CN113684443B - Auxiliary steel and preparation method thereof - Google Patents
Auxiliary steel and preparation method thereof Download PDFInfo
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- CN113684443B CN113684443B CN202111009946.0A CN202111009946A CN113684443B CN 113684443 B CN113684443 B CN 113684443B CN 202111009946 A CN202111009946 A CN 202111009946A CN 113684443 B CN113684443 B CN 113684443B
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 96
- 239000010959 steel Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 116
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 94
- 239000000956 alloy Substances 0.000 claims abstract description 94
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 63
- 239000011777 magnesium Substances 0.000 claims abstract description 63
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 62
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 60
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 50
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011701 zinc Substances 0.000 claims abstract description 46
- 239000011572 manganese Substances 0.000 claims abstract description 44
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 44
- 230000000149 penetrating effect Effects 0.000 claims abstract description 41
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 22
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 54
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 50
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 30
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 29
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims description 27
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims description 27
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 27
- 235000019270 ammonium chloride Nutrition 0.000 claims description 27
- 239000012286 potassium permanganate Substances 0.000 claims description 27
- 229910052742 iron Inorganic materials 0.000 claims description 25
- 239000002270 dispersing agent Substances 0.000 claims description 22
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 20
- 230000003213 activating effect Effects 0.000 claims description 18
- 239000012190 activator Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 22
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 77
- 230000008595 infiltration Effects 0.000 description 34
- 238000001764 infiltration Methods 0.000 description 34
- 239000002184 metal Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 24
- 230000007797 corrosion Effects 0.000 description 24
- 238000005260 corrosion Methods 0.000 description 24
- 230000000694 effects Effects 0.000 description 17
- 239000007921 spray Substances 0.000 description 15
- 239000002344 surface layer Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 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 10
- 238000012360 testing method Methods 0.000 description 10
- 239000011159 matrix material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 230000001360 synchronised effect Effects 0.000 description 7
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 239000011565 manganese chloride Substances 0.000 description 6
- 235000002867 manganese chloride Nutrition 0.000 description 6
- 229940099607 manganese chloride Drugs 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000012466 permeate Substances 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000007689 inspection Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 3
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910001325 element alloy Inorganic materials 0.000 description 3
- 239000006023 eutectic alloy Substances 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- -1 zinc-magnesium-aluminum Chemical compound 0.000 description 2
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 229910017706 MgZn Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000012042 active reagent Substances 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002436 steel type Substances 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/52—Embedding in a powder mixture, i.e. pack cementation more than one element being diffused in one step
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Prevention Of Electric Corrosion (AREA)
Abstract
The application provides an accessory steel and a preparation method thereof, wherein the accessory steel comprises a base material and an alloy layer, and the alloy layer is an alloy layer containing multiple elements formed by penetrating a powder penetrating agent into the surface of the base material; the alloy layer comprises the following components in percentage by weight: 50-75wt% of zinc, 10-20wt% of aluminum, 3-10wt% of magnesium, 0.15-1.5wt% of manganese and the balance of components in the base material. For the accessory steel protected by the application, when the ratio of zinc, aluminum, magnesium and manganese in the alloy layer is the ratio of claim 1, and the alloy layer is larger than 20 mu m, the hardness, the salt fog resistance and the like of the accessory steel are all optimal, the comprehensive performance is high, the service life of the accessory steel is greatly prolonged, and the preparation method is simple, the cost is low, and the accessory steel has larger application and popularization.
Description
Technical Field
The application relates to the chemical field, in particular to the related technical fields of accessory steel surface treatment and the like, and particularly relates to accessory steel and a preparation method thereof.
Background
The railway bridge is a very vulnerable road section in the whole railway system, because the service environment of the railway bridge has the comprehensive effects of high humidity, high wind speed, frequent vibration and the like. The auxiliary steel structure in the railway bridge is of great importance, and a plurality of events which cause safety problems of the railway bridge caused by corrosion of the auxiliary steel structure of the bridge occur every year.
The subsidiary steel structure of railroad bridge mainly includes: the support pre-buried plate, T-shaped steel, pre-buried sleeve, hanging basket, fence and the like. The materials are mainly Q235 and Q345.
The existing corrosion prevention treatment method for the railway bridge auxiliary steel structure mainly comprises powder zinc impregnation and closed passivation treatment, and the closed passivation layer is easy to fall off under the comprehensive factors of alternating load, sand wind, acid rain, ultraviolet and the like, so that the actual service life of the railway bridge auxiliary steel structure is difficult to reach the design life. Therefore, a railway bridge auxiliary steel structure product with high corrosion resistance and high wear resistance needs to be developed, and the use of a railway system is better met. In the art, related researches are mature, and the related researches want to break through various barriers in the prior art have a great challenge.
Disclosure of Invention
In view of the above, the embodiment of the application provides an accessory steel and a preparation method thereof, which are used for solving the technical defects in the prior art.
An application provides auxiliary steel, which comprises a base material and an alloy layer, wherein the alloy layer is formed by penetrating a powder penetrating agent into the surface of the base material to form a multi-element alloy layer;
the alloy layer comprises the following components in percentage by weight: 50-75wt% of zinc, 10-20wt% of aluminum, 3-10wt% of magnesium, 0.15-1.5wt% of manganese and the balance of components in the base material.
Further, the thickness of the alloy layer is greater than 20 μm, such as 20 μm to 80 μm.
Further, the balance contains iron, and the content of the iron is not less than 8%.
Further, in the alloy layer, the content of manganese is 5% to 10%, preferably 6% to 8%, of the content of magnesium.
Further, the powder penetrating agent is a multi-element powder penetrating agent, and the components and parts by weight of the components comprise: 55-80 parts of zinc powder, 10-25 parts of zinc-aluminum alloy powder, 8-25 parts of aluminum-magnesium alloy powder, 0.1-1 part of rare earth oxide and 1-5 parts of activating agent, wherein the activating agent contains Mn. Preferably, the zinc powder is 60-73 parts, the zinc-aluminum alloy powder is 15-20 parts, the aluminum-magnesium alloy powder is 15-20 parts, the rare earth oxide is 0.4-0.7 part, and the activator is 2-4 parts.
Further, the activator is ammonium chloride and potassium permanganate, wherein in the activator, the potassium permanganate accounts for 5 to 20 weight percent, and the balance is ammonium chloride.
Further, the powder infiltration agent also comprises a catalyst and a dispersing agent, wherein in the powder infiltration agent, the weight part of the catalyst is 0.5-2 parts, preferably 0.6-1.2 parts.
The weight portion of the dispersing agent is 20-60 portions, preferably 25-35 portions.
Further, the dispersant is at least one of alumina, silica, magnesia, aluminum nitride, silicon nitride and silicon carbide.
Further, the catalyst is manganese dioxide.
Further, the rare earth oxide includes cerium oxide and/or lanthanum oxide.
Further, in the zinc-aluminum alloy powder, the aluminum content is 5 to 40 weight percent, and the balance is zinc.
Further, in the aluminum magnesium alloy powder, the aluminum content is 30 to 60 weight percent, and the balance is magnesium.
Another aspect of the present application is to provide a method for preparing an accessory steel according to any one of the preceding paragraphs, the method comprising:
step1: adopting a co-permeation process, and rotating the powder permeation agent and the matrix together in a co-permeation device so as to uniformly mix the permeation agent;
step2: heating the co-permeation device, and preserving heat for 1-10 hours after heating to a preset temperature to finish zinc permeation;
preferably, vacuumizing the co-permeation device to make the vacuum degree smaller than 100Pa, and then heating; more preferably, the reaction temperature in Step2 is between 400 ℃ and 450 ℃ and the reaction time is more than 1 hour.
Further, in Step2, the process of the present application,
(1) vacuumizing the co-permeation device to make the vacuum degree of the co-permeation device smaller than 100Pa;
(2) then the temperature in the co-permeation device is increased to be within the range of 100-200 ℃ and the residence time is more than 1 hour, such as 1-3 hours. Ensures that the ammonium chloride can be fully decomposed under the temperature condition while the potassium permanganate is not decomposed. The following reaction occurs at this time: 2KMnO 4 +16HCl＝2KCl+2MnCl 2 +5Cl 2 ↑+8H 2 O；
(3) Then the temperature is increased to 400-450 ℃ for 1-9 hours, and the zincification is completed.
The beneficial effects of the application are as follows:
the application breaks through the obstacle in the prior art, improves the suitability of the surface layer, the powder penetrating agent, the preparation method and the like of the auxiliary steel, so that the obtained auxiliary steel has excellent performance and good appearance visual effect, and can prevent the alloy layer from falling off under the conditions of alternating load, sand wind, acid rain, ultraviolet and the like, and has long service life. Has great application and popularization prospect. Specifically:
for the accessory steel protected by the application, when the ratio of zinc, aluminum, magnesium and manganese in the alloy layer is the ratio of claim 1 and the alloy layer is larger than 20 mu m, the hardness, brittleness, plasticity, salt spray resistance and the like of the accessory steel are all optimal, namely the comprehensive performance is high, and the service life of the accessory steel is greatly prolonged.
According to the multi-component penetrant for preparing the auxiliary steel alloy layer, the auxiliary steel can be obtained by co-permeation with an auxiliary steel matrix through the multi-component penetrant components and the selection of the contents of the components, the contents of the metal elements in the auxiliary steel are gradually reduced from the surface layer to the deep layer, no deposition phenomenon exists, the penetration depth is deep, the falling phenomenon does not occur, the hardness can reach about HV430-440, and the auxiliary steel can resist a 3500-hour neutral salt spray test after sand blowing. The ratio of the components in the penetrating agent not only can prepare the auxiliary steel, but also has the advantages of no waste phenomenon, synchronous penetration, good effect and low comprehensive cost.
For the preparation method, the preparation method is designed aiming at the type of the penetrating agent and the action of each component in the penetrating agent, and can assist the penetrating agent to enter the auxiliary steel matrix efficiently and orderly to obtain the alloy layer. The preparation method is low in temperature and can be completed only at 400-450 ℃, the defect that the mechanical properties of the auxiliary steel are easily deteriorated due to the fact that the temperature is too high is avoided, and the preparation method is simple to operate, low in cost and high in economic benefit.
In conclusion, the auxiliary steel provided by the application can be applied to complex or harsh environments, has long service life and low cost, is easy to popularize and use, and has excellent application prospect.
Drawings
FIG. 1 is a schematic view showing the appearance of an accessory steel treated with a infiltrant according to an embodiment of the present application; fig. 1A is a schematic view of a hanging basket in a high-speed railway pier inspection facility, fig. 1B is a schematic view of an inspection ladder, and fig. 1C is a schematic view of a steel beam in auxiliary steel.
FIG. 2 is a schematic cross-sectional view of an embodiment of the present application after infiltration of the supplemental steel.
FIG. 3 is a photograph of a cross-section of an attached steel salt spray of an embodiment of the present application after 3000 hours.
Detailed Description
The following describes specific embodiments of the present application with reference to the drawings.
In the present application, unless otherwise indicated, scientific and technical terms used herein have the meanings commonly understood by one of ordinary skill in the art. Also, reagents, materials, and procedures used herein are reagents, materials, and conventional procedures widely used in the corresponding field.
Example 1
The embodiment provides an accessory steel, which comprises a base material and an alloy layer, wherein the alloy layer is formed by penetrating a powder penetrating agent into the surface of the base material to form the alloy layer containing multiple elements.
The alloy layer comprises the following components in percentage by weight: 50-75wt% of zinc, 10-20wt% of aluminum, 3-10wt% of magnesium, 0.15-1.5wt% of manganese, and the balance of 5-36.75wt% of components in the base material, wherein if the base material consists of iron, nickel and other alloy elements, the base material is expected to be iron, nickel and other alloy elements, if the base material only consists of iron and nickel, the balance is iron and nickel, and if the base material consists of only iron, the balance is iron, and the like.
Preferably, the alloy layer comprises the following components in percentage by weight: 60-70wt% of zinc, 14-18wt% of aluminum, 5-8wt% of magnesium, 0.4-0.64 wt% of manganese and the balance of components in a base material, wherein the components in the base material are generally 10-20wt%, and the components permeated in the alloy layer are aluminum, magnesium, zinc and manganese, and for example, the content of the permeated components in the alloy layer can be any one of the following groups: (1) 60wt% of zinc, 18wt% of aluminum, 5wt% of magnesium and 0.64wt% of manganese; (2) 70wt% of zinc, 14wt% of aluminum, 8wt% of magnesium and 0.4wt% of manganese; (3) 65wt% of zinc, 16wt% of aluminum, 6wt% of magnesium and 0.48 wt% of manganese; (4) 70wt% of zinc, 16wt% of aluminum, 7wt% of magnesium and 0.55wt% of manganese.
The thickness of the alloy layer is greater than 20 μm, such as 20 μm to 80 μm, specifically, such as 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, etc. In the system of the application, the thickness of the alloy layer is generally between 50 and 75 μm, such as 53 μm, 58 μm, 62 μm, 67 μm, etc., which is far beyond the level of the prior art. The powder is immersed uniformly and the immersed depth is deeper, so that the overall properties of corrosion resistance, wear resistance, plasticity, rigidity and the like of the auxiliary steel are more excellent, and the auxiliary steel can be used in environments with high requirements on the auxiliary steel such as railways.
Preferably, the balance contains iron, and the content of iron is not less than 8%. In practice, the auxiliary steel is generally of steel structure, and iron is the main component, so that the content of iron is generally more than 10%. In the system of the application, manganese in the alloy layer can also form a composite system with iron, so that the detrimental effects of iron can be reduced and the wear resistance and corrosion resistance of iron can be increased.
As a further preferred embodiment, the manganese content in the alloy layer is 5% to 10%, preferably 6% to 8%, such as 5%, 6%, 7%, 8%, 9%, 10% of the magnesium content. During infiltration of the powder into the secondary steel, the infiltration layer or secondary steel may have some amount of iron, which, as mentioned above, is an important factor affecting the corrosion resistance of the high magnesium content structure of the surface layer. The addition of manganese can greatly reduce the deleterious effects of iron in the percolated layer. Manganese is added into the seepage layer, mainly for improving the corrosion resistance and the wear resistance of the seepage layer surface layer. When the magnesium contains 1-15% of manganese, the corrosion resistance of the surface layer can be greatly improved, the defect caused by the high content of local magnesium is avoided, and a compound with better performance can be produced with the magnesium. In particular, because excessive magnesium is easily concentrated in the outermost layer of the infiltration layer in the zinc-magnesium-aluminum infiltration layer, the surface layer of the infiltration layer structure can be corroded rapidly in the corrosion process due to the excessive magnesium. Manganese is added into the infiltration layer structure, mainly to improve the corrosion resistance of the infiltration layer surface layer. However, if the manganese content is too much, the plasticity of the alloy layer may be lowered, so that in the system of the application, the content is suitable, other metal components can be balanced, and the comprehensive effect of the auxiliary steel is increased.
In this example, it is shown by a large amount of experimental data that when the alloy layer contains the above-described specific amount of alloy components, and the alloy layer is more than 20 μm, the hardness, brittleness, plasticity, salt spray resistance, and the like thereof are optimal. Namely, when the metal alloy layer on the surface of the auxiliary steel contains specific contents of zinc, aluminum, magnesium and manganese, the corrosion resistance and the wear resistance of the auxiliary steel are greatly improved, and the service life is greatly prolonged.
Example 2
Based on the example 1, we know that the alloy layer of the accessory steel has good comprehensive properties such as corrosion resistance, wear resistance and the like when the alloy layer contains specific contents of zinc, aluminum, magnesium and manganese. How these components can be made to have these contents in the alloy layer, mainly by using the following multi-component powder infiltrant, the accessory steel in the examples can be obtained.
The multicomponent powder penetrating agent comprises the following components in parts by weight: 55-80 parts of zinc powder, 10-25 parts of zinc-aluminum alloy powder, 8-25 parts of aluminum-magnesium alloy powder, 0.1-1 part of rare earth oxide and 1-5 parts of activating agent, wherein the activating agent contains Mn. Preferably, the zinc powder is 60-73 parts, the zinc-aluminum alloy powder is 15-20 parts, the aluminum-magnesium alloy powder is 15-20 parts, the rare earth oxide is 0.4-0.7 part, and the activating agent is 2-4 parts. The components of the multi-component powder penetrating agent can be any one of the following components: (1) 60 parts of zinc powder, 20 parts of zinc-aluminum alloy powder, 15 parts of aluminum-magnesium alloy powder, 0.7 part of rare earth oxide and 2 parts of activating agent; (2) 73 parts of zinc powder, 15 parts of zinc-aluminum alloy powder, 20 parts of aluminum-magnesium alloy powder, 0.4 part of rare earth oxide and 4 parts of activating agent; (3) 65 parts of zinc powder, 18 parts of zinc-aluminum alloy powder, 16 parts of aluminum-magnesium alloy powder, 0.5 part of rare earth oxide and 3 parts of activating agent; (4) 70 parts of zinc powder, 16 parts of zinc-aluminum alloy powder, 18 parts of aluminum-magnesium alloy powder, 0.6 part of rare earth oxide and 4 parts of activating agent.
Wherein the activator is ammonium chloride and potassium permanganate, and the potassium permanganate accounts for 5-20wt%, preferably 10-18wt%, such as 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 18wt%, and the rest is ammonium chloride. The potassium permanganate starts to decompose approximately at 220 ℃ to 350 ℃, the decomposition starting temperature of the ammonium chloride is 100 ℃, and the ammonium chloride can react with the potassium permanganate at 100-200 ℃ to generate substances capable of penetrating into manganese and catalyzing penetration or reaction of other components. Other ammonium halides are not preferred structures because the hydrogen fluoride from which ammonium fluoride is decomposed does not react with potassium permanganate, whereas ammonium bromide, ammonium iodide, ammonium fluoride are not used because the decomposition temperature is higher than that of potassium permanganate.
As a further preferred embodiment, a catalyst and/or a dispersant is also included in the powder infiltrant, wherein the weight parts of the catalyst in the powder infiltrant are 0.5-2 parts, preferably 0.6-1.2 parts, such as 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts.
As a further preferred embodiment, the catalyst is manganese dioxide which aids in the penetration of manganese after the potassium permanganate reaction, and which also reacts with ammonium chloride to promote the diffusion of magnesium, aluminum, zinc into the diffusion layer, but which does not itself contain manganese in the alloy layer.
In a further preferred embodiment, the dispersant is 20 to 60 parts by weight. Preferably, the dispersant is 25 to 35 parts, such as 25 parts, 28 parts, 30 parts, 32 parts, 35 parts.
Preferably, the dispersant is preferably at least one of alumina, silica, magnesia, aluminum nitride, silicon nitride and silicon carbide. These dispersants are effective in preventing metal powders from binding in the system of the present application.
As a further preferred embodiment, the rare earth oxide is a nano rare earth oxide comprising cerium oxide and/or lanthanum oxide. The rare earth oxide has the function of accelerating permeation.
As a further preferred embodiment, in the zinc-aluminum alloy powder, the aluminum content is 5wt% to 40wt%, preferably 15wt% to 30wt%, and the balance is zinc, for example, the aluminum content may be 15wt%, 18wt%, 20wt%, 22wt%, 25wt%, 28wt%, 30wt%, or the like. The zinc-aluminum alloy powder can promote a certain amount of aluminum to synchronously infiltrate in the process of zinc impregnation; if the aluminum content in the zinc-aluminum alloy powder is too high, the synchronous infiltration effect of aluminum is poor, and therefore, the proportion is optimal. Moreover, if a certain amount of aluminum is synchronously infiltrated into the infiltration layer, aluminum and iron in the matrix can form an iron-aluminum intermetallic compound phase, so that the method has obvious effect on improving the overall wear resistance of the infiltration layer.
In the aluminum magnesium alloy powder, the aluminum content is 30 to 60 weight percent, and the balance is magnesium, for example, the aluminum content can be 30 weight percent, 40 weight percent, 45 weight percent, 50 weight percent, 55 weight percent, 60 weight percent and the like. The two are eutectic alloys, and when the mass ratio of the two is in the proportion, the melting point of the alloy is just about 450 ℃, and is far lower than that of the elemental magnesium and aluminum, and the elemental magnesium and aluminum are both higher than that of 650 ℃, so that the powder zinc-impregnation process is more beneficial to promoting the synchronous infiltration of the magnesium and the aluminum, and the infiltration uniformity and the infiltration amount are better compared with other proportions, so that the comprehensive effect is better. In addition, by forming the magnesium and aluminum into alloy powder, the defects that the magnesium powder is easy to explode, is easy to oxidize and is difficult to continuously infiltrate when the content is small, and the metal performance is lowered due to local overmuch are avoided. Moreover, in the system of the application, the magnesium content in the aluminum magnesium alloy powder is generally not more than 70wt%, and as the zinc magnesium permeate layer is easy to concentrate excessive magnesium in the outermost layer of the permeate layer, the corrosion resistance and the wear resistance of the permeate layer surface layer are relatively poor due to excessive magnesium.
In this example, the multi-component powder infiltrant used contained pure zinc powder which was able to penetrate normally in the process of the application; the alloy powder comprises zinc-aluminum alloy powder and aluminum-magnesium alloy powder, wherein the zinc-aluminum alloy powder enables a certain amount of aluminum to be permeated simultaneously when zinc is permeated through the alloy powder. The aluminum magnesium alloy powder is eutectic alloy, and the melting point of the aluminum magnesium alloy powder and the eutectic alloy powder is low in the proportion given by the application, so that synchronous infiltration of magnesium and aluminum is promoted while zinc impregnation is facilitated in the system and the infiltration method of the application. The multi-element powder penetrating agent also contains an activating agent, wherein the ammonium chloride in the activating agent is more, and the activating agent can decompose and provide ammonia and hydrogen halide gas, so that the activating agent can clean the surface of a metal pieceThe hydrogen halide can activate other components to promote the zinc impregnation. Meanwhile, hydrogen halide can react with potassium permanganate, the generated manganese chloride can be used as a manganese source to enable manganese to enter the permeation layer, and the manganese chloride also has a certain effect of promoting metal permeation, and more importantly, chloride ions in the active manganese chloride also help to promote manganese to permeate into the permeation layer tissue. The reaction of potassium permanganate and hydrogen chloride can not only provide manganese chloride and manganese permeation agent, but also generate potassium chloride, which is a good catalyst and is favorable for the permeation of various metals. However, pure manganese metal cannot permeate, and manganese chloride is basically hydrated manganese chloride, cannot be used, and is also not preferable to directly add potassium chloride because of being hydrated potassium chloride. In addition, the application realizes synchronous infiltration of aluminum, magnesium and manganese in the zinc impregnation process by matching with the functions of rare earth oxide, dispersing agent and the like. The synchronous infiltration is achieved as much as possible, so that a certain metal element is not easy to enrich in the surface layer to influence the performance, and the system can enable the thickness of the infiltration layer to reach 20-100 mu m while synchronously infiltration, so that the metal can realize excellent corrosion resistance and wear resistance. More importantly, in the percolated layer, the system of the application also allows zinc and magnesium to act, thus increasing its corrosion resistance. Specifically, the atomic radius of zinc is 0.1332 nanometers, the atomic radius of magnesium is 0.1598 nanometers, the difference of the atomic radii of the zinc and the magnesium is less than 15 percent, and meanwhile, the magnesium and the zinc are in close-packed hexagonal structures, so that the magnesium and the zinc can jointly act to form a seepage layer. Although magnesium itself is not corrosion-resistant, it can occupy part of the zinc atom sites in the zinc crystal structure, especially at grain boundaries, and a certain amount of magnesium can be accumulated at weak grain boundaries of zinc and form MgZn by high temperature reaction 2 、Mg 2 Zn 11 Equal zinc magnesium alloy phase, mgZn 2 、Mg 2 Zn 11 The isoalloy phase itself is a highly corrosion-resistant phase, and the formation of the grain boundaries promotes the change of the original weak grain boundary structure to the strong grain boundary structure, and in particular, the strong grain boundary structure is opaque to corrosive substances such as chloride ions, and can block the corrosive substances from the outside. At the same time, mgZn 2 、Mg 2 Zn 11 In the corrosion process of the zinc-magnesium alloy phase,the corrosion product is changed from a loose structure of common powder zincification into a compact structure, so that the corrosion resistance of the metal piece is greatly improved, and the service life of the metal piece is greatly prolonged.
In summary, as shown in fig. 1, the auxiliary steel provided in this embodiment is a schematic diagram of different types of auxiliary steel after the penetrating agent treatment of the present application, where fig. 1A is a high-speed railway pier inspection facility, namely, a basket, fig. 1B is an inspection ladder, and fig. 1C is a schematic diagram of a steel beam in the auxiliary steel. The processed subsidiary steel has good comprehensive performance, and the multi-element powder penetrating agent can realize that the alloy layer of the subsidiary steel product contains specific content of aluminum, magnesium, zinc and manganese, so that the penetrating agent complements the subsidiary steel product, and the excellent corrosion resistance and wear resistance of the subsidiary steel product are comprehensively realized.
Example 3
On the basis of the embodiment 1 and/or the embodiment 2, the embodiment discloses a preparation method of the auxiliary steel, which comprises the following steps:
step1: the powder penetrant and the matrix are rotated together in a multi-element alloy co-permeation furnace by adopting a rotary furnace co-permeation process, so that the uniform mixing of the powder penetrant is ensured, and the uniform reaction can be ensured; for uniform mixing and uniform reaction, the conventional technology in the field can be realized at present, and the method is very basic condition guarantee.
Step2: heating the co-permeation device, and preserving heat for 1-10 hours, usually 4-7 hours after heating to a preset temperature to finish zinc permeation;
preferably, the co-permeation furnace is evacuated to a vacuum degree of less than 100Pa, and then subjected to a temperature-raising treatment, and it is noted that the vacuum degree is maintained throughout the reaction. The reaction temperature in Step2 is 400-450 ℃ and the reaction time is more than 1 hour.
As a further preferred embodiment, in Step2,
(1) vacuumizing the co-permeation furnace to make the vacuum degree smaller than 100Pa, heating, and maintaining the vacuum degree smaller than 100Pa to rapidly pump out generated chlorine and water vapor. Prevent the water vapor from affecting the powder permeation and prevent the potential safety hazard caused by chlorine.
(2) The temperature in the co-cementation furnace is then raised to a temperature in the range of 100 ℃ to 200 ℃ for a residence time of greater than 1 hour, typically 1 to 3 hours, such as 1 hour, 2 hours, 3 hours. Ensure that the ammonium chloride can be fully decomposed under the temperature condition (the decomposition starting temperature of the ammonium chloride is 100 ℃ and the ammonium chloride is decomposed into HCl), while the potassium permanganate is not decomposed, and the following reaction formula occurs at the moment: 2KMnO 4 +16HCl＝2KCl+2MnCl 2 +5Cl 2 ↑+8H2O；
(3) Then the temperature is increased to 400-450 ℃ for 1-9 hours, usually 2-5 hours, such as 2 hours, 3 hours, 4 hours and 5 hours, to finish the zincification.
In the method and the penetrating agent system of the embodiment, the temperature is lower, and the method and the penetrating agent system can be completed only at 400-450 ℃, so that the defect that the mechanical property of the auxiliary steel is easily deteriorated due to the too high temperature is avoided.
In this example, the above specific reaction was used to obtain the accessory steel according to example 1, while the reaction effect of the present application was improved, and the penetrant was effectively used and effectively permeated into the accessory steel.
Example 4
The preparation method comprises the following steps: the multi-element powder infiltration agent and the accessory steel are placed into a multi-element alloy infiltration furnace by adopting a rotary furnace body infiltration process, and the multi-element powder infiltration agent and the accessory steel rotate together to ensure uniform mixing and uniform reaction of the infiltration agent. After the two are mixed, the vacuum is pumped to the co-permeation furnace so that the vacuum degree is less than 100Pa, and then the temperature in the co-permeation device is increased to about 130 ℃ for 2 hours. Then the temperature was raised to about 420℃for a further 5 hours.
Experimental example 1: multicomponent powder penetrating agent: 65 parts of zinc powder, 18 parts of zinc-aluminum alloy powder, 16 parts of aluminum-magnesium alloy powder, 0.5 part of cerium oxide and/or lanthanum oxide, 3 parts of an activator, 30 parts of a dispersing agent and 1 part of manganese dioxide.
Wherein the activator is ammonium chloride and potassium permanganate, and in the activator, the potassium permanganate accounts for 16wt% and the ammonium chloride accounts for 84%.
The dispersing agent is aluminum oxide and magnesium oxide, and the weight ratio of the aluminum oxide to the magnesium oxide is 3:1.
In the zinc-aluminum alloy powder, the aluminum content is 25wt%, and the balance is zinc;
in the aluminum magnesium alloy powder, the aluminum content is 50wt%, and the balance is magnesium.
The multi-element powder penetrating agent and the accessory steel in the experimental example are prepared into the processed accessory steel with the surface containing the alloy layer of the application by adopting the method.
Experimental example 2: multicomponent powder penetrating agent: 73 parts of zinc powder, 15 parts of zinc-aluminum alloy powder, 20 parts of aluminum-magnesium alloy powder, 0.4 part of lanthanum oxide, 4 parts of an activator, 30 parts of a dispersing agent and 0.5 part of manganese dioxide.
Wherein the activator is ammonium chloride and potassium permanganate, and in the activator, the potassium permanganate accounts for 18wt% and the ammonium chloride accounts for 82%.
The dispersing agent is aluminum nitride and magnesium oxide, and the weight ratio of the aluminum nitride to the magnesium oxide is 1:2.
In the zinc-aluminum alloy powder, the aluminum content is 15wt percent, and the balance is zinc;
in the aluminum magnesium alloy powder, the aluminum content is 35wt%, and the balance is magnesium.
The multi-element powder penetrating agent and the accessory steel in the experimental example are prepared into the processed accessory steel with the surface containing the alloy layer of the application by adopting the method.
Experimental example 3: multicomponent powder penetrating agent: 60 parts of zinc powder, 20 parts of zinc-aluminum alloy powder, 15 parts of aluminum-magnesium alloy powder, 0.7 part of cerium oxide, 2 parts of an activator, 25 parts of a dispersing agent and 0.5 part of manganese dioxide.
Wherein the activator is ammonium chloride and potassium permanganate, and in the activator, the potassium permanganate accounts for 10wt% and the ammonium chloride accounts for 85%.
The dispersing agent is alumina and silica, and the weight ratio of the alumina to the silica is 1:1.
In the zinc-aluminum alloy powder, the aluminum content is 30 weight percent, and the balance is zinc;
in the aluminum magnesium alloy powder, the aluminum content is 55wt%, and the balance is magnesium.
The multi-element powder penetrating agent and the accessory steel in the experimental example are prepared into the processed accessory steel with the surface containing the alloy layer of the application by adopting the method.
Blank control: the attached steel is not subjected to any treatment.
Manganese is not added: the potassium permanganate in the experimental example 1 is removed, and the simple removal has a large influence on the product performance, so that the magnesium content is increased by one third, and 1 part of the active reagent magnesium chloride is added, so that the product comprehensive performance is high.
The untreated steel used in the above examples, blank, method without manganese addition, and the like were the same. The main component of the auxiliary steel is iron.
The following table shows the results of neutral salt spray tests performed after sand blowing on the auxiliary steels obtained in the methods of experimental example 1, experimental example 2, experimental example 3, blank control and no manganese addition.
| Performance in use | Experimental example 1 | Experimental example 2 | Experimental example 3 | Blank control | No addition of manganese |
| Hardness (HV) | 438 | 430 | 434 | 348 | 386 |
| Salt fog resistanceTest | ＞3500h | ＞3500h | ＞3500h | ＜100h | ＜2000h |
| Sulfur dioxide resistance | Strong strength | Strong strength | Strong strength | Weak and weak | Preferably, it is |
From the above table, the comprehensive effects of the experimental examples were excellent. As shown in the table above, the original surface of the matrix has microhardness HV348, and does not contain HV386 of manganese after infiltration, but the hardness of the matrix can be greatly improved between HV430 and HV440, so that the wear resistance of the matrix is improved, and the effect is excellent. And the salt fog resistance performance in the experimental example is excellent, the salt fog resistance test shows that the salt fog resistance is more than 3500h, compared with the effect in the blank control and the non-manganese addition, the salt fog resistance test has very surprise, and the service life of the auxiliary steel can reach 100 years or more through reasonable conjecture of comprehensive practical application. Fig. 3 shows a microscopic photograph of a cross section of a salt spray of 3000 hours, which shows that the thickness of the alloy layer can be about 27 μm after a salt spray test of 3000 hours, and the effect is obvious. In the test without manganese, the salt spray test was only 2000 hours.
FIG. 2 is a schematic drawing of a section electron microscope of experimental example 1 after infiltration of infiltrant into the surface of the accompanying steel by the method of the present application. The thickness of the alloy layer is relatively uniform, and the thickness is relatively thick, and the average thickness is about 60-70 mu m. The alloy layer of experimental example 1 was impregnated with 66wt% of zinc, 15.2wt% of aluminum, 7.8wt% of magnesium, 0.55wt% of manganese, 10wt% of iron, and the other components of nickel or others contained in the matrix. In the surface layer, the content of each metal was 74.1% of zinc, 18.9% of aluminum, 9.3% of magnesium, 0.7% of manganese, 5% of iron and the balance of nickel. The metal content in the alloy layer is basically uniform from top to bottom and is less, and the phenomenon of deposition at a certain place is avoided. In the direction from the table to the inside, the content of each element is 70.2 percent of zinc, 17.4 percent of aluminum, 8.9 percent of magnesium and 0.68 percent of manganese at the depth of about 10 mu m; the contents of the respective elements were 63.5% of zinc, 12.3% of aluminum, 6.7% of magnesium and 0.41% of manganese at a depth of about 30. Mu.m, 28.2% of zinc, 7.1% of aluminum, 2.7% of magnesium and 0.19% of manganese at a depth of about 50. Mu.m. The surface of the experimental example of the application is smooth, flat, light in color and beautiful.
As is clear from the above experiments, the multi-element metal penetrating agent of the application can obtain the metal penetrating amount as described in the example 1, has obviously improved salt spray resistance and wear resistance, has good sulfur dioxide resistance effect, and is suitable for being used in a severe environment.
Example 5
To further investigate the secondary steel of the present application, the present inventors have also performed various tests on the treated secondary steel, such as the thickness of the alloy layer, and the distribution of the metal elements among the different thicknesses.
Comparative example 1: the content of each metal powder of the multi-component powder infiltrant was the same as that of experimental example 1 in example 4, and the preparation was the same, except that: with metal Mn, the same mole number of Mn as potassium permanganate was added, and the activator was only ammonium chloride in the same amount as in experimental example 1.
Comparative example 2: the content of each metal powder of the multi-component powder infiltrant was the same as that of experimental example 1 in example 4, and the preparation was the same, except that: ammonium chloride is not added.
Comparative example 3: the content of each metal powder of the multi-component powder infiltrant was the same as that of experimental example 1 in example 4, and the preparation was the same, except that: potassium permanganate is not required.
Comparative example 4: the content of each metal powder of the multi-component powder infiltrant was the same as that of experimental example 1 in example 4, and the preparation was the same, except that: the ammonium chloride is exchanged for ammonium fluoride.
Comparative example 5: the content of each metal powder of the multi-component powder infiltrant was the same as that of experimental example 1 in example 4, and the preparation was the same, except that: the ammonium chloride is exchanged for ammonium bromide.
Comparative example 6: the respective metal powder contents of the multi-component powder infiltrant were the same as those of experimental example 1 in example 4, except that: the preparation method comprises directly heating to about 420 deg.C.
The abrasion resistance and corrosion resistance of the above examples were tested, and the content of the infiltrated metal in the alloy layer thereof was tested.
As is clear from the above table, the overall effect of experimental example 1 was very excellent, and it was described in example 4. Although the comparative example 1 also has a certain manganese content, the content is extremely low, the content of other aluminum, magnesium and the like in the alloy layer is greatly reduced, and magnesium is mainly concentrated in a shallow layer and is hardly detected after 20 mu m; and the overall thickness of the alloy layer was significantly different from that of experimental example 1. For comparative examples 2 to 5, the resistance model is also obviously smaller than that of the experimental example, the thickness of the seepage layer is also obviously smaller than that of the experimental example, in addition, the seepage layer hardly contains manganese element, and the salt spray resistance is poor and the corrosion resistance is obviously inferior to that of the experimental example. For comparative example 6, the overall properties were smaller than those of the experimental example, although the contents of various elements in the alloy layer were substantially within the scope of the present application, due to the change of conditions in the production method.
The salt spray test is shown in the following table:
from the above table, the red rust still does not appear after 3500h in experimental example 1, and the salt fog resistance is more than 3500h; comparative example 6 shows red rust at 3500 hours, its salt spray resistance is > 3000 hours, and less than 3500 hours; comparative examples 3 and 5, which both showed a large amount of white rust at about 2000 hours, showed significant red rust at 3000 hours, and had a salt spray resistance of < 3000 hours; the comparative examples 1, 2 and 4 showed red rust at 2000 hours, and their salt spray resistance was < 2000 hours.
The contents of the components in the penetrating agent are set according to the characteristics of interaction or mutual restriction among the components, and the effects of the penetrating agent are achieved through the combined action of the components, so that manganese element is an important component in the penetrating agent, and if the manganese element cannot be penetrated normally or is penetrated in a small amount, the manganese element has a large influence on the performance of the auxiliary steel. In fact, if the alloy layer does not contain manganese, better performance can be achieved by adjusting the proportion of other components, the type and addition amount of auxiliary agents, and the like. However, according to the functions of the auxiliary steel and the like, the applicant finds that the comprehensive performance of the added manganese is better through experiments and research and development. Therefore, on the premise of adding manganese, the research test adopts the proportion of manganese and other components, and the performance difference is very large if the proportion or other components are unsuitable. Therefore, under the condition of the application, if the amount of one component is greatly adjusted or the component is added little or one or more components are replaced, the property of the auxiliary steel is extremely likely to be greatly influenced.
Example 6
Experimental example: as in experimental example 1 in example 4.
Comparative group 1: multicomponent powder penetrating agent: 50 parts of zinc powder, 45 parts of zinc-aluminum alloy powder, 35 parts of aluminum-magnesium alloy powder, 3 parts of an activating agent, 0.4 part of cerium oxide, 30 parts of a dispersing agent and 1.0 part of manganese dioxide. The other steps are the same as in experimental example 1.
Comparative group 2: multicomponent powder penetrating agent: 50 parts of zinc powder, 5 parts of zinc-aluminum alloy powder, 5 parts of aluminum-magnesium alloy powder, 3 parts of an activating agent, 0.4 part of lanthanum oxide, 30 parts of a dispersing agent and 1.0 part of manganese dioxide.
Comparative group 3: multicomponent powder penetrating agent: 35 parts of zinc powder, 5 parts of zinc-aluminum alloy powder, 5 parts of aluminum-magnesium alloy powder, 3 parts of an activating agent, 0.4 part of cerium oxide, 30 parts of a dispersing agent and 0.1 part of manganese dioxide.
Comparative group 4: multicomponent powder penetrating agent: 50 parts of zinc powder, 45 parts of zinc-aluminum alloy powder, 30 parts of aluminum-magnesium alloy powder, 3 parts of an activating agent, 0.4 part of cerium oxide, 30 parts of a dispersing agent and 1.0 part of manganese dioxide. The activator is ammonium chloride and potassium permanganate, wherein the proportion of the potassium permanganate in the activator is 60wt%, and the ammonium chloride is 40%
The other parts of the above comparative group (including the preparation method) were identical to those of the experimental group 1, and the hardness and neutral salt spray resistance were measured as follows.
The metal content of the alloy layers in the above comparative groups is not consistent with the scope of the present application, i.e., is not within the scope of example 1 or claim 1 of the present application. The corrosion resistance of the comparative group as a whole was weak. The magnesium and aluminum contents in comparative example 1 were greatly increased and concentrated mainly in the surface layer and depth of 15 μm, and local magnesium content was excessive, affecting the performance, and the waste was serious and the cost was high.
The magnesium and aluminum contents in comparative example 2 were greatly reduced, and the overall properties were lowered.
The zinc powder in comparative example 3 is greatly reduced, the metal component permeated in the alloy layer is mainly concentrated within 15 mu m, the whole alloy thickness is small and is basically between 10 and 30, the hardness is greatly reduced, and the corrosion resistance is weak.
The hardness of comparative example 4 was lowered, the plasticity was remarkably lowered, and the instantaneous impact resistance was lowered and the vehicle was easily damaged when passing through. And the instantaneous impact resistance of comparative examples 3 and 2 was also significantly reduced.
Thus, in the present application, the various components and the amounts of the various components complement each other and the reduction, increase or replacement of a component has a greater impact on the properties of the attached steel.
In the present application, it should be noted that there are a plurality of factors that can affect the properties of the steel attached after the infiltration of the metal element, which are not only related to the proportion of the metal element in the alloy layer, but also have a great relationship with diffusion or infiltration, such as the same metal content as in the present embodiment, but if the infiltration is uneven, there are cases where some portions are deposited more and other portions are too few, etc., the improvement properties of the metal may be extremely weak, and sometimes not only the properties of the metal surface layer may be improved, but also the properties may be reduced. Moreover, the same metal content, if infiltrated to too shallow a depth, can also greatly affect the metal properties. The auxiliary steel type of the application can realize synchronous infiltration and deep infiltration by matching with the penetrant of the application, and each metal is uniformly reduced from the surface layer to the inner layer of the alloy layer, the situation of local overmuch certain metal is avoided, and manganese is greatly compounded with iron and magnesium by adding ammonium chloride and potassium permanganate under specific conditions, so that the alloy layer with increased metal performance is formed, and side effects possibly brought by magnesium and harm of iron in the auxiliary steel are greatly reduced or avoided. The method of the application has better effect.
In the application, all raw material powders are market products, and can be purchased normally, and alloy powders such as zinc-aluminum alloy powder, aluminum-magnesium alloy powder and the like can be purchased.
Unless otherwise indicated, numerical ranges herein include not only the entire range within both of its endpoints, but also the several sub-ranges contained therein.
While the preferred embodiments and examples of the present application have been described in detail with reference to the accompanying drawings, the present application is not limited to the above-described embodiments and examples, and various changes may be made within the knowledge of those skilled in the art without departing from the spirit of the present application.
Claims (11)
1. An accessory steel comprises a base material and an alloy layer, wherein the alloy layer is formed by penetrating a powder penetrating agent into the surface of the base material to form an alloy layer containing a plurality of metal elements; the method is characterized in that:
the alloy layer comprises the following components in percentage by weight: 50-75wt% of zinc, 10-20wt% of aluminum, 3-10wt% of magnesium, 0.15-1.5wt% of manganese and the balance of components in the base material;
the powder penetrating agent is a multi-element powder penetrating agent, and comprises the following components in parts by weight: 55-80 parts of zinc powder, 10-25 parts of zinc-aluminum alloy powder, 8-25 parts of aluminum-magnesium alloy powder, 0.1-1 part of rare earth oxide and 1-5 parts of activating agent;
the activator is ammonium chloride and potassium permanganate, wherein the potassium permanganate accounts for 5-20wt% and the balance is ammonium chloride.
2. An accessory steel as claimed in claim 1, wherein the alloy layer has a thickness of 20 μm to 80 μm.
3. An accessory steel as claimed in claim 1, wherein the balance comprises iron and the iron content is not less than 8%.
4. An accessory steel according to claim 1, characterized in that in the alloy layer the manganese content is 5-10% of the magnesium content.
5. The accessory steel of claim 1, wherein the powder infiltrant further comprises a dispersant and a catalyst, wherein in the powder infiltrant, the weight part of the dispersant is 20-60 parts, and the weight part of the catalyst is 0.5-2 parts.
6. The accessory steel of claim 5, wherein the dispersant is at least one of aluminum oxide, silicon oxide, magnesium oxide, aluminum nitride, silicon nitride, and silicon carbide;
the rare earth oxide comprises cerium oxide and/or lanthanum oxide;
the catalyst is manganese dioxide.
7. An accessory steel according to claim 1, wherein in the zinc-aluminium alloy powder, the aluminium content is 5-40 wt% with the remainder being zinc;
in the aluminum magnesium alloy powder, the aluminum content is 30 to 60 weight percent, and the balance is magnesium.
8. A method for producing an accessory steel according to any one of claims 1-7, characterized in that the method is:
step1: adopting a co-permeation process, and rotating the powder permeation agent and the base material together in a co-permeation device so as to uniformly mix the permeation agent;
step2: and (3) heating the co-permeation device, and preserving heat for 1-10 hours after heating to a preset temperature to finish the zinc permeation.
9. The method for producing an auxiliary steel according to claim 8, wherein the co-cementation apparatus is evacuated to a vacuum of less than 100Pa and then subjected to a temperature-increasing treatment.
10. The method for producing an accessory steel according to claim 8, wherein the reaction temperature in Step2 is 400 ℃ to 450 ℃ and the reaction time is more than 1 hour.
11. The method for producing an accessory steel according to claim 8, wherein Step2 comprises the steps of:
(1) vacuumizing the co-permeation device to make the vacuum degree smaller than 100Pa, and maintaining the vacuum degree in the reaction process;
(2) then the temperature in the co-permeation device is increased to be within the range of 100 ℃ to 200 ℃ and stays for 1 to 3 hours;
(3) then the temperature is increased to 400-450 ℃ for 1-9 hours, and the zincification is completed.
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