referring to Fig. 4 A-4D, the typical hybrid powder image that shown is before and after MPT, wherein Fig. 4 A correspondence is titanium valve before the MPT, Fig. 4 B correspondence be TiB before the MPT 2Powder, Fig. 4 C correspondence be alloying powder (concrete is the Al-V powder) before the MPT and Fig. 4 D correspondence be mixed-powder behind the MPT.Than not carrying out the powder that MPT handles, the performance of the powder that MPT handled 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 to the influence of sintered density:
Process time (hour) Density (gram/cubic centimetre)
0 3.06
4 3.97
8 4.05
12 4.12
[0032] compacting before the sintering and relevant tap density can be by multiple vibration, rock or relevant stirring means obtains.A kind of method that improves the preceding 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 heating these green component with 2-5 ℃/minute speed reaches desirable sintering temperature up to them, 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 long more further to improve sintered density more.
[0033] size variable of precursor material, but the typical size range that is used to prepare the titanium powder of Ti6Al4V MMC is between the 9-75 micron extensively, 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 thing 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 the Size Distribution and the pattern of two kinds of typical Ti6Al4V particles especially, wherein Fig. 5 correspondence is 325 purpose titanium valves, and Fig. 6 correspondence is 250 purpose titanium valves.
[0034] typical TiB 2Particle size is at the 5-75 micron, can obtain by the self propagating high temperature synthetic method, 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 (green compact just) and the sintering, shows how by TiB 2Obtain TiB with the Ti sintering reaction.The precursor that is used to obtain result shown in Figure 7 comprises titanium, TiH 2, Al-V40 alloy 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, p0.cm 14.4
Elastic modelling quantity, GPa 550
[0035] TiB 2Has close density with Ti6Al4V.This helps they are mixed.Yet, have been found that TiB 2Reduce the sintered density of titanium MMC greatly.Work as TiB 2Content surpass 7wt%, the density after the forging also begins to reduce greatly.A kind of possible explanation may be that the relative density of boron (being approximately 2.34 gram/cubic centimetres) and titanium (about 4.5 gram/cubic centimetres) differs greatly.
[0036] 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→AlVX+Al 2O 3+Q。
[0037] 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.
[0038] 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 comprises the influence (Figure 11 B, 11D, 11F and 11H) of other treatment step, comprises 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 influence of the microstructure of boron source material after to sintering, that forge and annealing.Particularly, they have shown the influence to hole of forging temperature and annealing temperature.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.
[0039] at this referring to Fig. 1, operation numerous examples of 500 are feasible behind the sintering, for example machining (comprising deburring), surface pressurization shot-peening or press or the like again.Another example comprises the step of anti-oxidation.In this case, can at room temperature apply coating on 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 the temperature that raises a little, in the time of for example about 70 ℃, can apply coating with brush, the described parts of subsequent drying some coatings at parts.
[0040] than the Ti6Al4V alloy of not strengthening, described Ti6Al4V MMC has higher intensity and elastic modelling quantity.Like this, TiB 2For the Ti6Al4V titanium alloy is excellent strengthening material.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 of Qiang Huaing is not 980MPa.Rockwell hardness is higher than 43.Structural detail example according to one aspect of the invention preparation is the connecting rod (connecting rod) that is used for automobile engine, still those skilled in the art should understand that also to prepare many other elements.
[0041], obviously can under the situation of the category of the present invention that does not depart from appended claim and limited, carry out various changes for the ordinary skill in the art though purpose has in order to demonstrate the invention provided some representative embodiment and details.

Claims (20)

1. preparation comprises the method for the composite component of titanium alloy matrix and titanium diboride reinforcement body, and this method comprises:
The multiple precursor material that will comprise pure basically titanium, titantium hydride, alloying material and boron source material mixes;
The described mixture of compacting; With
The mixture of the described compacting of sintering makes in described sintering process, described boron source material and described pure basically titanium react with preparation titanium boride and described titantium hydride become activation with described mixture in any oxygen of existing react.
2. the method for claim 1, wherein said precursor material is a 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 surface of described pure basically titanium.
4. method as claimed in claim 3, wherein said remove comprise be placed on described multiple precursor material in the inert environments and make they be rotated mixing until time ratio as.
5. method as claimed in claim 4, wherein said rotation mixes and comprises that rotating speed is at least about 3600 rpms, continues about at least 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 about 3-7wt%.
8. the method for claim 1, wherein said heating 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, bolt, securing member, spiral bearing spring and gas extraction system.
13. the method for claim 1 further comprises at least one sintering rear surface modification operation.
14. method as claimed in claim 13, wherein said at least one sintering rear surface modification operation is selected from deburrs, reduces hole and lubricant impregnation.
15. 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 pure basically titanium, titantium hydride, alloying material and boron source material;
With the ambiance in the alternative basically described mixer of inert fluid;
With the minimum scheduled time of the predetermined speed rotating spoon of minimum, until obtaining 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) from described titanium powder, removed oxidation film basically; With
With described mixture sintering.
16. method as claimed in claim 15, wherein said agitator comprise through a plurality of balls based on titanium of structure to rotate in described mixer.
17. method as claimed in claim 15, the predetermined speed of wherein said minimum are about 3600 rev/mins, the described minimum scheduled time is about 4 hours.
18. the method for the titanium-based metal matrix composite element that the preparation titanium boride is strengthened, described method comprises:
At least basically pure titanium powder is mixed with alloying material and boron source material, make that the most of basically of any oxide who forms therefrom removed on described pure basically titanium powder;
Described mixture compacted is become the shape of described element; With
The mixture of the described compacting of sintering makes in described sintering process, and described boron source material and described pure basically titanium react, with the hardening constituent that obtains being made of described titanium boride.
19. method as claimed in claim 18 also is included in before the described mixing, adds titantium hydride in described pure basically titanium powder, alloying material and boron source material.
20. method as claimed in claim 18, further comprise in case described sintering finish, to described element forge and anneal at least a.
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