CN105403093B - High corrosion-proof titanium alloy heat exchanger - Google Patents
High corrosion-proof titanium alloy heat exchanger Download PDFInfo
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- CN105403093B CN105403093B CN201510915464.XA CN201510915464A CN105403093B CN 105403093 B CN105403093 B CN 105403093B CN 201510915464 A CN201510915464 A CN 201510915464A CN 105403093 B CN105403093 B CN 105403093B
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/081—Heat exchange elements made from metals or metal alloys
- F28F21/086—Heat exchange elements made from metals or metal alloys from titanium or titanium alloys
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
- F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
- F28F19/04—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of rubber; of plastics material; of varnish
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
The invention discloses a kind of high corrosion-proof titanium alloy heat exchanger, including heat-exchange device one and heat-exchange device two, one end of the heat-exchange device one is equipped with an outer chamber, the other end is equipped with an inner chamber body, one end of the outer chamber is equipped with a heat source import, middle part is equipped with a cold liquid inlet, the other end is connected with the heat-exchange device one, the top of the heat-exchange device two is equipped with a thermal source outlet, lower part is equipped with stent, the cantilever end of heat-exchange device two is equipped with an end socket, the end socket is equipped with a cold liquid outlet, the cold liquid inlet is goed deep into inside the outer chamber with a heat exchange inner cavity being connected and being integrated certainly.The high corrosion-proof titanium alloy heat exchanger of the present invention can adapt to the strong acid-base environment in chemical industry, simple and reasonable, and heat exchange efficiency is high, and durable, less scaling, leakproofness is good；A kind of highly corrosion resistant titanium alloy of titanium alloy heat-exchange tube is also provided at the same time, titanium alloy heat-exchange tube is possessed preferably corrosion resistance, consistency higher, can adapt to various complex environments at 400 DEG C completely.
Description
Technical field
The present invention relates to anticorrosion equipment field, more particularly to a kind of high corrosion-proof titanium alloy heat exchanger.
Background technology
Heat exchanger in industrial circle using quite varied, in oil refining, chemical industry, petrochemical industry, metallurgy, electric power, light industry, food
It is commonly used etc. industry, the energy can be saved, makes full use of the energy, realizes the recycling of high temperature low temperature heat energy, heat exchanger is a kind of
Realize the energy-saving equipment of heat transfer between material.Heat exchanger can be divided into carbon steel according to material, stainless steel, titanium alloy, glass,
Plastics, graphite, can be divided into the forms such as spiral plate, tablet, spray, tubulation according to the structure used.Traditional heat exchanger, exists
Take up a large area, the shortcomings that metal consumption is more, under strong acid environment, the problem of corrosion resistance is low, and heat exchange efficiency is low.
The content of the invention
The goal of the invention of the present invention is：For above-mentioned problem, there is provided a kind of high corrosion-proof titanium alloy heat exchanger, energy
The strong acid-base environment in chemical industry is enough adapted to, simple in structure, it is reasonable to set, and heat exchange efficiency is high, durable, less scaling, sealing
Property is good；A kind of highly corrosion resistant titanium alloy of titanium alloy heat-exchange tube is also provided at the same time, possesses titanium alloy heat-exchange tube
Preferably corrosion resistance, consistency higher, can reach 92.5%, can adapt to various complex environments at 400 DEG C completely.In addition,
By optimizing preparation process, titanium alloy heat-exchange tube is also equipped with good plasticity and intensity, improve the processability of titanium alloy
Can, make titanium alloy that there is excellent cold-bending property and cold-press moulding performance, manufacture easy to process.
The technical solution adopted by the present invention is as follows：A kind of high corrosion-proof titanium alloy heat exchanger, including heat-exchange device one and heat
Switch two, one end of the heat-exchange device one are equipped with an outer chamber, and the other end is equipped with an inner chamber body, the outer chamber
One end is equipped with a heat source import, and middle part is equipped with a cold liquid inlet, and the other end is connected with the heat-exchange device one, the inner chamber body
One end be connected with the heat-exchange device one, the other end connects the heat-exchange device two, the heat-exchange device two it is upper
Portion is equipped with a thermal source outlet, and lower part is equipped with stent, and the cantilever end of heat-exchange device two is equipped with an end socket, and the end socket is equipped with one
Cold liquid outlet, the cold liquid inlet are goed deep into inside the outer chamber with a heat exchange inner cavity being connected and being integrated certainly, and the heat is handed over
Change inner cavity and run through the heat-exchange device one and heat-exchange device two, and be connected in the end socket and be integrated certainly, it is such to set
Putting makes cold liquid and heat source are separated from each other in heat exchanging process, and isolation is good, will not interpenetrate pollution, ensure that work
The stability of work.
Further, the heat-exchange device one is titanium alloy heat-exchange tube, and tube wall changes cumuliformis in winding, heat-exchange device one
It is tightly connected with the inner chamber body connection by being brazed form, heat-exchange device one is equipped with the outer chamber connection
Installation base, the installation base are tightly connected with the outer chamber, and so setting can be such that heat source is annularly flowed along tube wall
It is dynamic, extend residence time of the heat source in pipe, and then heat-exchange time is added, improve heat exchange efficiency；And handed in titanium alloy heat
Change and installation base is set on pipe, titanium alloy heat-exchange tube can be made to be realized with outer chamber and be tightly connected well, even if because of outside
Reason and shake, its leakproofness will not be influenced.
Further, the heat-exchange device two is columnar structured for one, and heat-exchange device two is connected with the inner chamber body
One end is equipped with a circle mounting flange, and the mounting flange, from being integrated, uniformly divides with the heat-exchange device two on mounting flange
Several mounting grooves are furnished with, bolt is equipped with the mounting groove, mounting flange is tightly connected by bolt and the inner chamber body.If
The purpose for putting heat-exchange device two is to be on the one hand to increase heat exchange efficiency, is on the other hand to precipitate the dirt in heat source
After heat-exchange device one exchanges heat, its heat and flowing velocity substantially reduce for dirt, i.e. heat source, except in order to make full use of waste heat
Outside, incrustation scale can be crystallized out in heat source, these incrustation scales can be attached in tube wall if discharging not in time, so as to influence to exchange heat, reduced
Heat exchange efficiency, by the precipitation of heat-exchange device two, can make incrustation scale absorption exchange heat on heat-exchange device two without influencing,
It is also convenient for when clearing up at the same time quick.
Further, the outer chamber is columnar structured for one, and the one end of outer chamber with heat source import is closed, and the other end is equipped with
Through hole, the inner chamber body is also columnar structured for one, and the both ends of inner chamber body also are provided with through hole.
Further, the heat exchange inner cavity is cylindrical shape, and barrel also changes cumuliformis for winding, and the diameter of heat exchange inner cavity is less than
The diameter of the heat-exchange device one and heat-exchange device two, is coated with one layer of polytetrafluoroethyl-ne on the inside and outside wall of heat exchange inner cavity
Alkene film, the thickness of the polytetrafluoroethylene film is 200-500 μm.The barrel of heat exchange inner cavity is also configured to winding to change cumuliformis,
The circulation effect of heat source can be increased, increase heat exchange area, further improve heat exchange efficiency, and poly- four are set in heat exchange inner cavity
Fluoride film can reduce depending on for the incrustation scale produced in heat transfer process and crystal, heat exchange inner cavity is kept clean, maintain
Heat exchange efficiency.
Further, strainer is additionally provided with the cold liquid inlet and heat source import, the strainer is fixedly mounted on the cold liquid
On the inner wall of import and heat source import, this prevents other debris enter high corrosion-proof titanium alloy heat exchanger in, ensure heat exchange
Passage is unobstructed.
Further, titanium alloy heat-exchange tube used in the heat-exchange device one is made with highly corrosion resistant titanium alloy,
The highly corrosion resistant titanium alloy is made of the component of following mass percent：Aluminium is 4.5-5.3%, tin 1.8-2.3%, and nickel is
0.05-0.15%, yttrium 0.005-0.056%, iridium 0.05-0.087%, chromium 0.1-0.23%, molybdenum 0.2-0.38%, manganese are
0.7-1.2%, vanadium 4.5-6.1%, niobium 0.2-1.2%, zirconium 0.12-1.2%, surplus are titanium and its inevitable impurity.
Further, the highly corrosion resistant titanium alloy is made by following steps：
Step 1, according to the titanium alloy component ratio of standby highly corrosion resistant of drawing up, matched raw material titanium deal and other
The deal of alloying element is added, then by raw material titanium and other addition alloying elements respectively with ball mill grinding into powder, until
Untill the particle mean size of powder is less than 60 μm, then obtained raw material titanium valve and other addition alloying element powders are added together
Into three-dimensional material mixer, and it is uniformly mixed under argon gas atmosphere protection, obtains mixture A；
The mixture A obtained in step 1, be fitted into the mould made in advance by step 2, is 350- in compacting pressure
Mixture A is pressed into required shape with cold isostatic pressing process under 370MPa, obtains pressed compact B, pressed compact B is then put into vacuum-sintering
In stove；
After the completion of step 3, step 2, to vacuum-sintering stove evacuation until vacuum reaches 5 × 10-4Pa, then passes to argon
Gas is further continued for being evacuated to 5 × 10 until recovery normal pressure-4Pa, then argon gas is passed through, repetitive operation is three times；
After the completion of step 4, step 3, start vacuum-sintering, heating vacuum sintering furnace is to 1250-1300 DEG C, heating rate control
Make in 7-10 DEG C/min, then keep the temperature 6-7h, finally cool to room temperature with the furnace, obtain titanium alloy heat-exchange tube.
Further, in step 1, the raw material titanium is the high-purity titanium that production is decomposed with titanium iodide method, its purity is 99.7-
99.9%；In step 4, needed in vacuum-sintering and cooling procedure to vacuumize and keep always in vacuum sintering furnace vacuum for 5 ×
10-4Below Pa.
Further, the titanium alloy heat-exchange tube obtained by above-mentioned technique also needs to be heat-treated, its heat treatment process bag
Include following steps：
Step 1, quenching：Titanium alloy heat-exchange tube is placed in heat-treatment furnace, heats titanium alloy heat-exchange tube to 930 DEG C,
Heating rate control is in 90-100 DEG C/h, insulation 1-2.5h, then water quenching to room temperature；
After the completion of step 2, quenching, continue titanium alloy heat-exchange tube being placed in heat-treatment furnace, heat titanium alloy heat exchange
For pipe to 505 DEG C, heating rate control is air-cooled to room temperature after 60-70 DEG C/h, insulation 4-6h.
In the formula of the highly corrosion resistant titanium alloy of the present invention, aluminium is typical α stable elements, and aluminium can play in titanium
Good solution strengthening effect, can improve the heat endurance and elasticity modulus of titanium alloy, reduce the rigidity of titanium alloy, improve it and add
Work performance, is alloying element important in titanium alloy, but after the mass fraction of aluminium is more than 6%, ordered phase occurs in titanium alloy
Ti3Al and become fragile, this is unfavorable for the processing performance and mechanical property of titanium alloy very much, therefore the content control of aluminium exists in the present invention
4.5-5.3%；Tin belongs to neutral element in titanium alloy, can strengthen α phases, and improves the creep resisting ability of titanium alloy；Nickel adds
Enter mainly to further improve the corrosion resistance of titanium alloy, expand the scope of application of titanium alloy；The addition of yttrium can refine titanium
The crystalline phase of alloy, improves its mechanical property, and with the increase of yttrium content, thinning effect enhancing, thinning effect does not continue to strengthen,
The reason is that yttrium is added in titanium alloy, and it is to exist in the form of little particle yttrium oxide, when yttrium content reaches 0.12%, little particle yttrium
Oxide is thicker, increasing number, and thinning effect does not continue to strengthen, and considers, and in the present invention, the content control of yttrium exists
0.005-0.056%；The addition of iridium can reduce the hydrogen overvoltage of titanium alloy, natural potential is maintained to passive state regional effect, energy
The corrosion resistance of titanium alloy is further improved, when the content of iridium is less than 0.05%, the enhancing to titanium alloy corrosion resistance is unknown
It is aobvious, its effect can not be played, when the content of iridium is higher than 0.15%, the enhancing to titanium alloy corrosion resistance is slowed down, and effect is not shown
Write, and since the price of raw material iridium is high, usage amount should not be excessive, therefore, considers, the content control of iridium in the present invention
System is in 0.05-0.087%；Chromium is beta stable element, and eutectoid reaction can occur in titanium alloy, its critical concentration is than β isomorphous elements
It is all low, therefore its stable β phases ability is bigger than β isomorphous elements, under general cooling condition, β phases can decompose completely, when having alloy
Reinforcing ability is imitated, improves the heat resistance of titanium alloy, produces dispersion-strengthened action, it is contemplated that the quality of β phases point in alpha and beta type titan alloy
Number is generally in 4-6%, and therefore, the dosage of chromium should not be excessive, and the content of chromium is controlled in 0.1-0.23% in the present invention；Molybdenum and vanadium are in titanium
Solution strengthening effect can be played in alloy, and the heat endurance and creep resistance of titanium alloy can be improved, increases the content of β phases, and makes β
It is mutually more stable；Manganese is eutectoid type beta stable element, and the room temperature ductility of titanium alloy can be improved by adding a small amount of manganese, in machining titanium alloy
During, to the pinning effect of the imperfect dislocation of titanium alloy when manganese eliminates room temperature, the mobility of super-dislocation is added, is reduced
The stacking fault energy of titanium alloy, and then improved the plasticity of titanium alloy, this is extremely important to titanium alloy product, this causes titanium
Alloy work in-process is not in obvious crackle, and then ensures processing quality；The addition of niobium has greatly to providing low Young's modulus
Help, since niobium isomorphism β-stabilizer is enough after quick cooling by reducing beta transus temperature and slowing down in cooling procedure
The precipitation of α phases assists to form α ' martensitic phases (hexagonal crystallographic texture) from β phases field, improves the intensity of titanium alloy；Zirconium is as one
Kind reinforced alloys element, can reduce the transition temperature of β phases, so as to assist to form α ' martensitic phases, and will not reduce titanium conjunction
The ductility and bending property of gold.
In preparation process, the titanium alloy of the highly corrosion resistant of high-compactness is obtained by using powder metallurgic method, into
One step ensures that titanium alloy possesses excellent mechanical property, meanwhile, simplify existing powder metallurgic method and prepare titanium alloy technique, shorten titanium
The manufacturing cycle of alloy, improves work efficiency, in addition, being handled by a large number of experiments, and to data, obtains optimal work
Skill parameter, by using these technological parameters, improves the consistency of titanium alloy, consistency can reach 92.5%.And to be made after
Titanium alloy be heat-treated, the tensile strength and elongation of titanium alloy can be further improved, make titanium alloy below 400 DEG C
When with stable tissue and higher creep ability, being capable of the long-term work below 400 DEG C.
In conclusion by adopting the above-described technical solution, the beneficial effects of the invention are as follows：The high corrosion resistant titanium of the present invention closes
Golden heat exchanger can adapt to the strong acid-base environment in chemical industry, simple in structure, and it is reasonable to set, and heat exchange efficiency is high, durable, is not easy
Fouling, leakproofness are good；A kind of highly corrosion resistant titanium alloy of titanium alloy heat-exchange tube is also provided at the same time, hands over titanium alloy heat
The standby preferably corrosion resistance of pipe is changed, consistency higher, can reach 92.5%, can adapt to various complexity rings at 400 DEG C completely
Border.In addition, by optimizing preparation process, titanium alloy heat-exchange tube is also equipped with good plasticity and intensity, improve titanium alloy
Processing performance, make titanium alloy that there is excellent cold-bending property and cold-press moulding performance, manufacture easy to process.
Brief description of the drawings
Fig. 1 is a kind of high corrosion-proof titanium alloy heat exchanger structure schematic diagram of the present invention.
Fig. 2 is the SEM metallographic structure figures of the highly corrosion resistant titanium alloy of the present invention.
Marked in figure：1 is heat-exchange device one, and 2 be heat-exchange device two, and 3 be outer chamber, and 4 be inner chamber body, and 5 be heat source
Import, 6 be cold liquid inlet, and 7 be thermal source outlet, and 8 be stent, and 9 be end socket, and 10 be cold liquid outlet, and 11 be installation base, and 12 be peace
Flange is filled, 13 be heat exchange inner cavity, and 14 be strainer.
Embodiment
Below in conjunction with the accompanying drawings, the present invention is described in detail.
In order to which the object, technical solution and advantage of invention are more clearly understood, with reference to the accompanying drawings and embodiments, to this
Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.
Embodiment one
As shown in Figure 1, a kind of high corrosion-proof titanium alloy heat exchanger, including heat-exchange device 1 and heat-exchange device 22, institute
The one end for stating heat-exchange device 1 is equipped with an outer chamber 3, and the other end is equipped with an inner chamber body 4, and one end of the outer chamber 3 is equipped with
One heat source import 5, middle part are equipped with a cold liquid inlet 6, and the other end is connected with the heat-exchange device 1, and the one of the inner chamber body 4
End is connected with the heat-exchange device 1, and the other end connects the heat-exchange device 22, the top of the heat-exchange device 22
Equipped with a thermal source outlet 7, lower part is equipped with stent 8, and the cantilever end of heat-exchange device 22 is equipped with an end socket 9, is set on the end socket 9
There is a cold liquid outlet 10, it is simultaneously one certainly that the cold liquid inlet 6, which gos deep into the inside of outer chamber 3 with a heat exchange inner cavity 13 to be connected,
The heat-exchange device 1 and heat-exchange device 22 are run through in body, the heat exchange inner cavity 13, and in the end socket 9 be connected and from
Be integrated, the heat-exchange device 1 is titanium alloy heat-exchange tube, and tube wall changes cumuliformis in winding, heat-exchange device 1 with it is described
Inner chamber body connection is tightly connected by being brazed form, and heat-exchange device 1 is equipped with installation with 3 connection of outer chamber
Boss 11, the installation base 11 are tightly connected with the outer chamber 3, and the heat-exchange device 22 is columnar structured for one, heat
One end that switch 22 is connected with the inner chamber body 4 is equipped with a circle mounting flange 12, and the mounting flange 12 is handed over the heat
Changing device 22 is evenly distributed with several mounting grooves, bolt is equipped with the mounting groove, pacify from being integrated on mounting flange 12
Dress flange 12 is tightly connected by bolt and the inner chamber body 4, and the outer chamber 3 is columnar structured for one, and outer chamber 3 is with heat source
One end of import 5 is closed, and the other end is equipped with through hole, and the inner chamber body 4 is also columnar structured for one, and the both ends of inner chamber body 4 are also set
There is a through hole, the heat exchange inner cavity 13 is cylindrical shape, and barrel also changes cumuliformis for winding, and the diameter of heat exchange inner cavity 13 is less than described
The diameter of heat-exchange device 1 and heat-exchange device 22, is coated with one layer of polytetrafluoroethyl-ne on the inside and outside wall of heat exchange inner cavity 13
Alkene film, the thickness of the polytetrafluoroethylene film is 200-500 μm（Optimum thickness be 350 μm, naturally it is also possible to select 200 μm or
500 μm of person）, strainer 14 is additionally provided with the cold liquid inlet 6 and heat source import 5, and the strainer 14 is fixedly mounted on the cold liquid
Into on the inner wall of 6 mouthfuls and heat source import 5.
Cold liquid is entered in heat exchange inner cavity 13 from cold liquid inlet 6, is then discharged from cold liquid outlet 10, heat source from heat source into
Mouth 5 enters in high corrosion-proof titanium alloy heat exchanger, then discharges high corrosion-proof titanium alloy heat exchanger from thermal source outlet 7, in the process,
Heat source is flowed around heat exchange inner cavity, and heat exchange occurs with the cold flow in heat exchange inner cavity 13, and heat exchange is simple in structure tight than big
Gather, less scaling, leakproofness is good.
In the present embodiment, titanium alloy heat-exchange tube highly corrosion resistant titanium alloy system used in the heat-exchange device 1
Form, the highly corrosion resistant titanium alloy is made of the component of following mass percent：Aluminium is 4.8%, tin 2.1%, and nickel is
0.12%, yttrium 0.047%, iridium 0.061%, chromium 0.16%, molybdenum 0.31%, manganese 0.9%, vanadium 5.4%, niobium 0.7%, zirconium
For 0.89%, surplus is titanium and its inevitable impurity, and the highly corrosion resistant titanium alloy is made by following steps：
Step 1, according to the titanium alloy component ratio of standby highly corrosion resistant of drawing up, matched raw material titanium deal and other
The deal of alloying element is added, then by raw material titanium and other addition alloying elements respectively with ball mill grinding into powder, until
Untill the particle mean size of powder is less than 60 μm, then obtained raw material titanium valve and other addition alloying element powders are added together
Into three-dimensional material mixer, and it is uniformly mixed under argon gas atmosphere protection, obtains mixture A, wherein, the raw material titanium is to use iodate
Titanium method decomposes the high-purity titanium of production, its purity is 99.7%；
The mixture A obtained in step 1, be fitted into the mould made in advance by step 2, is 355MPa in compacting pressure
It is lower that mixture A is pressed into required shape with cold isostatic pressing process, pressed compact B is obtained, then pressed compact B is put into vacuum sintering furnace；
After the completion of step 3, step 2, to vacuum-sintering stove evacuation until vacuum reaches 5 × 10-4Pa, then passes to argon
Gas is further continued for being evacuated to 5 × 10 until recovery normal pressure-4Pa, then argon gas is passed through, repetitive operation is three times；
After the completion of step 4, step 3, start vacuum-sintering, to 1270 DEG C, heating rate is controlled 8 heating vacuum sintering furnace
DEG C/min, 6.5h is then kept the temperature, finally cools to room temperature with the furnace, obtains titanium alloy heat-exchange tube, wherein, vacuum-sintering and cooling
During need to vacuumize and keep always in vacuum sintering furnace vacuum be 5 × 10-4Below Pa.
In the present embodiment, the titanium alloy heat-exchange tube obtained by above-mentioned technique also needs to be heat-treated, it is heat-treated
Technique includes following steps：
Step 1, quenching：Titanium alloy heat-exchange tube is placed in heat-treatment furnace, heats titanium alloy heat-exchange tube to 930 DEG C,
Heating rate control is in 93 DEG C/h, insulation 2h, then water quenching to room temperature；
After the completion of step 2, quenching, continue titanium alloy heat-exchange tube being placed in heat-treatment furnace, heat titanium alloy heat exchange
For pipe to 505 DEG C, heating rate control is air-cooled to room temperature after 64 DEG C/h, insulation 5.5h.
Embodiment two
The embodiment is identical with embodiment one, its difference is, the highly corrosion resistant titanium alloy is by following quality
The component composition of percentage：Aluminium is 4.5%, tin 1.8%, nickel 0.15%, yttrium 0.005%, iridium 0.087%, chromium 0.1%,
Molybdenum is 0.38%, manganese 0.7%, vanadium 6.1%, niobium 0.2%, zirconium 1.2%, and surplus is titanium and its inevitable impurity, described
Highly corrosion resistant titanium alloy is made by following steps：
Step 1, according to the titanium alloy component ratio of standby highly corrosion resistant of drawing up, matched raw material titanium deal and other
The deal of alloying element is added, then by raw material titanium and other addition alloying elements respectively with ball mill grinding into powder, until
Untill the particle mean size of powder is less than 60 μm, then obtained raw material titanium valve and other addition alloying element powders are added together
Into three-dimensional material mixer, and it is uniformly mixed under argon gas atmosphere protection, obtains mixture A, wherein, the raw material titanium is to use iodate
Titanium method decomposes the high-purity titanium of production, its purity is 99.8%；
The mixture A obtained in step 1, be fitted into the mould made in advance by step 2, is 350MPa in compacting pressure
It is lower that mixture A is pressed into required shape with cold isostatic pressing process, pressed compact B is obtained, then pressed compact B is put into vacuum sintering furnace；
After the completion of step 3, step 2, to vacuum-sintering stove evacuation until vacuum reaches 5 × 10-4Pa, then passes to argon
Gas is further continued for being evacuated to 5 × 10 until recovery normal pressure-4Pa, then argon gas is passed through, repetitive operation is three times；
After the completion of step 4, step 3, start vacuum-sintering, heating vacuum sintering furnace is to 1250-1300 DEG C, heating rate control
Then system keeps the temperature 6h, finally cools to room temperature with the furnace, obtain titanium alloy heat-exchange tube in 10 DEG C/min, wherein, vacuum-sintering and
Need to be 5 × 10 to vacuumizing and keeping vacuum in vacuum sintering furnace always in cooling procedure-4Below Pa.
In the present embodiment, the titanium alloy heat-exchange tube obtained by above-mentioned technique also needs to be heat-treated, it is heat-treated
Technique includes following steps：
Step 1, quenching：Titanium alloy heat-exchange tube is placed in heat-treatment furnace, heats titanium alloy heat-exchange tube to 930 DEG C,
Heating rate control is in 90 DEG C/h, insulation 1h, then water quenching to room temperature；
After the completion of step 2, quenching, continue titanium alloy heat-exchange tube being placed in heat-treatment furnace, heat titanium alloy heat exchange
For pipe to 505 DEG C, heating rate control is air-cooled to room temperature after 60 DEG C/h, insulation 4h.
Embodiment three
The embodiment is identical with embodiment one and embodiment two, its difference is, the highly corrosion resistant titanium alloy
It is made of the component of following mass percent：Aluminium is 5.3%, tin 1.8%, nickel 0.05%, yttrium 0.056%, iridium 0.05%,
Chromium is 0.1%, molybdenum 0.38%, manganese 1.2%, vanadium 4.5%, niobium 1.2%, zirconium 0.12%, and surplus is for titanium and its unavoidably
Impurity, the highly corrosion resistant titanium alloy is made by following steps：
Step 1, according to the titanium alloy component ratio of standby highly corrosion resistant of drawing up, matched raw material titanium deal and other
The deal of alloying element is added, then by raw material titanium and other addition alloying elements respectively with ball mill grinding into powder, until
Untill the particle mean size of powder is less than 60 μm, then obtained raw material titanium valve and other addition alloying element powders are added together
Into three-dimensional material mixer, and it is uniformly mixed under argon gas atmosphere protection, obtains mixture A, wherein, the raw material titanium is to use iodate
Titanium method decomposes the high-purity titanium of production, its purity is 99.7%；
The mixture A obtained in step 1, be fitted into the mould made in advance by step 2, is 370MPa in compacting pressure
It is lower that mixture A is pressed into required shape with cold isostatic pressing process, pressed compact B is obtained, then pressed compact B is put into vacuum sintering furnace；
After the completion of step 3, step 2, to vacuum-sintering stove evacuation until vacuum reaches 5 × 10-4Pa, then passes to argon
Gas is further continued for being evacuated to 5 × 10 until recovery normal pressure-4Pa, then argon gas is passed through, repetitive operation is three times；
After the completion of step 4, step 3, start vacuum-sintering, to 1300 DEG C, heating rate control exists heating vacuum sintering furnace
10 DEG C/min, 7h is then kept the temperature, finally cools to room temperature with the furnace, obtain titanium alloy heat-exchange tube, wherein, vacuum-sintering and cooling
During need to vacuumize and keep always in vacuum sintering furnace vacuum be 5 × 10-4Below Pa.
In the present embodiment, the titanium alloy heat-exchange tube obtained by above-mentioned technique also needs to be heat-treated, it is heat-treated
Technique includes following steps：
Step 1, quenching：Titanium alloy heat-exchange tube is placed in heat-treatment furnace, heats titanium alloy heat-exchange tube to 930 DEG C,
Heating rate control is in 93 DEG C/h, insulation 2.5h, then water quenching to room temperature；
After the completion of step 2, quenching, continue titanium alloy heat-exchange tube being placed in heat-treatment furnace, heat titanium alloy heat exchange
For pipe to 505 DEG C, heating rate control is air-cooled to room temperature after 70 DEG C/h, insulation 4h.
Example IV
The embodiment is identical with embodiment one, embodiment two and embodiment three, its difference is, the highly corrosion resistant
Property titanium alloy is made of the component of following mass percent：Aluminium is 4.7%, tin 2.3%, nickel 0.05%, yttrium 0.056%, iridium
For 0.05%, chromium 0.1%, molybdenum 0.2%, manganese 0.7%, vanadium 4.5%, niobium 0.2%, zirconium 1.2%, surplus is for titanium and its not
Evitable impurity, the highly corrosion resistant titanium alloy are made by following steps：
Step 1, according to the titanium alloy component ratio of standby highly corrosion resistant of drawing up, matched raw material titanium deal and other
The deal of alloying element is added, then by raw material titanium and other addition alloying elements respectively with ball mill grinding into powder, until
Untill the particle mean size of powder is less than 60 μm, then obtained raw material titanium valve and other addition alloying element powders are added together
Into three-dimensional material mixer, and it is uniformly mixed under argon gas atmosphere protection, obtains mixture A, wherein, the raw material titanium is to use iodate
Titanium method decomposes the high-purity titanium of production, its purity is 99.9%；
The mixture A obtained in step 1, be fitted into the mould made in advance by step 2, is 363MPa in compacting pressure
It is lower that mixture A is pressed into required shape with cold isostatic pressing process, pressed compact B is obtained, then pressed compact B is put into vacuum sintering furnace；
After the completion of step 3, step 2, to vacuum-sintering stove evacuation until vacuum reaches 5 × 10-4Pa, then passes to argon
Gas is further continued for being evacuated to 5 × 10 until recovery normal pressure-4Pa, then argon gas is passed through, repetitive operation is three times；
After the completion of step 4, step 3, start vacuum-sintering, heating vacuum sintering furnace is to 1250-1300 DEG C, heating rate control
Make in 9 DEG C/min, then keep the temperature 6.5h, finally cool to room temperature with the furnace, obtain titanium alloy heat-exchange tube, wherein, vacuum-sintering
With needed in cooling procedure to vacuumize and keep always in vacuum sintering furnace vacuum be 5 × 10-4Below Pa.
In the present embodiment, the titanium alloy heat-exchange tube obtained by above-mentioned technique also needs to be heat-treated, it is heat-treated
Technique includes following steps：
Step 1, quenching：Titanium alloy heat-exchange tube is placed in heat-treatment furnace, heats titanium alloy heat-exchange tube to 930 DEG C,
Heating rate control is in 100 DEG C/h, insulation 2h, then water quenching to room temperature；
After the completion of step 2, quenching, continue titanium alloy heat-exchange tube being placed in heat-treatment furnace, heat titanium alloy heat exchange
For pipe to 505 DEG C, heating rate control is air-cooled to room temperature after 67 DEG C/h, insulation 5h.
Embodiment five
The embodiment is identical with embodiment one, embodiment two, embodiment three and example IV, its difference is, institute
Highly corrosion resistant titanium alloy is stated to be made of the component of following mass percent：Aluminium is 5.3%, tin 1.9%, nickel 0.08%, and yttrium is
0.034%, iridium 0.061%, chromium 0.23%, molybdenum 0.2%, manganese 0.93%, vanadium 5.3%, niobium 0.73%, zirconium 1.0% is remaining
Measure and be made for titanium and its inevitable impurity, the highly corrosion resistant titanium alloy by following steps：
Step 1, according to the titanium alloy component ratio of standby highly corrosion resistant of drawing up, matched raw material titanium deal and other
The deal of alloying element is added, then by raw material titanium and other addition alloying elements respectively with ball mill grinding into powder, until
Untill the particle mean size of powder is less than 60 μm, then obtained raw material titanium valve and other addition alloying element powders are added together
Into three-dimensional material mixer, and it is uniformly mixed under argon gas atmosphere protection, obtains mixture A, wherein, the raw material titanium is to use iodate
Titanium method decomposes the high-purity titanium of production, its purity is 99.7%；
The mixture A obtained in step 1, be fitted into the mould made in advance by step 2, is 350- in compacting pressure
Mixture A is pressed into required shape with cold isostatic pressing process under 370MPa, obtains pressed compact B, pressed compact B is then put into vacuum-sintering
In stove；
After the completion of step 3, step 2, to vacuum-sintering stove evacuation until vacuum reaches 5 × 10-4Pa, then passes to argon
Gas is further continued for being evacuated to 5 × 10 until recovery normal pressure-4Pa, then argon gas is passed through, repetitive operation is three times；
After the completion of step 4, step 3, start vacuum-sintering, to 1280 DEG C, heating rate is controlled 7 heating vacuum sintering furnace
DEG C/min, 7h is then kept the temperature, finally cools to room temperature with the furnace, obtains titanium alloy heat-exchange tube, wherein, vacuum-sintering and cooled
Cheng Zhongxu is 5 × 10 to vacuumizing and keeping vacuum in vacuum sintering furnace always-4Below Pa.
In the present embodiment, the titanium alloy heat-exchange tube obtained by above-mentioned technique also needs to be heat-treated, it is heat-treated
Technique includes following steps：
Step 1, quenching：Titanium alloy heat-exchange tube is placed in heat-treatment furnace, heats titanium alloy heat-exchange tube to 930 DEG C,
Heating rate control is in 95 DEG C/h, insulation 1.5h, then water quenching to room temperature；
After the completion of step 2, quenching, continue titanium alloy heat-exchange tube being placed in heat-treatment furnace, heat titanium alloy heat exchange
For pipe to 505 DEG C, heating rate control is air-cooled to room temperature after 67 DEG C/h, insulation 6h.
As shown in Fig. 2, Fig. 2 be the present invention highly corrosion resistant titanium alloy SEM metallographic structure figures, its metallographic structure for α+
β phases, have good comprehensive mechanical property, and intensity is higher, and plasticity is good, and metallographic small particles yttrium oxide Dispersed precipitate is in group
Between knitting, the crystalline phase tissue of titanium alloy is refined, consistency is high, improves its mechanical property.Titanium alloy is made in each embodiment
Heat-exchange tube respectively takes a sample, mechanical property when then testing its 400 DEG C with electronic universal mechanics machine, its result is as follows
Shown in table：
As seen from the above table, at 400 DEG C, the tensile strength of highly corrosion resistant titanium alloy of the invention reaches 680MPa, bends
Take intensity and reach 590MPa, elongation percentage reaches 13%, and the contraction percentage of area reaches 46%, and residual stress is less than 0.1%, therefore has
Good comprehensive mechanical property, intensity is higher, and plasticity is good, and specific strength is big.By titanium alloy heat-exchange tube made from each embodiment
In respectively take a sample again, by sample be put into boiling mass fraction be 10% hydrochloric acid in soak 100h after, measure sample mean corrosion
Speed is less than 7.0mm/a（Year）, it is after soaking 100h in 5% sulfuric acid, to measure sample mean by the mass fraction that sample is put into boiling
Corrosion rate is less than 3.0 mm/a（Year）, it is after soaking 100h in 60% nitric acid, to measure examination by the mass fraction that sample is put into boiling
Sample average corrosion rate is less than 0.01mm/a（Year）, therefore, highly corrosion resistant titanium alloy of the invention possesses excellent corrosion energy
Power.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of high corrosion-proof titanium alloy heat exchanger, including heat-exchange device one（1）With heat-exchange device two（2）, it is characterised in that
The heat-exchange device one（1）One end be equipped with an outer chamber（3）, the other end is equipped with an inner chamber body（4）, the outer chamber（3）
One end be equipped with a heat source import（5）, middle part is equipped with a cold liquid inlet（6）, the other end and the heat-exchange device one（1）Even
Connect, the inner chamber body（4）One end and the heat-exchange device one（1）Connection, the other end connect the heat-exchange device two
（2）, the heat-exchange device two（2）Top be equipped with a thermal source outlet（7）, lower part is equipped with stent（8）, heat-exchange device two
（2）Cantilever end be equipped with an end socket（9）, the end socket（9）It is equipped with a cold liquid outlet（10）, the cold liquid inlet（6）Deeply
The outer chamber（3）An internal and heat exchange inner cavity（13）It is connected and is integrated certainly, the heat exchange inner cavity（13）Through described
Heat-exchange device one（1）With heat-exchange device two（2）, and in the end socket（9）It is connected and is integrated certainly, the heat-exchange device
One（1）Titanium alloy heat-exchange tube used is made with highly corrosion resistant titanium alloy, and the highly corrosion resistant titanium alloy is by following
The component composition of mass percent：Aluminium is 4.5-5.3%, tin 1.8-2.3%, nickel 0.05-0.15%, yttrium 0.005-
0.056%, iridium 0.05-0.087%, chromium 0.1-0.23%, molybdenum 0.2-0.38%, manganese 0.7-1.2%, vanadium 4.5-6.1%,
Niobium is 0.2-1.2%, zirconium 0.12-1.2%, and surplus is titanium and its inevitable impurity, the highly corrosion resistant titanium alloy by
Following steps are made：
Step 1, the titanium alloy component ratio according to standby highly corrosion resistant of drawing up, have matched deal and other additions of raw material titanium
The deal of alloying element, then by raw material titanium and other addition alloying elements respectively with ball mill grinding into powder, until powder
Particle mean size be less than 60 μm untill, then by obtained raw material titanium valve and other addition alloying element powders be added to three together
Tie up in batch mixer, and be uniformly mixed under argon gas atmosphere protection, obtain mixture A；
The mixture A obtained in step 1, be fitted into the mould made in advance by step 2, is 350-370MPa in compacting pressure
It is lower that mixture A is pressed into required shape with cold isostatic pressing process, pressed compact B is obtained, then pressed compact B is put into vacuum sintering furnace；
After the completion of step 3, step 2, to vacuum-sintering stove evacuation until vacuum reaches 5 × 10-4Pa, it is straight to then pass to argon gas
To normal pressure is recovered, it is further continued for being evacuated to 5 × 10-4Pa, then argon gas is passed through, repetitive operation is three times；
After the completion of step 4, step 3, start vacuum-sintering, to 1250-1300 DEG C, heating rate control exists heating vacuum sintering furnace
7-10 DEG C/min, 6-7h is then kept the temperature, finally cools to room temperature with the furnace, obtain titanium alloy heat-exchange tube.
2. high corrosion-proof titanium alloy heat exchanger as claimed in claim 1, it is characterised in that the heat-exchange device one（1）For titanium
Alloy heat-exchange tube, tube wall change cumuliformis in winding, heat-exchange device one（1 ）With the inner chamber body（4）Connection passes through soldering
Form is tightly connected, heat-exchange device one（1）With the outer chamber（3）Connection is equipped with installation base（11）, the installation
Boss（11）With the outer chamber（3）It is tightly connected.
3. high corrosion-proof titanium alloy heat exchanger as claimed in claim 2, it is characterised in that the heat-exchange device two（2）For one
It is columnar structured, heat-exchange device two（2）With the inner chamber body（4）One end of connection is equipped with a circle mounting flange（12）, it is described
Mounting flange（12）With the heat-exchange device two（2）From being integrated, mounting flange（12）On be evenly distributed with several installations
Groove, the mounting groove is interior to be equipped with bolt, mounting flange（12）Pass through bolt and the inner chamber body（4）It is tightly connected.
4. high corrosion-proof titanium alloy heat exchanger as claimed in claim 3, it is characterised in that the outer chamber（3）For a cylindrical shape
Structure, outer chamber（3）Band heat source import（5）One end it is closed, the other end is equipped with through hole, the inner chamber body（4）Also it is a cylinder
Shape structure, inner chamber body（4）Both ends also be provided with through hole.
5. high corrosion-proof titanium alloy heat exchanger as claimed in claim 4, it is characterised in that the heat exchange inner cavity（13）For cylinder
Shape, barrel also change cumuliformis for winding, heat exchange inner cavity（13）Diameter be less than the heat-exchange device one（1）And heat-exchange device
Two（2）Diameter, be coated with a strata tetrafluoroethylene, the thickness of the polytetrafluoroethylene film on the inside and outside wall of heat exchange inner cavity
Spend for 200-500 μm.
6. the high corrosion-proof titanium alloy heat exchanger as described in one of claim 1-5, it is characterised in that the cold liquid inlet（6）With
Heat source import（5）Place is additionally provided with strainer（14）, the strainer（14）It is fixedly mounted on the cold liquid inlet（6）And heat source import
（5）Inner wall on.
7. high corrosion-proof titanium alloy heat exchanger as claimed in claim 6, it is characterised in that in step 1, the raw material titanium is to use iodine
Change the high-purity titanium that titanium method decomposes production, its purity is 99.7-99.9%；In step 4, needed in vacuum-sintering and cooling procedure pair
It is 5 × 10 to be vacuumized always in vacuum sintering furnace and keep vacuum-4Below Pa.
8. high corrosion-proof titanium alloy heat exchanger as claimed in claim 7, it is characterised in that the titanium alloy obtained by above-mentioned technique
Heat-exchange tube also needs to be heat-treated, its heat treatment process includes following steps：
Step 1, quenching：Titanium alloy heat-exchange tube is placed in heat-treatment furnace, heating titanium alloy heat-exchange tube is to 930 DEG C, heating
Speed control is in 90-100 DEG C/h, insulation 1-2.5h, then water quenching to room temperature；
After the completion of step 2, quenching, continue titanium alloy heat-exchange tube being placed in heat-treatment furnace, heating titanium alloy heat-exchange tube is extremely
505 DEG C, heating rate control is air-cooled to room temperature after 60-70 DEG C/h, insulation 4-6h.
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| JP5148820B2 (en) * | 2005-09-07 | 2013-02-20 | 株式会社イーアンドエフ | Titanium alloy composite material and manufacturing method thereof |
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