CN106636742B - A kind of ZSA-3 titanium alloy tubes, preparation method and applications - Google Patents
A kind of ZSA-3 titanium alloy tubes, preparation method and applications Download PDFInfo
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- CN106636742B CN106636742B CN201611019842.7A CN201611019842A CN106636742B CN 106636742 B CN106636742 B CN 106636742B CN 201611019842 A CN201611019842 A CN 201611019842A CN 106636742 B CN106636742 B CN 106636742B
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/06—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of tubes or metal hoses; Combined procedures for making tubes, e.g. for making multi-wall tubes
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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
- C22C1/02—Making non-ferrous alloys by melting
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Abstract
It is composed of the following components by mass percentage the invention discloses a kind of 3 titanium alloy tubes of ZSA, preparation method and applications：Al 4.6 5.4%；V 3.6 4.4%；Mo 0.4 1.3%；Zr 1.6 2.4%, Fe≤0.12%；C≤0.08%；N≤0.05%；H≤0.015%；O≤0.2%；Surplus is Ti.The titanium alloy tube has corrosion resistant feature at high temperature, especially to H at 150 DEG C 260 DEG C of oil operating mode2S、CO2Corrosion there is high resistance, corrosion rate to fall below 0.0006mm/a or less；It is provided simultaneously with excellent room-temperature mechanical property, tensile strength is 830 1200MPa, and yield strength is 750 1120MPa, and elongation is 10 20%.Its service life is long, has replenished domestic blank, has broad application prospects.
Description
Technical field
The present invention relates to titanium alloy preparing technical fields, and in particular to a kind of ZSA-3 titanium alloy tubes, preparation method and its answers
With.
Background technology
As the world is to the growing of petroleum resources demand, the exploitation of oil gas field is promoted gradually to develop in depth.Ultra-deep
Superelevation kill-job oil/gas well becomes very common.Investigation is shown, is more than 11% well, bottom hole temperature (BHT) in marine drilling in the following 3-5
It will be above 175 DEG C.Drilling well under all high temperature of various degrees, the hyperbaric environment such as land many oil fields in China with it is complete
Well problem, if block, bottom pressure are more than 130MPa to Tarim Basin library vehicle newly developed in front of the mountains, bottom hole temperature (BHT) is up to 183-204 DEG C.It is high
Super pressure-high temperature, continuing to bring out for high pressure high temperature well cause exploration and development difficulty gradually to increase, and key problem is the material of tubing string
Select permeability.Since high pressure-temperature, high pressure high temperature well typically contain H2S and CO2, CO under hot conditions2And H2The corrosivity of S
It is extremely strong, in the development process of petroleum gas, CO2And H2The gases such as S and medium have become the corrosion of tubing the main corruption in oil field
Erosion problem, therefore there is an urgent need to develop the anti-corrosion petroleum pipe of the high temperature of high intensity.
CN103643082A discloses a kind of high strength petroleum and covers effective titanium alloy and its side for manufacturing petroleum casing pipe
Method is divided into Fe by controlling its group<0.3%；C<0.08%；N<0.05%；H<0.015%；0<0.2%；Al5.5-6.8%；
V3.5-4.5%；Mo2.5-3.5%；The petroleum casing pipe with good mechanical properties and longer life has been prepared in surplus Ti.
CN103341520A discloses a kind of rectangular sections TB9 and admires alloy wire preparation process, more by special-shaped wire-drawing die
High intensity is prepared in passage cold drawing, rectangular section TB9 (Ti-3Al-8V-6Cr-4Zr-4Mo) of high tenacity is admired alloy cold silk
Material makes silk material have the cold technique for coiling performance of preferable spring, and after ageing strengthening is heat-treated, the intensity of silk material is 1240-
1380MPa, elongation percentage and reduction of area are respectively greater than 10% and 20%.
Baoju Titanium Industry Co., Ltd. is to meet continent oil-gas mining demand, solves etching problem, realizes that oil well is permanent
Property exploitation, retrofited to Ti-6Al-4V, develop TC4S alloy extrusion pipes, to meet high yield and high impact property
It is required that.The extruding tubing has been produced in batches, which see the table below.
Although all there is above-mentioned titanium alloy tube good mechanical performance, its high temperature corrosion resistance still to have deficiency.TC4 alloys
Pipe is only at 60 DEG C -80 DEG C to H2S、CO2Corrode resistant, is difficult that meet present oil well harsh once temperature is higher than 80 DEG C
Bottom hole temperature (BHT), pressure and corrosive conditions condition, therefore there is an urgent need to develop the anti-corrosion petroleum pipelines of new high temperature.
Invention content
In view of the shortcomings of the prior art, the present invention provides a kind of ZSA-3 titanium alloy tubes, has resistance to H at high temperature2S and CO2It is rotten
The characteristics of erosion, at 150 DEG C -260 DEG C of oil operating mode, H2S、CO20.0006mm/a is fallen below to its corrosion rate hereinafter, should
Titanium alloy tube is provided simultaneously with excellent room-temperature mechanical property, tensile strength 830-1200MPa, yield strength 760-
1120MPa, elongation 10-20% are a kind of resistance to H of high temperature resistant2S、CO2The material of corrosion, has replenished domestic blank, has wide
Wealthy application prospect.
To achieve the above object, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of ZSA-3 titanium alloy tubes, the ZSA-3 titanium alloy tubes press mass percentage
It is composed of the following components：
The present invention is by the mating reaction between above-mentioned Al, V, Mo, Zr and Ti each component with certain content, in each group
On the basis of the effect being respectively provided with, the performance of titanium alloy is further improved, especially in tetra- kinds of elements of Al, V, Mo, Zr
On the basis of specific components content, specific adding proportion between each element is controlled, the ZSA-3 titanium alloy tubes being prepared is made to obtain
Obtained the anti-CO at 150-260 DEG C2And H2The ability of S corrosion, is provided simultaneously with good mechanical property.
Although Mo elements and Zr elements all have some excellent performances, it is simple by its with Al elements and V members
Element prepares titanium alloy, is merely capable of increasing the mechanical performance and part resistance to corrosion of titanium alloy, not have at high temperature
Anti- CO2And H2The ability of S corrosion controls the adding proportion of the two, Mo and Zr phases only in the content range of above-mentioned Mo and Zr
Synergistic effect is just will produce between mutually, resistance to CO under titanium alloy high-temperature can be greatly improved2And H2The ability of S corrosion.
Above-mentioned Fe, C, N, H and O are the impurity unavoidably brought into actual production, its content is controlled in above range
Within the performance for the ZSA-3 titanium alloy tubes being finally prepared can't be had an impact, therefore it is repeated no more.
The content of Al is 4.6-5.4% in ZSA-3 titanium alloy tubes of the present invention, for example, can be 4.6%, 4.7%,
4.8%, the specific point value between 4.9%, 5.0%, 5.1%, 5.2%, 5.3% or 5.4% and above-mentioned numerical value, is limited to a piece
Width and for concise consideration, the specific point value that range includes described in the present invention no longer exclusive list.
Al is most common addition element in titanium alloy, and the effect that Al primarily serves solution strengthening is added in titanium alloy,
There is positive effect for the room temperature and elevated temperature strength, reduction proportion, increase elasticity modulus that improve alloy.Suitable Al elements can
The effective tensile strength for increasing titanium alloy, but the addition of excessive Al meeting the moulding of alloy, toughness and stress corrosion are not
Profit.
The content of V is 3.6-4.4% in ZSA-3 titanium alloy tubes of the present invention, for example, can be 3.6%, 3.7%,
3.8%, the specific point value between 3.9%, 4.0%, 4.1%, 4.2%, 4.3% or 4.4% and above-mentioned numerical value, is limited to a piece
Width and for concise consideration, the specific point value that range includes described in the present invention no longer exclusive list.
V element can play the role of solution strengthening β phases, and significantly reduce transformation temperature, increase quenching degree, improve alloy
Intensity, toughness and wearability.When V element is very few, low-alloyed thermal stability can significantly drop.
For the present invention, the ratio of Al elements and V element is not in the range of above-mentioned Al and V content, in titanium alloy
It is preferably too low or excessively high, if the ratio of the two is less than 1.1:1 or be higher than 1.5:When 1, it can be caused with the Mo elements being subsequently added and
Synergistic effect weakens or disappears between Zr, and the effect of the present invention is not achieved.
The content of Mo is 0.4-1.3% in ZSA-3 titanium alloy tubes of the present invention, for example, can be 0.4%, 0.5%,
0.6%, the specific point value between 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2% or 1.3% and above-mentioned numerical value,
As space is limited and for concise consideration, the specific point value that range described in the present invention no longer exclusive list includes.
Mo elements have the effect of raising creep resistance, can effectively improve the corrosion resistance of alloy, especially anti-gap
The ability of corrosion.The very few corrosion resisting property that can lead to alloy of Mo elements is insufficient.
The content of Zr is 1.6-2.4% in ZSA-3 titanium alloy tubes of the present invention, for example, can be 1.6%, 1.7%,
1.8%, the specific point value between 1.9%, 2.0%, 2.1%, 2.2%, 2.3% or 2.4% and above-mentioned numerical value, is limited to a piece
Width and for concise consideration, the specific point value that range includes described in the present invention no longer exclusive list.
There is Zr elements corrosion resistance, usually suitable Zr elements that are added into titanium alloy can improve the anti-corrosion of titanium alloy
Property and heat resistance.
In the present invention, on the basis of above-mentioned Mo and Zr contents, the addition ratio of Mo and Zr in the ZSA-3 titanium alloy tubes
Example is (0.2-0.75):1, such as can be 0.2:1、0.3:1、0.4:1、0.5:1、0.6:1、0.7:1 or 0.75:1, and
Specific point value between above-mentioned numerical value, as space is limited and for concise consideration, range packet described in the present invention no longer exclusive list
The specific point value included.
In the content range of above-mentioned Mo and Zr, the above proportional region is selected to be added so that Mo and Zr are mutual
Synergistic effect is generated, together with same Al and V with special ratios, greatly improves resistance to CO under titanium alloy high-temperature2And H2S corrodes
Ability.
In ZSA-3 titanium alloy tubes of the present invention in addition to containing Al, Mo, V and Zr, also contain Fe, C, O, H and N etc. one
A little impurity elements, " the surplus Ti " is it is meant that in addition to above-mentioned alloy compositions Al, Mo, V, Zr and Impurity Fe, C, O, H, N
Component be Ti.
Preferably, ZSA-3 titanium alloy tubes of the present invention are composed of the following components by mass percentage：
Preferably, ZSA-3 titanium alloy tubes of the present invention are composed of the following components by mass percentage：
Select above-mentioned preferably constituent content that the mechanical strength of ZSA-3 titanium alloy tubes can be made to be improved, under high temperature
To CO2、H2The resistance of S corrosion also can be promoted further.
Second aspect, the present invention provide a kind of preparation method of ZSA-3 titanium alloy tubes, the described method comprises the following steps：
(1) Ti, Al, V, Mo and Zr are subjected to dispensing, carry out melting after dispensing, obtains alloy cast ingot；
(2) step (1) described alloy cast ingot is forged, the bar obtained after forging is processed into optical wand, to optical wand
It is heated, keeps the temperature laggard eleven punch 11；
(3) bar after step (2) described perforation is rolled after pipe is repaired, after obtain production tube；
(4) step (3) production tube being subjected to normalized treatment, temper is carried out after cooling, tempering terminates postcooling,
Obtain ZSA-3 titanium alloy tubes.
According to the present invention, the temperature of step (1) described melting is 1680-3000 DEG C, for example, can be 1680 DEG C, 1700
℃、1800℃、1900℃、2000℃、2100℃、2200℃、2300℃、2400℃、2500℃、2600℃、2700℃、2800
DEG C, 2900 DEG C or the specific point value between 3000 DEG C and above-mentioned numerical value, as space is limited and for concise consideration, the present invention
The specific point value that no longer range described in exclusive list includes.
According to the present invention, time of step (1) the melting postcooling is 90-180min, for example, can be 90min,
100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min or 180min and above-mentioned numerical value
Between specific point value, as space is limited and for concise consideration, range described in the present invention no longer exclusive list includes specific
Point value.
According to the present invention, step (2) temperature to optical wand heating is 890-1000 DEG C, such as can be 890 DEG C,
900 DEG C, 910 DEG C, 920 DEG C, 930 DEG C, 940 DEG C, 950 DEG C, 960 DEG C, 970 DEG C, 980 DEG C, 990 DEG C or 1000 DEG C and above-mentioned
Specific point value between numerical value, as space is limited and for concise consideration, range includes described in the present invention no longer exclusive list
Specific point value.
According to the present invention, the speed of step (2) described perforation is 15-60mm/s, such as can be 15mm/s, 20mm/s,
Specific point value between 25mm/s, 30mm/s, 35mm/s, 40mm/s, 45mm/s, 55mm/s or 60mm/s and above-mentioned numerical value,
As space is limited and for concise consideration, the specific point value that range described in the present invention no longer exclusive list includes.
Optical wand described in step (2) of the present invention means：The bar obtained after forging pulls down oxide skin and crackle etc. with lathe
Optical wand is obtained after defect.
The time of step (2) the of the present invention heat preservation calculates as follows：
Soaking time (min)=(diameter of rod/2) min+ (30-60) min；The unit of wherein diameter of rod is mm.
According to the present invention, the speed of step (3) described rolling is 20-50 times/min, such as can be 20 times/min, 25
It is specific between secondary/min, 30 times/min, 35 times/min, 40 times/min, 45 times/min or 50 time/min and above-mentioned numerical value
Value, as space is limited and for concise consideration, the specific point value that range includes described in the present invention no longer exclusive list.
According to the present invention, the feed of step (3) described rolling is 3-6mm/ times, such as can be 3mm/ times, 3.5mm/
Secondary, 4mm/ times, 4.5mm/ times, 5mm/ times, 5.5mm/ times or the specific point value between 6mm/ times and above-mentioned numerical value, are limited to a piece
Width and for concise consideration, the specific point value that range includes described in the present invention no longer exclusive list.
According to the present invention, the passage of step (3) described rolling is 2-5 times, such as can be 2 times, 3 times, 4 times or 5 times.
Passage described in step (3) of the present invention means：It is rolled by milling train, rolls the primary deformation of primary generation, claim
For rolling pass, every time rolling reduction 20%-50%.
According to the present invention, the temperature of step (4) described normalized treatment is 750 DEG C -850 DEG C, for example, can be 750 DEG C, 760
DEG C, 770 DEG C, 780 DEG C, 790 DEG C, 800 DEG C, 810 DEG C, 820 DEG C, 830 DEG C, between 840 DEG C or 850 DEG C and above-mentioned numerical value
Specific point value, as space is limited and for concise consideration, the specific point value that range includes described in the present invention no longer exclusive list.
According to the present invention, the soaking time of step (4) described normalized treatment is 45-90min, for example, can be 45min,
It is specific between 50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min or 90min and above-mentioned numerical value
Point value, as space is limited and for concise consideration, the specific point value that range includes described in the present invention no longer exclusive list.
According to the present invention, the temperature of step (4) described temper is 450 DEG C -650 DEG C, for example, can be 450 DEG C, 470
DEG C, 490 DEG C, 500 DEG C, 530 DEG C, 550 DEG C, 570 DEG C, 600 DEG C, it is specific between 620 DEG C or 650 DEG C and above-mentioned numerical value
Value, as space is limited and for concise consideration, the specific point value that range includes described in the present invention no longer exclusive list.
According to the present invention, the soaking time of step (4) described temper is 120-240min, such as can be
120min、130min、140min、150min、160min、170min、180min、190min、200min、210min、220min、
Specific point value between 230min or 240min and above-mentioned numerical value, as space is limited and for concise consideration, the present invention is no longer
The specific point value that range described in exclusive list includes.
In the preparation method of ZSA-3 titanium alloy tubes described in second aspect of the present invention, various equipment and technological means are all made of
Equipment and conventional method generally in the art, does not limit this.
Illustratively, the preparation method of ZSA-3 titanium alloy tubes of the present invention includes the following steps：
(1) Ti, Al, V, Mo and Zr are subjected to dispensing, melting are carried out in vaccum consumable electrode electric arc furnace, smelting temperature is
1680-3000 DEG C, alloy cast ingot is obtained by cooling cycle water cooling, the complete postcooling 90-180min of melting in fusing；
(2) step (1) described alloy cast ingot is forged, the bar obtained after forging is machined to optical wand, then will
Optical wand is packed into electric furnace and is heated at 890-1000 DEG C, comes out of the stove after heat preservation, with Mannesmann piercing mill with 15-60mm/s's
Punching rate is to the bar after coming out of the stove into eleven punch 11；
(3) bar after step (2) described perforation is rolled after pipe is repaired with the mill speed of 20-50 times/min
System, feed are 3-6mm/ times, and production tube is obtained after rolling 2-5 passages；
(4) step (3) production tube is subjected to normalized treatment, normalizing temperature is 750 DEG C -850 DEG C, and soaking time is
Then 45-90min is cooled down in air；Then the production tube after normalized treatment is subjected to temper, temperature 450
It DEG C -650 DEG C, soaking time 120-240min, is cooled down in air after tempering to get to ZSA-3 titanium alloy tubes.
The third aspect, the present invention provide a kind of application of ZSA-3 titanium alloy tubes in exploitation of oil-gas field, the ZSA-3 titaniums
Compo pipe is due to good mechanical property, and to H at 150 DEG C -260 DEG C2S、CO2There is high resistance to corrosion,
Meet bottom hole temperature (BHT) harsh in oil/gas well, pressure and corrosive conditions condition, it can be as a kind of novel corrosion-and high-temp-resistant
Oil-gas pipeline and be widely used in exploitation of oil-gas field field.
Compared with prior art, the present invention at least has the advantages that：
(1) the ZSA-3 titanium alloy tubes that the present invention is prepared, have resistance to H at high temperature2S and CO2The characteristics of corrosion,
At 150 DEG C -260 DEG C of oil operating mode, H2S、CO20.0006mm/a is fallen below to its corrosion rate hereinafter, being that a kind of high temperature resistant is resistance to
The material of corrosion, service life is significantly larger than other tubing in high temperature oil well.
(2) the ZSA-3 titanium alloy tubes that the present invention is prepared have good room-temperature mechanical property, tensile strength 830-
1200MPa, yield strength 750-1120MPa, elongation 10-20% meet the requirement to compo pipe intensity in industry, fit
For oil exploitation under high temperature and pressure.
(3) the ZSA-3 titanium alloy tubes that the present invention is prepared have replenished domestic blank, have broad application prospects.
Specific implementation mode
For ease of understanding, it is as follows to enumerate embodiment by the present invention.It will be understood to those of skill in the art that following embodiment is only
The preferred embodiment of the present invention is only used for helping to understand the present invention, thus should not be taken as limiting the scope of the invention.
Embodiment 1
Dispensing is carried out by following components：Al 4.6%, V 3.6%, Mo 0.4%, Zr 1.6%, Fe 0.05%, C
0.03%, N 0.01%, H 0.008%, O 0.07%, surplus Ti；It is carried out in vaccum consumable electrode electric arc furnace after dispensing
Melting, smelting temperature are 1680 DEG C, and alloy casting is obtained by cooling cycle water cooling, the complete postcooling 90min of melting in fusing
Ingot；It is machined to optical wand after alloy cast ingot is carried out forging bar, then its optical wand is packed into electric furnace and is heated, is heated up
To 890 DEG C, bar uses Mannesmann piercing mill into eleven punch 11 after coming out of the stove, and punching rate is 15mm per second；Pipe enters rolling after repairing,
Mill speed 20 times per minute, each 3mm of feed is 5 passages by billet production to production tube rolling pass, obtains finished product
Pipe；Normalized treatment is carried out to production tube, normalizing temperature is 850 DEG C, soaking time 90min, after air cooling, is carried out at tempering
It manages, 650 DEG C, soaking time 240min of temperature, after air cooling, ZSA-3 titanium alloy tubes has been prepared.
Embodiment 2
Dispensing is carried out by following components：Al 5.2%, V 4%, Mo 1%, Zr 2%, Fe 0.085%, C 0.055%,
N 0.03%, H 0.011%, O 0.13%, surplus Ti；Melting is carried out after dispensing in vaccum consumable electrode electric arc furnace, is melted
It is 2300 DEG C to refine temperature, and alloy cast ingot is obtained by cooling cycle water cooling, the complete postcooling 135min of melting in fusing；It will close
Golden ingot casting is machined to optical wand after carrying out forging bar, then its optical wand is packed into electric furnace and is heated, and is warming up to 950
DEG C, bar uses Mannesmann piercing mill into eleven punch 11 after coming out of the stove, punching rate is 40mm per second；Pipe enters rolling, rolling after repairing
Speed 35 times per minute, each 4mm of feed is 3 passages by billet production to production tube rolling pass, obtains production tube；It is right
Production tube carries out normalized treatment, and normalizing temperature is 800 DEG C, soaking time 60min, after air cooling, carries out temper, returns
After air cooling, ZSA-3 titanium alloy tubes have been prepared in 500 DEG C, soaking time 180min of fiery temperature.
Embodiment 3
Dispensing is carried out by following components：Al 5.4%, V 4.4%, Mo 1.3%, Zr 2.4%, Fe 0.12%, C
0.08%, N 0.05%, H 0.015%, O 0.2%, surplus Ti；It is melted in vaccum consumable electrode electric arc furnace after dispensing
Refining, smelting temperature are 3000 DEG C, and alloy cast ingot is obtained by cooling cycle water cooling, the complete postcooling 180min of melting in fusing；
It is machined to optical wand after alloy cast ingot is carried out forging bar, then its optical wand is packed into electric furnace and is heated, is warming up to
1000 DEG C, bar uses Mannesmann piercing mill into eleven punch 11 after coming out of the stove, and punching rate is 60mm per second；Pipe enters rolling after repairing,
Mill speed 50 times per minute, each 6mm of feed is 2 passages by billet production to production tube rolling pass, obtains finished product
Pipe；Normalized treatment is carried out to production tube, normalizing temperature is 750 DEG C, soaking time 45min, after air cooling, is carried out at tempering
It manages, 450 DEG C, soaking time 120min of temperature, after air cooling, ZSA-3 titanium alloy tubes has been prepared.
Embodiment 4
Compared with Example 2, in addition to by the additive amount of Mo in dispensing and Zr " Mo1%, Zr2% " be changed to " Mo0.4%,
(adding proportion of Mo and Zr are 0.17 to Zr2.4% ":1), other conditions and 2 all same of embodiment.
Embodiment 5
Compared with Example 2, in addition to by the additive amount of Mo in dispensing and Zr " Mo1%, Zr2% " be changed to " Mo1.3%,
(adding proportion of Mo and Zr are 0.81 to Zr1.6% ":1), other conditions and 2 all same of embodiment.
Comparative example 1
Compared with Example 2, in addition to there is no Mo, other conditions and 2 all same of embodiment in raw material.
Comparative example 2
Compared with Example 2, in addition to there is no Zr, other conditions and 2 all same of embodiment in raw material.
Comparative example 3
Compared with Example 2, in addition to there is no V, other conditions and 2 all same of embodiment in raw material.
Comparative example 4
Compared with Example 2, in addition to there is no Al, other conditions and 2 all same of embodiment in raw material.
Comparative example 5
Compared with Example 2, other than dispensing " Mo 1% " is changed to " Mo 0.3% ", other conditions and embodiment 2
All same.
Comparative example 6
Compared with Example 2, other than dispensing " Mo 1% " is changed to " Mo 1.4% ", other conditions are equal with embodiment 2
It is identical.
Comparative example 7
Compared with Example 2, other than dispensing " Zr 2% " is changed to " Zr 1.5% ", other conditions are equal with embodiment 2
It is identical.
Comparative example 8
Compared with Example 2, other than dispensing " Zr 2% " is changed to " Zr 2.5% ", other conditions are equal with embodiment 2
It is identical.
Comparative example 9
Compared with Example 2, in addition to by dispensing, " Al 5.2%, V 4%, Mo 1%, Zr 2% " is changed to " Al3%, V
8%, Cr 6%, Mo 4%, Zr 4% " outside, other conditions and 2 all same of embodiment.
Comparative example 10
Compared with comparative example 9, in addition to removing in component " Cr 6% ", other conditions are identical as comparative example 9.
Corrosion resistance is tested：The ZSA-3 titanium alloy samples being prepared are placed in H2S、CO2Under partial pressure, at 150-260 DEG C
Its corrosion weight loss is tested in temperature range.Test evaluation standard calculates a year corrosion rate according to sample mass difference before and after corrosion,
The extent of corrosion of sample is judged according to NACE standards RP-0775-91.
Mechanics Performance Testing：
Test tensile strength, yield strength and the elongation percentage of ZSA-3 titanium alloy samples, testing standard：GB/T 228.1：
2010；ASTM E8/E8M-11；JIS Z2241-2011.
Experiment condition is as follows：
Test stagnation pressure：25MPa；Temperature：150-260℃；H2S is divided：7MPa；CO2Partial pressure：11MPa test periods：720 is small
When.
Embodiment 1-5 and comparative example 1-10 the titanium alloy sample prepared are surveyed using above-mentioned corrosion resistance test method
Examination wherein set experimental temperature as 150 DEG C in embodiment 1, experimental temperature is set in embodiment 3 as 205 DEG C, other embodiment with
Comparative example experimental temperature is 260 DEG C, weighs before and after corroding to sample, calculates its year corrosion rate；It tests at room temperature
The tensile strength, yield strength and elongation percentage of titanium alloy sample made from embodiment and comparative example, experimental result such as 1 institute of table
Show.
Table 1
As seen from the above table：The front and back mass change of ZSA-3 titanium alloy tubes sample corrosion is minimum in embodiment 1-3, year corrosion
Rate falls below 0.0006mm/a hereinafter, the corrosion stability for the sample that wherein embodiment 2 obtains is best, and annual corrosion rate is
0.0002mm/a illustrates that titanium alloy tube prepared by the present invention has excellent resistance to H at 150-260 DEG C2S、CO2The ability of corrosion.This
Outside, not within the scope of the present invention, the titanium alloy sample being prepared exists the ratio of component, constituent content and Mo and Zr
By H at 150-260 DEG C2S、CO2The corrosion of faster rate cannot reach effect obtained by the present invention.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (17)
1. a kind of ZSA-3 titanium alloy tubes, which is characterized in that the ZSA-3 titanium alloy tubes are by mass percentage by following components
Composition：
2. ZSA-3 titanium alloy tubes as described in claim 1, which is characterized in that the ZSA-3 titanium alloy tubes are contained by quality percentage
It measures composed of the following components：
3. ZSA-3 titanium alloy tubes as described in claim 1, which is characterized in that the ZSA-3 titanium alloy tubes are contained by quality percentage
It measures composed of the following components：
4. a kind of preparation method of ZSA-3 titanium alloy tubes as described in any one of claims 1-3, which is characterized in that the side
Method includes the following steps：
(1) Ti, Al, V, Mo and Zr are subjected to dispensing, carry out melting after dispensing, obtains alloy cast ingot；
(2) step (1) described alloy cast ingot is forged, the bar obtained after forging is processed into optical wand, optical wand is carried out
Heating, keeps the temperature laggard eleven punch 11；
(3) bar after step (2) described perforation is rolled after pipe is repaired, production tube is obtained after rolling；
(4) step (3) production tube is subjected to normalized treatment, carries out temper after cooling, tempering terminate postcooling to get
To ZSA-3 titanium alloy tubes.
5. method as claimed in claim 4, which is characterized in that the temperature of step (1) described melting is 1680-3000 DEG C.
6. method as claimed in claim 4, which is characterized in that the time of step (1) the melting postcooling is 90-
180min。
7. method as claimed in claim 4, which is characterized in that step (2) temperature to optical wand heating is 890-1000
℃。
8. method as claimed in claim 4, which is characterized in that the speed of step (2) described perforation is 15-60mm/s.
9. method as claimed in claim 4, which is characterized in that the speed of step (3) described rolling is 20-50 times/min.
10. method as claimed in claim 4, which is characterized in that the feed of step (3) described rolling is 3-6mm/ times.
11. method as claimed in claim 4, which is characterized in that the passage of step (3) described rolling is 2-5 times.
12. method as claimed in claim 4, which is characterized in that the temperature of step (4) described normalized treatment is 750 DEG C -850
℃。
13. method as claimed in claim 4, which is characterized in that the soaking time of step (4) described normalized treatment is 45-
90min。
14. method as claimed in claim 4, which is characterized in that the temperature of step (4) described temper is 450 DEG C -650
℃。
15. method as claimed in claim 4, which is characterized in that the soaking time of step (4) described temper is 120-
240min。
16. the preparation method of ZSA-3 titanium alloy tubes as claimed in claim 4, which is characterized in that the method includes following steps
Suddenly：
(1) Ti, Al, V, Mo and Zr are subjected to dispensing, melting are carried out in vaccum consumable electrode electric arc furnace, smelting temperature is
1680-3000 DEG C, alloy cast ingot is obtained by cooling cycle water cooling, the complete postcooling 90-180min of melting in fusing；
(2) step (1) described alloy cast ingot is forged, the bar obtained after forging is machined to optical wand, then by optical wand
It is packed into electric furnace and is heated at 890-1000 DEG C, come out of the stove after heat preservation, with Mannesmann piercing mill with the perforation of 15-60mm/s
Speed is to the bar after coming out of the stove into eleven punch 11；
(3) bar after step (2) described perforation is rolled after pipe is repaired with the mill speed of 20-50 times/min,
Feed is 3-6mm/ times, and production tube is obtained after rolling 2-5 passages；
(4) step (3) production tube is subjected to normalized treatment, normalizing temperature is 750 DEG C -850 DEG C, soaking time 45-
Then 90min is cooled down in air；Then by after normalized treatment production tube carry out temper, temperature be 450 DEG C-
It 650 DEG C, soaking time 120-240min, is cooled down in air to get to ZSA-3 titanium alloy tubes after tempering.
17. a kind of application of ZSA-3 titanium alloy tubes as described in any one of claims 1-3 in exploitation of oil-gas field.
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| CN109161727B (en) * | 2018-10-19 | 2020-09-22 | 中国航发北京航空材料研究院 | Titanium alloy for manufacturing electric arc/electron beam fuse additive and preparation method thereof |
| CN109622659A (en) * | 2018-12-17 | 2019-04-16 | 安徽宝泰特种材料有限公司 | A kind of manufacturing method of heavy caliber TC4 titanium alloy thick-wall seamless material |
| CN111349817B (en) * | 2020-04-27 | 2021-09-28 | 中世钛业有限公司 | Titanium alloy drill rod, preparation method and application thereof |
| CN111593230B (en) * | 2020-04-30 | 2021-08-31 | 中国石油天然气集团有限公司 | Pipe for 930 MPa-level ultrahigh-strength titanium alloy drill rod and manufacturing method thereof |
| CN112442613A (en) * | 2020-11-09 | 2021-03-05 | 中国石油天然气集团有限公司 | 105ksi titanium alloy pipe for petroleum drill pipe and manufacturing method thereof |
| CN113369811A (en) * | 2021-06-04 | 2021-09-10 | 成都日进冶金锻造有限公司 | Production process of hydrogen sulfide corrosion resistant forge piece |
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