CN1659295A - Beta type titanium alloy and process for producing the same - Google Patents
Beta type titanium alloy and process for producing the same Download PDFInfo
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- CN1659295A CN1659295A CN038132583A CN03813258A CN1659295A CN 1659295 A CN1659295 A CN 1659295A CN 038132583 A CN038132583 A CN 038132583A CN 03813258 A CN03813258 A CN 03813258A CN 1659295 A CN1659295 A CN 1659295A
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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
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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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/106—Other heavy metals refractory metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
Abstract
The present invention provides a type titanium alloy characterized by consisting of, by mass %, V: 15 to 25%, Al: 2.5 to 5%, Sn: 0.5 to 4%, O (Oxygen): not more than 0.20%, H: not more than 0.03%, Fe: not more than 0.40%, C: not more than 0.05% and N: not more than 0.02%, and the balance Ti and impurities. The present invention also provides a method of manufacturing a type titanium alloy characterized by comprising the following steps (a) to (c): (a) Preparing a type titanium alloy consisting of, by mass %, V: 15 to 25%, Al: 2.5 to 5%, Sn: 0.5 to 4%, O (Oxygen): not more than 0.20%, H: not more than 0.03%, Fe: not more than 0.40%, C: not more than 0.05% and N: not more than 0.02%, and the balance Ti and impurities. (b) Pickling the type titanium alloy in an aqueous solution including 3 to 40 mass % of HF, and (c) Further pickling the type titanium alloy in an aqueous solution including 3 to 6 mass % of HF and 5 to 20 mass % of HNO 3 .
Description
Technical field
The present invention relates to lower in the resistance to deformation of cold rolling processing under the state after the solid solution, have a manufacture method that becomes high-intensity beta titanium alloy and this alloy after good deformability, the burin-in process.
Background technology
Titanium alloy is because density is low, intensity is high, among practical metallic substance, has high specific strength (strength/density), and excellent corrosion resistance, therefore very extensive with material, tableware with material, medical machine material, glasses with purposes in the material etc. with material, golf club with the trolley part headed by the aircraft material.Along with its widespread use, require the further improvement of character of titanium alloy or the reduction of price more.
Titanium alloy roughly is divided into α (close-packed hexagonal crystalline substance: hcp) type, β (body-centered cubic crystalline substance: bcc) type and type alpha+beta from the crystal structure of the phase of the metal structure that constitutes its normal temperature.Industrial titanium or the alloy that has added a small amount of Al etc. are the α type, and well-known as high-strength alloy, the Ti-6Al-4V alloy that is used for aircraft etc. is a type alpha+beta, and the β type is to have increased the alloy that more makes the content of the mutually stable element of β than type alpha+beta.
The in general cold rolling processibility of titanium alloy is relatively poor, and manufacturing cost increases thus.In the low pure titanium of the better oxygen level of cold rolling processibility, the undercapacity of the parts of formed thereby is difficult to need in the parts of high specific strength to be applied to.On the other hand, as the high titanium alloy of intensity, though most representative Ti-6Al-4V intensity is high, the deformability extreme difference under the normal temperature only can't form the purpose shape by hot rolling processing or machining, and manufacturing cost raises.
According to aforesaid situation, the titanium alloy of β type with crystal structure of body-centered cubic crystalline substance receives publicity.The alloy of β type for example is Ti-3Al-8V-6Cr-4Mo-4Zr alloy or Ti-15V-3Cr-3Al-3Sn.These β type alloys are implemented solution treatment and to form the deformability of the cold rolling processing of β when single-phase big, carry out burin-in process after the processing and separate out the α phase, can improve intensity, have Ideal Characteristics as precise part with material.
But, even known up to now beta titanium alloy deformability is good, but the resistance to deformation height.So even carrying out under the cold rolling forged situation, moulds such as punch die or tapping machine are just done to split or are broken into pieces under the less access times of being everlasting.In addition, be used for the cold rolling Yanzhong that machined material is made, the cylinder wearing and tearing are bigger, are easy to generate adhesion under the situations such as cold rolling wire drawing.
As the invention that solves this kind problem, announcing in No. 2669004 communique of patent has V:15～25%, Al:2.5～5%, Sn:0.5～4%, oxygen: below 0.12%, remainder is the invention of the alloy (being designated hereinafter simply as the Ti-20V-4Al-1Sn alloy) of Ti and impurity.Though this alloy deformability is roughly the same with beta titanium alloy in the past, not only the intensity of solution treatment state is low, and resistance to deformation is low, and the intensity height after the burin-in process.But when the alloy of making this invention, when forming various parts, the deformability the β treated state under is not necessarily stably good, and resistance to deformation is instability also.In addition, the big difficult point of change that also has the intensity after wearing out.
Summary of the invention
One of purpose of the present invention is, providing can be easily and stably realize the titanium alloy of the characteristic that intensity after cold rolling excellent processability under the state of solid solution and the burin-in process is high.
Two of purpose of the present invention is, is provided for reducing the acid washing method of its H (hydrogen) content when making described titanium alloy.
Beta titanium alloy is the β as the high temperature phase of titanium to be chilled to room temperature mutually and the alloy of the quasi-steady β phase that produces.As the alloying element that is used to make this β phase stabilization, V, Mo, Nb, Ta, Cr, Fe, Mn etc. are arranged, but in the middle of them, less as the sclerosis of solid solution, few, utilize the aging element that can obtain high strength and metastable cheapness to the detrimentally affect of processibility, V and Mo are arranged.But, Mo is owing to have fusing point height, easily segregation, and make difficult points such as the resistance to deformation of hot rolling processibility or cold rolling processing uprises because of the interpolation of Mo, therefore select V, intensity during for burin-in process rises and makes it to contain Al, in order to realize suppressing the purpose of solution hardening, the part of Al is replaced into Sn, become the Ti-20V-4Al-1Sn alloy.
In the process of making this more alloy, find that having differs and stably obtain surely the problem of cold rolling processibility and the aging property strengthened, the inventor has carried out various research in order to understand its reason and to find its countermeasure.At first,, change the combination of the scope of content, investigated processibility and aging V, Al and the Sn of main composition.But,, except what show its influence, do not find special remarkable influence to characteristic variations when the change of these main components during near the border of the scope of content.
But, in described fact-finding process, the clear discovery in β type Ti-20V-4Al-1Sn alloy, the containing of the element of the impurity that generally is counted as titanium of O (oxygen), H, Fe, C and N, to the characteristic of this alloy, promptly cold rolling processibility and aging after intensity improve king-sized influence arranged.These impurity elements by the standard code of titaniums such as JIS-H-4600, JIS-H-4605 or JIS-H-4607 or titanium alloy content separately.But this regulation is not to be object with the β type Ti-20V-4Al-1Sn alloy that utilizes the present invention to improve.
For the effect of described each element, known have a following situation.
O is a α phase stabilizing element, when containing more for a long time, then can hinder the mutually single-phase change of β of solution treatment, but can make the alloy sclerosis in addition again, increases resistance to deformation, and deformability is also reduced.Therefore H can postpone to separate out the aging sclerosis that causes mutually by α owing to be β phase stabilizing element, hinders by the aging intensity that causes and improves.Though Fe is a β phase stabilizing element, owing to can improve the intensity of the alloy after the solution treatment, and increase resistance to deformation, therefore be not suitable for containing more.C forms the precipitate of carbide, and resistance to deformation and deformability are all reduced greatly.Though N β mutually in solid solution about 1%, can cause the reduction greatly of ductility, and reduce deformability.
But, situation for β type Ti-20V-4Al-1Sn alloy, even impurity is restricted in the scope by described JIS standard code, also find to have the element that in this scope, can't easily reduce, even be defined as in addition in the standard, also find the element that has its amount bigger to the properties influence of this alloy.This be because, be the alloy of α type or type alpha+beta by the titanium alloy of HS standard code, and relative with it, the Ti-20V-4Al-1Sn alloy is a β type alloy.
For example, β type alloy and α type alloy or type alpha+beta alloy phase ratio very easily absorb hydrogen.Particularly,, must delay in cold rolling and carry out desquamation in order to obtain surface of good for carrying out the situation that thickness is the plate made of the cold rolling calendering below the 5mm.In this desquamation method, mechanically grind the method for cutting the surface though also have, this method processing speed is slow, the finished product rate variance.So, adopt the pickling that utilizes hydrofluoric acid or fluorine nitric acid usually.But solid solution has formed the situation of the Ti-20V-4Al-1Sn alloy of β type for being used for cold rolling calendering, will absorb the hydrogen that surpasses the boundary number that is limited by described JIS standard significantly in pickling.Even the pickling condition is carried out various adjustment, also be difficult to the minimizing that realizes that it is enough.In addition, because described alloy contains the composition that increases oxide skin, therefore can increase because of the elongation of pickling time absorbs hydrogen.
β type alloy can be after being processed into desired shape, carries out burin-in process and improve intensity.But the hydrogen that is contained can significantly hinder aging sclerosis, elongates ageing treatment time, thus the aging sclerosis of the intensity that is difficult to realize to achieve the goal.In addition, hydrogen can reduce the ductility of alloy and processibility is worsened, and toughness is also deteriorated significantly.Though in a vacuum can dehydrogenation by heat, need to handle for a long time, in addition,, so be difficult to practicability owing in this processings, also can produce agingly.
Should in the manufacturing processed of this Ti-20V-4Al-1Sn alloy sheets, avoid the absorption of the hydrogen that causes by the pickling that is used for desquamation.So, to being minimal acid washing method to adopt described later hydrogen absorb is suppressed, and the hydrogen richness after the pickling that also can sneak into inevitably is a prerequisite therein, see that the reduction that whether can compensate the aging speed that is caused by this hydrogen by the impurity element amount of controlling other and processibility or flexible reduce, the influence of the content of O, Fe, N and C is investigated.Found that by to these each elements and protium together, restriction content separately just can obtain the Ti-20V-4Al-1Sn alloy of excellent characteristic stably.Based on these results of study, further clear and definite final condition, thus finished the present invention.Purport of the present invention is the titanium alloy of following (1) to (3) and the manufacture method that (4) reach the titanium alloy of (5).
(1) a kind of beta titanium alloy, it is characterized in that, in quality %, by V:15～25%, Al:2.5～5%, Sn:0.5～4%, below the O:0.20%, below the H:0.03%, below the Fe:0.40%, below the C:0.05%, below the N:0.02%, remainder is that Ti and impurity constitute.
(2) a kind of beta titanium alloy, it is characterized in that, in quality %, by V:15～25%, Al:2.5～5%, Sn:0.5～4%, below the O:0.12%, below the H:0.03%, below the Fe:0.15%, below the C:0.03%, below the N:0.02%, remainder is that Ti and impurity constitute.
(3) a kind of beta titanium alloy, it is characterized in that, in quality %, comprise that V:15～25%, Al:2.5～5%, Sn:0.5～4%, O:0.12% are following, H:0.03% is following, Fe:0.15% is following, C:0.03% is following, N:0.02% is following and respectively less than 3% from Zr, Mo, Nb, Ta, Cr, Mn, Ni, Pd and Si, select more than one, remainder is made of Ti and impurity.
(4) a kind of manufacture method of beta titanium alloy, it is characterized in that, will in quality % by V:15～25%, Al:2.5～5%, Sn:0.5～4%, below the O:0.20%, below the H:0.03%, below the Fe:0.40%, below the C:0.05%, below the N:0.02%, remainder is the beta titanium alloy that Ti and impurity constitute, at first the HF in order to 3～40 quality % is the solution acid pickling of principal constituent, then with containing the HF of 3～6 quality % and the HNO of 5～20 quality %
3Solution acid pickling.
(5) a kind of manufacture method of beta titanium alloy, it is characterized in that, to comprise V:15～25% in quality %, Al:2.5～5%, Sn:0.5～4%, below the O:0.20%, below the H:0.03%, below the Fe:0.40%, below the C:0.05%, N:0.02% following and respectively less than 3% from Zr, Mo, Nb, Ta, Cr, Mn, Ni, more than one that select among Pd and the Si, the beta titanium alloy that remainder is made of Ti and impurity, at first the HF in order to 3～40 quality % is the solution acid pickling of principal constituent, then with containing the HF of 3～6 quality % and the HNO of 5～20 quality %
3Solution acid pickling.
Description of drawings
Fig. 1 is the figure of expression hydrogen richness to the influence of the variation of the hardness that causes because of wearing out of titanium alloy.
Embodiment
The qualification of the composition element of beta titanium alloy of the present invention be the reasons are as follows.And the content of each composition is all used quality % meter.
V：15～25％
V is used for β phase stabilization and makes that alloy organizing is the monophasic important element of β under the room temperature.When less than 15% the time, carry out from pyritous β phase state begin utilize the solution treatment of chillings such as water-cooled the time, will produce Ma Shi type tissue, cold rolling processibility is deteriorated significantly.When surpassing 25%, then can make the aging hardening variation of β type alloy, required time lengthening in the burin-in process also can't obtain enough reinforcements in addition after burin-in process.In addition, the resistance to deformation of the cold rolling processing of alloy also increases.
Al：2.5～5％
Though β type alloy finally carries out burin-in process and strengthens, rise in order to obtain enough intensity this moment, makes it to contain Al.The effect of separating out of separating out and promote the α phase that the ω phase that suppresses to make alloy embrittlement is also arranged in burin-in process in addition.This kind effect less than 2.5% o'clock just insufficient, surpass the hardness then can increase the β state under at 5% o'clock, make cold rolling processibility reduction.So be made as 2.5～5%.
Sn：0.5～4％
Though Sn has the effect identical with described Al, owing to the hardness that can as Al, not increase under the β state, therefore replace with Sn by reducing Al, just can suppress the resistance to deformation increase.If therefore the effect of this kind Sn is made as content more than 0.5% because content is not obvious at least.On the other hand, when Sn contains quantitative change for a long time,, therefore be made as till 4% owing to still can increase the hardness of alloy after the βization.
O (oxygen): below 0.20%
O can reduce the deformability of alloy, cold rollingly adds the generation that can cause crackle man-hour what carry out intensity, and resistance to deformation also increases.Though its amount is few more good more, adopt as not producing below 0.20% of obvious dysgenic boundary number.And, be more preferably and be made as below 0.12%.
Below the H:0.03%
H since not only the α phase when making burin-in process separate out delay, reduce by the aging intensity that causes and rise, but also can make ductility and toughness variation, therefore few more good more.But, in the Ti-20V-4Al-1Sn alloy of the β type that absorbs hydrogen easily, also have acid cleaning process absorption in addition, particularly,, therefore be difficult to be reduced to the amount below 0.005% owing to must pickling carry out desquamation for the situation of thin plate.So though lower value is not particularly limited, higher limit adopts its little border of influence, be made as till 0.03%.More preferably be made as below 0.01%.
To be expressed as follows the investigation example of hydrogen richness aging hardened influence.
The firm and hard solution treatment of executing is rolled in the hot rolling that alloy is consisted of the thickness 5mm of V:20.0%, Al:3.2%, Sn:1.0%, O:0.11%, H:0.015%, Fe:0.10%, C:0.01%, N:0.01%, remainder: Ti and impurity, after having carried out the shot shot-peening, change hydrogen richness by changing the pickling time, under 450 ℃, carried out burin-in process.Solution treatment is to heat after 5 minutes under 850 ℃ in atmosphere, carries out the processing of water-cooled.
To the result of the investigation of the changes in hardness that causes by digestion time as shown in Figure 1.Hardness Hv is the Vickers' hardness of experiment load 1kgf.
As seen from Figure 1, when hydrogen richness is 0.015% or 0.025%, because of achieve the goal hardness and saturated of 12 hours burin-in process.In contrast, even handle 20 hours, when hydrogen richness is 0.040% or 0.065%, do not reach enough hardness yet.For the situation of these alloys, reach hydrogen richness and be the hardness that is obtained in 0.015% or 0.025% the alloy, must surpass the burin-in process of 20 hours long duration, lack practicality.And, when hydrogen richness is 0.100%, as shown in the figure, can't harden basically.
Can see that according to described experimental result the content of the H of alloy preferably is suppressed at below 0.03%.
Below the Fe:0.40%
Fe makes β phase stabilization and the sclerosis of retarding ageing processing owing to identical with hydrogen, increases resistance to deformation in addition, and is therefore few more good more.As mentioned above, owing to be difficult to avoid containing of hydrogen, therefore, reach till 0.40% at the most as the boundary number that can not bring tangible resistance to deformation to increase.And preferred Fe content is below 0.15%.
Below the C:0.05%
C is that deformability reduces greatly owing to making ductility, and is therefore few more good more.Boundary number as not bringing tangible deformability to reduce reaches till 0.05% at the most.More preferably below 0.03%.
Below the N:0.02%
N is owing to deformability is reduced greatly, and is therefore few more good more.Boundary number as not bringing tangible deformability to reduce is made as till 0.02%.
Described O, Fe, C and N impurity element not only derive from the titanium sponge of raw material, and can enter in the process of the melting of thereafter alloy or heat in the titanium alloy and increase, but also can't be reduced to raw material its below content.So, need select the poor titanium sponge of these impurity as raw material, in addition, reduce the pollution of manufacturing processed as far as possible.
Zr, Mo, Nb, Ta, Cr, Mn, Ni, Pd and Si
Alloy of the present invention can also be in the scope of not damaging action effect of the present invention except V, Al and Sn, contain separately less than 3% from Zr, Mo, Nb, Ta, Cr, Mn, Ni, Pd and Si, select more than one.These compositions can not damage other characteristic such as the deformability of alloy of the present invention, and help the intensity of the alloy after the burin-in process to improve.The preferred content of composition separately is 0.1～1%.
Preferred 20～130 μ m of average crystallite particle diameter when forming β type alloy through solution treatment.This be because, if less than 20 μ m, then resistance to deformation becomes big, processing difficulties, and during greater than 130 μ m, deformability reduces, and adds to be easy to generate crackle man-hour also can produce undercapacity after aging.In addition, though burin-in process is carried out, be made as described scope by the crystallization particle diameter with the β phase under common 400～500 ℃, the particle diameter of the α phase of separating out through wearing out will become 0.02～0.2 μ m of ideal scope, and intensity, toughness are also very good.
Described preferred average crystallite particle diameter can obtain by adopting following creating conditions.
Though alloy of the present invention or alloy sheets are that the forging melting is the starting material of required composition, its hot rolling is delayed, carry out cold rolling calendering, carry out solution treatment and make thereafter, but in order to form the β type alloy that cold rolling processibility is the described average crystallite particle diameter that deformability is good and resistance to deformation is low, the following setting of preferably will creating conditions.
The starting material Heating temperature of hot rolling calendering adopts 900～1050 ℃ and gets final product.This is because during less than 900 ℃, the resistance to deformation of hot rolling processing is bigger, burden to processing units will be excessive, and when surpassing 1050 ℃, it is violent not only to add the oxidation of pining for, bring the reduction of material use efficiency, and thickization of crystal grain, the alloy characteristic after the processing is also exerted an influence.In addition, the temperature in the hot rolling processing even the temperature that has between waiting time of deformation processing and deformation processing reduces, rises because of processing thermogenetic temperature, also preferably is in 750～1050 ℃ above scope of β phase transformation.
After the hot rolling processing, average cooling rate is that chilling more than 30 ℃/minute gets final product as water-cooled etc.This be because, if cool off slowly, then α will separate out and harden mutually, the processing of the rolled material difficulty that becomes is wound into the plate of coiling and just might be able to not launches.When the cold rolling calendering of implementing operation thereafter or cold rolling drawing etc., enough softening in order to obtain, for example pass continuous pickling annealing device (HAP), carry out solution treatment and desquamation.Solution treatment be the βization processing be preferably in be heated to be 750～950 ℃ after water-cooled.This be because, at this moment,, then have forming a β mutually inadequate situation mutually if less than 750 ℃, if surpass 950 ℃, then have the possibility of thickization of crystal grain.Be made as abundant solid solution the heat-up time of solution treatment and avoided get final product in 1～30 minute of useless heating.
The average crystallite particle diameter less than the condition of 20 μ m be the temperature of hot rolling processing near the β phase transformation or than its lower temperature, and the temperature among the HAP reach 750 ℃ near the time.So, preferably avoid this kind condition.But, even when sacrificing the high strength after cold rolling processibility also will obtain burin-in process when how much, also the hot rolling processing temperature can be made as below the β phase transformation, the temperature among the HAP is positioned near 750 ℃, make the average crystallite particle diameter less than 20 μ m, for example be made as 10 μ m.
Though desquamation never hydrogen absorbs this point and considers preferably to utilize grinding of coil grinding machine etc. to cut, productivity difference and cost height.So, to implement according to the mode that hydrogen is sneaked into as far as possible when utilizing the desquamation of pickling.
Hydrogen absorbs and not only fully desquamation but also can remove the α shell as doing one's utmost to suppress, and utilizes cold rolling calendering manufacturing to have the pickling condition of plate on the surface of beauty, and for example following setting gets final product.And so-called α shell is meant that oxygen can invade the hard and crisp oxygen-rich layer on the surface of beta titanium alloy.
1. before pickling, implement shot peening.
2. being in the aqueous solution of principal constituent under 20～70 ℃, at HF, in 10 minutes, carry out pickling with 3～40 quality %.
3. under 20～70 ℃, at the HNO of HF that contains 3～6 quality % and 5～20 quality %
3The fluorine aqueous nitric acid in, in 20 minutes, carry out pickling.
Though also can not carry out shot peening 1., when implementing slight shot peening, just can shorten the pickling time.Be to be used for adding crackle in oxide skin.
The described aqueous solution 2. also can contain and has reductibility and suppress nitric acid that hydrogen absorbs, hydrogen peroxide etc. except the HF as 3～40 quality % of principal constituent.For example, also can use the waste liquid (hydrofluoric acid is principal constituent, and comprises minor components such as acetic acid) that produces in the semi-conductor manufacturing process.
The described aqueous solution 3. is except the HF of 3～6 quality % and the HNO of 5～20 quality %
3The fluorine aqueous nitric acid beyond, can also contain impurity such as minor components such as hydrogen peroxide with reductibility, acetic acid.
Pickling is at first carried out in the aqueous solution that with 2. hydrofluoric acid is principal constituent.Though utilize the pickling of hydrofluoric acid to produce effect in removing descaling, hydrogen absorbs many especially when the pickling of α shell is removed.So, rest on and make that the α shell is the longest also will to remain in 10 minutes with interior degree, carry out following pickling 3. then.The oxygen-rich layer that produces under the oxide skin is that the α shell can utilize the fluorine nitric acid liquid to remove effectively.Utilize the pickling of fluorine nitric acid liquid to utilize the reductive action of nitric acid, though the few advantage of hydrogen absorption is arranged, work as oxide skin more for a long time, the time required in removing extends, and the possibility that makes surface roughening in part generation corrosion is arranged.So, utilize with 2. hydrofluoric acid be the pickling of the aqueous solution of principal constituent after, utilize the pickling of fluorine nitric acid liquid 3..But owing to promptly use the fluorine nitric acid liquid, after process was long-time, hydrogen absorbs also can be increased, and therefore preferably was made as in 20 minutes.
In described pickling, with temperature be made as 20～70 ℃ be because, under less than 20 ℃ temperature, will the overspending time in squama or oxygen-rich layer are removed, when surpassing 70 ℃, surface roughening becomes seriously, it is many that the evaporation of oxygen also becomes.During all less than 3 quality %, then Fan Ying speed became slow to the concentration of HF in 2. solution and solution 3..On the other hand, in solution 2., if surpass 40 quality %, then reaction became violent, just had problem on safety, in addition, also was difficult to carry out the adjustment of etching extent.3. in the solution, when surpassing 6 quality %, it is serious that the surface roughening after the pickling becomes.In addition, in solution 3., add the HNO of 5～20 quality %
3, be to suppress effect that hydrogen absorbs, and during less than 5 quality %, then this effect is insufficient because this has, when surpassing 20 quality %, then effect is saturated and form waste.
If because the dipping time of pickling is longer, then the hydrogen amount sharply increases, the generation of the squama when therefore suppressing heating as far as possible, when squama more for a long time, can use simultaneously to grind to cut and wait mechanical descaling method.
Cold rolling processing makes the crystallization particle diameter for the β after processing below 130 μ m in handling, preferably working modulus more than 30% (if plate then rolls percentage of elongation more than 30%, if bar then relative reduction in area more than 30%).Though more also it doesn't matter for working modulus, can't process because of work hardening, the upper limit naturally and understandably just is restricted.
The β that cold rolling is delayed changes mutually, also comprises annealing, by getting final product with the speed of cooling refrigerative solution treatment more than the air cooling to be heated to after 750～900 ℃.The situation of the Heating temperature scope of the solution treatment before the reason of preferred 750～900 ℃ rate of heating and the described cold rolling processing is identical, served as when low, then β change mutually insufficient, thickization of crystal grain then when too high.Too short or the long β that similarly causes changes insufficient or thickization of crystal grain mutually owing to heat-up time, therefore is made as to get final product in 1～30 minute.And the heating of the solution treatment that this cold rolling is delayed is preferably in a vacuum or in the rare gas elementes such as highly purified Ar, He.This be because, the heating under the surface oxidation condition is then in order to remove the deoxidation mulch film, i.e. desquamation just need utilize the pickling of fluorine nitric acid etc., consequently, hydrogen is invaded in the alloy, hydrogen richness is above limit value.
Hot rolling is delayed, and prolongs though carry out cold rolling usually after carrying out solution treatment, also can be processed into desired shape under cold rolling calendering state, carries out burin-in process thereafter.At this moment, just can form the parts that crystal grain is fine, intensity is high.
The burin-in process that is used to strengthen of β type alloy of the present invention preferably is made as 400～500 ℃.Though utilizing wears out fine α is separated out mutually, and can strengthen thus, if in aging sclerosis, need the long period with next at 400 ℃, and the ductility after strengthening extremely reduces and the toughness variation, and more than 500 ℃ the time, then forming thick α grain mutually, intensity reduces.
Embodiment
The titanium alloy of the composition shown in table 1 and the table 2 is utilized the melting of water-cooled copper crucible consumable electrode type Vacuum Arc dissolving stove (VAR), form the ingot of diameter 140mm.These ingots are heated the hot rolling calendering starting material that thick 50mm, wide 150mm are forged in also hot rolling down at 1000 ℃.These starting material are heated to 950 ℃, and the hot rolling calendering finishes calendering down at 800 ℃, and the water spray cooling is cooled to 300 ℃ with 200 ℃/minute of average cooling rates immediately, places cooling thereafter.Solution treatment to firm and hard the executing of this hot rolling calendering " 880 ℃ of following 10 minutes heating back water-cooleds ".
After the solution treatment, after having implemented shot peening, be immersed in HF:4 quality %, 30 ℃ the hydrofluoric acid aqueous solution 4 minutes, then at HNO
3: dipping is 10 minutes in the fluorine nitric acid that 10 quality %, HF:4 quality %, temperature are 30 ℃, remove and scale and oxygen-rich layer, then grind cut two surfaces after, carry out 80% cold rolling calendering, form 3mm thickness.
Hydrogen amount in the table is that the value of taking sample analysis and getting is delayed in cold rolling.Split from the limit of this cold rolling time-delay that a situation arises, judged the deformability of the β type alloy after the solid solution.And, in experiment numbers 20,21 and 30, the time that is immersed in HF:4 quality %, 30 ℃ the hydrofluoric acid was made as about 15 minutes, the hydrogen amount is increased.
Cold rolling is delayed, and implements 850 ℃ of following heating 5 minutes in a vacuum, carries out the annealing and the solution treatment of water-cooled again, takes the stretching experiment sheet of No. 13 B of JIS from the plate of gained, has measured tensile strength.From the size of this tensile strength, can infer the resistance to deformation that adds man-hour.
In addition, use and do not produce the plate that bigger limit is split, under 475 ℃, carry out the burin-in process of heating in 20 hours, take the stretching experiment sheet of No. 13 B of JIS the plate after aging, measured tensile strength and extensibility in the cold rolling Yanzhong.These measurement results are illustrated in table 1 and the table 2 simultaneously.
Can know from the result of table 1 and table 2 and to see, though it mainly forms experiment numbers 1～24 and all meets the Ti-20V-4Al-1Sn alloy, but compare with the material of experiment numbers 20～33, the material of experiment numbers 1～19 is more good aspect cold rolling processibility, and intensity and extensibility after aging are very good.This is the effect of bringing by the content that limits unsteered in the past H, Fe, C and N, thus the clear and definite importance that suppresses the content of these elements lower.
The industrial possibility of utilizing
According to the present invention, now the Ti-20V-4Al-1Sn alloy of the β type that uses forms littler and the alloy that deformability is better of resistance to deformation.The reduction of the manufacturing cost of the prolongation of the die life in the time of like this, just can going far towards the cylinder of cold rolling processing such as cold rolling calendering and cold rolling drawing or the life-time dilatation of punch die, cold rolling forging etc., high-intensity titanium alloys parts.
The valve parts, space shuttle that titanium alloy of the present invention not only can be used for automobile are with industrial machine usefulness such as parts, and for example can also be applicable to the material of the exercise such as daily necessities, golf club of glasses and so on.
Manufacturing method according to the invention, the cold rolling rolled material of can workmanship stable titanium alloy.
Table 1
| Experiment numbers | Chemical constitution (quality %) [remainder is Fe and impurity] | The cold rolling calendering crackle of ※ | After the solid solution | After the burin-in process | Remarks | ||||||||||
| ? ??V | ? ??Al | ? ??Sn | ? ??O | ? ??H | ? ??Fe | ? ??C | ? ??N | Other | Tensile strength (MPa) | Crystallization particle diameter (μ m) | Tensile strength (MPa) | Extensibility (%) | |||
| ?1 ?2 ?3 ?4 ?5 ?6 ?7 ?8 ?9 ?10 ?11 ?12 ?13 ?14 ?15 ?16 ?17 ? ?18 ? ?19 ? ? | ??16.0 ??20.0 ??24.2 ??20.0 ??20.0 ??20.0 ??20.0 ??20.0 ??20.0 ??20.2 ??20.2 ??20.2 ??20.2 ??20.2 ??20.2 ??20.2 ??20.2 ? ??20.2 ? ??20.2 ? ? | ??3.2 ??3.2 ??3.2 ??2.5 ??4.0 ??3.0 ??3.0 ??3.2 ??3.2 ??3.4 ??3.4 ??3.3 ??3.3 ??3.3 ??3.3 ??3.3 ??3.3 ? ??3.3 ? ??3.3 ? ? | ??1.0 ??1.0 ??1.2 ??1.0 ??1.1 ??1.9 ??1.0 ??1.0 ??1.0 ??1.0 ??1.0 ??1.0 ??1.0 ??1.0 ??1.0 ??1.0 ??1.0 ? ??1.0 ? ??1.0 ? ? | ??0.10 ??0.11 ??0.09 ??0.09 ??0.11 ??0.10 ??0.08 ??0.11 ??0.11 ??0.10 ??0.10 ??0.10 ??0.10 ??0.10 ??0.10 ??0.10 ??0.10 ? ??0.10 ? ??0.10 ? ? | ??0.020 ??0.015 ??0.010 ??0.022 ??0.021 ??0.018 ??0.028 ??0.015 ??0.020 ??0.006 ??0.007 ??0.008 ??0.007 ??0.020 ??0.021 ??0.020 ??0.021 ? ??0.020 ? ??0.021 ? ? | ??0.10 ??0.11 ??0.11 ??0.10 ??0.09 ??0.09 ??0.10 ??0.10 ??0.05 ??0.11 ??0.11 ??0.11 ??0.13 ??0.11 ??0.13 ??0.11 ??0.13 ? ??0.11 ? ??0.13 ? ? | ??0.01 ??0.01 ??0.02 ??0.01 ??0.01 ??0.01 ??0.01 ??0.01 ??0.02 ??0.02 ??0.01 ??0.01 ??0.01 ??0.01 ??0.01 ??0.01 ??0.01 ? ??0.01 ? ??0.01 ? ? | ??0.01 ??0.01 ??0.02 ??0.01 ??0.01 ??0.01 ??0.01 ??0.01 ??0.02 ??0.01 ??0.01 ??0.02 ??0.02 ??0.02 ??0.02 ??0.02 ??0.02 ? ??0.02 ? ??0.02 ? ? | ?- ?- ?- ?- ?- ?- ?- ?- ?- ?- ?- ?- ?- ?Zr：0.3 ?Cr：0.4 ?Mo：0.3 ?Pd：0.1 ?Cr：0.4 ?Zr：0.3 ?Cr：0.2 ?Zr：0.2 ?Cr：0.2 ?Nb：0.2 | ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ? ○ ? | ?735 ?700 ?725 ?676 ?725 ?720 ?685 ?700 ?685 ?700 ?705 ?695 ?695 ?720 ?740 ?730 ?740 ? ?745 ? ?745 ? ? | ???90 ???80 ???70 ???80 ???60 ???70 ???70 ???60 ???70 ???60 ???60 ???70 ???70 ???65 ???65 ???65 ???65 ? ???65 ? ???60 ? ? | ??1250 ??1230 ??1220 ??1200 ??1320 ??1250 ??1230 ??1270 ??1265 ??1285 ??1285 ??1280 ??1280 ??1290 ??1290 ??1290 ??1290 ? ??1295 ? ??1300 ? ? | ??12.5 ??12.6 ??12.9 ??13.0 ??10.5 ??12.1 ??14.5 ??12.5 ??12.3 ??12.8 ??13.0 ??12.8 ??12.9 ??12.8 ??12.9 ??12.8 ??12.5 ? ??12.5 ? ??12.3 ? ? | The inventive example " " " " " " " " " " " " " " " " " " |
[-] is impurity level.
The ※ crackle estimates zero: flawless △: the limit split little *: the limit is split greatly
Table 2
| Experiment numbers | Chemical constitution (quality %) [remainder is Fe and impurity] | The cold rolling calendering crackle of ※ | After the solid solution | After the burin-in process | Remarks | ||||||||||
| ? ??V | ? ????Al | ? ????Sn | ? ??O | ? ???H | ? ???Fe | ? ??C | ? ???N | Other | Tensile strength (MPa) | Crystallization particle diameter (μ m) | Tensile strength (MPa) | Extensibility (%) | |||
| 20 21 22 23 24 25 26 27 28 29 30 31 32 33 | ??20.0 ??20.0 ??20.0 ??20.0 ??20.0 ?*12.0 ??20.1 ??20.1 ??20.1 ?*27.1 ??20.0 ??20.0 ??15.0 ?*4.0 | ????3.2 ????3.2 ????3.2 ????3.2 ????3.2 ????3.0 ???*6.0 ????3.0 ????3.0 ????3.0 ????3.0 ????3.0 ????3.0 ???*6.0 | ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ???*5.0 ????1.0 ????1.0 ????1.2 ????1.2 ????3.0 ????*- | ??0.11 ??0.11 ??0.11 ??0.11 ??0.11 ??0.10 ??0.10 ??0.10 ?*0.30 ??0.10 ??0.10 ??0.10 ??0.12 ??0.12 | ??*0.042 ??*0.060 ???0.020 ???0.022 ???0.018 ???0.020 ???0.015 ???0.010 ???0.022 ???0.021 ??*0.060 ???0.020 ???0.017 ???0.015 | ??*0.41 ???0.10 ??*0.45 ???0.10 ???0.11 ???0.12 ???0.12 ???0.11 ???0.09 ???0.11 ???0.11 ???0.11 ???0.11 ???0.10 | ?*0.06 ??0.02 ??0.02 ?*0.07 ??0.01 ??0.01 ??0.01 ??0.01 ??0.01 ??0.02 ??0.02 ??0.02 ??0.01 ??0.01 | ??*0.05 ???0.01 ???0.02 ???0.02 ??*0.12 ???0.01 ???0.01 ???0.01 ???0.01 ???0.02 ???0.02 ???0.02 ???0.01 ???0.01 | ?- ?- ?- ?- ?- ?- ?- ?- ?- ?- ?- ?*Zr：4.0 ?*Cr：3.0 ??- | △ ○ ○ △ △ × × △ × ○ ○ × ○ × ? | ??810 ??710 ??790 ??760 ??760 ??900 ??930 ??800 ??900 ??780 ??695 ??910 ??820 ??1060 | ??50 ??70 ??65 ??60 ??70 ??100 ??60 ??60 ??60 ??60 ??65 ??65 ??90 ??55 | 1,090 905 1100 accident accident accident accidents, 1250 accidents, 1,100 900 accidents, 1280 accidents | 9.5 14.8 12.1 accident accident accident accidents, 6.5 accidents, 18.5 15.0 accidents, 11.0 accidents | Comparative example " " " " " " " " " " " " " |
* label table be shown in the present invention outside the fixed scope.[-] is impurity level.
The ※ crackle estimates zero: flawless △: the limit split little *: the limit is split greatly
Claims (5)
1. beta titanium alloy, it is characterized in that, in quality % by V:15～25%, Al:2.5～5%, Sn:0.5～4%, below the O:0.20%, below the H:0.03%, below the Fe:0.40%, below the C:0.05%, below the N:0.02%, remainder is that Ti and impurity constitute.
2. beta titanium alloy, it is characterized in that, in quality % by V:15～25%, Al:2.5～5%, Sn:0.5～4%, below the O:0.12%, below the H:0.03%, below the Fe:0.15%, below the C:0.03%, below the N:0.02%, remainder is that Ti and impurity constitute.
3. beta titanium alloy, it is characterized in that, in quality % comprise V:15～25%, Al:2.5～5%, Sn:0.5～4%, below the O:0.20%, below the H:0.03%, below the Fe:0.40%, below the C:0.05%, below the N:0.02% and respectively less than 3% among Zr, Mo, Nb, Ta, Cr, Mn, Ni, Pd and the Si more than one of being selected from, remainder is made of Ti and impurity.
4. the manufacture method of a beta titanium alloy, it is characterized in that, will in quality % by V:15～25%, Al:2.5～5%, Sn:0.5～4%, below the O:0.20%, below the H:0.03%, below the Fe:0.40%, below the C:0.05%, below the N:0.02%, remainder is the beta titanium alloy that Ti and impurity constitute, at first the HF in order to 3～40 quality % is the solution acid pickling of principal constituent, then with containing the HF of 3～6 quality % and the HNO of 5～20 quality %
3Solution acid pickling.
5. the manufacture method of a beta titanium alloy, it is characterized in that, to comprise V:15～25% in quality %, Al:2.5～5%, Sn:0.5～4%, below the O:0.20%, below the H:0.03%, below the Fe:0.40%, below the C:0.05%, N:0.02% is following and respectively less than 3% the Zr that is selected from, Mo, Nb, Ta, Cr, Mn, Ni, among Pd and the Si more than one, the beta titanium alloy that remainder is made of Ti and impurity, at first the HF in order to 3～40 quality % is the solution acid pickling of principal constituent, then with containing the HF of 3～6 quality % and the HNO of 5～20 quality %
3Solution acid pickling.
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| JP2002169441 | 2002-06-11 | ||
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| CN1659295A true CN1659295A (en) | 2005-08-24 |
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| US (1) | US20060062685A1 (en) |
| EP (1) | EP1533391A4 (en) |
| KR (1) | KR20050005506A (en) |
| CN (1) | CN1659295A (en) |
| TW (1) | TWI278520B (en) |
| WO (1) | WO2003104506A1 (en) |
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- 2003-06-09 EP EP03736120A patent/EP1533391A4/en not_active Withdrawn
- 2003-06-09 WO PCT/JP2003/007297 patent/WO2003104506A1/en not_active Application Discontinuation
- 2003-06-09 CN CN038132583A patent/CN1659295A/en active Pending
- 2003-06-11 TW TW092115877A patent/TWI278520B/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| EP1533391A8 (en) | 2006-04-26 |
| US20060062685A1 (en) | 2006-03-23 |
| KR20050005506A (en) | 2005-01-13 |
| TW200401833A (en) | 2004-02-01 |
| EP1533391A4 (en) | 2006-02-15 |
| TWI278520B (en) | 2007-04-11 |
| EP1533391A1 (en) | 2005-05-25 |
| WO2003104506A1 (en) | 2003-12-18 |
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