阅读说明：本技术 一种注射成形镍基合金粉、注射成形方法及镍基合金制品 (A kind of injection moulding nickel-base alloy powder, ejection forming method and nickel-based alloy articles ) 是由 何浩 李益民 黄雨晴 余勇 胡幼华 于 2019-09-29 设计创作，主要内容包括：本法公开了一种注射成形镍基合金粉,包括按质量百分比的如下组分：11.5-13.5％Cr、5.50-6.40％Al、3.80-4.80％Mo、2.0-3.0％Co、1.80-2.50％Nb、0-1.0％Fe、0.50-1.00％Ti、0-0.5％Si、0.06-0.15％Zr、0.08-0.16％C、0-0.5％Mn、0.008-0.02％B,余量为Ni。本发明还公开了一种采用上述镍基合金粉的注射成形方法及镍基合金制品。本发明所得产品的相对密度大于99.2％,硬度在40HRC以上；抗拉强度在1150-1400Mpa之间。(This law discloses a kind of injection moulding nickel-base alloy powder, including following component by mass percentage: 11.5-13.5%Cr, 5.50-6.40%Al, 3.80-4.80%Mo, 2.0-3.0%Co, 1.80-2.50%Nb, 0-1.0%Fe, 0.50-1.00%Ti, 0-0.5%Si, 0.06-0.15%Zr, 0.08-0.16%C, 0-0.5%Mn, 0.008-0.02%B, surplus Ni.The invention also discloses a kind of ejection forming methods and nickel-based alloy articles using above-mentioned nickel-base alloy powder.The relative density of products obtained therefrom of the present invention is greater than 99.2%, and hardness is in 40HRC or more；Tensile strength is between 1150-1400Mpa.)

1. a kind of injection moulding nickel-base alloy powder, it is characterised in that: including following component by mass percentage: 11.5- 13.5%Cr, 5.50-6.40%Al, 3.80-4.80%Mo, 2.0-3.0%Co, 1.80-2.50%Nb, 0-1.0%Fe, 0.50-1.00%Ti, 0-0.5%Si, 0.06-0.15%Zr, 0.08-0.16%C, 0-0.5%Mn, 0.008-0.02%B, it is remaining Amount is Ni.

2. injection moulding nickel-base alloy powder according to claim 1, it is characterised in that: said components are pressed by following raw material Mass ratio is prepared to obtain:

NbC powder: 0.5-1%

Co powder: 2-3%

Surplus is 713C high temperature master alloy powder.

3. injection moulding nickel-base alloy powder according to claim 2, it is characterised in that: the middle position of 713C high temperature master alloy powder Partial size is 5-15 microns, and the median of NbC powder is 15-20 microns, and the median of Co powder is 5-15 microns.

4. the ejection forming method of injection moulding nickel-base alloy powder described in a kind of Claims 2 or 3, which is characterized in that including such as Lower step:

It takes 713C high temperature master alloy powder, NbC powder and cobalt powder to adjust the quality proportioning of each raw material, prepares nickel-base alloy powder；

Above-mentioned nickel-base alloy powder and binder are subjected to mixing, after obtaining injection moulding feeding, successively passes through injection moulding, take off Nickel-based alloy articles are obtained after rouge, pre-sintering, high temperature sintering, cooling；Wherein,

The technique of high temperature sintering are as follows: base will be pre-sintered in the sealed furnace that nitrogen pressure is 0.55-0.6Mpa, with 5-8 DEG C/min Heating speed be warming up to brine hardening after 1290-1300 DEG C of heat preservation 3-3.5 hours, obtain nickel-based alloy articles.

5. ejection forming method according to claim 4, it is characterised in that: pre-sintering process are as follows: by what is obtained after degreasing Degreased blank is warming up to 200-250 DEG C in a nitrogen atmosphere, with the acceleration of 3-4 DEG C/min, keeps the temperature 150min, then with 1-1.5 DEG C/ The heating speed of min is warming up to 400-420 DEG C, keeps the temperature 180-200min, is warming up to 580- with the heating speed of 2-2.5 DEG C/min 600 DEG C, 50-60min is kept the temperature, then 840-850 DEG C is warming up to the heating speed of 3-5 DEG C/min and is pre-sintered, kept the temperature After 100-120min, furnace cooling obtains being pre-sintered base.

6. ejection forming method according to claim 4, it is characterised in that: injection molding process are as follows: feeding to be heated to It 150-160 DEG C, is injected at 90-95MPa into mold, is demoulded after cooling, obtain injection base.

7. ejection forming method according to claim 4, it is characterised in that: injection molding process are as follows: binder is used and accounted for The wax-based binder of nickel-base alloy powder quality 30-40%, comprising solid paraffin, polypropylene, olive oil, castor oil, brazil wax and Palm wax, each component mass percent are as follows:

Solid paraffin 25-40%, polypropylene 15-30%, olive oil 5-10%, castor oil 10-25%, brazil wax and palm wax 10-20%.

8. ejection forming method according to claim 7, it is characterised in that: degreasing process are as follows: obtain injection moulding It injects base and first impregnates 5-6h progress solvent degreasing in heptane, solvent degreasing temperature is 30-40 DEG C, then carries out thermal debinding, In 850-900 DEG C of degreasing 1-1.5 hours is heated under nitrogen protection.

9. ejection forming method according to claim 4, it is characterised in that: it is kneaded in three-dimensional rotation mixing machine uniformly, Mixing time at least 0.5 hour, 150-155 DEG C of temperature；Kneading machine revolving speed is 85-90r/min, makes nickel-base alloy powder and binder It is sufficiently mixed uniformly, obtains feeding.

10. the nickel-based alloy articles that any one of the claim 4-9 ejection forming method is prepared.

Technical field

The present invention relates to powder metallurgical technology more particularly to a kind of injection moulding nickel-base alloy powders, injection moulding side Method and nickel-based alloy articles.

Background technique

Turbocharger is a kind of air compressor, increases air inflow by compressed air.It is arranged using engine Exhaust gas inertia impulsive force out pushes the indoor turbine of turbine, and turbine drives coaxial impeller again, impeller force feed is by air-filtering The air that device pipeline is sent is allowed to pressurization and enters cylinder.When engine speed increase, the exhaust gas velocity of discharge and secondary speed Synchronous to increase, impeller just compresses more air and enters cylinder, and the pressure and density of air increase more combustions that can burn Material increase accordingly fuel quantity and adjusts the revolving speed of engine, so that it may increase the output power of engine.Due to turbocharging The discharge that device can improve HP, hp/litre, improve engine, to the development important role of automobile industry, as turbine The shift fork of one of booster base components should cause our enough attention.

Because the working environment of shift fork is special, good high temperature resistant and wear-resisting property are needed to have, common shifting fork is common Material mainly has 310 stainless steels etc., but the high temperature resistance of 310 stainless steels is insufficient.Common forming method has very much, such as casts It makes, forge and welding forming etc..Though casting technique is relatively simple, expensive, and there are various defects, such as stomata, Shrinkage porosite, shrinkage cavity, crackle etc..For current shift fork, main failure mode be due to for fatigue fracture, it is further to its Analysis, it is found that the surface texture of breaking part is not up to standard, surface hardness is insufficient and be the main reason for causing fatigue strength insufficient.

713C nickel base superalloy steel has high rigidity, can still keep its chemical stabilization at high temperature (900 DEG C) Property.High temperature alloy generallys use Investment casting technology production and processing.Though it is relatively simple to cast 713C high-temperature alloy steel technique, Its is expensive, and formed precision is not high, ingredient and nonuniform organization phenomenon easily occurs.These phenomenons drastically influence alloy Use reliability and casting yield rate so that the feasibility of casting 713C high-temperature alloy steel production shift fork is insufficient.If I Be desirable for 713C high-temperature alloy steel and prepare shift fork, must just solve the problem in preparation 713C high-temperature alloy steel.

Metal injection moulding (Metal Injection Molding, abbreviation MIM) can be produced with lower cost to be had There is the high-performance profiled metal part of complicated shape, reduces material loss.MIM technology is due to using a large amount of binder conduct Enhance the means of flowing, it is possible to which the metal parts of the various complicated shapes of the random molding as in plastics industry, this is to pass Uniting powder metallurgy molding technique can not be attainable.Moreover, because injection moulding is a kind of near-net-shape technique, substantially Following process is not needed, so that part manufacturing cost substantially reduces, the part for being previously required to tens machining processes can be with one Secondary molding obtains.In addition, flow of powder fills the uniformity of die cavity when due to injection moulding, so that density is equal everywhere for MIM product It is even, the inevitable Density Distribution inhomogeneities of conventional casting techniques before avoiding.

But current MIM high temperature alloy is mainly sintering atmosphere and impurity element to high temperature alloy using limited reason Performance has significant impact, and the unexcellent meeting of sintering process is so that it lacks corresponding mechanical property.Just so far, Song Renjin Although et al. studied to preparing the sintering process of IN713C alloy using MIM method, having obtained relative density is 98.0% sintering tensile sample, room temperature tensile intensity are l046MPa, hardness 37.3HRC.But prepared by the above method High temperature alloy be not able to satisfy the performance requirement of turbocharger product, the especially requirement of hardness and long term high temperature performance.

Summary of the invention

It is an object of the invention to overcome the deficiency of the prior art, and it is easy to provide a kind of reasonable mixture ratio of components, sintering process Control, injection moulding nickel-base alloy powder, ejection forming method and the nickel-based alloy articles that sintered product density is big, intensity is high.

A kind of injection moulding nickel-base alloy powder, including following component by mass percentage: 11.5-13.5%Cr, 5.50-6.40%Al, 3.80-4.80%Mo, 2.0-3.0%Co, 1.80-2.50%Nb, 0-1.0%Fe, 0.50-1.00% Ti, 0-0.5%Si, 0.06-0.15%Zr, 0.08-0.16%C, 0-0.5%Mn, 0.008-0.02%B, surplus Ni.

Further, said components are prepared in mass ratio by following raw material and are obtained:

NbC powder: 0.5-1%

Co powder: 2-3%

Surplus is 713C high temperature master alloy powder.

Further, the median of 713C high temperature master alloy powder is 5-15 microns, and the median of NbC powder is 15-20 Micron, the median of Co powder are 5-15 microns.

A kind of ejection forming method of above-mentioned injection moulding nickel-base alloy powder, includes the following steps:

It takes 713C high temperature master alloy powder, NbC powder and cobalt powder to adjust the quality proportioning of each raw material, prepares nickel-base alloy powder；

Above-mentioned nickel-base alloy powder and binder are subjected to mixing, after obtaining injection moulding feeding, successively by being injected into Nickel-based alloy articles are obtained after shape, degreasing, pre-sintering, high temperature sintering, cooling；Wherein,

The technique of high temperature sintering are as follows: base will be pre-sintered in the sealed furnace that nitrogen pressure is 0.55-0.6Mpa, with 5-8 DEG C/heating speed of min is warming up to brine hardening after 1290-1300 DEG C of heat preservation 3-3.5 hours, obtain nickel-based alloy articles.

Further, the technique of pre-sintering is formulated according to its DSC curve, by the degreased blank obtained after degreasing in nitrogen Under atmosphere, it is warming up to 200-250 DEG C with the acceleration of 3-4 DEG C/min, keeps the temperature 150min, then with the heating speed of 1-1.5 DEG C/min Degree is warming up to 400-420 DEG C, keeps the temperature 180-200min, is warming up to 580-600 DEG C with the heating speed of 2-2.5 DEG C/min, protects Then warm 50-60min is warming up to 840-850 DEG C with the heating speed of 3-5 DEG C/min and is pre-sintered, keep the temperature 100-120min Afterwards, furnace cooling obtains being pre-sintered base.

Further, feeding is heated to 150-160 DEG C, is injected at 90-95MPa into mold, is demoulded after cooling, Obtain injection base.

Further, binder is using accounting for the wax-based binder of nickel-base alloy powder quality 30-40%, comprising solid paraffin, Polypropylene, olive oil, castor oil, brazil wax and palm wax, each component mass percent are as follows:

Solid paraffin 25-40%, polypropylene 15-30%, olive oil 5-10%, castor oil 10-25%, brazil wax and palm fibre Palmitic acid wax 10-20%.

Further, the injection base that injection moulding obtains first is impregnated into heptane 5-6h and carries out solvent degreasing, solvent is de- Rouge temperature is 30-40 DEG C, then carries out thermal debinding, is heated to 850-900 DEG C of degreasing 1-1.5 hours under nitrogen protection.

Thermal debinding concrete technology is that 2 DEG C/min is warming up to 200 DEG C, keeps the temperature 1h；4 DEG C/min is warming up to 425 DEG C, keeps the temperature 1h； 3 DEG C/min is warming up to 600 DEG C, keeps the temperature 20min；5 DEG C/min is warming up to 880 DEG C, keeps the temperature 1h, rear furnace cooling

Further, it is kneaded in three-dimensional rotation mixing machine uniformly, mixing time at least 0.5 hour, temperature 150-155 ℃；Kneading machine revolving speed is 85-90r/min, is sufficiently mixed nickel-base alloy powder and binder uniformly, obtains feeding.

The present invention also protects a kind of nickel-based alloy articles that above-mentioned ejection forming method is prepared.

Principle and advantage

The present invention combines specific preparation process by adjusting the ingredient of 713C alloy, and performance has been prepared and has been much better than The nickel-based alloy articles of 713C alloy.The relative density of products obtained therefrom of the present invention is greater than 99.2%, and hardness is in 42HRC or more；It is anti- Tensile strength is between 1150-1300Mpa.

Its specific mechanism is briefly described as below:

γ ' phase has can be improved the study found that adding Co element powders on the basis of 713C high temperature alloy powder in inventor The solution temperature of (Ni3Al intermetallic compound), so as to improve the creep rupture strength of alloy, the product of acquisition is opposite Density is greater than 99.2%, and hardness is in 40HRC or more；Tensile strength is between 1150-1400Mpa.At 800 DEG C, 440Mpa is constant Load effect is lower to carry out stress rupture test, the results showed that the sample fracture time, longest was up to 1200h.

Inventor is further study show that the additive amount of Co element powders compares convenient, excessively high Co in 2.0-3.0wt% Additive amount can make that more grain boundary carbide and a large amount of transgranular needle-shaped μ phases are precipitated in alloy, drop low-alloyed toughness, make to close There is notch sensitivity, comprehensive mechanical property decline in gold, and too low Co additive amount has no significant effect γ ' phase.

In the application, by adding the NbC powder of specified particle diameter in original powder, the NbC powder of addition is in sintering, NbC Powder will not all melt in sintering, and the evengranular dispersion of the tiny NbC not melted in the liquid phase, is on the one hand used as and strengthens Growing up for matrix grain is mutually hindered, plays the role of refined crystalline strengthening, on the other hand can also play stable liquid phase, improve product The purpose of dimensional accuracy, dimensional accuracy can control in ± 0.02mm.

Inventor also the study found that NbC powder addition amount be not it is The more the better, be limited to 0.5-1wt% range effect Fruit is best, and hardening constituent is excessively high to be will lead to its interaction and form reticular structure, reduces toughness of material and comprehensive mechanical property, mistake Inefficient fruit is unobvious.In addition, NbC is added directly in the form of NbC powder particle, and in such a way that Nb powder and C powder individually add Compare, not only can better control hardening constituent content, nor easy oxygenation.

It is employed nitrogen as in the application and carries out pressure sintering for protective atmosphere, nitrogen serves not only as protective atmosphere and avoids burning Sample oxidation when knot, nitrogen are also used as solution strengthening element, form NbN hardening constituent with the Nb element in matrix, improve alloy Performance, pressurization can be such that nitrogen is preferably dissolved into enhancing invigoration effect in matrix.The pressure of nitrogen is stablized in 0.55- 0.6Mpa mutually forms reticular structure, so that material than conveniently, it is excessive that hypertonia will lead to the second phase content in crystal boundary Material toughness sharply declines；And then strengthening effect is unobvious for hypotony.

The type of cooling uses salt hardening in the application, and salt hardening limits the diffusion velocity of element, it is strong to increase Co element solid solution The effect of change, and due to using fast cooling technology, γ ' phase size becomes more tiny and Dispersed precipitate, therefore the drawing of product It stretches and the more former similar product of yield strength increases, obtain the product of function admirable.

In conclusion the present invention has been attempted for the first time by suitable NbC and C_oIt is introduced into 713C, and by this kind of material application In products such as turbocharger products, is acted synergistically by each component and preparation process, obtained the product of superior performance. Sintering process of the present invention is easily-controllable, and sintered product density is big, good mechanical performance high temperature resistance is good, it can be achieved that the big rule of industrialization Mould production, especially suitable for making product.

Specific embodiment

Technical solution of the present invention is clearly and completely described below in conjunction with the embodiment of the present invention, it is clear that institute The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the implementation in the present invention Example, it is obtained by those of ordinary skill in the art without making creative efforts every other