CN110218908A - A kind of Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy and preparation method thereof - Google Patents
A kind of Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloys and preparation method thereof, the Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is made according to mass percent of following raw materials: 5.5% Al, 1.0~4.0% Zr, 0.5~2.0% Sn, 0.3~2.0% Mo, 0.4~1.5% Nb, surplus Ti.Room-Temperature Fracture Toughness, compressive strength, compression limit dependent variable and the etch resistant properties that the present invention passes through characterization alloy, and carry out orthogonal, optimizing obtained Ti-5.5Al-4.0Zr-1.0Sn-0.3Mo-1.0Nb titanium alloy is a kind of novel nearly alpha titanium alloy, have both excellent Room-Temperature Fracture Toughness, higher room temperature compressive strength, compression limit dependent variable and good etch resistant properties, it is expected to be applied to marine engineering equipment, have a good application prospect.
Description
Technical field
The present invention relates to a kind of titanium alloys and preparation method thereof, and in particular to a kind of Ti-Al-Zr-Sn-Mo-Nb is high-strength resistance to
Lose titanium alloy and preparation method thereof.
Background technique
China is an economic giant, big to the demand of the energy.According to " world energy outlook 2030 " forecast analysis, China
It will be the maximum user of the following oil consumption growth.To the year two thousand thirty, Chinese petroleum consumption will increase by 8,000,000 barrel per days, reach
17500000 barrel per days are more than the U.S. and become the maximum oil consumption country in the world.Therefore, supply and demand huge so how is solved
Contradiction is the major issue of China's economic development faces.China is an ocean big country, and ocean area is the 1/3 of land area,
Land coastline length is more than 18000 kms, enjoys sovereignty and jurisdictional oceanic area close to 3,000,000 sq-kms.China
There are the petroleum resources of very abundant at the South Sea, and petroleum-in-place is about 230~30,000,000,000 tons, account for China's petroleum resources three/
One.Therefore, offshore and gas development has become the major fields of China's energy strategy.For this purpose, developing advanced ocean engineering dress
Lay-by material has highly important strategic importance.
In view of Service Environment, marine engineering equipment material therefor need high intensity, high tenacity, it is anticorrosive the features such as.Titanium
And titanium alloy has the characteristics that density is low, specific strength is high, corrosion resistance is strong, it is especially non-to the immunocompetence of naval air environment erosion
It is often outstanding, it is a kind of good lightweight structural material, referred to as " marine metal ", is important strategy metal material.However, with
Ocean engineering fast development and application operating condition it is increasingly harsh, higher want is proposed to the performance of ocean titanium alloy
It asks, especially emphasizes it with superior intensity and sea water resistance (or resistance to complex dielectrics) corrosive nature, therefore there is an urgent need to send out
Novel high-strength corrosion-resistant erosion titanium alloy is opened up, this work has great scientific research value and economic benefit, while to construction ocean
Power also has extremely important influence.
CN102839297A discloses a kind of high-temperature titanium alloy and preparation method thereof, which is Ti-Al-Zr-Sn-
Mo-Nb titanium alloy system, by mass percentage by Al:5.5%~7%, Sn:2%~4%, Zr:8%~11%, Mo:0.4%
~1.2%, the Ti of Nb:0.4%~1.5%, W:0.5%~1.5%, Si:0.15%~0.3% and surplus is made, invention
Purpose is to solve the high-temperature titanium alloy of existing method preparation and tensile strength and prolong under 700 DEG C of short time high temperature operating condition
The problem of rate difference is stretched, the ocean engineering application potential of the alloy system is not probed into, i.e., does not study the normal of the alloy system
Warm mechanical property and corrosive nature.
CN104018027A discloses a kind of heat resistance titanium alloy and its machining manufacture and application, the alloy
Ingredient is Al:5.4%~6.3% by mass percentage；Sn:3.0%~5.0%；Zr:2.5%~6.4%；Mo:0.0~
0.96%；Si:0.25%~0.5%, Nb:0.2%~0.5%；Ta:0.3%~3.4%；W:0.2%~1.6%；C:0.0
~0.07%；O≤0.17%；Fe≤0.03%, surplus are Ti and inevitable impurity element, are mainly also to lay particular emphasis on material
The high temperature application of material has not focused on the ambient temperature mechanical properties and corrosive nature of alloy.
CN107058801A discloses a kind of cast titanium alloy suitable for 560~650 DEG C, the alloying component include Ti,
Al, Sn, Zr, Mo, Nb, Si, Ta and/or C, surplus are impurity, but the design of the alloy is also for meeting high temperature application.
In short, Ti-Al-Zr-Sn-Mo-Nb titanium alloy system is mainly used in high-temperature field at present, about the alloy system
Application in terms of ocean engineering is rarely reported, and therefore, the purpose of the present invention is intended to the comprehensive room temperature power for measuring the alloy system
Performance and corrosive nature are learned, to realize its application in terms of ocean engineering.
Summary of the invention
In order to solve the problems, such as that the intensity of existing titanium alloy, corrosion resistance are unable to further satisfaction ocean engineering service condition,
The present invention provides a kind of Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloys and preparation method thereof.The present invention is by characterizing not
The performance of congruent Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy obtains having both excellent Room-Temperature Fracture Toughness, higher
Room temperature compressive strength, compression limit dependent variable and good etch resistant properties Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium
Alloy.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is made according to mass percent of following raw materials:
5.5% Al, 1.0~4.0% Zr, 0.5~2.0% Sn, 0.3~2.0% Mo, 0.4~1.5% Nb, surplus are
Ti。
A kind of preparation method of above-mentioned Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy, comprising the following steps:
Step 1: purity is selected to be above 99% Ti, Al, Zr, Sn, Mo, Nb as raw material, above-mentioned raw materials surface is used
Sand paper polishing scale removal, then cleans 5~10min using acetone, industrial alcohol ultrasonic oscillation respectively, ultrasonic power is
0.1~0.5W/cm2；
Step 2: being placed on water cooling after the raw material drying after cleaning step 1 using vacuum non-consumable arc furnace melting
In copper crucible, furnace body vacuum degree is evacuated to 5Pa using mechanical pump hereinafter, being then turned on automatic vacuum, vacuum degree is evacuated to 5 ×
10-3For Pa hereinafter, closing automatic vacuum, being subsequently charged with air pressure in the argon gas to furnace body as protective atmosphere is 0.05~0.06MPa,
Tungsten electrode is dropped to from 1~2mm of material, starts striking, slowly mention melting electric current by the power supply for opening vacuum non-consumable arc furnace
Electric current is kept after rising between 450~500A, after raw material is completely melt as liquid, is continued 2~3min of melting, is then shut off electricity
Stream, after 10~15s of alloy natural cooling, is overturn；
Step 3: the alloy after overturning is reentered into melting in water jacketed copper crucible, melting condition is identical as step 2,
Alloy is completely melt as after liquid, maintenance 2~3min of melting is then shut off electric current, to 10~15s of alloy natural cooling
Afterwards, it is overturn；
Step 4: repeating step 3 4~6 times, the preparation of Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is completed.
Compared with the prior art, the present invention has the advantage that
1, Room-Temperature Fracture Toughness, compressive strength, compression limit dependent variable and corrosion stability that the present invention passes through characterization alloy
Can, and orthogonal is carried out, the tissue and performance of the Ti-Al-Zr-Sn-Mo-Nb alloy of a variety of heterogeneities are explored,
Optimal alloying component is determined are as follows: Ti-5.5Al-4.0Zr-1.0Sn-0.3Mo-1.0Nb (mass fraction).
2, the Ti-5.5Al-4.0Zr-1.0Sn-0.3Mo-1.0Nb titanium alloy that present invention optimization obtains is a kind of novel nearly α
Type Titanium Alloy, has both excellent Room-Temperature Fracture Toughness, higher room temperature compressive strength, compression limit dependent variable and good anti-
Corrosion energy is expected to be applied to marine engineering equipment, have a good application prospect.
3, titanium alloy of the invention is that conventional titanium alloy vacuum non-consumable melting obtains, and preparation method is simple.
Detailed description of the invention
Fig. 1 is each component alloy three point bending test load-displacement curves: (a) A-1~A-4, (b) A-5~A-8, (c)
A9~A12, (d) A-13~A-16；
Fig. 2 is each component titanium alloy Room-Temperature Fracture Toughness KIC value figure；
Fig. 3 is each component Alloy At Room Temperature compression test load-deformation curve: (a) A-1~A-4, (b) A-5~A-8, (c)
A-9~A-12, (d) A-13~A-16；
Fig. 4 is the compression yield strength figure of each component alloy；
Fig. 5 is the limiting strain magnitude figure of each component alloy；
Fig. 6 is working electrode schematic diagram；
Fig. 7 is open circuit potential-time graph of each component alloy in 3.5wt.%NaCl solution: (a) A-1~A-4,
(b) A-5~A-8, (c) A-9~A-12, (d) A-13~A-16；
Fig. 8 is the open circuit potential value figure of each component alloy；
Fig. 9 is polarization curve of each component alloy in 3.5wt.%Nacl solution: (a) A-1~A-4, (b) A-5~A-
8, (c) A-9~A-12, (d) A-13~A-16；
Figure 10 is each component alloy corrosion current value IcorrFigure；
Figure 11 is alloy Y three point bending test load-displacement curves figure；
Figure 12 is each component titanium alloy fracture toughness property KIC value figure of the Y containing optimized alloy；
Figure 13 is optimized alloy Y room temperature compression test stress-strain curve；
Figure 14 is the compression yield strength figure of each component alloy of the Y containing optimized alloy；
Figure 15 is the limiting strain spirogram of each component alloy of the Y containing optimized alloy；
Figure 16 is open circuit potential-time plot of the optimized alloy Y in 3.5wt.%NaCl solution；
Figure 17 is the open circuit potential value figure of each component alloy of the Y containing optimized alloy；
Figure 18 is polarization curve of the optimized alloy Y in 3.5wt.%NaCl solution；
Figure 19 is each component alloy corrosion current value I of the Y containing optimized alloycorrFigure.
Specific embodiment
Below with reference to embodiment, further description of the technical solution of the present invention, and however, it is not limited to this, all right
Technical solution of the present invention is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be contained
Lid is within the protection scope of the present invention.
Embodiment 1:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 1.0~4.0% Zr, 0.5~2.0% Sn, 0.3~2.0% Mo, 0.4~1.5% Nb, surplus
For Ti.
Embodiment 2:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 1.0% Zr, 0.5% Sn, 0.3% Mo, 0.4% Nb, surplus Ti.
Embodiment 3:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 1.0% Zr, 1.0% Sn, 0.8% Mo, 0.7% Nb, surplus Ti.
Embodiment 4:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 1.0% Zr, 1.5% Sn, 1.5% Mo, 1.0% Nb, surplus Ti.
Embodiment 5:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 1.0% Zr, 2.0% Sn, 2.0% Mo, 1.5% Nb, surplus Ti.
Embodiment 6:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 2.0% Zr, 0.5% Sn, 0.8% Mo, 1.5% Nb, surplus Ti.
Embodiment 7:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 2.0% Zr, 1.0% Sn, 1.5% Mo, 0.4% Nb, surplus Ti.
Embodiment 8:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 2.0% Zr, 1.5% Sn, 2.0% Mo, 0.7% Nb, surplus Ti.
Embodiment 9:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 2.0% Zr, 2.0% Sn, 0.3% Mo, 1.0% Nb, surplus Ti.
Embodiment 10:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 3.0% Zr, 0.5% Sn, 1.5% Mo, 1.0% Nb, surplus Ti.
Embodiment 11:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 3.0% Zr, 1.0% Sn, 2.0% Mo, 0.7% Nb, surplus Ti.
Embodiment 12:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 3.0% Zr, 1.5% Sn, 0.3% Mo, 0.4% Nb, surplus Ti.
Embodiment 13:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 3.0% Zr, 2.0% Sn, 0.8% Mo, 1.5% Nb, surplus Ti.
Embodiment 14:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 4.0% Zr, 0.5% Sn, 2.0% Mo, 0.7% Nb, surplus Ti.
Embodiment 15:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 4.0% Zr, 1.0% Sn, 0.3% Mo, 1.0% Nb, surplus Ti.
Embodiment 16:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 4.0% Zr, 1.5% Sn, 0.8% Mo, 1.5% Nb, surplus Ti.
Embodiment 17:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 4.0% Zr, 2.0% Sn, 1.5% Mo, 0.4% Nb, surplus Ti.
Embodiment 18:
In the present embodiment, Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is according to mass percent by following raw material systems
At: 5.5% Al, 4.0% Zr, 1.0% Sn, 0.3% Mo, 1.0% Nb, surplus Ti.
Embodiment 19:
Present embodiments provide a kind of preparation of Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy described in embodiment 1-18
Method the described method comprises the following steps:
Step 1: purity is selected to be above 99% Ti, Al, Zr, Sn, Mo, Nb as raw material, above-mentioned raw materials surface is used
Sand paper polishing scale removal, then cleans 5~10min using acetone, industrial alcohol ultrasonic oscillation respectively, ultrasonic power is
0.1~0.5W/cm2；
Step 2: using vacuum non-consumable arc furnace, (model JVAM-1B type, producer are that Shenyang gold grinds new material preparation
Technology Co., Ltd.) melting, it is placed in water jacketed copper crucible after the raw material drying after step 1 is cleaned, using mechanical pump by furnace
Body vacuum degree is evacuated to 5Pa hereinafter, being then turned on automatic vacuum, and vacuum degree is evacuated to 5 × 10-3Pa hereinafter, close automatic vacuum, with
Being filled with air pressure in the argon gas to furnace body as protective atmosphere afterwards is 0.05~0.06MPa, opens the electricity of vacuum non-consumable arc furnace
Tungsten electrode is dropped to from 1~2mm of material, starts striking, slowly keeps melting current boost to after between 450~500A by source
Electric current, after raw material is completely melt as liquid, continue 2~3min of melting, be then shut off electric current, to alloy natural cooling 10~
After 15s, overturn；
Step 3: the alloy after overturning is reentered into melting in water jacketed copper crucible, melting condition is identical as step 2,
Alloy is completely melt as after liquid, maintenance 2~3min of melting is then shut off electric current, to 10~15s of alloy natural cooling
Afterwards, it is overturn；
Step 4: repeating step 3 4~6 times, the preparation of Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is completed.
Embodiment 20:
In the present embodiment, specific preparation process is as follows for Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy:
(1) preparation of raw material
It selects purity to be above 99% Ti, Al, Zr, Sn, Mo, Nb as raw material, above-mentioned raw materials sand for surface paper is beaten
It grinds off and descales, then clean 5min, ultrasonic power 0.3W/cm using acetone, industrial alcohol ultrasonic oscillation respectively2,
Then each element mass fraction accurate weighing is pressed, for alloy melting use.
Each element ingredient section is determined according to the relevant designs criterion such as Al equivalent, Mo equivalent in Titanium Alloy Design, in this area
Interior interval water intaking level values, 16 groups of horizontal orthogonal experiment groups of four factor of composition four.The ingredient orthogonal design table of 16 groups of designs and
Element level factor is as shown in table 1.It combines obtained specific alloying component and is shown in Table 2.
Each factor level table of 1 orthogonal test of table (wt.%)
2 orthogonal experiment each component alloying component table of table
(2) melting of alloy
The raw material after cleaning is placed in water jacketed copper crucible using vacuum non-consumable arc furnace, and one piece of pure titanium ingot is put
In a wherein crucible, furnace body vacuum degree is evacuated to 5Pa hereinafter, being then turned on automatic vacuum, by vacuum degree using mechanical pump
It is evacuated to 5 × 10-3Pa is hereinafter, close automatic vacuum.It is close to be then charged with air pressure in the argon gas to furnace body as protective atmosphere
0.05MPa or so to prevent metal charge to be oxidized, while also guaranteeing to discharge in fusion process.The pure titanium ingot of melting first
Tungsten electrode is then adjusted to start striking from 1~2mm of raw material or so, slowly by melting by 1min to eliminate oxygen remaining in furnace chamber
Current boost keeps electric current to after between 450~500A, after raw material is completely melt as liquid, continues 2~3min of melting, then
Electric current is closed, is overturn after alloy is cooling；It is above repeatedly to operate 5 times to obtain the uniform alloy of ingredient.
The alloy obtained to the present embodiment is analyzed as follows:
(1) Room-Temperature Fracture Toughness of Ti-Al-Zr-Sn-Mo-Nb system alloy
Unilateral Notched Izod beam method will be taken to test each component alloy to obtain the fracture toughness of each component alloy.
Sample is that the method that relatively uniform position uses wire cutting among the button ingot after Overheating Treatment intercepts 2 × 4 × 20mm3's
Cuboid sample, and in intermediate prefabricated 2mm deep torn grain, surface is polishing to without obvious wire cutting scratch.Test equipment is
Instron5569 electronic universal tester.Three-point bending fixture is installed on electronic universal tester (U.S., Instron556)
Place sample afterwards makes above pressure head face crackle in centre, then controls pressure head and slowly pushes, loading speed 0.2mm/min,
Until breaking (load sharply declines) stopping.
The test data that breaking load is in median in test three times is taken to draw each component displacement-load curves, such as Fig. 1
It is shown.The fracture toughness K of sampleICValue is calculated by formula (1) and (2):
Wherein,It is for independent variableFunction, value can calculate with following formula:
In formula, PQFor breaking load N；B is sample thickness, 2mm；L is three-point bending mold span, 16mm；W is that sample is wide
Degree, 4mm；A is precrack notch depth, 2mm.
By every group of alloy K that experiment calculation obtains three timesICValue is averaged, and is determined as the K of the component alloyICValue, table 3 are
For the specific Fracture Toughness of each component alloy.Furthermore relatively strong and weak for the various alloy fracture toughness of visual representation, using broken line
Scheming (Fig. 2) indicates.
The fracture toughness of 3 each component alloy of table
In conjunction with table 3 and Fig. 2 it is found that the Fracture Toughness of each component alloy is in 50.56~71.07MPam1/2Between, respectively
The average Fracture Toughness of component alloy is in 50MPam1/2More than, illustrate that each component alloy fracture performance is better, together
When again it can be seen that, best and worst difference 20.51MPam in 16 components1/2, this illustrates added pivot cellulose content
There is large effect to the performance of alloy.In this 16 component alloy, that behave oneself best is A-9 (Ti-5.5Al-3.0Zr-
0.5Sn-1.5Mo-1.0Nb), Fracture Toughness 71.07MPam1/2, showing worst is A-1 (Ti-5.5Al-1.0Zr-
0.5Sn-0.3Mo-0.4Nb), Fracture Toughness 50.56MPam1/2。
(2) the room temperature compression performance of Ti-Al-Zr-Sn-Mo-Nb system alloy
It is from each component button ingot centre with wire cutting interception size from Radius Sample it is each
Three progress room temperature compression experiments.Compression experiment is carried out with electronic universal tester, each component alloy is tested three times.Figure
3 for each component alloy test three times in compression yield strength take median when room temperature compression test load-deformation curve.Table 4
For the compression yield strength and ultimate extension dependent variable of each component alloy.
4 each component alloy compression yield strength of table and ultimate extension dependent variable
In order to more intuitively show the variation of heat treatment front and back each component alloy compression performance, by the data column in upper table
Shape figure is indicated, as shown in Figure 4,5.From the point of view of Fig. 4,5 and table 4, the yield strength of each group alloy is higher, is located at 800MPa
Above in the majority, as intensity increases plasticity decline, but alloy limiting strain amount is mostly 20% or more, each group alloy comprehensive performance
Preferably, this is because the elements such as Al, Zr, Mo, Nb play solution strengthening in titanium alloy, the increase of Sn content can make alloy
Intensity improves, but in certain content on plasticity without influence.
(4) electrochemical corrosion performance of Ti-Al-Zr-Sn-Mo-Nb system alloy
Using dynamic method to each component alloy carry out three-electrode system electrochemical test, the system mainly by working electrode,
Reference electrode and auxiliary electrode composition, wherein each component alloy is saturated calomel as auxiliary electrode as working electrode, platinum electrode
Electrode is as reference electrode.Sample preparation it is as follows: by Wire EDM means button ingot bosom position interception 10 ×
10×10mm3Square, gradually polished using sand paper after ultrasonic cleaning, optics be polished to after gradually polish with sand paper and is shown
Without scratches visible, sample work area is 10 × 10mm for micro mirror lower surface2Square, lap uses epoxy resin sealing,
And drawn with a copper conductor from the sample back side, working electrode schematic diagram is illustrated in fig. 6 shown below, and should ensure that conducting wire not in experimentation
It is contacted with solution.The corrosive liquid of test is the NaCl solution of 3.5wt.%, and volume is about 300ml.
Sample is stood 3600s, open-circuit current potential in the solution first to be detected, obtains OCP curve, as shown in Figure 7.
Open circuit potential-time graph is corrosion potential, that is, open circuit potential of the sample in corrosive liquid under conditions of no impressed current
Variation, this parameter represents the state of the macroscopic property of material and the surface of material, and what is reflected is that sample is corroding
The size of the trend of self-corrosion occurs in liquid, open circuit potential is bigger, and the tendency that sample corrodes is smaller, and corrosive power is got over
It is good.For the accuracy for guaranteeing experimental result, each component alloy standing time answers long enough, is set as 3600s.It can be seen that with
The extension of standing time, the open circuit potential curve of each component alloy gradually tend towards stability, show in titanium alloy surface shape
At stable oxidation film, a stable open circuit potential value has been finally obtained.
According to the OCP curve of alloy, the open circuit potential of available 16 component alloy is as shown in table 5, in order to more clearly see
Out between different component open circuit potential difference, open circuit potential value is made into histogram, as shown in Figure 8, it can be seen that, alloy is opened
For road current potential more than -0.4084V, overall performance is good, wherein what is behaved oneself best is A-12 alloy, showing worst is A-1
Alloy illustrates that the different content of different-alloy element can have an impact the corrosive nature of alloy.
Open circuit potential value of the 5 each component alloy of table in 3.5wt.%Nacl solution
The test of dynamic potential polarization curve is carried out after open circuit potential is stablized, experimental setup parameters are as follows: sweep speed is
0.001V/s, measurement current potential are -0.8~+2.5V, and the polarization curve measured by Tafel linear extrapolation method as shown in figure 9, obtained
The each component alloy corrosion current potential E arrivedcorrValue and corrosion current value IcorrIt is shown in Table 6.For corrosion behavior, material is generally concerned
The corrosion rate of material generally evaluates the electrochemical corrosion behavior of material with corrosion current, sees each component to be more intuitive
Alloy corrosion current value IcorrDifference.By the corrosion current data in table 7 with histogram graph representation (Figure 10).
6 each component alloy corrosion current potential E of tablecorrWith corrosion current Icorr
| Sample Number | Sample constituents | Ecorr/V | Icorr/×10-8A |
| A-1 | Ti-5.5Al-1.0Zr-0.5Sn-0.3Mo-0.4Nb | -0.647 | 13.82 |
| A-2 | Ti-5.5Al-1.0Zr-1.0Sn-0.8Mo-0.7Nb | -0.655 | 17.75 |
| A-3 | Ti-5.5Al-1.0Zr-1.5Sn-1.5Mo-1.0Nb | -0.597 | 13.67 |
| A-4 | Ti-5.5Al-1.0Zr-2.0Sn-2.0Mo-1.5Nb | -0.573 | 18.75 |
| A-5 | Ti-5.5Al-2.0Zr-0.5Sn-0.8Mo-1.5Nb | -0.508 | 12.47 |
| A-6 | Ti-5.5Al-2.0Zr-1.0Sn-1.5Mo-0.4Nb | -0.511 | 7.992 |
| A-7 | Ti-5.5Al-2.0Zr-1.5Sn-2.0Mo-0.7Nb | -0.561 | 12.83 |
| A-8 | Ti-5.5Al-2.0Zr-2.0Sn-0.3Mo-1.0Nb | -0.619 | 12.31 |
| A-9 | Ti-5.5Al-3.0Zr-0.5Sn-1.5Mo-1.0Nb | -0.555 | 14.78 |
| A-10 | Ti-5.5Al-3.0Zr-1.0Sn-2.0Mo-0.7Nb | -0.451 | 3.397 |
| A-11 | Ti-5.5Al-3.0Zr-1.5Sn-0.3Mo-0.4Nb | -0.446 | 4.988 |
| A-12 | Ti-5.5Al-3.0Zr-2.0Sn-0.8Mo-1.5Nb | -0.221 | 3.096 |
| A-13 | Ti-5.5Al-4.0Zr-0.5Sn-2.0Mo-0.7Nb | -0.565 | 13.35 |
| A-14 | Ti-5.5Al-4.0Zr-1.0Sn-0.3Mo-1.0Nb | -0.556 | 12.12 |
| A-15 | Ti-5.5Al-4.0Zr-1.5Sn-0.8Mo-1.5Nb | -0.645 | 14.34 |
| A-16 | Ti-5.5Al-4.0Zr-2.0Sn-1.5Mo-0.4Nb | -0.470 | 11.17 |
All in all, the passivation section of alloy is larger, and the corrosion current order of magnitude is 10-8, corrosion current is very small, opens
Road current potential is larger, indicates that the tendency corroded of alloy and corrosion rate are all very small, and whole group alloy all shows excellent resistance to
Corrosion energy.
(5) orthogonal calculation of Ti-Al-Zr-Sn-Mo-Nb system alloy
Here, handled using synthesis necessary technology orthogonal experiment data, first respectively each index by single index into
Row range analysis, the optimal ingredient for obtaining each performance indicator and each factor are to the influence degree of the performance indicator, then each
The result of performance Index Calculation analysis carries out overall balance, so that it is determined that each factor level optimal or transferring to combine.
As shown in table 7 to each component Alloy At Room Temperature fracture toughness range analysis process, calculated result is shown for single finger
Mark the optimal alloy compositions of Room-Temperature Fracture Toughness are as follows: Ti-5.5Al-4.0Zr-2.0Sn-1.5Mo-1.0Nb, according to four kinds of differences
Fracture toughness average value of the main alloying element under different level acquires very poor R, can determine each element according to very poor size
To the influence degree of alloy Room-Temperature Fracture Toughness.Very poor calculated result shows that each main alloying element is to material Room-Temperature Fracture Toughness
Influence degree sequence are as follows: Zr > Nb > Mo > Sn.
The orthogonal range analysis of 7 each component Alloy At Room Temperature fracture toughness of table
The test result range analysis process of each component Alloy At Room Temperature compressive strength and limiting strain amount is as shown in table 8, more
Index orthogonal calculation the results show that under single index, the optimal alloy group of alloy compression yield strength is divided into Ti-5.5Al-
4.0Zr-2.0Sn-0.3Mo-1.0Nb, under single index, the optimal alloy group of alloy compression limit dependent variable is divided into Ti-
5.5Al-1.0Zr-1.0Sn-2.0Mo-0.4Nb.It is strong according to compression yield of four kinds of different main alloying elements under different level
Angle value and compression limit dependent variable can be in the hope of the very poor R of each element.It is sorted by very poor size it is found that each main alloying element pair
The influence degree of usable material chamber temperature compressive strength sorts are as follows: Zr > Sn > Mo > Nb, to the influence journey of usable material chamber temperature and pressure contracting limiting strain amount
Degree sequence are as follows: Zr > Nb > Mo > Sn.
The orthogonal range analysis of 8 each component alloy compression performance of table
To the orthogonal range analysis of each component alloy electrochemical corrosion performance as shown in table 9,10.Due to corrosion current value
IcorrSmaller expression material corrosion is slower, and corrosion resistance is better, therefore K value is smaller indicates certain element at which level anti-corrosion
Performance is better, which is the preferred levels of element thus.And open circuit potential is then that more just, corrosion resistance is better.Calculate knot
Fruit shows that the optimal alloy group to single index open circuit potential is divided into Ti-5.5Al-3.0Zr-2.0Sn-0.8Mo-1.5Nb, to list
The optimal alloy group of one index corrosion current is divided into Ti-5.5Al-3.0Zr-1.0Sn-0.3Mo-0.4Nb.It is sorted by very poor size
Know, each main alloying element sorts to the influence degree of material corrosion current potential are as follows: Zr > Sn > Nb > Mo, to the shadow of material corrosion electric current
The degree of sound sequence are as follows: Zr > Nb > Sn > Mo.
The orthogonal range analysis of 9 each component alloy open circuit potential of table
The orthogonal range analysis of 10 each component alloy corrosion current of table
Overall balance is carried out to the calculated result of above-mentioned each performance indicator, when Zr is containing measuring 3.0%, electrochemical corrosion performance
Reach best, room temperature compressive strength, compression limit dependent variable and fracture toughness are also preferable.When Sn is containing measuring 1.5%, room temperature compression
Intensity reaches best with electrochemical corrosion performance, and ensure that fracture toughness and compression limit dependent variable are also preferable.Mo content is
When 0.3%, alloy compression performance, fracture toughness and electrochemical corrosion performance are preferable.When Nb is containing measuring 0.4%, room temperature compression
Intensity, compression limit dependent variable and electrochemical corrosion performance reach best, and fracture toughness is also preferable.Work as in conjunction with Al equivalent with Mo
Criterion is measured, final determination is optimized to be divided into Y:Ti-5.5Al-4.0Zr-1.0Sn-0.3Mo-1.0Nb.
(6) performance verification of optimized alloy
The fracture toughness of optimized alloy is tested, using unilateral Notched Izod beam method to optimized alloy Ti-5.5Al-
4.0Zr-1.0Sn-0.3Mo-1.0Nb carries out the test of fracture toughness, and alloy takes the mode of median by test three times, obtains
Displacement-load curves are as shown in figure 11, substitute into maximum load and obtain the K of optimized alloyICFor 71.29MPam1/2, by orthogonal reality
It tests component alloy and the value of optimized alloy Y compares, it can be seen that, optimize the Fracture Toughness of component Y from histogram 12
It is highest, although differing seldom with A-9 alloy highest in 16 components, has reached peak in 16 component alloys, it is excellent
Change significant effect.
Next the test that room temperature compression is carried out to optimized alloy Ti-5.5Al-4.0Zr-1.0Sn-0.3Mo-1.0Nb, is closed
Gold takes the mode of median by test three times, obtains that load-deformation curve is as shown in figure 13, the yield strength of optimized alloy Y
For 987.62MPa, limiting strain amount is 24.64%, and orthogonal experiment component alloy and the value of optimized alloy Y are compared, from
It can be seen that, the yield strength of optimization component Y reaches highest in histogram 14 and Figure 15, higher than 16 groups of alloys of orthogonal design,
With increasing for intensity, plasticity is necessarily declined, and the limiting strain amount of optimized alloy is 24.64%, also greater than partial orthogonality
The alloy of design is integrally located at by-level, and optimized alloy has highest yield strength and good limiting strain amount, therefore
It is considered that the reasonability and successful of optimum results.
Three-electrode system electrochemical test is carried out to optimization ingredient Ti-5.5Al-4.0Zr-1.0Sn-0.3Mo-1.0Nb, is obtained
OCP curve to optimized alloy is illustrated in fig. 16 shown below, it can be seen that, optimized alloy Y prolongs with standing time in OCP curve
Long, open circuit potential gradually rises, until finally tending towards stability, obtaining open circuit potential is -0.2613V.In order to more clearly see
The open circuit potential value of optimized alloy and 16 component alloys is made into histogram such as Figure 17 institute by the open circuit potential value of optimized alloy out
Show, open circuit potential value is bigger, represents that the tendency that it corrodes is smaller, and corrosion resistance is smaller.It can see in histogram
Although the open circuit potential value of optimized alloy is not the largest, value is greater than most of alloy, is only smaller than A-12 and A-16 two and combines
Gold, and differ smaller with the value of A-16 alloy, it is believed that the open circuit potential of optimized alloy is excellent in.
Polarization curve is as shown in figure 18, and analysis can obtain the self-corrosion electricity of optimized alloy according to Tafel linear extrapolation method
Position and corrosion current.For the purposes of convenient for comparison, corrosion current value to be done to histogram is as shown in figure 19, the corruption of optimized alloy
Although erosion electric current is not the smallest but is less than most orthogonal design alloy, and the performance of its polarization curve is combined, it can be with
Think the excellent corrosion-proof performance of optimized alloy.Optimized alloy has excellent performance to prove the reasonability of orthogonal calculation.
From the above analysis: passing through the Ti-5.5Al-4.0Zr-1.0Sn-0.3Mo-1.0Nb of orthogonal experiment optimization design
Alloy has both excellent Room-Temperature Fracture Toughness, higher room temperature compressive strength, compression limit dependent variable and good corrosion stability
Can, it is expected to be applied to marine engineering equipment, have a good application prospect.
Claims (10)
1. a kind of Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy, it is characterised in that the Ti-Al-Zr-Sn-Mo-Nb is high-strength
Corrosion resistant Ti alloy is made according to mass percent of following raw materials: 5.5% Al, 1.0~4.0% Zr, 0.5~2.0%
Sn, 0.3~2.0% Mo, 0.4~1.5% Nb, surplus Ti.
2. Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy according to claim 1, it is characterised in that the matter of the Zr
Measuring percentage is 1.0%, 2.0%, 3.0% or 4.0%.
3. Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy according to claim 1, it is characterised in that the matter of the Sn
Measuring percentage is 0.5%, 1.0%, 1.5% or 2.0%.
4. Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy according to claim 1, it is characterised in that the matter of the Mo
Measuring percentage is 0.3%, 0.8%, 1.5% or 2.0%.
5. Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy according to claim 1, it is characterised in that the matter of the Nb
Measuring percentage is 0.4%, 0.7%, 1.0% or 1.5%.
6. Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy according to claim 1, it is characterised in that the Ti-Al-
Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is made according to mass percent of following raw materials: 5.5% Al, 4.0% Zr,
1.0% Sn, 0.3% Mo, 1.0% Nb, surplus Ti.
7. the preparation side of Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy described in a kind of claim 1-6 any claim
Method, it is characterised in that described method includes following steps:
Step 1: purity is selected to be above 99% Ti, Al, Zr, Sn, Mo, Nb for raw material, by above-mentioned raw materials sand for surface paper
Then polishing scale removal is cleaned using acetone, industrial alcohol ultrasonic oscillation respectively；
Step 2: being placed on water-cooled copper earthenware after the raw material drying after cleaning step 1 using vacuum non-consumable arc furnace melting
In crucible, furnace body vacuum degree is evacuated to 5Pa hereinafter, being then turned on automatic vacuum using mechanical pump, vacuum degree is evacuated to 5 × 10-3Pa
Hereinafter, closing automatic vacuum, being subsequently charged with air pressure in the argon gas to furnace body as protective atmosphere is 0.05~0.06MPa, is opened
Tungsten electrode is dropped to from 1~2mm of material, starts striking, slowly extremely by melting current boost by the power supply of vacuum non-consumable arc furnace
Electric current is kept after between 450~500A, after raw material is completely melt as liquid, is continued 2~3min of melting, is then shut off electric current,
After 10~15s of alloy natural cooling, overturn；
Step 3: the alloy after overturning is reentered into melting in water jacketed copper crucible, after alloy is completely melt as liquid, keep
Continue 2~3min of melting, is then shut off electric current, after 10~15s of alloy natural cooling, is overturn；
Step 4: repeating step 3 4~6 times, the preparation of Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy is completed.
8. the preparation method of Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy according to claim 7, it is characterised in that
The ultrasonic oscillation scavenging period is 5~10min, and ultrasonic power is 0.1~0.5W/cm2。
9. the preparation method of Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy according to claim 7, it is characterised in that
In the step 3, melting condition is identical as step 2.
10. Ti-Al-Zr-Sn-Mo-Nb high strength anti-corrosion titanium alloy described in a kind of claim 1-6 any claim is in ocean work
Application in terms of journey.
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| CN114807721A (en) * | 2021-01-27 | 2022-07-29 | 叶均蔚 | Low modulus corrosion resistant alloy and use thereof |
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| CN113564417A (en) * | 2021-06-10 | 2021-10-29 | 云南钛业股份有限公司 | High-strength titanium alloy and preparation method thereof |
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