CN118951003A - A composite nitrided alloy ball, preparation method and application in steel - Google Patents
A composite nitrided alloy ball, preparation method and application in steel Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 106
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 101
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 68
- 239000010959 steel Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 150000004767 nitrides Chemical class 0.000 claims abstract description 63
- 239000002245 particle Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000005484 gravity Effects 0.000 claims abstract description 6
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 claims description 31
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 6
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 claims description 6
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 claims description 6
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001337 iron nitride Inorganic materials 0.000 claims description 5
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 4
- 229910001018 Cast iron Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004375 Dextrin Substances 0.000 claims description 3
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- 229920002472 Starch Polymers 0.000 claims description 3
- 229910001315 Tool steel Inorganic materials 0.000 claims description 3
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 claims description 3
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
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- 235000019425 dextrin Nutrition 0.000 claims description 3
- 239000011499 joint compound Substances 0.000 claims description 3
- 235000013379 molasses Nutrition 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims 2
- 238000005121 nitriding Methods 0.000 abstract description 55
- 239000000853 adhesive Substances 0.000 abstract description 13
- 230000001070 adhesive effect Effects 0.000 abstract description 13
- 239000002893 slag Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 238000005728 strengthening Methods 0.000 description 12
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 239000008188 pellet Substances 0.000 description 11
- 229910052720 vanadium Inorganic materials 0.000 description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 9
- 239000006260 foam Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910001199 N alloy Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- 229910000742 Microalloyed steel Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- PNXOJQQRXBVKEX-UHFFFAOYSA-N iron vanadium Chemical compound [V].[Fe] PNXOJQQRXBVKEX-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- JMAHHHVEVBOCPE-UHFFFAOYSA-N [Fe].[Nb] Chemical compound [Fe].[Nb] JMAHHHVEVBOCPE-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010079 rubber tapping Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000592 Ferroniobium Inorganic materials 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 229910000628 Ferrovanadium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PWKWDCOTNGQLID-UHFFFAOYSA-N [N].[Ar] Chemical compound [N].[Ar] PWKWDCOTNGQLID-UHFFFAOYSA-N 0.000 description 1
- HJIYJLZFNBHCAN-UHFFFAOYSA-N [V].[C] Chemical compound [V].[C] HJIYJLZFNBHCAN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 238000009851 ferrous metallurgy Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
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- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- ZFGFKQDDQUAJQP-UHFFFAOYSA-N iron niobium Chemical compound [Fe].[Fe].[Nb] ZFGFKQDDQUAJQP-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 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 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- -1 nitrogen carbides Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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Landscapes
- Powder Metallurgy (AREA)
Abstract
The invention discloses a composite nitriding alloy ball block, a preparation method and application thereof in steel, and belongs to the technical field of nitriding alloy materials. The composite nitriding alloy ball block is formed by mixing a first substance and a second substance, wherein the first substance is in a particle shape and/or a powder shape and contains 93-98 wt% of nitride with the granularity smaller than 10 mm; the second substance contains 2-7 wt% of adhesive and water, and the viscosity value of the adhesive is more than or equal to 10 mPa.s; the composite nitriding alloy ball block is one or more of a sphere, an ellipse, a prism, a square, a cuboid, a polygon and a hemisphere; the average grain diameter of the composite nitriding alloy ball block is 1-65mm; the specific gravity of the composite nitriding alloy ball block is 1.1-6.7g/cm 3.
Description
Technical Field
The invention belongs to the technical field of nitriding alloy materials, and particularly relates to a composite nitriding alloy ball block, a preparation method and application thereof in steel.
Background
The nitriding alloy is widely used in the ferrous metallurgy process, and in actual steel production, in order to improve the strength of steel, ferrovanadium or ferroniobium and other alloys need to be added in the steelmaking process to achieve the effect through microalloying. In order to fully exert the microalloy strengthening effect of vanadium and niobium, a proper amount of nitriding alloy is generally required to be added in steelmaking, and carbonitride is formed by the microalloy elements vanadium and niobium, so that the precipitation, solid solution strengthening and precipitation strengthening effects of the microalloy elements are improved. The general method for microalloying molten steel mainly comprises the following steps: 1) Adding vanadium-nitrogen alloy and niobium-iron alloy; 2) Adding a vanadium iron alloy and adding a nitriding alloy at the same time; 3) Adding the niobium-iron alloy and the nitriding alloy.
The most common mode of adding the nitriding alloy into molten steel is as follows: firstly, crushing different kinds of nitriding alloy primary blocks into small blocks with certain particle sizes (the particle size range of the common block size is 10-100 mm), then mixing one or more crushed nitriding alloy primary blocks together according to a proportion, and adding the crushed nitriding alloy primary blocks into molten steel in the tapping process. Patent document 1 chinese patent CN106244770a discloses a microalloy reinforcing agent, which can be suitable for the requirements of different microalloy steel grades, and can be made into alloy blocks with the grain size of 5-45 mm with vanadium nitride.
The above alloy lump inevitably causes the following problems: 1) The structure of the original block of the nitriding alloy is compact, molten steel is difficult to penetrate from the surface layer to the inner core part of the original block of the nitriding alloy in a short time (2-5 minutes) in the tapping process, and the added nitriding alloy cannot be penetrated, so that the utilization rate of the original block of the nitriding alloy is greatly reduced; 2) The nitriding alloy primary block generates a composition gradient from outside to inside in the nitriding process, particularly an N element gradient is larger, and the primary block is crushed into small blocks; the elements are non-uniform, thereby affecting the reinforcing effect on steel; 3) The dissolution speed of the several nitriding alloy primary blocks added into molten steel is greatly different, so that the steel strengthening effect is greatly fluctuated; 4) The inherent characteristics of the original block of the nitriding alloy cause poor stability of the strengthening effect of molten steel, poor controllability and low hit rate of the microalloying strengthening target.
Disclosure of Invention
1. Problems to be solved
Aiming at the technical problem that the prior original block of the nitriding alloy cannot be permeated in a short time due to compact structure, the invention aims to provide the composite nitriding alloy ball block, optimize the structure and the component uniformity of the original block of the nitriding alloy, and uniformly distribute the alloy ball block in molten steel so as to improve and stabilize the use effect of the composite nitriding alloy ball block.
The invention further aims at providing a preparation method of the composite nitriding alloy ball block.
Another object of the invention is to provide the use of a composite nitrided alloy pellet in steel.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
The first aspect of the present invention provides a composite nitrided alloy pellet, which is produced by mixing a first substance and a second substance, wherein the first substance is in the form of particles and/or powder, and contains 93-98 wt% of nitrides with particle size smaller than 10mm (the proportion and types of the nitrides are not limited and can be matched in any proportion), so as to optimize the structure and the uniformity of components of the nitrided alloy pellet; the second substance contains 2-7 wt% of adhesive and water (the water is added), the viscosity value of the adhesive is more than or equal to 10mPa.s, the viscosity value ensures the bonding strength of the ball block, and the ball block is not easy to crush.
The shape of the ball block is one or more of a sphere, an ellipse, a prismatic shape, a regular cube, a cuboid, a polygon, a hemispherical shape and an irregular ball block, and the specific gravity of the composite nitriding alloy ball block is 1.1-6.7g/cm 3;
the average particle size of the spherical blocks is 1-65mm, and compared with the original blocks, the spherical blocks have small particles and large contact area with molten steel, and are more beneficial to melting.
According to any one of the embodiments of the first aspect of the object of the present invention, the binder is one or more of molasses, starch, polyvinyl alcohol, dextrin, cellulose polymer, white mud, clay, bentonite, cement, water glass.
According to any one of the embodiments of the first aspect of the object of the present invention, the nitride is one or more of vanadium nitride, silicon nitride, titanium nitride, niobium nitride, iron silicon nitride, manganese silicon nitride, chromium nitride.
According to any one of the embodiments of the first aspect of the object of the present invention, the composite nitrided alloy pellet is produced and shaped by different types of pellet and/or block making machines.
According to any one of the first aspect of the object of the present invention, the foam killer further comprises 0-10 wt% of foam killer, and the foam killer is one of CaF 2 and sodium carbonate.
The second aspect of the invention provides a method for preparing the composite nitriding alloy ball block according to the first aspect, comprising the following steps: mixing nitride with particle size smaller than 10mm with binder; the nitride is selected from one or more of vanadium nitride, silicon nitride, titanium nitride, niobium nitride, silicon iron nitride, silicon manganese nitride, chromium nitride, and the size of the crushed and ground nitride is 0 to 10mm, i.e. less than 10mm, since they cannot be compressed; molding without adhesive, mixing with adhesive, and making into ball.
According to any one of the embodiments of the second aspect of the object of the present invention, the nitride comprises vanadium nitride, the phases of which include a VN phase, a V 2 N phase and a V 3 N phase; wherein the VN phase accounts for 65-90 wt%, and the sum of the V 2 N and V 3 N phases accounts for 10-35 wt%.
According to any one of the embodiments of the second aspect of the object of the invention, the VN phase is in a proportion of 80% by weight and the sum of the V 2 N and V 3 N phases is in a proportion of 20% by weight.
According to any one of the embodiments of the second aspect of the object of the present invention, the nitride comprises silicon nitride, the phases of the silicon nitride comprise an alpha-Si 3N4 and a beta-Si 3N4 phase, the alpha-Si 3N4 phase accounts for 79-96 wt% and the beta-Si 3N4 phase accounts for 4-21 wt%.
According to any one of the embodiments of the second aspect of the object of the present invention, the nitrided alloy pellet is composed of nitride powder and granules in different proportions, wherein the powder with the particle diameter of less than 0.01mm accounts for less than 6%, the powder with the particle diameter of 0.01mm-0.04mm accounts for 27% or less, the powder with the particle diameter of 0.04mm-10mm accounts for 67% or more, the total proportion is 100%, and the powder (80 mesh-400 mesh) pellets can be all obtained.
In a third aspect, the present invention provides a composite nitrided alloy pellet according to the first aspect or a composite nitrided alloy pellet obtained by the method of manufacture according to the second aspect, and the composite nitrided alloy pellet according to the present invention is used in steel, including but not limited to high chromium cast iron, high strength steel strip, non-quenched and tempered steel, high strength H-section steel, high speed tool steel, high strength pipeline steel, V-grade screw steel, HRB500 (E) high strength anti-seismic steel, HRB400 (E) steel, HRB600 steel, Q620D steel, etc.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) The composite nitriding alloy ball block can comprise 93-98 wt% of at least one nitride with granularity smaller than 10mm, 2-7 wt% of adhesive and water, and the nitride is mixed with the adhesive to prepare the ball block, so that the structure and the component uniformity of the original nitriding alloy block can be optimized, and the alloy ball block can be uniformly distributed in molten steel, thereby improving and stabilizing the use effect of the composite nitriding alloy ball block;
(2) The composite nitriding alloy ball block comprises the defoaming agent, so that the problem that a large amount of smoke and foam slag are generated in the application process of some single nitriding alloy original blocks (such as SiN, siFeN, siMnN) can be solved, and the application environment is effectively improved;
(3) According to the composite nitriding alloy ball block, at least one nitride is adjusted to be proportioned to prepare the ball block, so that the required element components can be accurately achieved, and the cost performance of steel microalloying efficiency is improved;
(4) The composite nitride alloy ball block comprises a silicon nitride phase, wherein the silicon nitride phase comprises an alpha-Si 3N4 phase and a beta-Si 3N4 phase, the alpha-Si 3N4 phase accounts for 79-96 wt% and the beta-Si 3N4 phase accounts for 4-21 wt%; the analysis shows that the alpha-Si 3N4 whisker has smooth surface, a large number of defects and a large number of bifurcation whiskers; the surface of the beta-Si 3N4 crystal whisker is smooth and basically free of defects, and the forked crystal whisker is few, so that the alloy material has better crushing performance, the crushing efficiency is improved, the powder occupancy rate is reduced, the raw material loss is reduced, the site dust is avoided, and the environmental quality is improved;
(5) According to the preparation method, the process steps of the nitriding alloy are improved, for example, the cooling speed is controlled to be 3-5 ℃/s in the cooling process, so that the phase of vanadium nitride precipitated in the nitriding alloy block comprises a VN phase, a V 2 N phase and a V 3 N phase; wherein the VN phase accounts for 65-90 wt%, the sum of the V 2 N phase and the V 3 N phase accounts for 10-35 wt%, and the alloy block of the material has better crushing performance;
(6) Compared with the prior art, the cored wire is added at a station of a refining station by using a special wire feeder, so that the operation is inconvenient, the composite nitriding alloy ball block is added at any time and any place according to the process and working conditions in the whole process of microalloying, and is free from the influence of the process station, and convenient and quick to use.
Drawings
The technical solution of the present invention will be described in further detail below with reference to the accompanying drawings and examples, but it should be understood that these drawings are designed for the purpose of illustration only and thus are not limiting the scope of the present invention. Moreover, unless specifically indicated otherwise, the drawings are intended to conceptually illustrate the structural configurations described herein and are not necessarily drawn to scale.
FIG. 1 is a physical diagram of a composite nitrided alloy ball block according to example 1 of the present invention;
FIG. 2 is a physical diagram of a composite nitrided alloy ball block according to example 2 of the present invention;
FIG. 3 is a physical diagram of a composite nitrided alloy ball block according to example 3 of the present invention;
FIG. 4 is a physical diagram of a composite nitrided alloy ball block according to example 4 of the present invention;
FIG. 5 is a schematic view showing a structure of a pair of extrusion dies according to the present invention;
fig. 6 is a schematic view showing another structure of the extrusion die according to the present invention.
Detailed Description
The present disclosure may be understood more readily by reference to the following description taken in conjunction with the accompanying drawings and examples, all of which form a part of this disclosure. It is to be understood that this disclosure is not limited to the particular products, methods, conditions, or parameters described and/or shown herein. Further, the terminology used herein is for the purpose of describing particular embodiments by way of example only and is not intended to be limiting unless otherwise indicated.
It is also to be appreciated that certain features of the disclosure may, for clarity, be described herein in the context of separate embodiments, but may also be provided in combination with each other in a single embodiment. That is, each separate embodiment is contemplated to be combinable with any other embodiment, and to be considered as representing a different embodiment, unless expressly incompatible or specifically excluded. Conversely, various features of the disclosure that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. Finally, although a particular embodiment may be described as part of a series of steps or as part of a more general structure, each step or sub-structure itself may also be considered a separate embodiment.
Unless otherwise indicated, it should be understood that each individual element in the list and each combination of individual elements in the list are to be construed as different embodiments. For example, a list of embodiments denoted as "A, B or C" should be interpreted to include embodiments "a", "B", "C", "a or B", "a or C", "B or C" or "A, B or C".
In this disclosure, the singular forms "a," "an," and "the" also include the corresponding plural referents, and reference to a particular value includes at least the particular value unless the context clearly dictates otherwise. Thus, for example, reference to "a substance" is a reference to at least one of such a substance and equivalents thereof.
Terms including ordinal numbers such as "first" and "second" may be used to explain various components or fluids, but the components, fluids are not limited by these terms. Accordingly, these terms are merely used to distinguish one component/fluid from another component/fluid without departing from the teachings of the present disclosure.
When items are described using the conjunctive terms "… … and/or … …," etc., the description should be understood to include any one of the associated listed items, as well as all combinations of one or more of the same.
In general, the use of the term "about" refers to an approximation that may vary depending on the desired properties obtained by the disclosed subject matter, and will be interpreted in a context-dependent manner based on the function. Thus, one of ordinary skill in the art will be able to interpret a degree of variability on an individual case basis. In some cases, the number of significant digits used in expressing a particular value can be a representative technique for determining the variance allowed by the term "about. In other cases, a gradient in a series of values may be used to determine the range of differences permitted by the term "about". Further, all ranges in this disclosure are inclusive and combinable, and reference to a value recited in a range includes each value within the range.
The composite nitriding alloy ball block is prepared by mixing a first substance and a second substance, wherein the first substance is in a particle shape and/or a powder shape, and the main component of the first substance comprises 93-98 wt% of nitride with the granularity smaller than 10 mm. The nitride alloy ball block consists of nitride powder and particles in different proportions, wherein the powder with the particle size of less than 0.01mm accounts for less than 6%, the powder with the particle size of 0.01mm-0.04mm accounts for less than or equal to 27%, the powder with the particle size of 0.04mm-10mm accounts for more than or equal to 67%, the total proportion is calculated to be 100%, and the powder (80-400 meshes) ball pressing can be realized.
Wherein the nitride is one or more of vanadium nitride, silicon nitride, titanium nitride, niobium nitride, ferrosilicon nitride, manganese silicon nitride and chromium nitride. These nitrides contain N element, and by adding the alloy globules to the microalloyed steel, the interaction of the nitrogen element with the microalloyed element forms nitrides or nitrogen carbides in the form of precipitation reactions in the ferrite.
The nitrides of the microalloying elements are more stable than the carbides and have a smaller tendency to polymerize, and the nitrogen addition maximizes the ratio of the particle volume fraction to the particle size, thereby maximizing the critical microstructure of the microalloyed steel, i.e., grain refinement and precipitation strengthening. The nitride particles can improve the austenite grain refinement temperature in the heating process, prevent the growth of grains in the rolling process, delay recrystallization, increase the phase transformation ratio, increase precipitation strengthening and the like.
In addition, preferably, the nitride contains vanadium nitride and silicon nitride, and the alloy element vanadium exists on a matrix and a grain boundary mainly in the form of carbon and nitride in the steel, so as to play roles of precipitation strengthening and grain growth inhibition. The solubility of vanadium in ferrite is much smaller than that in austenite, and along with the progress of phase transformation, under certain thermodynamic and kinetic conditions, vanadium carbon and nitride are precipitated in phase boundaries, grains can be refined by accelerated cooling in a two-phase region, the precipitation of the carbon and the nitride is controlled, and the size and the distribution of precipitates determine the effect of precipitation strengthening. As vanadium and nitrogen have strong affinity, adding a certain amount of nitrogen while adding a certain amount of vanadium can make the strengthening effect more effective.
The invention provides a preparation method of vanadium nitride, silicon nitride and the like, which comprises the following steps:
step S1, selecting raw materials: vanadium iron, vanadium pentoxide, vanadium-containing slag, ferrosilicon, metallic silicon or ferrotitanium;
s2, respectively crushing the materials selected in the step S1, and then grinding the materials into powder with the granularity of 120-600 meshes;
step S3, mixing the raw material fine powder obtained in the step S2 according to 60% of silicon element, 15% of vanadium element and 12% of titanium element, adding polyborosiloxane accounting for 2% of the total raw material fine powder mass fraction and 7% of graphite carbon reducer, uniformly mixing, and briquetting under the pressure of 120Mpa by using a strong ball press;
step S4, putting the pressed block obtained in the step S3 into a pretreatment furnace, heating to 680 ℃ for heat preservation, and filling protective gas (argon-nitrogen mixed gas, wherein the purity of Ar gas is 99%, and the purity of N 2 is 98%) into a hearth for pretreatment for 5 hours;
S5, placing the pretreated pressed block into a nitriding furnace for nitriding treatment; nitrogen is introduced in the nitriding treatment process, the pressure is 0.2Mpa, the temperature is firstly increased to 1000 ℃ for 3 hours, then the temperature is increased to 1200 ℃ for 9 hours, the temperature is continuously increased to 1350 ℃ for 8 hours, and the temperature is kept for 12 hours until the temperature is increased to 1600 ℃;
and S6, after nitriding treatment is finished, naturally cooling to below 300 ℃ along with a furnace, and then discharging from the furnace and cooling to room temperature to obtain the vanadium nitride and other alloys with the particle size of 3-70 mm.
Further, the second substance contains 2-7 wt% of adhesive and water, after the adhesive is mixed and stirred with the water, the viscosity value of the adhesive is more than or equal to 10mPa.s, preferably between 10mPa.s and 100mPa.s, and the ball forming rate of the invention is 98%, and the ball is relatively complete after 2 meters falling, which is enough to indicate that the bonding strength of the ball is relatively high.
1-4, The shape of the spherical block is one or more of a sphere, an ellipse, a prismatic shape, a regular cube, a cuboid shape, a polygonal shape, a hemispherical shape and an irregular spherical block, and the specific gravity of the composite nitriding alloy spherical block is 1.1-6.7g/cm 3; the average particle size of the spherical blocks is 1-65mm, and compared with the original blocks, the spherical blocks have small particles and large contact area with molten steel, and are more beneficial to melting.
In some embodiments of the present invention, the sphere block shape may be made into various shapes, preferably a sphere, an ellipse, a prism, a polygon. The composite nitride alloy ball blocks are produced and formed by different types of ball making machines and/or block making machines, and the ball making machines and/or the block making machines can adopt opposite extrusion dies, as shown in fig. 5 and 6, so as to produce corresponding shapes.
In some embodiments of the invention, the binder is one or more of molasses, starch, polyvinyl alcohol, dextrin, cellulose polymer, soda ash, lime mud, clay, bentonite, cement, water glass. Some of these binders mentioned above are organic compounds which participate in the combustion (above 1000 ℃) during the preparation process, converting into carbon elements; some inorganic compounds are decomposed into oxides at high temperature, such as silicon dioxide, aluminum oxide and the like, and particularly, the water glass forms a net structure after dehydration, so that the strength of the composite nitriding alloy ball block is improved.
In the smelting process of steel, in the carburetion process (carbon-oxygen reaction), the addition of the primary alloy globules promotes deoxidization reaction, thereby increasing smoke; in addition, the primary alloy blocks are added into molten steel, the residence time of N 2,N2 gas generated after thermal decomposition in slag is prolonged, a large amount of gas is very easy to be discharged from slag in a furnace in a short time, the slag in the furnace is driven to foam rapidly and rise rapidly, and finally splash-state foam slag is formed, if the foam slag is generated in a large amount and cannot be eliminated in time, even slag overflow accidents occur in extreme cases, and the molten steel alloying chemical industry is possibly directly deteriorated.
On the basis of the above, the alloy ball blocks contain 0-10 wt% of defoaming agent, preferably, 3% of CaF 2.CaF2 can reduce the viscosity of slag, lower the melting temperature of slag and sharply reduce the foaming performance of slag. When the CaF 2 content exceeds 10%, the thickening and defoaming effects are no longer obvious.
The preparation method of the composite nitriding alloy ball block comprises the following steps: mixing nitride with particle size smaller than 10mm with binder; the nitride is selected from one or more of vanadium nitride, silicon nitride, titanium nitride, niobium nitride, silicon iron nitride, silicon manganese nitride, chromium nitride, and the size of the crushed and ground nitride is 0 to 10mm, i.e. less than 10mm, since they cannot be compressed; molding without adhesive, mixing with adhesive, and making into ball.
The nitriding alloy material adopts the qualitative analysis and the quantitative analysis of an X-ray diffractometer. Comparing the lattice plane spacing and diffraction intensity measured on the material with diffraction data of a standard phase through phase-to-phase analysis to determine the phase existing in the material; determining the content of each phase in the material according to the intensity of the diffraction pattern; silicon nitride, vanadium nitride and other nitrides were measured respectively, wherein diffraction peaks of silicon nitride and vanadium nitride appear in the RXD diagram, thereby determining that vanadium nitride and silicon nitride are contained in the alloy block.
Wherein the nitride comprises vanadium nitride, and the phases of the vanadium nitride comprise a VN phase, a V 2 N phase and a V 3 N phase; wherein the VN phase accounts for 65-90 wt%, and the sum of the V 2 N and V 3 N phases accounts for 10-35 wt%. Preferably, the VN phase is 80 wt%, and the sum of the V 2 N and V 3 N phases is 20 wt%. The mixing ratio between the two phases V 2 N and V 3 N is not set, and may be any mixing ratio.
It should be noted that the impurity dispersity in the internal structure of the vanadium nitride is reduced and/or homogenized, so that reasonable number of impurity gap positions exist among the microcosmic vanadium nitride crystals, and the positions can be easily broken and crushed under the action of external force, thereby improving the crushing efficiency; in addition, the internal crystal of vanadium nitride has relatively regular crystal morphology and single inter-connection mode, and the powder obtained by final crushing is relatively regular in shape and even in particle size distribution.
However, in the prior art, the content of broken powder of vanadium nitride below 0.1mm reaches 70% (the content of fine powder smaller than 0.01mm exceeds 5 percent), which is disadvantageous for the preparation of the cored wire on one hand, and the loss of vanadium nitride raw material is large due to the fact that the fine powder is too much and dust is large on site. According to the final statistics of each batch of production on site, the loss rate of the impact crusher for crushing vanadium nitride reaches about 3%, the loss is serious, and the environment in a factory is also greatly polluted.
Furthermore, the nitride contains silicon nitride, and surprisingly, the inventors found that the phase of silicon nitride precipitated inside the nitrided alloy pellet includes an α -Si 3N4 and a β -Si 3N4 phase, the α -Si 3N4 phase accounts for 79-96 wt% and the β -Si 3N4 phase accounts for 4-21 wt%. The analysis shows that the alpha-Si 3N4 whisker has smooth surface, a large number of defects and a large number of bifurcation whiskers; the surface of the beta-Si 3N4 whisker is smooth, basically has no defect, and has few forked whiskers.
According to the standard: (1) GB/T20567-2020 vanadium-nitrogen alloy; (2) GB/T24583.1-2019 titrimetry of ferrous ammonium sulfate for determining vanadium content of vanadium-nitrogen alloy; (3) GB/T24583.2-2019 "inert gas melt thermal conductivity method for determining nitrogen content of vanadium-nitrogen alloy"; (4) GB/T24583.8-2019 "determination of vanadium nitrogen alloy silicon, manganese, phosphorus and aluminium content" inductively coupled plasma atomic emission spectrometry; (5) GB/T37258-2018 silicon nitride ceramic powder, specific contents of silicon nitride, vanadium nitride and other nitrides are obtained.
[ Use in Steel ] the alloy buttons may be used in steel, in particular specialty steels; the application comprises that the multi-element nitriding alloy material is used for smelting high-strength steel, H-shaped steel and high-chromium cast iron.
The application of the composite nitriding alloy ball block obtained by the preparation method in steel is not limited to high-chromium cast iron, high-strength strip steel, non-quenched and tempered steel, high-strength H-shaped steel, high-speed tool steel, high-strength pipeline steel, V-grade screw steel, HRB500 (E) high-strength anti-seismic steel, HRB400 (E) steel, HRB600 steel, Q620D steel and the like.
Data comparison as shown in the following table:
Comparing the results of comparative examples 1 and 2 with examples 1-4, the nitriding alloy raw block was added to the molten steel, and the N 2,N2 gas generated after thermal decomposition drove the slag in the furnace to foam rapidly and rise sharply in the slag, forming a splash-like foamy slag, whereas examples 1-4 were substantially free of splash-like foamy slag.
The phases of example 1, which were examined, gave silicon nitride, included an alpha-Si 3N4 phase and a beta-Si 3N4 phase, the alpha-Si 3N4 phase being 90% by weight and the beta-Si 3N4 phase being 10% by weight.
The VN phase accounts for 70 wt%, and the sum of the V 2 N phase and the V 3 N phase accounts for 30 wt%. The mixing ratio between the two phases V 2 N and V 3 N is not set, and may be any mixing ratio.
The phases from example 2 to give silicon nitride included an alpha-Si 3N4 and a beta-Si 3N4 phase, the alpha-Si 3N4 phase being 89 wt% and the beta-Si 3N4 phase being 11 wt%.
The VN phase accounts for 80 wt%, and the sum of the V 2 N phase and the V 3 N phase accounts for 20 wt%. The mixing ratio between the two phases V 2 N and V 3 N is not set, and may be any mixing ratio.
The phases from example 3 that gave silicon nitride included an alpha-Si 3N4 and beta-Si 3N4 phase, with a proportion of 85% by weight of the alpha-Si 3N4 phase and a proportion of 15% by weight of the beta-Si 3N4 phase.
The VN phase accounts for 75 wt%, and the sum of the V 2 N and V 3 N phases accounts for 25 wt%. The mixing ratio between the two phases V 2 N and V 3 N is not set, and may be any mixing ratio.
The composite nitriding alloy ball block has at least the following effects:
1) The ball making block with at least one nitride in the regulated proportion can reach the required element components precisely and raise the cost performance of steel microalloying efficiency; the field use shows that the alloy ball blocks can be uniformly distributed in the molten steel, so that the use effect of the composite nitride alloy ball blocks is improved and stabilized;
2) The nitriding alloy ball can be adjusted and controlled to achieve proper specific gravity (specific gravity 1.1-6.7g/cm 3) and porosity (7-46%), and the melting speed and melting rate are improved by 20-30%;
3) The alloy balls can be adjusted to reach a proper melting point (such as silicon iron nitride, 1430-1560 ℃), and the melting speed and the melting rate of the alloy balls in molten steel can be regulated and stabilized;
4) The ball blocks with the shapes and the sizes (masses) are achieved through the selection of the extrusion die (shown in fig. 5 and 6) and the control of the ball making pressure (the pressing block of the powerful ball press under the pressure of more than 110 Mpa), so that the ball block is suitable for wider different application processes and working conditions;
5) The ball is crushed after being made, the surface area and the surface roughness of the materials are increased, the contact surface and the permeability of molten steel are increased, and the improvement of the melting speed and the melting rate is facilitated.
The alloy ball block has the advantages that:
1. The melting rate and the yield of the alloy element in molten steel are improved; 2. the strengthening efficiency and the stability of molten steel are improved; 3. the method is suitable for different steel grades and different microalloying processes; 4. the cost performance of the application is improved, and the application cost is obviously reduced.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; the term and/or any and all combinations including one or more of the associated listed items.
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