CN106435267B - A kind of heat resistant and wear resistant damage titanium composite material and preparation method thereof - Google Patents
A kind of heat resistant and wear resistant damage titanium composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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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
- C22C1/1036—Alloys containing non-metals starting from a melt
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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
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
Abstract
The invention belongs to field of compound material more particularly to a kind of heat resistant and wear resistant damage titanium composite material and preparation method thereof.It is as follows that based composites raw material forms components by weight percentage: Al 6-7%, Sn 3-4.5%, Zr 8-10%, Mo 0.8-1%, Si 0.2-0.3%, Nb 0.8-1%, W 0.8-1%, add the reinforced phase of the mass fraction of 4.5%-6.5%, surplus Ti.The abrasion-resistant titanium basic composite material can use at high temperature, mutually enhance titanium alloy material by hybrid buildup, the titanium composite material of high abrasion degree when having reached high temperature, to widen the application range of titanium alloy.
Description
Technical field
The invention belongs to field of compound material more particularly to a kind of heat resistant and wear resistant damage titanium composite material and its preparation sides
Method.
Background technique
Titanium alloy is the alloy that other elements are added by base of titanium and form, and has very high specific strength, in aerospace
Field is used widely, frequently as the important feature material of aircraft and spacecraft.In recent years, since titanium alloy is with good
Corrosion resistance, high temperature performance, the application in the fields such as petroleum and chemical industry are gradually expanded, and are used as heat exchanger, reaction tower, steaming
Structural material under the conditions of the corrosion such as blade, valve, the pump line road of vapour turbine or distinct temperature.
For existing titanium alloy material compared with steel material, that there is also wearabilities is low, is difficult to machining and elasticity modulus
Low disadvantage hinders the weakness that the expansion of titanium alloy application range, especially hardness are low, wear-resisting property is poor.The hardness of pure titanium
About HV150-200, titanium alloy are typically not greater than HV350.Such hardness number is not able to satisfy actual production in many cases,
The requirement of application.The low wearability of titanium alloy is attributable to two principal elements: first is that inductile shearing drag and low processing are hard
Rate；Second is that the protective effect of oxide on surface is very low.The oxidation film that oxygen in titanium alloy and air is formed, the oxidation film are rubbing
It wipes and is easily peeled off in contact；Simultaneously in the case where more rugged environment and generation crevice corrosion, the corrosion resistant of titanium alloy
Corrosion will also substantially reduce.Currently, usually titanium alloy is surface-treated in order to improve the corrosion resistance of titanium alloy, such as
The techniques such as nitriding, anodic oxidation, differential arc oxidation.But if thin film only is applied in titanium alloy surface with these techniques at present, only
It is only the corrosion resistance for enhancing titanium alloy surface layer, is not the corrosion resistance for promoting titanium alloy substrate；And these techniques by
Very thin in depth of penetration, the long period works under friction environment, will lead to coating and is worn, destroys the corrosion resistant on surface
Lose layer.
Titanium alloy, when fine motion abrasion occurs for prepared part, can cause fatigue strength since its wearability is poor
Decline rapidly, therefore it is difficult to accomplish on the modified fluoromaterials such as engineering goods, automobile component largely otherwise exist using titanium alloy
Security risk.In order to meet the market demand of titanium alloy, the titanium composite material for developing a kind of heat resistant and wear resistant damage is needed.
Summary of the invention
The present invention is in view of the above-mentioned problems, provide a kind of abrasion-resistant titanium basic composite material that can be used at high temperature, by mixing
Reinforced phase enhances titanium alloy material, the titanium composite material of high abrasion degree when having reached high temperature, to widen answering for titanium alloy
Use range.
To achieve the goals above, the present invention provides a kind of heat resistant and wear resistants to damage titanium composite material, and raw material composition is pressed
Weight percent proportion is as follows: Al 6-7%, Sn 3-4.5%, Zr 8-10%, Mo 0.8-1%, Si 0.2-0.3%, Nb
For 0.8-1%, W 0.8-1%, the reinforced phase of the mass fraction of 4.5%-6.5%, surplus Ti are added.
The reinforced phase is the combination of TiB or TiB and TiC.
To achieve the goals above, the present invention also provides the heat resistant and wear resistant damage titanium composite material preparation method,
Specific step is as follows.
Step 1, stock: titanium sponge, sponge zirconium, the aluminium tin containing 50% tin of mass fraction and 50% aluminium are weighed by weight percentage
Alloy, granularity 0.25-3mm；Aluminium molybdenum alloys containing mass fraction 50% molybdenum and 50% aluminium, granularity 0.4-4mm；Containing quality
Score is the aluminium niobium alloy of 50% niobium and 50% aluminium, granularity 0.25-2mm；Fine aluminium beans, granularity 6-9mm, pure tungsten powder,
Granularity is 0.4-1 μm, pure silicon powder, and granularity is 125-325 mesh, and reinforced phase granularity is 0.01-2mm.
Step 2, melting: melting, monitor system 320- are carried out using vacuum consumable water jacketed copper crucible induction skull crucible
345kW carries out melting under vacuum condition, and suction to 0.15Pa keeps the temperature 5-8min after melting, holding temperature is not less than fusing point
1995 DEG C of temperature, obtain alloy solution；Under the vacuum condition of vacuum consumable water jacketed copper crucible induction skull crucible, by alloy solution
It is cast in formwork for cylindrical columns, in air, cooled to room temperature obtains alloy cast ingot.
Step 3, ingot casting analysis: it is sampled with 20 lathes from alloy cast ingot top, middle part, lower part, is analyzed with spectroanalysis instrument
Chemical analysis and impurity composition, the then transformation temperature of analysis of material whether uniform come the chemical analysis for analyzing ingot casting with this.
Step 4, forging: being 1050-1100 DEG C by the qualified alloy of ingot ingot casting preheating of step (3) detection to temperature, and
45min is kept at such a temperature, is forged with 5000t hydraulic press, and the total deformation of draw out is not less than 85% three times, forging
Make completion.
Beneficial effects of the present invention.
In composite material of the invention, the heat resistance of titanium alloy is can be improved in Mo, makes titanium alloy material under high temperature environment
Extended using the time, Mo solution strengthening β phase, and significantly reduce the transformation temperature of titanium alloy, increase harden ability, to enhance heat treatment
Strengthening effect, the effect that Mo improves creep resistance is better than vanadium, can also improve the corrosion resistance of alloy；It is compacted that resisting for alloy can be improved in Si
Denaturation energy, but excessive element silicon cannot be added, because silicide will continue on crystal boundary and phase boundary in high temperature exposes for a long time
It is precipitated and constantly accumulates, will affect thermal stability, silicone content of the present invention controls 0.2-0.3%, and silicon can be completely dissolved in can in matrix
To obtain optimal croop property.
The content range (Al 6-7%, Sn 3-4.5%, Zr 8-10%) that Al, Sn, Zr are controlled in the present invention, more than one
After determining range, constituent content is higher, and the contraction percentage of area reduces more after heat exposure.Because Al, Sn and Ti form Ti3Al、
Ti3The content of Sn, Al, Sn, Zr control, and on the one hand can promote Ti3On the other hand Zr also can be generated in the ordering of Al3Al、
Zr3The compounds such as Sn；Zr is often used as improving a kind of effective element of heat resistance, it and titanium form continuous α and β solid solution,
Diffusion velocity in titanium is slower, and restricted silicide is grown up the effect being allowed in disperse state, makes tiny Precipitation of Silicide
It is mutually uniformly distributed, addition Zr can be such that the creep limit of titanium alloy significantly improves；For high aluminum and titanium alloy, a small amount of Zr is added can be with
Increase α2(α2One of titanium alloy microstructure) with the mispairing coefficient of matrix, promote dislocation bypass mechanism to be formed, increase material
The plasticity of material.
The increase of aluminium content is advantageous to the raising of the creep-resistant property and antioxygenic property of titanium alloy, still, while also leading
Cause the plasticity and deformability decline of titanium alloy.The amount for Nb, W element being added in the present invention is no more than 1%, lower than molten in α titanium
(2%) Nb can achieve 20%, W also can achieve Xie Du, can make α2The C curve of phase moves right, α2The precipitation of phase is slack-off, and nucleation is equal
It is even, increase the plasticity and toughness of material；And reduce the tendency of ordering, the effect to become fragile is slowed down, both can be improved in this way
Creep-resistant property, and thermal stability can be improved；If but both constituent contents are excessively high (more than 1%), especially more than dissolve
Degree, will be such that remaining β phase increases, and at high temperature after long-term exposure, remaining β phase necessarily be made largely to decompose and reduce alloy thermostabilization
Property, and then reduce the wear-resisting property under the conditions of titanium alloy high-temperature.
Titanium composite material of the present invention is added to reinforced phase, and the selection of reinforced phase is to improve material against oxidative ability, intensity
It is foundation with hardness, this requires reinforced phases to have the characteristics that high rigidity, high-melting-point.It selects TiC and TiB as reinforcement, is
Due to the density of the two and the similar density of titanium, fusing point is respectively 3067 DEG C and 2200 DEG C, and thermal expansion coefficient is 8 × 10-6/ DEG C left side
The right side, it is close with titanium alloy thermal expansion coefficient (coefficient of expansion 8.2).Due to these physical properties of reinforced phase, so that itself and titanium alloy
Compatibility between matrix is good.The addition of reinforced phase is so that the intensity of titanium composite material is significantly increased, but moulds simultaneously
Property also decline therewith, and in titanium composite material Nb, W element addition, and its plasticity is made to increase, and it is anti-to improve high temperature
Oxidation susceptibility.The interaction of multiple element of the present invention and reinforced phase, so that titanium composite material hardness improves, wearability increases
By force, while there is good comprehensive performance.
The present invention adds reinforced phase using titanium alloy as matrix, and the interface binding power between reinforced phase and matrix is stronger.It is compound
Material can cause to damage under the working environment of fretting wear to the interface between reinforcement and matrix, occur in ambient temperature
When variation or when fretting wear generates temperature change, reinforced phase and matrix can be caused while expanding contraction, if thermal expansion system
Number difference is larger, can cause the debonding at interface.But the heat between the reinforced phase and matrix of titanium composite material of the present invention
Relatively, interface binding power is strong for the coefficient of expansion.The titanium composite material of this method preparation, due to microcosmic in addition reinforced phase
C, B element and titanium alloy substrate react generation in reaction, and the bond strength between obtained reinforcement and matrix is high,
Final material property obtained is preferably also.Therefore, have in reinforced phase and with titanium composite material made by the titanium matrix
There is good wearability.
In conclusion titanium composite material of the present invention, is to enhance interface binding power by addition reinforced phase, so that material
Enhanced strength, while adding the interaction of Nb, elements such as w and reinforced phase, i.e., under the premise of proof strength, improve material
The plasticity of material, while high-temperature oxidation resistance is also improved, so that the hardness of titanium composite material improves, wearability enhancing.?
At 650 DEG C, good tensile strength and elongation still can have, and titanium composite material breakthrough titanium alloy is not wear-resisting
Technological difficulties.
Detailed description of the invention
Fig. 1 is the microscopic structure for the titanium composite material that embodiment 1 adds reinforced phase TiB.
Fig. 2 is the microscopic structure for the titanium composite material that embodiment 2 adds reinforced phase TiB+TiC.
Fig. 3 is the friction coefficient curve of 1 titanium composite material of embodiment.
Fig. 4 is the XRD curve of 1 titanium composite material of embodiment.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.
Embodiment 1.
A kind of abrasion-resistant titanium basic composite material used at a temperature of 650 DEG C includes Al 6%, Sn 4%, Zr by weight percentage
10%, Mo 1%, Si 0.25%, Nb 1%, W 1% add the TiB of 5% mass fraction, surplus Ti.
The present embodiment is using the ingot casting of 15kg as standard.
Step 1: stock: preparation titanium sponge 11.32kg, sponge zirconium 1.55kg by weight percentage, the aluminium tin containing 50% tin
Alloy 1.2kg, the aluminium molybdenum alloys 0.3kg containing 50% molybdenum, the aluminium niobium alloy 0.3kg containing 50% niobium, fine aluminium beans 0.04kg, tungsten
0.152kg, silicon 0.0378kg, TiB 0.75kg.
Step 2: melting: carrying out melting using vacuum cold-crucible induction skull crucible.It is the true of 335kW in monitor system
Carrying out melting under empty condition, suction to 0.15Pa keeps the temperature 8min and obtains alloy solution after melting, and 2000 DEG C of holding temperature.
Under vacuum conditions, further alloy solution is cast in formwork for cylindrical columns, in air, cooled to room temperature obtains
Alloy cast ingot.
Step 3: ingot casting is analyzed: with 20 lathes from ingot casting sampling, analytical chemistry composition and impurity composition are analyzed with this
Whether the chemical analysis of ingot casting is uniform, then the transformation temperature of analysis of material.
Step 4: forging: being 1100 DEG C by the qualified ingot casting preheating of step (3) detection to temperature, and protect at such a temperature
45min to be held, is forged with 5000t hydraulic press, the first fire pulling deflection is 40%, it melts down and is heated to 1100 DEG C, heat preservation
30min；Second fire pulling deflection is 30%, melts down and is heated to 1075 DEG C, keeps the temperature 30min；It is 25% that third fire, which pulls out deflection,
The total deformation forged three times is greater than 85%, and forging is completed.
Embodiment 2.
A kind of abrasion-resistant titanium basic composite material mass percent is by Al 6.3%, Sn 4.5%, Zr 8.8%, Mo 0.82%, Si
0.3%, Nb 0.87%, W 0.87%, add the TiC of the TiB of 2.5% mass fraction and 3.5% mass fraction and the Ti of surplus
It is made.
Embodiment 3.
A kind of abrasion-resistant titanium basic composite material mass percent is by Al 7%, Sn 3%, Zr 8%, Mo 0.8%, Si 0.2%, Nb
0.8%, the Ti of W 0.8%, the TiC and surplus that add the TiB of 2.5% mass fraction and 2.5% mass fraction is made.
One, following performance detection analysis is carried out to the titanium composite material of above-described embodiment.
Microstructure observation is carried out to embodiment 1, sees Fig. 1.It can be observed that TiB is mostly distributed along crystal boundary, size is smaller, main
To illustrate that the high-temperature stability of TiB is fine, strengthen wearability when titanium composite material high temperature to be needle-shaped.If reinforced phase is
TiC and TiB, i.e. embodiment 2, then TiC is mostly larger-size graininess or strip, and TiB is graininess or fibrous structure,
See Fig. 2.
Measuring friction coefficient is carried out to embodiment 1, sees Fig. 3.As can be seen from the figure under room temperature and the condition of high temperature, friction
Coefficient is very stable, does not fluctuate with the extension of time, this illustrates that its wear-resisting property is stablized, not by the shadow of temperature and time
It rings.
XRD analysis is carried out to embodiment 1, sees Fig. 4.It can be seen from the figure that other than Ti matrix, existing reinforced phase is
TiB has no the generation of other impurities phase, this illustrates the presence that TiB can be stable in the composite.From the analysis result of XRD
From the point of view of, the phase that other elements reaction generates is had no in titanium composite material obtained, illustrates that other alloying elements such as Al, Si are dissolved
To among matrix, chemical reaction does not occur between added each element in matrix alloy and generates impurity yet.
Tension test is carried out to embodiment 1, is measured at room temperature, tensile strength is >=1200MPa, and elongation is
10% or so；At 650 DEG C of high temperature, tensile strength is >=600MPa, and elongation is 25% or so.Currently used high temperature titanium closes
Golden TC11, when room temperature, tensile strength is >=890MPa, elongation 10%；At 450 DEG C of high temperature, tensile strength be >=
620MPa, elongation 10%.
Claims (7)
1. a kind of heat resistant and wear resistant damages titanium composite material, which is characterized in that it is as follows that raw material forms components by weight percentage: Al
For 6-7%, Sn 3-4.5%, Zr 8-10%, Mo 0.8-1%, Si 0.2-0.3%, Nb 0.8-1%, W 0.8-1%, addition
The reinforced phase of the mass fraction of 4.5%-6.5%, surplus Ti；The reinforced phase is the combination of TiB or TiB and TiC.
2. composite material as described in claim 1, which is characterized in that it is as follows that raw material forms components by weight percentage: Al
6%, Sn 4%, Zr 10%, Mo 1%, Si 0.25%, Nb 1%, W 1% add the TiB of 5% mass fraction, surplus Ti.
3. composite material as described in claim 1, which is characterized in that it is as follows that raw material forms components by weight percentage: Al
6.3%, Sn 4.5%, Zr 8.8%, Mo 0.82%, Si 0.3%, Nb 0.87%, W 0.87%, add 2.5% mass fraction
The TiC and surplus of the mass fraction of TiB and 3.5% are Ti.
4. composite material as described in claim 1, which is characterized in that it is as follows that raw material forms components by weight percentage: Al
7%, Sn 3%, Zr 8%, Mo 0.8%, Si 0.2%, Nb 0.8%, W0.8% add the TiB's and 2.5% of 2.5% mass fraction
The TiC and surplus of mass fraction are Ti.
5. the preparation method of the heat resistant and wear resistant damage titanium composite material as described in claim 1-4 is any, the specific steps are as follows:
Step 1, stock: weighing titanium sponge by weight percentage, and sponge zirconium is closed containing the aluminium tin of 50% tin of mass fraction and 50% aluminium
Gold, granularity 0.25-3mm；Aluminium molybdenum alloys containing mass fraction 50% molybdenum and 50% aluminium, granularity 0.4-4mm；Containing quality point
Number is the aluminium niobium alloy of 50% niobium and 50% aluminium, granularity 0.25-2mm；Fine aluminium beans, granularity are 6 ~ 9mm, pure tungsten powder, particle
Degree is 0.4-1 μm, pure silicon powder, and granularity is 125 ~ 325 mesh, and reinforced phase granularity is 0.01-2mm；
Step 2, melting: carrying out melting using vacuum consumable water jacketed copper crucible induction skull crucible, and monitor system is 320 ~ 345kW,
Melting is carried out under vacuum condition, suction to 0.15Pa keeps the temperature 5 ~ 8min after melting, holding temperature is not less than melting temperature
1995 DEG C, obtain alloy solution；Under the vacuum condition of vacuum consumable water jacketed copper crucible induction skull crucible, alloy solution is cast
Into formwork for cylindrical columns, in air, cooled to room temperature obtains alloy cast ingot；
Step 3, ingot casting analysis: it is sampled with 20 lathes from alloy cast ingot top, middle part, lower part, with spectroanalysis instrument analytical chemistry
Composition and impurity composition, the then transformation temperature of analysis of material whether uniform come the chemical analysis for analyzing ingot casting with this；
Step 4, forging: it is 1050-1100 DEG C that step 3, which is detected qualified ingot casting preheating to temperature, and is kept at such a temperature
45min is forged with 5000t hydraulic press, three times the total deformation > 85% of draw out, and forging is completed.
6. the preparation method of heat resistant and wear resistant damage titanium composite material as claimed in claim 5, which is characterized in that described three
Secondary draw out is specially that the first fire pulling deflection is 40%, melts down and is heated to 1100 DEG C, keeps the temperature 30min；Second fire pulling becomes
Shape amount is 30%, melts down and is heated to 1075 DEG C, keeps the temperature 30min；It is 25% that third fire, which pulls out deflection, total change of draw out three times
Shape amount is 85%, and forging is completed.
7. the titanium composite material as described in claim 1-4 is any is applied in the environment that temperature is 650 DEG C.
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