CN106834806B - A kind of corrosion-resistant zinc alloy and preparation method thereof - Google Patents
A kind of corrosion-resistant zinc alloy and preparation method thereof Download PDFInfo
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- 230000007797 corrosion Effects 0.000 title claims abstract description 83
- 238000005260 corrosion Methods 0.000 title claims abstract description 83
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 53
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 52
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 38
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 34
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011701 zinc Substances 0.000 claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 27
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 23
- 229910000906 Bronze Inorganic materials 0.000 claims abstract description 19
- 239000010974 bronze Substances 0.000 claims abstract description 19
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001000 nickel titanium Inorganic materials 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 11
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 238000013461 design Methods 0.000 claims abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 241001062472 Stokellia anisodon Species 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 230000032683 aging Effects 0.000 abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005275 alloying Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000004512 die casting Methods 0.000 abstract 1
- 238000003723 Smelting Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 229910001069 Ti alloy Inorganic materials 0.000 description 6
- XUDNJARNPKNDSJ-UHFFFAOYSA-N [Ti].[Cu].[Zn] Chemical compound [Ti].[Cu].[Zn] XUDNJARNPKNDSJ-UHFFFAOYSA-N 0.000 description 6
- 229910001122 Mischmetal Inorganic materials 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000008399 tap water Substances 0.000 description 5
- 235000020679 tap water Nutrition 0.000 description 5
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical group [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000006056 electrooxidation reaction Methods 0.000 description 4
- -1 0.50% Chemical compound 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910001015 Alpha brass Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 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
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium 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
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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
- C22C18/02—Alloys based on zinc with copper as the next major constituent
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Prevention Of Electric Corrosion (AREA)
Abstract
本发明属于有色金属材料制造技术领域，具体涉及一种含铍耐蚀锌合金及其制备方法。本发明所述耐蚀合金以质量百分数计包括：铜0.50～0.75％，镍0.50～0.75％，钛0.05～0.10％，铍0.01～0.02％，镧0.003～0.006％，铈0.006～0.01％，杂质含量≤0.05％；余量为锌。该耐蚀锌合金以电解铜、铍青铜、Zn‑Ni‑Ti中间合金、锌箔包覆稀土元素等措施加入合金元素；采用模铸，其后对合金进行一次热处理，得到耐蚀锌合金。该耐蚀锌合金的腐蚀电位较正，不易发生腐蚀；即使发生腐蚀，其腐蚀速率也很小，这大大减缓了材料的老化速率。本发明组分设计合理，制备工艺简单、易控，便于大规模的工业化应用。The invention belongs to the technical field of non-ferrous metal material manufacturing, and in particular relates to a beryllium-containing corrosion-resistant zinc alloy and a preparation method thereof. The corrosion-resistant alloy of the present invention comprises, in mass percentage, copper 0.50-0.75%, nickel 0.50-0.75%, titanium 0.05-0.10%, beryllium 0.01-0.02%, lanthanum 0.003-0.006%, cerium 0.006-0.01%, impurities Content≤0.05%; balance is zinc. In the corrosion-resistant zinc alloy, alloying elements are added by means of electrolytic copper, beryllium bronze, Zn-Ni-Ti master alloy, and zinc foil-coated rare earth elements; die-casting is adopted, and then the alloy is subjected to a heat treatment to obtain the corrosion-resistant zinc alloy. The corrosion-resistant zinc alloy has a relatively positive corrosion potential and is not easy to corrode; even if corrosion occurs, the corrosion rate is very small, which greatly slows down the aging rate of the material. The composition of the invention is reasonable in design, the preparation process is simple and easy to control, and is convenient for large-scale industrial application.
Description
Technical Field
The invention belongs to the technical field of non-ferrous metal materials, and particularly relates to a corrosion-resistant zinc alloy and a preparation method thereof.
Background
The zinc alloy has low melting point, good mechanical property, low processing energy consumption, cheap and easily-obtained raw materials, and can effectively save materials and production cost. At present, the zinc alloy has been widely applied to the aspects of hardware daily use, mechanical accessories, building material decoration, electronic components, instruments, commemorative coins and the like, and meanwhile, the zinc alloy also has potential application prospects in many aspects.
Among zinc alloys, wrought zinc-copper-titanium alloys are widely used as structural materials. The copper content of the commonly used wrought zinc-copper-titanium alloy is 0.5 to 1.5 percent, and the titanium content is 0.1 to 0.5 percent. The Cu and Ti in the zinc-copper-titanium alloy have excellent physical and mechanical properties under the combined action, and the main characteristics are as follows: the creep resistance is high, and the time required for the creep deformation amount to reach 1 percent is nearly 500 times that of pure zinc; the thermal expansion coefficient is reduced by about 30 percent compared with pure zinc; the tensile strength is comparable to the annealing state of the alpha brass and is improved by more than 50 percent compared with pure zinc; excellent in molding and machining characteristics. However, the zinc-copper-titanium alloy product is in practical use, especiallyIt is used for hardware, bathroom, decoration and the like and contains Cl-In a humid environment, the alloy is easy to generate intercrystalline corrosion, pitting corrosion and the like, so that the surface quality is reduced, the size is unstable, the ageing resistance is reduced, and the application range of the alloy is severely limited. Although the zinc alloy can be protected by adopting a plating method to improve the corrosion resistance, the damage and the falling of a plating layer can be caused by some factors in the processing and the using process, so that the zinc matrix is exposed to a corrosive medium to form local corrosion. Therefore, the improvement of the corrosion resistance of the zinc alloy is the key to promote the application of the zinc alloy, and is an important technical problem which is highly concerned by the industry.
Relevant researches show that the corrosion resistance of the zinc alloy can be improved by adding different alloy elements into a zinc matrix and adjusting the adding range of the alloy elements. Common additive elements in the industry include aluminum, copper, magnesium, titanium, nickel, manganese, chromium, rare earth elements and the like. The Be-containing corrosion-resistant zinc alloy is not described in the prior art.
Disclosure of Invention
The invention mainly aims to solve the problem that the deformed zinc-copper-titanium alloy contains Cl-The corrosion-resistant zinc alloy has the problem of lower corrosion resistance in a humid environment, and provides a corrosion-resistant zinc alloy component and a smelting preparation method thereof. The corrosion-resistant zinc alloy consists of zinc, copper, nickel, titanium, beryllium, rare earth and inevitable impurities, and the corrosion resistance of the multi-element zinc alloy is improved by adjusting and optimizing the proportion of Zn to alloy elements such as Cu, Ti, Ni, Be, La, Ce and the like while the mechanical property of the multi-element zinc alloy is ensured.
The invention relates to a corrosion-resistant zinc alloy which contains beryllium.
The invention relates to a corrosion-resistant zinc alloy which is characterized in that: in the corrosion-resistant zinc alloy, the mass percentage of beryllium is 0.01-0.05%.
The invention relates to a corrosion-resistant zinc alloy which is characterized in that: the corrosion-resistant zinc alloy contains Ni, and the mass percentage of Ni in the corrosion-resistant zinc alloy is 0.50-1.00%.
The invention relates to a corrosion-resistant zinc alloy which contains copper, nickel, titanium, beryllium, rare earth elements and zinc.
As a preferable scheme, the corrosion-resistant zinc alloy comprises the following components in percentage by mass:
0.50 to 1.00 percent of copper,
0.50 to 1.00 percent of nickel,
0.05 to 0.20 percent of titanium,
0.01 to 0.05 percent of beryllium,
0.001 to 0.01% of lanthanum,
0.002-0.01% of cerium,
the impurity content is less than or equal to 0.05 percent;
the balance being the zinc.
As a further preferable scheme, the corrosion resistant zinc alloy comprises the following components in percentage by mass:
0.50 to 0.75% copper, such as 0.50%, 0.52%, 0.55%, 0.58%, 0.6%, 0.62%, 0.64%, 0.68%, 0.71%, 0.73%, 0.75% can be further preferred;
0.50 to 0.75% nickel, such as 0.50%, 0.53%, 0.58%, 0.61%, 0.62%, 0.64%, 0.66%, 0.68%, 0.71%, 0.73%, 0.75% can be further preferred;
0.05-0.10% of titanium, such as 0.05%, 0.06%, 0.07%, 0.082%, 0.091%, 0.1% can be further optimized;
beryllium 0.01-0.02%, such as 0.01%, 0.011%, 0.012%, 0.013%, 0.014%, 0.015%, 0.016%, 0.017%, 0.018%, 0.019%, 0.02% can be further preferred;
lanthanum 0.003-0.006%, such as 0.003%, 0.004%, 0.005%, 0.006% can be further preferred;
cerium 0.005-0.01%, such as 0.005%, 0.006%, 0.007%, 0.008%, 0.009%, 0.01% can be further preferred;
the impurity content is less than or equal to 0.05 percent;
the balance being the zinc.
The invention relates to a preparation method of a corrosion-resistant zinc alloy, which comprises the following steps:
step one
Distributing and taking a copper source, a nickel source, a titanium source, a beryllium source, a rare earth source and a zinc source according to a design group;
step two
Adding the copper source, the nickel source, the titanium source, the beryllium source, the rare earth source and the zinc source into a smelting furnace for smelting, and casting to obtain an ingot;
step three
And (4) preserving the heat of the ingot obtained in the step two at 320-390 ℃, and discharging from the furnace for air cooling after heat preservation to obtain the corrosion-resistant zinc alloy.
The invention relates to a preparation method of corrosion-resistant zinc alloy,
in the first step, the copper source is electrolytic copper and beryllium bronze, the beryllium source is beryllium bronze, and the electrolytic copper is further preferably electrolytic copper with the purity of more than 99.9%; the beryllium bronze is preferably QBe2 beryllium bronze.
In the first step, the nickel source and the titanium source are Zn-Ni-Ti ternary intermediate alloy, preferably Zn-10Ni-2Ti ternary intermediate alloy; further preferably Zn-10Ni-2Ti ternary intermediate alloy prepared by vacuum melting.
In the first step, the zinc source is pure zinc and a Zn-Ni-Ti ternary intermediate alloy, and the Zn-Ni-Ti ternary intermediate alloy is preferably a Zn-10Ni-2Ti ternary intermediate alloy; further preferably Zn-10Ni-2Ti ternary intermediate alloy prepared by vacuum melting.
In the first step, the rare earth source is lanthanum-cerium mixed rare earth. Preferably, the Ce content in the lanthanum-cerium mixed rare earth is 65 wt.%, the La content is 34 wt.%, and the balance is other rare earth elements. For industrial production, the lanthanum-cerium mischmetal is a commercially available Ce + La mischmetal.
The invention relates to a preparation method of a corrosion-resistant zinc alloy, which comprises the steps of placing the prepared electrolytic copper, beryllium bronze and Zn-Ni-Ti ternary intermediate alloy at the bottom of a high-purity graphite crucible when the copper source is electrolytic copper and beryllium bronze, the nickel source and the titanium source are Zn-Ni-Ti ternary intermediate alloy, the zinc source is pure zinc and Zn-Ni-Ti ternary intermediate alloy, and the rare earth source is lanthanum and cerium mixed rare earth, placing the prepared electrolytic copper, beryllium bronze and Zn-Ni-Ti ternary intermediate alloy on the electrolytic copper, beryllium bronze and Zn-Ni-Ti ternary intermediate alloy, placing the graphite crucible into a medium-frequency induction furnace, heating to 900-1000 ℃, uniformly stirring after the electrolytic copper, beryllium bronze and Zn-Ni-Ti ternary intermediate alloy are completely melted, cooling to 800-850 ℃, and placing the prepared lanthanum in the medium-frequency induction furnace, And (3) wrapping the cerium mischmetal by using zinc foil, putting the wrapped cerium mischmetal into a smelting furnace, smelting, standing, and casting the cerium mischmetal into a steel mold after the temperature of the melt is reduced to 680-720 ℃ to obtain the ingot. The zinc foil is prepared from pure zinc. The pure zinc is industrial pure zinc.
The preparation method of the corrosion-resistant zinc alloy comprises the third step of placing the ingot obtained in the second step into a heating furnace, preserving the heat for 2-3 hours, preferably for 2.5 hours at 320-390 ℃, preferably 350 ℃, discharging the ingot after heat preservation, and air cooling to obtain the corrosion-resistant zinc alloy.
The invention relates to a preparation method of a corrosion-resistant zinc alloy, and the smelting mode is non-vacuum smelting.
Principles and advantages
The corrosion-resistant zinc alloy is formed by adding a proper amount of copper, nickel, titanium, beryllium and rare earth elements on the basis of industrial pure Zn, has good corrosion resistance, and can be used for hardware, bathrooms, decoration and the like containing Cl-In a humid environment. The deformed zinc alloy material for hardware not only requires excellent molding and machining characteristics, but also requires good corrosion resistance in a humid environment.
According to the invention, a proper amount of Be is added into the zinc alloy, so that slag can Be reduced, the purity is improved, and the fluidity is improved during smelting; after the alloy is obtained, the added Be can form a layer of compact protective oxidation film on the surface of the alloy, and can reduce the oxidation and corrosion of the surface of the Zn alloy at room temperature. Meanwhile, Be in the alloy can change the shape of an intermetallic compound of a brittle impurity Fe, so that the strength and the plasticity of the alloy are improved.
According to the invention, a proper amount of Ni element is selected and added, and the cathode reaction of electrochemical corrosion can Be inhibited through the synergistic effect of Ni and Be, so that a corrosion product is changed, and a compact basic chlorination product film is formed, and the film has poor conductivity, thereby blocking the further corrosion of the zinc alloy.
In the invention, the addition of a proper amount of rare earth elements can refine the matrix structure and reduce the number of dendrites and the dendrite spacing; rare earths can also act with impurities that segregate at grain boundaries to mitigate segregation. Rare earth Ce can obviously refine as-cast structure, and improve the mechanical property and the local corrosion resistance of the alloy; la can refine the primary phase alpha phase of the zinc alloy, improve the appearance and distribution of the phase and improve the plasticity and strength performance of the alloy. The heat treatment of 350 ℃/2.5h is carried out on the alloy, so that the segregation of alloy components is reduced, the structure is more stable, and the corrosion resistance is improved.
Compared with the prior zinc-copper-titanium alloy, the invention has the following advantages and effects:
(1) the preparation process is simple and convenient: beryllium bronze and Zn-Ni-Ti ternary intermediate alloy are added into pure zinc, and zinc foil is used for coating rare earth elements for graded mixed smelting, so that the operation is convenient, and the components can be ensured to be uniform and stable.
(2) The corrosion resistance is excellent: ni and Be are added to form a compact film, so that the contact between a corrosive medium and the surface of a material can Be hindered, and the further development of corrosion can Be inhibited. Electrochemical experiments were conducted in tap water and 3.5 wt.% NaCl solution, respectively, and the corrosion potential of the alloy of the present invention became positive, and the corrosion current density became significantly smaller, meaning that the corrosion rate was greatly reduced.
(3) The comprehensive performance is good: by adding a proper amount of rare earth elements, the alloy structure is refined, so that the corrosion resistance of the alloy is obviously improved, and the alloy also has good mechanical properties. Test results show that the alloy of the invention is subjected to homogenization heat treatment at 350 ℃/2.5h in an as-cast state, the tensile strength reaches more than 120MPa, and the elongation reaches more than 8%; after thermal deformation and annealing treatment at 170-220 ℃/6h for certain times, the tensile strength can reach more than 220MPa, and the elongation can reach more than 35%.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of examples. It should be noted that the following examples and comparative examples are only illustrative of the present invention and should not be construed as limiting the scope of the claims of the present invention.
Examples and comparative examples
Placing the prepared electrolytic copper, beryllium bronze and Zn-Ni-Ti ternary intermediate alloy at the bottom of a high-purity graphite crucible, placing the prepared pure zinc on the electrolytic copper, beryllium bronze and Zn-Ni-Ti ternary intermediate alloy, then placing the graphite crucible into a medium-frequency induction furnace, heating to the temperature of 900-1000 ℃, uniformly stirring after the electrolytic copper, beryllium bronze and Zn-Ni-Ti ternary intermediate alloy are completely melted, cooling to 800-850 ℃, then packaging the prepared lanthanum-cerium mixed rare earth by using a zinc foil, placing the zinc foil into a smelting furnace, smelting, standing, and casting into a steel mold after the temperature of a melt is reduced to 680-720 ℃ to obtain an ingot. Then the alloy is subjected to homogenization heat treatment at 350 ℃/2.5 h. And finally, sampling the alloy and performing an electrochemical corrosion experiment.
The alloy compositions of the examples and comparative examples are shown in Table 1, and the data of the electrochemical corrosion test are shown in Table 2.
Table 1 alloy compositions (wt.%) of examples and comparative examples
TABLE 2 electrochemical corrosion Performance parameters of the examples and comparative examples
As can be seen from the data in Table 2, examples 1, 2 and 3 all achieved better corrosion resistance with the optimized alloying ratio of the present invention. Comparative example 1 is more susceptible to corrosion because of the lack of Ni in the alloy composition, which has a corrosion potential negative than that of examples 1 and 2; after the corrosion started, the corrosion current density increased greatly, with comparative example 1 having a corrosion rate in tap water of about 8.9 times that of example 1 and a corrosion rate in 3.5 wt.% NaCl solution of 6.8 times. From the comparison, it is understood that the addition of Ni element can improve the corrosion resistance of the zinc alloy because Ni element suppresses the electrochemical cathode reaction, promotes the formation of basic zinc chloride film, and further inhibits the corrosion of the zinc alloy.
The alloy formulation of comparative example 2 lacks Be, the corrosion potential becomes negative, the corrosion rate in tap water is about 7.8 times that of example 1, and the corrosion rate in 3.5 wt.% NaCl solution is 5.9 times. From the comparison, the addition of the Be element can improve the corrosion resistance of the zinc alloy, because the Be can form a dense protective oxide film on the surface of the alloy, and can reduce the oxidation and corrosion of the surface of the Zn alloy at room temperature.
The alloy formulation of comparative example 3 lacks rare earth elements and the corrosion potential becomes negative, with a corrosion rate in tap water of about 3.7 times that of example 1 and a corrosion rate in 3.5 wt.% NaCl solution of 4.1 times. The rare earth elements mainly play the roles of grain refinement and melt purification in the zinc alloy.
The alloy formulation of comparative example 4 lacks Ni and Be, the corrosion potential becomes negative, and the corrosion rate in tap water is about 8.9 times that of example 1, and the corrosion rate in 3.5 wt.% NaCl solution is 7.6 times, and it is mainly illustrated by example 1 and comparative examples 1, 2, and 4 that Ni and Be may have synergistic effects.
The comparison between the example 1 and the examples 2 and 3 shows that after the components are optimized, the corrosion resistance of the product obtained in the example 1 is better than that of the products obtained in the examples 2 and 3.
Therefore, the corrosion-resistant zinc alloy has a positive corrosion potential, is not easy to corrode, has a low corrosion rate after corrosion occurs, and greatly reduces the aging process of materials due to corrosion, thereby providing an effective technical approach for developing new products.
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| CN114309068B (en) * | 2021-12-22 | 2024-04-19 | 江苏中矿大正表面工程技术有限公司 | A novel continuous casting and rolling preparation method for zinc alloy wire |
| CN119800156B (en) * | 2025-03-12 | 2025-05-16 | 广州市奥金金属制品有限公司 | A corrosion-resistant zinc alloy material and preparation method thereof |
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