CN115961228B - Preparation method of titanium plate for deep drawing - Google Patents
Preparation method of titanium plate for deep drawing Download PDFInfo
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- CN115961228B CN115961228B CN202310014741.4A CN202310014741A CN115961228B CN 115961228 B CN115961228 B CN 115961228B CN 202310014741 A CN202310014741 A CN 202310014741A CN 115961228 B CN115961228 B CN 115961228B
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000010936 titanium Substances 0.000 title claims abstract description 109
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005096 rolling process Methods 0.000 claims abstract description 150
- 238000011282 treatment Methods 0.000 claims abstract description 149
- 238000000137 annealing Methods 0.000 claims abstract description 90
- 238000005098 hot rolling Methods 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 51
- 238000005097 cold rolling Methods 0.000 claims abstract description 36
- 238000005242 forging Methods 0.000 claims abstract description 33
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 238000005554 pickling Methods 0.000 claims description 88
- 238000000227 grinding Methods 0.000 claims description 84
- 239000003513 alkali Substances 0.000 claims description 79
- 238000010438 heat treatment Methods 0.000 claims description 63
- 239000002253 acid Substances 0.000 claims description 50
- 238000005406 washing Methods 0.000 claims description 38
- 238000002791 soaking Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 17
- 229910003460 diamond Inorganic materials 0.000 claims description 16
- 239000010432 diamond Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000011265 semifinished product Substances 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 230000006698 induction Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 238000004381 surface treatment Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 description 23
- 238000001816 cooling Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 238000004321 preservation Methods 0.000 description 8
- 238000003723 Smelting Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000006911 nucleation Effects 0.000 description 1
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- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
Classifications
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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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Metal Rolling (AREA)
Abstract
The invention relates to a preparation method of a titanium plate for deep drawing, which comprises the following steps: step one: using a Brinell hardness HB of less than 95 of 0 A The grade titanium sponge is used as a raw material, and a vacuum consumable arc melting method is used for obtaining a titanium ingot through twice melting; step two: forging a titanium ingot into a titanium plate blank along the axial direction in one way; step three: hot rolling and cogging, and rolling along the direction perpendicular to the forging direction to obtain a rough rolled blank; step four: rolling with the second fire along the rolling direction of the third step to obtain a second fire plate blank; step five: hot rolling three fires, namely rolling along the direction perpendicular to the rolling direction of the step four to obtain a three fire plate blank; step six: carrying out surface treatment, annealing treatment and the like on the three-fire plate blank; step seven: cold rolling twice to obtain a cold-rolled sheet with the thickness of 0.4+/-0.02 mm; step eight: and (5) annealing the finished product. The invention prepares the thin titanium plate for deep drawing with high efficiency, low cost and stable quality through the steps of unidirectional forging, reversing hot rolling, twice cold rolling, no atmosphere protection or vacuum annealing and the like.
Description
Technical Field
The invention belongs to the technical field of titanium alloy plates, and particularly relates to a preparation method of a titanium plate for deep drawing.
Background
Commercially pure titanium is produced by melting titanium sponge to cast an ingot, and then forging, rolling, extruding, and other plastic working methods to process the ingot. The coarse columnar casting structure has poor mechanical property, and affects the use of titanium, so that the titanium ingot needs to be subjected to deformation and annealing treatment such as forging, rolling and the like to obtain an ideal structure, and the microstructure and the performance of the titanium plate are changed. However, the commercial pure titanium has the difficulties of obvious anisotropism, easy hydrogen absorption at high temperature and the like in the processing process, so that the preparation of the commercial pure titanium often needs severe equipment and strict technical conditions.
At present, in order to uniformly refine original crystal grains, in the production of a thin titanium plate, a pier pulling process is often required to be added in the forging process, the forging requirement is higher, the time is longer, and the temperature is reduced quickly in the forging process, so that the original crystal grains are heated by returning to the furnace for several times, the heat energy loss is large, and the economical efficiency is poor. In addition, titanium is easy to react with oxygen and hydrogen in the air at high temperature to form a gas absorbing layer, so that the hydrogen embrittlement of the material is caused, the workability of the material is reduced, particularly, the thin plate is particularly serious, and thus the annealing treatment furnace commonly used in the industry is an inert gas protection furnace or a vacuum furnace. However, the two annealing treatment furnaces have high manufacturing cost, high production cost and low production efficiency, and greatly limit the production capacity of the thin plate. Moreover, the two annealing furnaces can only adopt a coil type or stacking type to charge, so that the temperature uniformity of the whole stack of materials is difficult to ensure, the performance difference of the same coil or the same plate is overlarge, and the use stability is affected.
Patent application CN107723638A discloses a preparation method of a titanium plate for deep drawing, which uses titanium sponge with O content less than or equal to 0.05%, N content less than or equal to 0.006% and Fe content less than or equal to 0.05% as raw materials, smelting, casting and forging the titanium sponge, and drawing and/or upsetting for at least two times in the forging process to prepare a plate blank with good structure and slight texture, and then carrying out hot rolling, cold rolling, reversing rolling, annealing and subsequent treatment to obtain the pure titanium plate with proper crystal grains, qualified performance and higher cupping value. The patent consumes time and energy in the forging link, and the annealing of the finished plate needs more than 2 hours, and under the condition of adopting vacuum and argon filling circulation, the cost is high and the efficiency is lower. Patent application CN115323137A discloses a preparation method of a titanium plate for architectural decoration, which can increase the width and thickness of a titanium plate, improve the mechanical strength, control precision, roughness and flatness of a titanium plate product and improve the color and thickness uniformity of surface roughening, but the annealing process is still carried out under the protection of Ar atmosphere, so that the cost is too high, and the popularization and application are not facilitated.
It is urgent for the titanium industry to simplify the production process and reduce the production cost of titanium materials. In particular to the traditional production flow of the titanium plate, a new thought is necessary to be provided at production key nodes such as raw material selection, a smelting furnace, a forging mode, an annealing treatment mode, equipment, a rolling method and the like, and factors such as parameter design and/or control are assisted, so that a simple preparation method of the thin titanium plate for deep drawing with stable quality and excellent comprehensive performance is obtained.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a method for producing a titanium sheet for deep drawing, which uses steps such as unidirectional forging, reverse hot rolling, twice cold rolling, and annealing without atmosphere protection or vacuum, and which can produce a thin titanium sheet for deep drawing with high efficiency, low cost and stable quality.
Specifically, the invention provides a preparation method of a titanium plate for deep drawing, which comprises the following steps:
step one: using a Brinell hardness HB of less than 95 of 0 A The grade titanium sponge is used as a raw material, and a vacuum consumable arc melting method is utilized to obtain a titanium ingot through twice melting;
step two: forging a titanium ingot in one direction along the axial direction to obtain a titanium plate blank;
step three: hot rolling and cogging, namely heating the titanium plate blank to 800-850 ℃, and rolling along the direction perpendicular to the forging direction to obtain a rough rolled blank, wherein the deformation rate is more than 85%; carrying out alkali pickling treatment and grinding treatment on the rough rolled blank;
step four: heating the rough rolled blank to 750-800 ℃ by hot rolling second fire, rolling along the rolling direction of the step three, wherein the deformation rate is more than 65%, and cutting to obtain a second fire blank by fixed width;
step five: hot rolling with three fires, namely heating the slab with the two fires to 750-800 ℃, and rolling along the direction perpendicular to the rolling direction of the step four, wherein the deformation rate is more than 35%;
Step six: sequentially carrying out first round alkali pickling treatment, grinding treatment, semi-finished product annealing treatment and second round alkali pickling treatment on the three-fire plate blank;
step seven: performing cold rolling twice along the rolling direction of the fifth step to obtain a cold-rolled sheet with the thickness of 0.4+/-0.02 mm;
step eight: and carrying out finished product annealing treatment on the cold-rolled sheet.
The invention adopts 0 with easily available raw materials A The grade sponge titanium is smelted into ingots by a vacuum self-heating arc melting (VAR) method, and the difficulties of raw materials, equipment and processes are low. And then, one-way forging is carried out to obtain the titanium plate blank with the thickness H multiplied by the width B multiplied by the length L of (110-135 mm) multiplied by (600-700 mm) multiplied by (1000-1200 mm), so that the efficiency and energy consumption losses such as overlong forging time and the like caused by the original upsetting process are avoided. In particular, the invention adopts a rolling mode of reversing hot rolling, namely, after the traditional unidirectional rolling, the slab is rotated by 90 degrees and then is rolled in a unidirectional way again. The method generates a large amount of (0001) basal plane texture in the rolling process, increases the deformation resistance of hexagonal grains in the height direction, improves the anisotropism of the plate, and improves the plastic deformation ratio, and the processed pure titanium plate is in a TA1 rolling annealing state, and the formation of the recrystallization texture is mostly from the inheritance of deformation texture orientation. In the traditional full longitudinal rolling, the main slippage system of the plastic deformation of the titanium plate is that And-> Conical surface<c+a>Slip is generated to coordinate the c-axis motion, the basal plane texture disappears, the pyramid texture is obtained, and finally the anisotropic generation of the plate is caused. Eliminating the generation of the rolling texture is beneficial to the improvement of the strength index and the plasticity index of the titanium plate. The two subsequent cold rolling processes not only can realize further thinning of the titanium plate on the basis of improving the mechanical property of the titanium plate product, but also is beneficial to obtaining the required roughness and flatness. And the subsequent annealing treatment of the veneer finished product is combined, so that the internal stress in the rolling process can be effectively released, and the stability of the size and the performance of the plate can be effectively improved. In general, the invention is achieved byRaw material selection, high-efficiency smelting, unidirectional forging, reversing hot rolling, twice cold rolling, surface treatment, annealing treatment and other process links, and can prepare the Bao Chun titanium plate with the thickness of 0.4+/-0.02 mm, which has fine and uniform crystal grains, weakened anisotropism, high surface quality and stable size. The corresponding heating furnaces, hot rolling mills, cold rolling mills, annealing treatment equipment and the like adopted by the method are conventional equipment of a rolling mill, high-precision equipment such as an atmosphere protection furnace, a vacuum annealing furnace and the like is not needed, almost no additional investment is needed, the cost is low, and the popularization value is remarkable.
Further, 0 A The components and mass percentages of the grade titanium sponge are as follows: less than or equal to 0.03 percent of iron, less than or equal to 0.05 percent of oxygen, less than or equal to 0.01 percent of nitrogen, less than or equal to 0.01 percent of carbon, less than or equal to 0.003 percent of hydrogen, less than or equal to 0.01 percent of silicon, less than or equal to 0.06 percent of chlorine, less than or equal to 0.01 percent of magnesium, less than or equal to 0.01 percent of manganese, less than or equal to 0.01 percent of nickel, less than or equal to 0.01 percent of chromium, less than or equal to 0.02 percent of the sum of other impurity contents, and the balance of titanium. The invention selects 0A grade titanium sponge, and the low impurity percentage ensures the deep drawing performance of the finished product.
Further, the thickness H multiplied by the width B multiplied by the length L of the titanium plate blank in the second step is (110-135 mm) multiplied by (600-700 mm) multiplied by (1000-1200 mm); and thirdly, heating the titanium plate blank to 800-850 ℃, preserving heat for 120-150min, and rolling to obtain a rough rolled blank with the thickness of 12-15 mm. In the hot rolling cogging link, the deformation rate of the slab is higher, the thickness of the slab is obviously reduced, and the adjustment of the technical parameters such as the heating temperature, the heat preservation time and the like of the hot rolling cogging according to the size of the titanium slab is an important condition for obtaining the high-quality rough rolled slab.
And in the fourth step, heating the rough rolled blank to 750-800 ℃ and preserving heat for 15-20min, and rolling to obtain the second-fire blank with the thickness of 3-4 mm. As the thickness of the rough rolled blank relative to the titanium plate blank is obviously reduced, the heating and heat preservation time in the fourth step is correspondingly reduced relative to that in the third step, and the uniform heating of the plate blank can be ensured.
In the fourth step, the second hot rolling is carried out by adopting an asynchronous rolling mill set, wherein the asynchronous rolling mill set is provided with at least 1 group of different-speed asynchronous rolling mills and at least 1 group of different-diameter asynchronous rolling mills; the hot rolling direction is the same as the rolling direction of the third step, and the pressure among rollers of each rolling mill of the asynchronous rolling mill set is gradually increased along the rolling direction; different speedUpper roll speed V of asynchronous rolling mill 1 : lower roll speed V 2 1.3-1.5, the diameter R of the upper roller of the reducing asynchronous rolling mill 1 : lower roll diameter R 2 Is 1: (1.1-1.3).
In the fifth step, the second-fire plate blank is subjected to 90-degree reversing, heated to 750-800 ℃, and subjected to unidirectional rolling after heat preservation for 10-15min to obtain a third-fire plate blank with the thickness of 1.5-2 mm; in the sixth step, the annealing treatment of the semi-finished product comprises the following steps:
stacking 3-6 slabs;
heating the stacked slabs to 680+/-10 ℃ by adopting an electric furnace, and carrying out annealing treatment for 16-20min.
The reversing rolling can change the microcosmic stress state of the material, so that the crystal grains are not twisted only towards a certain fixed direction, the dislocation density of the deformation zone area is high, the storage energy is high, sufficient driving force is provided for nucleation, the generation of fine crystal grains is promoted, the strength of the pyramid-shaped texture can be effectively reduced, and the anisotropism is improved. Compared with unidirectional rolling, the structure of the titanium plate blank subjected to reversing rolling is more fully broken, no obvious anisotropy exists, the mechanical property difference of the plate in each direction is reduced, and the product consistency is better.
Asynchronous rolling, including different-speed asynchronous rolling and different-diameter asynchronous rolling, mainly utilizes the different linear speeds of the upper roller and the lower roller to enable the rolled piece to bear additional shearing deformation, and has the advantages of strong thinning capability, low rolling pressure, high rolling precision and the like. The asynchronous rolling mode fully utilizes the characteristics of severe plastic deformation, high precision and the like of the asynchronous rolling, is beneficial to improving the quality and the dimensional precision of the plate blank, can relatively reduce the subsequent rolling pass and improves the productivity.
The invention adopts a rolling mode combining reversing hot rolling and unidirectional asynchronous hot rolling, effectively reduces the thickness of the slab, simultaneously effectively weakens the rolling texture of the plate, is more beneficial to grain refinement and improves the comprehensive mechanical property. The hot rolling mode with the special design is adopted, so that the possible defect of unidirectional forging in the aspect of uniform grain refinement is better made up on the whole, and the product quality can be ensured on the basis of improving the production efficiency by avoiding the tedious links of the original upsetting process.
In order to further improve the sheet material anisotropy and the deep drawing performance, the reversing thickness of the hot rolling three-fire needs to be strictly executed according to the set cross ratio, so that the deformation degree before and after the reversing tends to be balanced, and the longitudinal and transverse difference is reduced to the greatest extent. Preferably, the total deformation before hot rolling three-fire change is as follows: the total deformation after the hot rolling three-fire change is 1 to 1.15, wherein the total deformation before the hot rolling three-fire change is (titanium plate thickness H-two-fire plate thickness H) 1 ) The total deformation after hot rolling for three fires is (thickness H of the two-fire slab) 1 Finished thickness H 2 )/H 1 . More preferably, the total deformation before hot rolling three-fire change is as follows: the total deformation after three-fire heat exchange is 1-1.13.
Further, in the step seven, cold rolling is carried out for the first time to obtain a cold-rolled blank with the thickness of 0.7-1.0 mm; re-rolling to obtain a cold-rolled sheet with the thickness of 0.4+/-0.02 mm; an intermediate annealing treatment and an alkali pickling treatment are performed between the two cold rolling, the intermediate annealing treatment comprising:
stacking 3-8 slabs;
heating the stacked slabs to 680+/-10 ℃ by adopting an electric furnace, and carrying out annealing treatment for 16-20min.
The intermediate annealing treatment is combined with the two cold rolling processes, so that on one hand, the problem of poor plate shape is effectively solved by utilizing the high temperature and proper tension conditions of the annealing treatment relative to the cold rolling process, and on the other hand, the internal stress of the primary cold rolling is released, and the damage to the plate blank caused by the secondary cold rolling is avoided. The plate blank stacking annealing mode is adopted for the intermediate annealing treatment, so that the advantages of the intermediate annealing treatment are exerted, and the treatment time is saved.
In the eighth step, the single cold-rolled sheet is heated to 680+/-10 ℃ on line by using an all-solid-state high-frequency induction heating device, and is annealed for 16-20min.
Preferably, the device can be heated on line by using a 50-100kW all-solid-state high-frequency induction heating device, the heating rate is 300-400 ℃/min, the temperature is increased to 680+/-10 ℃, and the infrared thermometer is used for accurately measuring the temperature; after heat preservation for 3-5min, carrying out step cooling treatment, comprising the following steps:
s7.1: cooling to 400 ℃ at a rate of not higher than 40 ℃/min;
s7.2: cooling to 200 ℃ at a rate of not higher than 60 ℃/min;
s7.3: cooling to room temperature at a rate of not more than 80 ℃/min.
In the eighth pair of finished product annealing treatment, although the continuous annealing conditions similar to the semi-finished product annealing treatment or intermediate goods returning treatment can be adopted, the single-plate step annealing treatment is more preferable, so that the plate stays in the high-temperature section for a longer time, the internal stress is fully released, microscopic and macroscopic defects are reduced or avoided, and then the cooling speed is increased, thereby ensuring the goods returning quality and improving the treatment efficiency.
Further, the alkali pickling treatment of the rough rolled blank, the three-fire plate blank and the cold rolled blank comprises the following steps:
A. alkali washing: soaking the plate blank in 460-520 deg.c alkali molten liquid for 5-15min; the alkali melt consists of 85-95wt% NaOH and 5-15wt% NaNO 3 Composition;
B. primary acid washing: soaking the sheet billet in a first acid solution at the temperature of below 60 ℃, pickling for less than 2min, washing with water, and drying; the first acid solution contains: 5-15wt% H 2 SO 4 And the balance being water;
C. secondary acid washing: soaking the sheet billet in a second acid solution at the temperature of below 60 ℃ for pickling for less than 5min; the second acid solution contains: 15-25wt% HNO 3 1-2% wtHF and the balance water.
The titanium material is easy to form an air absorption layer at high temperature, and the prior art is usually weakened by adopting a protective atmosphere or a vacuum environment, but the equipment requirement is high and the cost is high. According to the invention, a large number of experiments show that the gas-absorbing layer can be removed well through alkaline pickling treatment, and the surface oxide skin is removed through soaking alkaline washing in molten alkali solution, twice pickling and water explosion, so that the effect is obvious. Preferably, in the sixth step, the treatment of the three-fire slab further comprises adding a channel scraping treatment after the semi-finished product annealing treatment and the alkaline pickling treatment, similar to the secondary pickling, except that the adopted HF concentration is 2-3wt%, the surface of the slab can be further uniformly corroded by about 10-20 μm, and the residual getter layer is thoroughly removed, so that the whole processing process and the product performance are hardly affected.
Further, the grinding treatment of the rough rolled blank and the three-fire plate blank adopts a diamond grinding wheel, and comprises the following steps:
s1, rough grinding: the granularity of the rough grinding wheel is 100-150 meshes, the rotating speed is 1500-2000r/min, the feeding amount is 0.02-0.05 mm each time, and the feeding speed of the diamond grinding wheel is 800-1000 mm/min;
S2, fine grinding: the granularity of the fine grinding wheel is 200-300 meshes, the rotating speed is 3500r/min to 4000r/min, the feeding amount is less than 0.01mm each time, and the feeding speed is 300mm/min to 450mm/min.
And (3) grinding the plate blank subjected to the alkali pickling treatment by a grinding wheel according to the requirements of the treatment flow so as to sufficiently remove oxide skin on the surface and surface defects appearing due to rolling and the like. The slab is subjected to further treatments such as twice cold rolling after three-fire hot rolling, comprehensive surface treatment, annealing treatment and the like, so that the getter layer formed in the early hot rolling high-temperature stage is solved in advance, the annealing treatment process with lower temperature and shorter time is adopted, the subsequent generation of the getter layer is avoided or reduced, the influence of hydrogen embrittlement is relieved, the subsequent treatment pressure and difficulty can be effectively reduced, and the product quality is improved.
The preparation method of the titanium plate for deep drawing provided by the invention can be used for preparing the high-performance titanium plate with the thickness of 0.4+/-0.02 mm, the yield strength of more than 180MPa, the tensile strength of more than 290MPa and the elongation after fracture of more than 65%, wherein the thickness is smaller than the plate thickness lower limit value required by the national standard GB/T14845 (titanium plate for plate heat exchanger), the mechanical property can reach and exceed the standard requirement, the use amount of titanium materials is saved, and the production cost is reduced.
The invention has the advantages that:
1) The invention adopts unidirectional forging, reversing hot rolling with specific cross ratio, and combines reversing hot rolling with asynchronous hot rolling, which not only can remarkably save forging time, but also can effectively refine uniform original grains, improve anisotropy of the plate, and comprehensively improve mechanical property and quality stability of the plate.
2) The invention solves the getter layer formed in the early hot rolling high temperature stage in advance through the treatments of alkali pickling after hot rolling and before cold rolling, and then adopts the annealing treatment process with lower temperature and shorter time to reduce the getter layer generated in the subsequent annealing treatment, thereby avoiding the influence of hydrogen embrittlement; meanwhile, as the semi-finished product annealing treatment and the intermediate annealing treatment between two cold rolling are both continuous annealing by stacking the plate blanks, each section of the plate blanks is ensured to be in the same annealing treatment environment, the performance stability of the same plate and even the same batch of plates is greatly improved, and the defects of long annealing time, poor temperature uniformity, high equipment requirement and high cost of the existing annealing processes such as atmosphere gas protection or vacuum annealing furnaces are avoided.
3) The invention adopts the step annealing treatment of the veneer finished product, can effectively release the internal stress of the plate in time by means of the conditions of high temperature and the like during the treatment, and avoids the damage of the subsequent treatment to the plate or the unexpected change of the size of the plate; the annealing mode is beneficial to the slow and full release of internal stress of the plate in the high-temperature section, and then the temperature reduction is accelerated to improve the treatment efficiency, so that the efficiency and the product quality can be both considered.
Drawings
The above, as well as additional purposes, features, and advantages of exemplary embodiments of the present disclosure will become readily apparent from the following detailed description when read in conjunction with the accompanying drawings. In the drawings, several embodiments of the invention are shown by way of example and not by way of limitation, wherein dimensions, deformation ratios, etc. of the slab handling process are shown by way of example only.
FIG. 1 is a schematic flow chart of the preparation method of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to fig. 1 and the embodiment.
A preparation method of a titanium plate for deep drawing comprises the following steps:
step one: using a Brinell hardness HB of less than 95 of 0 A The grade titanium sponge is used as a raw material, and a vacuum consumable arc melting method is utilized to obtain a titanium ingot through twice melting; 0 A Components and mass percent of grade titanium spongeThe percentages are as follows: less than or equal to 0.03 percent of iron, less than or equal to 0.05 percent of oxygen, less than or equal to 0.01 percent of nitrogen, less than or equal to 0.01 percent of carbon, less than or equal to 0.003 percent of hydrogen, less than or equal to 0.01 percent of silicon, less than or equal to 0.06 percent of chlorine, less than or equal to 0.01 percent of magnesium, less than or equal to 0.01 percent of manganese, less than or equal to 0.01 percent of nickel, less than or equal to 0.01 percent of chromium, less than or equal to 0.02 percent of the sum of other impurity contents, and the balance of titanium;
step two: forging a titanium ingot into a titanium plate blank along the axial direction in one way, wherein the thickness H multiplied by the width B multiplied by the length L of the titanium plate blank is (110-135 mm) multiplied by (600-700 mm) multiplied by (1000-1200 mm);
Step three: hot rolling and cogging, namely heating a titanium plate blank to 800-850 ℃, preserving heat for 120-150min, and rolling along the direction perpendicular to the forging direction to obtain a rough rolled blank, wherein the deformation rate is more than 85%, and the rough rolled blank with the thickness of 12-15mm is obtained;
and (5) carrying out alkali pickling treatment and grinding treatment on the rough rolled blank.
Step four: heating the rough rolled blank to 750-800 ℃ by hot rolling second fire, preserving heat for 15-20min, rolling along the rolling direction of the step three, and cutting at a fixed width with a deformation rate of more than 65%, thereby obtaining a second fire plate blank with a thickness of 3-4 mm; the rolling is carried out by adopting an asynchronous rolling mill set for asynchronous hot rolling, wherein the asynchronous rolling mill set is provided with at least 1 group of different-speed asynchronous rolling mills and at least 1 group of different-diameter asynchronous rolling mills; the hot rolling direction is the same as the rolling direction of the third step, the pressure among the rollers of each rolling machine of the asynchronous rolling mill set is gradually increased along the rolling direction, and the upper roller speed V1 of the asynchronous rolling mill with different speeds is as follows: the lower roll speed V2 is 1.3-1.5, and the diameter R1 of the upper roll of the reducing asynchronous rolling mill is as follows: the lower roll diameter R2 is 1: (1.1-1.3);
step five: hot rolling the second-fire plate blank to 750-800 ℃, preserving heat for 10-15min, and rolling along the direction perpendicular to the rolling direction of the fourth step, wherein the deformation rate is more than 35%, so as to obtain the third-fire plate blank with the thickness of 1.5-2 mm;
Step six: sequentially carrying out alkaline pickling treatment, grinding treatment, semi-finished product annealing treatment and alkaline pickling treatment on the three-fire plate blank; preferably, after the semi-finished product annealing treatment and the pickling reduction treatment, a channel scraping treatment is further arranged; the annealing treatment comprises the following steps:
stacking 3-6 slabs;
heating the stacked slabs to 680+/-10 ℃ by adopting an electric furnace, and carrying out annealing treatment for 16-20min.
Step seven: performing cold rolling twice along the rolling direction of the step five, performing cold rolling once to obtain a cold rolled blank with the thickness of 0.7-1.0mm, and performing cold rolling again to obtain a cold rolled sheet with the thickness of 0.4+/-0.02 mm; an intermediate annealing treatment and an alkali pickling treatment are performed between the two cold rolling, the intermediate annealing treatment comprising:
stacking 3-8 slabs;
heating the stacked slabs to 680+/-10 ℃ by adopting an electric furnace, and carrying out annealing treatment for 16-20min.
Step eight: and carrying out finished product annealing treatment on the cold-rolled sheet. And (3) heating the single cold-rolled sheet on line to 680+/-10 ℃ by using an all-solid-state high-frequency induction heating device, and carrying out annealing treatment for 16-20min.
Specifically, an all-solid-state high-frequency induction heating device with the temperature of 50-100kW is used for on-line heating, the heating rate is 300-400 ℃/min, the heating is carried out to 680+/-10 ℃, and an infrared thermometer is used for accurately measuring the temperature; after heat preservation for 3-5min, carrying out step cooling treatment, comprising the following steps:
S7.1: cooling to 400 ℃ at a rate of not higher than 40 ℃/min;
s7.2: cooling to 200 ℃ at a rate of not higher than 60 ℃/min;
s7.3: cooling to room temperature at a rate of not more than 80 ℃/min.
Alkali pickling treatment of rough rolled blanks, three-fire plate blanks and cold rolled blanks comprises the following steps:
A. alkali washing: soaking the plate blank in 460-520 deg.c alkali molten liquid for 5-15min; the alkali melt consists of 85-95wt% NaOH and 5-15wt% NaNO 3 Composition;
B. primary acid washing: soaking the sheet billet in a first acid solution at the temperature of below 60 ℃, pickling for less than 2min, washing with water, and drying; the first acid solution contains: 5-15wt% H 2 SO 4 And the balance being water;
C. secondary acid washing: soaking the sheet billet in a second acid solution at the temperature of below 60 ℃ for pickling for less than 5min; the second acid solution contains: 15-25wt% HNO 3 1-2% wtHF and the balance water.
Wherein, as the thickness of the plate is reduced, the time of alkaline washing, primary acid washing and secondary acid washing can be relatively reduced.
The grinding treatment of the rough rolled blank and the three-fire plate blank adopts a diamond grinding wheel, and comprises the following steps:
s1, rough grinding: the granularity of the rough grinding wheel is 100-150 meshes, the rotating speed is 1500-2000r/min, the feeding amount is 0.02-0.05 mm each time, and the feeding speed of the diamond grinding wheel is 800-1000 mm/min;
S2, fine grinding: the granularity of the fine grinding wheel is 200-300 meshes, the rotating speed is 3500r/min to 4000r/min, the feeding amount is less than 0.01mm each time, and the feeding speed is 300mm/min to 450mm/min.
Example 1
A preparation method of a titanium plate for deep drawing comprises the following steps:
step one: using a Brinell hardness HB of 90 of 0 A The grade titanium sponge is used as raw material, and is smelted twice by utilizing a vacuum consumable arc smelting method to obtain a titanium ingot, 0 A The components and mass percentages of the grade titanium sponge are as follows: iron 0.023%, oxygen 0.035%, nitrogen 0.002%, carbon 0.007%, hydrogen 0.001%, silicon 0.002%, chlorine 0.003%, magnesium 0.003%, manganese 0.002%, nickel 0.001%, chromium 0.002%, the total content of other impurities 0.015%, and the balance being titanium.
Step two: the method comprises the steps of (1) forging a titanium ingot into a titanium plate blank along the axial direction in a unidirectional manner, wherein the thickness H multiplied by the width B multiplied by the length L of the titanium plate blank is 130mm multiplied by 650mm multiplied by 1100mm;
step three: and hot rolling and cogging, namely heating the titanium plate blank to 820 ℃, preserving heat for 135min, and rolling along the direction perpendicular to the forging direction to obtain a rough rolled blank with the thickness of 12 mm.
The rough rolled blank with the thickness of 12mm is subjected to alkali pickling treatment and grinding, wherein the alkali pickling treatment comprises the following steps:
A. alkali washing: soaking the plate blank in an alkali melt at 500 ℃ for 10min; the alkali melt was composed of 90wt% NaOH and 10wt% NaNO 3 Composition;
B. primary acid washing: soaking the sheet billet in a first acid solution at 55 ℃, pickling for 1.5min, washing with water, and drying; the first acid solution contains: 10wt% H 2 SO 4 And the balance being water;
C. secondary acid washing: soaking the sheet bar at 60deg.CAcid washing for 4.5min in the second acid liquor; the second acid solution contains: 20wt% HNO 3 1.5% wtHF and the balance water.
Grinding wheel polishing treatment is carried out on the plate blank subjected to alkali pickling treatment, and a diamond grinding wheel is adopted, and the method comprises the following steps:
s1, rough grinding: the granularity of the rough grinding wheel is 100 meshes, the rotating speed is 1800r/min, the feeding amount is 0.03mm each time, and the feeding speed of the diamond grinding wheel is 900mm/min;
s2, fine grinding: the granularity of the fine grinding wheel is 200 meshes, the rotating speed is 3800r/min, the feeding amount is 0.005mm each time, and the feeding speed is 400mm/min.
Step four: heating the rough rolled blank to 780 ℃ by hot rolling second fire, preserving heat for 20min, rolling along the rolling direction of the step three, and shearing at a fixed width to obtain a second fire blank with the thickness of 3.5 mm; the rolling is carried out by adopting an asynchronous rolling mill set for asynchronous hot rolling, wherein the asynchronous rolling mill set is provided with at least 1 group of different-speed asynchronous rolling mills and at least 1 group of different-diameter asynchronous rolling mills; the pressure among the rollers of each rolling mill of the asynchronous rolling mill set is gradually increased along the rolling direction, and the upper roller speed V1 of the asynchronous rolling mill with different speeds is as follows: lower roll speed V2 is 1.4, and diameter R1 of upper roll of reducing asynchronous rolling mill: the lower roll diameter R2 is 1:1.2;
Step five: and (3) hot rolling three-fire, namely heating the two-fire slab to 780 ℃, preserving heat for 15min, and rolling in the direction perpendicular to the rolling direction of the step four to obtain the three-fire slab with the thickness of 2 mm.
Step six: sequentially carrying out first round alkali pickling, grinding, semi-finished product annealing treatment and second round alkali pickling on a three-fire plate blank with the thickness of 2 mm:
the steps of the first round of alkali pickling and the second round of alkali pickling are the same as those of the alkali pickling treatment of the former rough rolled blank, and the difference is that the alkali pickling time is 8min, the primary pickling time is 1min, and the secondary pickling time is 3min;
the grinding wheel grinding treatment is the same as that of the grinding wheel grinding position of the previous rough rolled blank;
annealing the semi-finished product:
stacking 4 slabs;
and heating the stacked slabs to 680+/-10 ℃ by adopting an electric furnace, and carrying out annealing treatment for 18min.
Step seven: performing cold rolling twice along the rolling direction of the step five:
cold-rolling to a cold-rolled blank with the thickness of 0.8mm for one time;
and (3) intermediate annealing treatment: stacking 6 slabs; heating the stacked slabs to 680+/-10 ℃ by adopting an electric furnace, and carrying out annealing treatment for 17min;
the alkali pickling treatment has the same steps as those of the rough rolled blank, and is different in that the alkali pickling time is 5min, the primary pickling time is 0.5min, and the secondary pickling time is 1.5min;
And cold-rolled sheet having a thickness of 0.39mm was further cooled.
Step eight: and carrying out finished product annealing treatment on the cold-rolled sheet. And (3) carrying out on-line heating on the single cold-rolled sheet by using a 75kW all-solid-state high-frequency induction heating device, wherein the heating rate is 350 ℃/min, and the temperature is precisely measured by an infrared thermometer when the temperature is 680+/-10 ℃. After the heat preservation time is 5min, the step cooling treatment is carried out for about 13.5min, and the method comprises the following steps:
s7.1: cooling to 400 ℃ at a speed of 40 ℃/min;
s7.2: cooling to 200 ℃ at a speed of 50 ℃/min;
s7.3: cooling to room temperature at a speed of 75 ℃/min to obtain a finished titanium plate with a thickness of 0.39 mm.
Example 2
A preparation method of a titanium plate for deep drawing comprises the following steps:
step one: with Brinell hardness HB of 88 of 0 A The grade titanium sponge is used as raw material, and is smelted twice by utilizing a vacuum consumable arc smelting method to obtain a titanium ingot, 0 A The components and mass percentages of the grade titanium sponge are as follows: iron 0.018%, oxygen 0.032%, nitrogen 0.004%, carbon 0.008%, hydrogen 0.001%, silicon 0.001%, chlorine 0.004%, magnesium 0.002%, manganese 0.002%, nickel 0.003%, chromium 0.004%, the total content of other impurities is 0.013%, and the balance is titanium.
Step two: the method comprises the steps of (1) forging a titanium ingot into a titanium plate blank along the axial direction in a unidirectional manner, wherein the thickness H multiplied by the width B multiplied by the length L of the titanium plate blank is 125mm multiplied by 640mm multiplied by 1120mm;
Step three: and hot rolling and cogging, namely heating the titanium plate blank to 820 ℃, preserving heat for 125 minutes, and rolling along the direction perpendicular to the forging direction to obtain a rough rolled blank with the thickness of 11 mm.
The rough rolled blank with the thickness of 11mm is subjected to alkali pickling treatment and grinding, wherein the alkali pickling treatment comprises the following steps:
A. alkali washing: soaking the plate blank in an alkali melt at 500 ℃ for alkali washing for 9min; the alkali melt was composed of 90wt% NaOH and 10wt% NaNO 3 Composition;
B. primary acid washing: soaking the sheet billet in a first acid solution at 55 ℃, pickling for 1.5min, washing with water, and drying; the first acid solution contains: 10wt% H 2 SO 4 And the balance being water;
C. secondary acid washing: soaking the sheet billet in a second acid solution at the temperature of below 60 ℃ for pickling for 4min; the second acid solution contains: 20wt% HNO 3 1.5% wtHF and the balance water.
Grinding wheel polishing treatment is carried out on the plate blank subjected to alkali pickling treatment, and a diamond grinding wheel is adopted, and the method comprises the following steps:
s1, rough grinding: the granularity of the rough grinding wheel is 100 meshes, the rotating speed is 1800r/min, the feeding amount is 0.03mm each time, and the feeding speed of the diamond grinding wheel is 900mm/min;
s2, fine grinding: the granularity of the fine grinding wheel is 200 meshes, the rotating speed is 3800r/min, the feeding amount is 0.005mm each time, and the feeding speed is 400mm/min.
Step four: heating the rough rolled blank to 780 ℃ by hot rolling second fire, preserving heat for 20min, rolling along the rolling direction of the step three, and shearing at a fixed width to obtain a second fire blank with the thickness of 3.6 mm; the rolling is carried out by adopting an asynchronous rolling mill set for asynchronous hot rolling, wherein the asynchronous rolling mill set is provided with at least 1 group of different-speed asynchronous rolling mills and at least 1 group of different-diameter asynchronous rolling mills; the hot rolling direction is the same as the rolling direction of the third step, the pressure among the rollers of each rolling machine of the asynchronous rolling mill set is gradually increased along the rolling direction, and the upper roller speed V1 of the asynchronous rolling mill with different speeds is as follows: lower roll speed V2 is 1.4, and diameter R1 of upper roll of reducing asynchronous rolling mill: the lower roll diameter R2 is 1:1.2;
Step five: and (3) hot-rolling the three-fire slab, heating the two-fire slab to 780 ℃, and preserving heat for 15min, and rolling in the direction perpendicular to the rolling direction of the step four to obtain the three-fire slab with the thickness of 2.1 mm.
Step six: sequentially carrying out first round alkali pickling, grinding, semi-finished product annealing treatment and second round alkali pickling on a three-fire slab with the thickness of 2.1 mm:
the steps of the first round of alkali pickling and the second round of alkali pickling are the same as those of the alkali pickling treatment of the former rough rolled blank, and the difference is that the alkali pickling time is 7min, the primary pickling time is 1min, and the secondary pickling time is 3min;
the grinding wheel grinding treatment is the same as that of the grinding wheel grinding position of the previous rough rolled blank;
annealing the semi-finished product:
stacking 4 slabs;
and heating the stacked slabs to 680+/-10 ℃ by adopting an electric furnace, and carrying out annealing treatment for 18min.
Step seven: performing cold rolling twice along the rolling direction of the step five:
cold-rolling to a cold-rolled blank with the thickness of 0.8mm for one time;
and (3) intermediate annealing treatment: stacking 6 slabs; heating the stacked slabs to 680+/-10 ℃ by adopting an electric furnace, and carrying out annealing treatment for 17min;
the alkali pickling treatment has the same steps as those of the rough rolled blank, and is different in that the alkali pickling time is 5min, the primary pickling time is 0.5min, and the secondary pickling time is 1.5min;
And cold-rolled sheet having a thickness of 0.40mm was further cooled.
Step eight: carrying out finished product annealing treatment on the cold-rolled sheet, and carrying out on-line heating on the single cold-rolled sheet by using a 75kW all-solid-state high-frequency induction heating device, wherein the heating rate is 350 ℃/min, and the temperature is precisely measured by an infrared thermometer; after the heat preservation time is 4.5min, the step cooling treatment is carried out for about 14min, and the method comprises the following steps:
s7.1: cooling to 400 ℃ at a speed of 40 ℃/min;
s7.2: cooling to 200 ℃ at a speed of 50 ℃/min;
s7.3: cooling to room temperature at a speed of 60 ℃/min to obtain a finished titanium plate with a thickness of 0.40 mm.
Example 3
A preparation method of a titanium plate for deep drawing comprises the following steps:
step one: using BrucellaHardness HB of 92 0 A The grade titanium sponge is used as raw material, and is smelted twice by utilizing a vacuum consumable arc smelting method to obtain a titanium ingot, 0 A The components and mass percentages of the grade titanium sponge are as follows: iron 0.027%, oxygen 0.045%, nitrogen 0.003%, carbon 0.005%, hydrogen 0.001%, silicon 0.002%, chlorine 0.005%, magnesium 0.001%, manganese 0.002%, nickel 0.003%, chromium 0.002%, the total content of other impurities 0.016%, and the balance being titanium.
Step two: the method comprises the steps of (1) forging a titanium ingot into a titanium plate blank along the axial direction in a unidirectional manner, wherein the thickness H multiplied by the width B multiplied by the length L of the titanium plate blank is 128mm multiplied by 620mm multiplied by 1080mm;
Step three: and (3) hot rolling and cogging, namely heating the titanium plate blank to 820 ℃, preserving heat for 130min, and rolling along the direction perpendicular to the forging direction to obtain a rough rolled blank with the thickness of 11.5 mm.
The rough rolled blank with the thickness of 11.5mm is subjected to alkali pickling treatment and grinding, wherein the alkali pickling treatment comprises the following steps:
A. alkali washing: soaking the plate blank in an alkali melt at 500 ℃ for 10min; the alkali melt was composed of 90wt% NaOH and 10wt% NaNO 3 Composition;
B. primary acid washing: soaking the sheet billet in a first acid solution at 55 ℃, pickling for 1.5min, washing with water, and drying; the first acid solution contains: 10wt% H 2 SO 4 And the balance being water;
C. secondary acid washing: soaking the sheet billet in a second acid solution at the temperature of below 60 ℃ for pickling for 4min; the second acid solution contains: 20wt% HNO 3 1.5% wtHF and the balance water.
Grinding wheel polishing treatment is carried out on the plate blank subjected to alkali pickling treatment, and a diamond grinding wheel is adopted, and the method comprises the following steps:
s1, rough grinding: the granularity of the rough grinding wheel is 100 meshes, the rotating speed is 1800r/min, the feeding amount is 0.03mm each time, and the feeding speed of the diamond grinding wheel is 900mm/min;
s2, fine grinding: the granularity of the fine grinding wheel is 200 meshes, the rotating speed is 3800r/min, the feeding amount is 0.005mm each time, and the feeding speed is 400mm/min.
Step four: heating the rough rolled blank to 780 ℃ by hot rolling second fire, preserving heat for 20min, rolling along the rolling direction of the step three, and shearing at a fixed width to obtain a second fire blank with the thickness of 3.3 mm; the rolling is carried out by adopting an asynchronous rolling mill set for asynchronous hot rolling, wherein the asynchronous rolling mill set is provided with at least 1 group of different-speed asynchronous rolling mills and at least 1 group of different-diameter asynchronous rolling mills; the hot rolling direction is the same as the rolling direction of the third step, the pressure among the rollers of each rolling machine of the asynchronous rolling mill set is gradually increased along the rolling direction, and the upper roller speed V1 of the asynchronous rolling mill with different speeds is as follows: lower roll speed V2 is 1.4, and diameter R1 of upper roll of reducing asynchronous rolling mill: the lower roll diameter R2 is 1:1.2;
step five: and (3) hot rolling three-fire, namely heating the two-fire slab to 780 ℃, and preserving heat for 15min, and rolling in the direction perpendicular to the rolling direction of the step four to obtain the three-fire slab with the thickness of 1.9 mm.
Step six: sequentially carrying out first round alkali pickling, grinding, annealing treatment and second round alkali pickling on a three-fire plate blank with the thickness of 1.9 mm:
the steps of the first round of alkali pickling and the second round of alkali pickling are the same as those of the alkali pickling treatment of the former rough rolled blank, and the difference is that the alkali pickling time is 8min, the primary pickling time is 1min, and the secondary pickling time is 3min;
the grinding wheel grinding treatment is the same as that of the grinding wheel grinding position of the previous rough rolled blank;
Annealing the semi-finished product:
stacking 4 slabs;
and heating the stacked slabs to 680+/-10 ℃ by adopting an electric furnace, and carrying out annealing treatment for 18min.
Step seven: performing cold rolling twice along the rolling direction of the step five:
cold-rolling to a cold-rolled blank with the thickness of 0.8mm for one time;
and (3) intermediate annealing treatment: stacking 6 slabs; heating the stacked slabs to 680+/-10 ℃ by adopting an electric furnace, and carrying out annealing treatment for 17min;
the alkali pickling treatment has the same steps as those of the rough rolled blank, and is different in that the alkali pickling time is 5min, the primary pickling time is 0.5min, and the secondary pickling time is 1.5min;
and cold-rolled sheet having a thickness of 0.41mm was further cooled.
Step eight: and carrying out finished product annealing treatment on the cold-rolled sheet. The single cold-rolled sheet is heated on line by using a 75kW all-solid-state high-frequency induction heating device, the heating rate is 350 ℃/min, the temperature is increased to 680+/-10 ℃, and the infrared thermometer measures the temperature accurately; after the heat preservation time is 4min, the step cooling treatment is carried out for about 15, and the method comprises the following steps:
s7.1: cooling to 400 ℃ at a speed of 35 ℃/min;
s7.2: cooling to 200 ℃ at a speed of 50 ℃/min;
s7.3: cooling to room temperature at a rate of 60 ℃ per minute to obtain a finished titanium plate with a thickness of 0.41 mm.
Comparative example 1
The comparative example uses the same steps one to two, steps six to eight and surface treatment as in example 1, with the main difference that steps three to five use unidirectional hot rolling, specifically:
step three: hot rolling and cogging, namely heating a titanium plate blank with the thickness H multiplied by the width B multiplied by the length L of 130mm multiplied by 650mm multiplied by 1100mm to 820 ℃, and preserving heat for 135min; rolling along the forging direction (namely the length direction of the titanium plate blank) to obtain a rough rolled blank with the thickness of 12 mm;
the rough rolled blank with the thickness of 12mm is subjected to alkali pickling treatment and grinding, wherein the alkali pickling treatment comprises the following steps:
A. alkali washing: soaking the plate blank in an alkali melt at 500 ℃ for 10min; the alkali melt was composed of 90wt% NaOH and 10wt% NaNO 3 Composition;
B. primary acid washing: soaking the sheet billet in a first acid solution at 55 ℃, pickling for 1.5min, washing with water, and drying; the first acid solution contains: 10wt% H 2 SO 4 And the balance being water;
C. secondary acid washing: soaking the sheet billet in a second acid solution at the temperature of below 60 ℃ for pickling for 4.5min; the second acid solution contains: 20wt% HNO 3 1.5% wtHF and the balance water.
Grinding wheel polishing treatment is carried out on the plate blank subjected to alkali pickling treatment, and a diamond grinding wheel is adopted, and the method comprises the following steps:
s1, rough grinding: the granularity of the rough grinding wheel is 100 meshes, the rotating speed is 1800r/min, the feeding amount is 0.03mm each time, and the feeding speed of the diamond grinding wheel is 900mm/min;
S2, fine grinding: the granularity of the fine grinding wheel is 200 meshes, the rotating speed is 3800r/min, the feeding amount is 0.005mm each time, and the feeding speed is 400mm/min.
Step four: heating the rough rolled blank to 780 ℃ by hot rolling second fire, preserving heat for 20min, rolling along the rolling direction of the step three, and cutting to obtain a second fire blank with the thickness of 3.5 mm;
step five: hot rolling for three times, heating the plate blank with the second fire to 780 ℃, and preserving heat for 15min; rolling along the rolling direction of the step four to obtain the three-fire plate blank with the thickness of 2 mm.
And then sequentially carrying out steps six to eight to obtain a titanium plate sample with the thickness of 0.39 mm.
Comparative example 2
The comparative example uses the same steps one, two and six as in example 1, with the main difference that steps three to five use unidirectional hot rolling, step seven use two cold rolling without intermediate annealing treatment, and step eight use ordinary annealing treatment. The second step sequentially comprises the following steps:
step three: hot rolling and cogging, namely heating a titanium plate blank with the thickness H multiplied by the width B multiplied by the length L of 130mm multiplied by 650mm multiplied by 1100mm to 820 ℃, and preserving heat for 135min; and rolling along the forging direction (namely the length direction of the titanium plate blank) to obtain a rough rolled blank with the thickness of 12 mm.
The rough rolled blank with the thickness of 12mm is subjected to alkali pickling treatment and grinding, wherein the alkali pickling treatment comprises the following steps:
A. Alkali washing: soaking the plate blank in an alkali melt at 500 ℃ for 10min; the alkali melt was composed of 90wt% NaOH and 10wt% NaNO 3 Composition;
B. primary acid washing: soaking the sheet billet in a first acid solution at 55 ℃, pickling for 1.5min, washing with water, and drying; the first acid solution contains: 10wt% H 2 SO 4 And the balance being water;
C. secondary acid washing: soaking the sheet billet in a second acid solution at the temperature of below 60 ℃ for pickling for 4.5min; the second acid solution contains: 20wt% HNO 3 1.5% wtHF and the balance water.
Grinding wheel polishing treatment is carried out on the plate blank subjected to alkali pickling treatment, and a diamond grinding wheel is adopted, and the method comprises the following steps:
s1, rough grinding: the granularity of the rough grinding wheel is 100 meshes, the rotating speed is 1800r/min, the feeding amount is 0.03mm each time, and the feeding speed of the diamond grinding wheel is 900mm/min;
s2, fine grinding: the granularity of the fine grinding wheel is 200 meshes, the rotating speed is 3800r/min, the feeding amount is 0.005mm each time, and the feeding speed is 400mm/min.
Step four: heating the rough rolled blank to 780 ℃ by hot rolling second fire, preserving heat for 20min, rolling in the same direction along the three phases of the steps, and shearing at a fixed width to obtain a second fire blank with the thickness of 3.5 mm;
step five: hot rolling for three times, heating the plate blank with the second fire to 780 ℃, and preserving heat for 15min; rolling in the same direction in the four steps to obtain the three-fire slab with the thickness of 2 mm.
Step six was performed in the same manner as in example 1;
step seven: the rolling direction of the cold rolling is the same as that of the step five, and the cold rolling comprises the following steps: cold-rolling to a cold-rolled blank with the thickness of 0.8mm for one time; and cold-rolled sheet having a thickness of 0.39mm was further cooled.
Step eight: and heating the single cold-rolled sheet to 680+/-10 ℃ by adopting an electric furnace, and carrying out annealing treatment for 18min to obtain a titanium sheet sample with the thickness of 0.39 mm.
Comparative example 3
The comparative example uses a titanium plate sample for a plate heat exchanger of national standard GB/T14845.
The room temperature mechanical properties of examples 1-3 and comparative examples 1-2 were tested. The specific results are shown in Table 1:
TABLE 1 comparison of the Performance of examples 1-3 and comparative examples 1-3
The samples of example 1 and comparative examples 1 to 2 were subjected to thickness measurement at 6 measurement points, and the same plate difference (unit: mm) was calculated, and the specific numbers are shown in Table 2:
TABLE 2 results of thickness test for example 1, comparative examples 1-2
The properties of the finished titanium plates produced by the invention in examples 1-3 reach and exceed the national standards. It is worth pointing out that the thickness of the TA1 plate produced by the preparation method is smaller than the lower limit of the plate thickness required by GB/T14845, but the mechanical property is better, which is favorable for saving the use amount of titanium materials and reducing the production cost. In contrast, comparative examples 1 and 2, while substantially satisfying the requirements of GB/T14845, have insignificant performance advantages and significantly insufficient mechanical and other overall properties compared to examples 1-3, mainly due to the differences in the selection and combination of their preparation processes between reversing hot rolling and unidirectional rolling, resulting in differences in sheet grain uniformity, anisotropy, etc. In addition, the timely annealing treatment is beneficial to release of internal stress of the plate, improves rolling effect, and improves comprehensive properties such as mechanical property, dimensional stability, thickness uniformity and the like of the final plate.
As can be seen from Table 2, the titanium plate prepared in example 1 has a common plate difference of 0.011mm, and has good thickness uniformity, short correction time and good effect, and no subsequent correction or trimming process is required. Comparative examples 1 and 2, which were obtained by the single-direction rolling of the whole hot rolling process, resulted in insufficient grain refinement, remarkable anisotropy of sheet, and low performance and dimensional stability, were subjected to the two cold rolling and the intermediate annealing treatments and the final step annealing treatment, but were still remarkably insufficient in thickness uniformity. Whereas comparative example 2 did not undergo an intermediate annealing treatment in the two cold rolling treatments, and finally adopted the annealing treatment manner usual in the art, the annealing treatment was insufficient, and the thickness uniformity was significantly lower than in the previous examples and comparative examples.
According to the titanium plate processing method, the process links are scientifically designed and combined according to the performance and the processing characteristics of the titanium material, and suitable process parameters are searched out through a large number of experiments, so that the limit of titanium material processing on equipment is effectively reduced, the titanium plate special for deep drawing is simple and easy to process, the prepared titanium plate is stable in performance and size, and popularization and application of the titanium plate in the fields of medical treatment, environmental protection, aerospace and the like are facilitated.
The foregoing description of the preferred embodiments of the present invention has been presented for purposes of clarity and understanding, and is not intended to limit the invention to the particular embodiments disclosed, but is intended to cover all modifications, alternatives, and improvements within the spirit and scope of the invention as outlined by the appended claims.
Claims (10)
1. The preparation method of the titanium plate for deep drawing is characterized by comprising the following steps of:
step one: using a Brinell hardness HB of less than 95 of 0 A The grade titanium sponge is used as a raw material, and a vacuum consumable arc melting method is utilized to obtain a titanium ingot through twice melting;
step two: forging a titanium ingot in one direction along the axial direction to obtain a titanium plate blank;
step three: hot rolling and cogging, namely heating the titanium plate blank to 800-850 ℃, and rolling along the direction perpendicular to the forging direction to obtain a rough rolled blank, wherein the deformation rate is more than 85%; carrying out alkali pickling treatment and grinding treatment on the rough rolled blank;
step four: heating the rough rolled blank to 750-800 ℃ by hot rolling second fire, rolling along the rolling direction of the step three, wherein the deformation rate is more than 65%, and cutting to obtain a second fire blank by fixed width;
step five: hot rolling with three fires, namely heating the slab with the two fires to 750-800 ℃, and rolling along the direction perpendicular to the rolling direction of the step four, wherein the deformation rate is more than 35%;
Step six: sequentially carrying out first round alkali pickling treatment, grinding treatment, semi-finished product annealing treatment and second round alkali pickling treatment on the three-fire plate blank;
step seven: performing cold rolling twice along the rolling direction of the fifth step to obtain a cold-rolled sheet with the thickness of 0.4+/-0.02 mm;
step eight: and carrying out finished product annealing treatment on the cold-rolled sheet.
2. The method of claim 1, wherein 0 A The components and mass percentages of the grade titanium sponge are as follows: less than or equal to 0.03 percent of iron, less than or equal to 0.05 percent of oxygen, less than or equal to 0.01 percent of nitrogen, less than or equal to 0.01 percent of carbon, less than or equal to 0.003 percent of hydrogen, less than or equal to 0.01 percent of silicon, less than or equal to 0.06 percent of chlorine and magnesiumLess than or equal to 0.01 percent, less than or equal to 0.01 percent of manganese, less than or equal to 0.01 percent of nickel, less than or equal to 0.01 percent of chromium, less than or equal to 0.02 percent of the sum of other impurity contents, and the balance of titanium.
3. The production method according to claim 1 or 2, wherein the titanium plate blank of the second step has a thickness H x width B x length L of (110 to 135 mm) × (600 to 700 mm) × (1000 to 1200 mm); and thirdly, heating the titanium plate blank to 800-850 ℃, preserving heat for 120-150min, and rolling to obtain a rough rolled blank with the thickness of 12-15 mm.
4. The preparation method of claim 3, wherein in the fourth step, the rough rolled blank is heated to 750-800 ℃ and kept at the temperature for 15-20min for rolling, and a two-fire slab with the thickness of 3-4mm is obtained; performing asynchronous hot rolling by adopting an asynchronous rolling mill set, wherein the asynchronous rolling mill set comprises at least 1 group of different-speed asynchronous rolling mills and at least 1 group of different-diameter asynchronous rolling mills; the hot rolling direction is the same as the rolling direction of the third step, and the pressure among rollers of each rolling mill of the asynchronous rolling mill set is gradually increased along the rolling direction;
Upper roll speed V of asynchronous rolling mill 1 : lower roll speed V 2 1.3-1.5, the diameter R of the upper roller of the reducing asynchronous rolling mill 1 : lower roll diameter R 2 Is 1: (1.1-1.3).
5. The preparation method of claim 4, wherein in the fifth step, the two-fire slab is subjected to 90-degree reversing, heating to 750-800 ℃, preserving heat for 10-15min, and then one-way rolling to obtain a three-fire slab with the thickness of 1.5-2 mm; in the sixth step, the annealing treatment of the semi-finished product comprises the following steps:
stacking 3-6 slabs;
heating the stacked slabs to 680+/-10 ℃ by adopting an electric furnace, and carrying out annealing treatment for 16-20min.
6. The method of claim 4 or 5, wherein the total deformation before hot rolling three-fire change is: the total deformation after the hot rolling three-fire change is 1 to 1.15, wherein the total deformation before the hot rolling three-fire change is (titanium plate blank thickness H-two-fire plate blank)Thickness H 1 ) The total deformation after hot rolling for three fires is (thickness H of the two-fire slab) 1 Finished thickness H 2 )/H 1 。
7. The method according to claim 6, wherein in the seventh step, a cold rolling is performed to obtain a cold rolled blank having a thickness of 0.7 to 1.0 mm; re-rolling to obtain a cold-rolled sheet with the thickness of 0.4+/-0.02 mm; an intermediate annealing treatment and an alkali pickling treatment are performed between the two cold rolling, the intermediate annealing treatment comprising:
Stacking 3-8 slabs;
heating the stacked slabs to 680+/-10 ℃ by adopting an electric furnace, and carrying out annealing treatment for 16-20min.
8. The method according to claim 7, wherein in the eighth step, the single cold-rolled sheet is heated to 680.+ -. 10 ℃ on line by using an all-solid high frequency induction heating device, and annealed for 16-20min.
9. The method of producing as claimed in claim 7 or 8, wherein the alkali pickling treatment of the roughing, the triple-fire slab and the cold-rolled slab comprises the steps of:
A. alkali washing: soaking the plate blank in 460-520 deg.c alkali molten liquid for 5-15min; the alkali melt consists of 85-95wt% NaOH and 5-15wt% NaNO 3 Composition;
B. primary acid washing: soaking the sheet billet in a first acid solution at the temperature of below 60 ℃, pickling for less than 2min, washing with water, and drying; the first acid solution contains: 5-15wt% H 2 SO 4 And the balance being water;
C. secondary acid washing: soaking the sheet billet in a second acid solution at the temperature of below 60 ℃ for pickling for less than 5min; the second acid solution contains: 15-25wt% HNO 3 1-2% wtHF and the balance water.
10. The method of manufacturing according to claim 9, wherein the grinding treatment of the rough rolled blank and the three-fire slab is performed by using a diamond grinding wheel, comprising the steps of:
S1, rough grinding: the granularity of the rough grinding wheel is 100-150 meshes, the rotating speed is 1500-2000r/min, the feeding amount is 0.02-0.05 mm each time, and the feeding speed of the diamond grinding wheel is 800-1000 mm/min;
s2, fine grinding: the granularity of the fine grinding wheel is 200-300 meshes, the rotating speed is 3500r/min to 4000r/min, the feeding amount is less than 0.01mm each time, and the feeding speed is 300mm/min to 450mm/min.
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