CN107130249B - A kind of complex magnesium alloy sacrificial anode material and preparation method thereof containing Nd - Google Patents
A kind of complex magnesium alloy sacrificial anode material and preparation method thereof containing Nd Download PDFInfo
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- CN107130249B CN107130249B CN201710309376.4A CN201710309376A CN107130249B CN 107130249 B CN107130249 B CN 107130249B CN 201710309376 A CN201710309376 A CN 201710309376A CN 107130249 B CN107130249 B CN 107130249B
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- anode material
- sacrificial anode
- magnesium alloy
- complex magnesium
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- 239000010405 anode material Substances 0.000 title claims abstract description 54
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011777 magnesium Substances 0.000 claims abstract description 36
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 15
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 27
- 239000000956 alloy Substances 0.000 claims description 27
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 11
- 230000006698 induction Effects 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 3
- 229910021323 Mg17Al12 Inorganic materials 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 239000011575 calcium Substances 0.000 description 9
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- PEFIIJCLFMFTEP-UHFFFAOYSA-N [Nd].[Mg] Chemical compound [Nd].[Mg] PEFIIJCLFMFTEP-UHFFFAOYSA-N 0.000 description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 6
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 5
- 239000010431 corundum Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 239000007769 metal material Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- -1 is generated12Nd Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010120 permanent mold casting Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
- C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
- C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
- C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
- C23F13/12—Electrodes characterised by the material
- C23F13/14—Material for sacrificial anodes
-
- 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
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium 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)
- Prevention Of Electric Corrosion (AREA)
Abstract
The present invention relates to a kind of complex magnesium alloy sacrificial anode material and preparation method thereof containing Nd, belongs to sacrificial anode material technical field.Complex magnesium alloy sacrificial anode material containing Nd of the invention consists of the following mass percentage components: Zn 6.6%~6.8%, Nd 0.2%~0.4%, Ca 0.3%~0.5%, Sb 0.4%~0.6%, and surplus is Mg and inevitable impurity.Al is free of in magnesium alloy sacrificial anode material of the invention, avoids netted Mg17Al12The generation of phase, to guarantee that performance and control cost, the additional amount of Zn are selected as 6.6~6.8wt%；Micro Nd, Ca, Sb is added, generates dystectic Mg12Nd、Mg2Ca、Mg13Sb2Phase can be used as effective forming core core, refines crystal grain, improves the uniformity of tissue, and then consume magnesium-alloy anode material in corrosive environment uniformly.
Description
Technical field
The present invention relates to a kind of complex magnesium alloy sacrificial anode material and preparation method thereof containing Nd, belongs to sacrificial anode material
Expect technical field.
Background technique
Economic loss caused by the corrosion of metal material is huge, and carrying out electrochemical protection using sacrificial anode is that one kind prevents
The extension of the effective ways of metallic material corrosion, raising and service life to metal material corrosion resistance has important meaning
Justice.The chemical property of magnesium alloy is preferable, is often used as sacrificial anode material, protects to the cathode material of apparatus,
To extend the service life of cathode material.
But ordinary magnesium alloy anode material in the prior art, such as common trade mark AZ91 (Al 8.5-9.5wt%, Zn
0.45-0.9wt%, Mn 0.17-0.40wt%) etc., ingredient design and prepare it is technologic due to, lead to alloy grain
It is coarse, nonuniform organization, and element aluminum and magnesium form Mg17Al12Phase, and with net distribution in crystal boundary, it is easy to be formed with magnesium matrix
Micro cell, accelerates the consumption of sacrificial anode material, while keeping the consumption of anode material uneven, influences making for sacrificial anode material
Use the service life.
Summary of the invention
The purpose of the present invention is to provide a kind of complex magnesium alloy sacrificial anode material containing Nd, it is sacrificial to solve existing magnesium alloy
The problem of domestic animal anode material consumes unevenly in corrosive environment, influences service life.
The present invention also provides the preparation methods of above-mentioned magnesium alloy sacrificial anode material.
In order to achieve the goal above, the technical scheme adopted by the invention is that:
A kind of complex magnesium alloy sacrificial anode material containing Nd: consist of the following mass percentage components: Zn 6.6%
~6.8%, Nd 0.2%~0.4%, Ca 0.3%~0.5%, Sb 0.4%~0.6%, surplus is for Mg and inevitably
Impurity.
Complex magnesium alloy sacrificial anode material containing Nd of the invention, alloy compositions Mg-Zn-Nd-Ca-Sb, the alloy
Without Al, netted Mg is avoided17Al12The generation of phase, with Zn for main additional element, to guarantee performance and control cost, Zn's
Additional amount is selected as 6.6~6.8wt%；Be added micro Nd (0.2~0.4wt%), Ca (0.3%~0.5%), Sb (0.4%~
0.6%) dystectic Mg, is generated12Nd、Mg2Ca、Mg13Sb2Phase can be used as effective forming core core and change to refine crystal grain
Kind tissue, improves the uniformity of tissue, and then consume magnesium-alloy anode material in corrosive environment uniformly.
Not only consumption is uniform in corrosive environment for gained magnesium alloy sacrificial anode material, but also depletion rate is slow, uses the longevity
The long feature of life has broad application prospects suitable for the cathodic protection under soil, seawater, corrosion of water heater or similar environment.
The above-mentioned complex magnesium alloy sacrificial anode material containing Nd, consists of the following mass percentage components: Zn
6.8%, Nd 0.2%, Ca 0.5%, Sb 0.4%, surplus are Mg and inevitable impurity.
The impurity is Si, Fe, Cu and Ni element.
Gross mass content of the impurity in sacrificial anode material is less than 0.2%.
The raw material of the Nd is Mg-Nd intermediate alloy.
The raw material of the Ca is Mg-Ca intermediate alloy.
The preparation method of the above-mentioned complex magnesium alloy sacrificial anode material containing Nd, includes the following steps: to take formula ratio
Mg, Zn, Sb, Mg-Nd intermediate alloy and Mg-Ca intermediate alloy, in CO2+SF6Under mixed gas protected, it is warming up to 680-700 DEG C
After keep the temperature 4-6min, cast to obtain the final product.
Preferably, the preparation method of the above-mentioned complex magnesium alloy sacrificial anode material containing Nd, includes the following steps: to take and match
Mg, Zn, Sb, Mg-Nd intermediate alloy and Mg-Ca intermediate alloy just measured, in CO2+SF6Under mixed gas protected, heat up after fusing
It keeps the temperature 4-6min after to 680-700 DEG C, casts to obtain the final product.
Heating described in step 1) is in induction furnace progress.The heating uses corundum crucible.
Casting is to pour into magnesium liquid in steel die described in step 2).
The above-mentioned complex magnesium alloy sacrificial anode material containing Nd is among pure magnesium, pure zinc, star antimony and magnesium neodymium, magnesium calcium
Alloy is that raw material carries out made from induction furnace melting and permanent mold casting.The preparation method simple process, raw material sources are extensive.
Specific embodiment
The pure magnesium of raw material used in embodiment (Mg), fine aluminium (Al), pure zinc (Zn), magnesium neodymium intermediate alloy (Mg-Nd), magnesium calcium
(Mg-Ca) intermediate alloy is commercial product (industrial goods).Wherein, the purity of the pure magnesium of raw material (Mg), pure zinc (Zn), star antimony (Sb)
Be 99.8%, raw material magnesium neodymium (Mg-Nd), magnesium calcium (Mg-Ca) intermediate alloy purity be 99.5%.
Embodiment 1
The complex magnesium alloy sacrificial anode material containing Nd of the present embodiment, consists of the following mass percentage components: Zn
6.6%, Nd 0.4%, Ca 0.3%, Sb 0.6%, surplus are Mg and inevitable impurity.Wherein impurity element S i, Fe,
Gross mass content of the Cu and Ni in sacrificial anode material is less than 0.2%.
The preparation method of the complex magnesium alloy sacrificial anode material of the present embodiment includes the following steps: to take alloy raw material pure
Magnesium (Mg), pure zinc (Zn), star antimony (Sb) and magnesium neodymium (Mg-Nd) intermediate alloy, magnesium calcium (Mg-Ca) intermediate alloy, in CO2+SF6It is mixed
It closes under gas shield, keeps the temperature 5min after being warming up to 680 DEG C in induction furnace using corundum crucible, pour into steel die, obtain magnesium
Alloy cast ingot, the as described magnesium alloy sacrificial anode material.
Embodiment 2
The complex magnesium alloy sacrificial anode material containing Nd of the present embodiment, consists of the following mass percentage components: Zn
6.7%, Nd 0.3%, Ca 0.4%, Sb 0.5%, surplus are Mg and inevitable impurity；Wherein impurity element S i, Fe,
Gross mass content of the Cu and Ni in anode material is less than 0.2%.
The preparation method of the complex magnesium alloy sacrificial anode material of the present embodiment includes the following steps: to take alloy raw material pure
Magnesium (Mg), pure zinc (Zn), star antimony (Sb) and magnesium neodymium (Mg-Nd) intermediate alloy, magnesium calcium (Mg-Ca) intermediate alloy, in CO2+SF6It is mixed
It closes under gas shield, keeps the temperature 5min after being warming up to 690 DEG C in induction furnace using corundum crucible, pour into steel die, obtain magnesium
Alloy cast ingot, the as described magnesium alloy sacrificial anode material.
Embodiment 3
The complex magnesium alloy sacrificial anode material containing Nd of the present embodiment, consists of the following mass percentage components: Zn
6.8%, Nd 0.2%, Ca 0.5%, Sb 0.4%, surplus are Mg and inevitable impurity；Wherein impurity element S i, Fe,
Gross mass content of the Cu and Ni in anode material is less than 0.2%.
The preparation method of the complex magnesium alloy sacrificial anode material of the present embodiment includes the following steps: to take alloy raw material pure
Magnesium (Mg), pure zinc (Zn), star antimony (Sb) and magnesium neodymium (Mg-Nd) intermediate alloy, magnesium calcium (Mg-Ca) intermediate alloy, in CO2+SF6It is mixed
It closes under gas shield, keeps the temperature 5min after being warming up to 700 DEG C in induction furnace using corundum crucible, pour into steel die, obtain magnesium
Alloy cast ingot, the as described magnesium alloy sacrificial anode material.
Comparative example 1
The magnesium alloy sacrificial anode material of this comparative example is commercial Mg alloy AZ91.
Comparative example 2
The magnesium alloy sacrificial anode material of this comparative example consists of the following mass percentage components: 6.8% Zn,
0.5% Ca, 0.4% Sb, surplus Mg.
The preparation method of the magnesium alloy sacrificial anode material of this comparative example includes the following steps: to take the pure magnesium of alloy raw material
(Mg), pure zinc (Zn), star antimony (Sb) and magnesium calcium (Mg-Ca) intermediate alloy, in CO2+SF6Under mixed gas protected, using corundum earthenware
Crucible keeps the temperature 5min after being warming up to 700 DEG C in induction furnace, pours into steel die, obtains magnesium alloy ingot, the as described magnesium alloy
Sacrificial anode material.
Test example
Magnesium alloy sacrificial anode material obtained is detected in embodiment 1-3 and comparative example 1-2, and the results are shown in Table 1.
Magnesium alloy sacrificial anode material performance test results in 1 embodiment of table and comparative example
As it can be seen from table 1 the present invention gained complex magnesium alloy sacrificial anode material, open circuit potential be -1.68~-
1.72V, current efficiency are 55%~60%, and material consumption is uniform in corrosive environment, has broad application prospects.
Claims (7)
1. a kind of complex magnesium alloy sacrificial anode material containing Nd, it is characterised in that: consist of the following mass percentage components:
Zn 6.6%~6.8%, Nd 0.2%~0.4%, Ca 0.3%~0.5%, Sb 0.4%~0.6%, surplus is for Mg and inevitably
Impurity；
The preparation method of the complex magnesium alloy sacrificial anode material containing Nd, include the following steps: to take Mg, Zn of formula ratio,
Sb, Mg-Nd intermediate alloy and Mg-Ca intermediate alloy, in CO2+SF6Under mixed gas protected, kept the temperature after being warming up to 680-700 DEG C
4-6min casts to obtain the final product.
2. the complex magnesium alloy sacrificial anode material according to claim 1 containing Nd, it is characterised in that: by following quality hundred
Divide the group of ratio to be grouped as: Zn 6.8%, Nd 0.2%, Ca 0.5%, Sb 0.4%, surplus are Mg and inevitable impurity.
3. the complex magnesium alloy sacrificial anode material according to claim 1 containing Nd, it is characterised in that: the impurity is
Si, Fe, Cu and Ni element.
4. the complex magnesium alloy sacrificial anode material according to claim 1 containing Nd, it is characterised in that: the impurity is sacrificial
Gross mass content in domestic animal anode material is less than 0.2%.
5. a kind of preparation method of the complex magnesium alloy sacrificial anode material containing Nd as described in claim 1, it is characterised in that:
Include the following steps: Mg, Zn, Sb, Mg-Nd intermediate alloy for taking formula ratio and Mg-Ca intermediate alloy, in CO2+SF6Mixed gas
Under protection, keep the temperature 4-6min after being warming up to 680-700 DEG C, cast to obtain the final product.
6. the preparation method of the complex magnesium alloy sacrificial anode material according to claim 5 containing Nd, it is characterised in that: institute
Heating is stated to carry out in induction furnace.
7. the preparation method of the complex magnesium alloy sacrificial anode material according to claim 5 containing Nd, it is characterised in that: institute
Stating casting is to pour into magnesium liquid in steel die.
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| CN201710309376.4A CN107130249B (en) | 2017-05-04 | 2017-05-04 | A kind of complex magnesium alloy sacrificial anode material and preparation method thereof containing Nd |
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| CN107130249B true CN107130249B (en) | 2019-07-26 |
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| CN109943852A (en) * | 2019-05-10 | 2019-06-28 | 光钰科技（临沂）有限公司 | A kind of preparation method delaying sacrificial magnesium alloy anode corrosion rate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105734375A (en) * | 2016-04-12 | 2016-07-06 | 洛阳理工学院 | Sb-containing magnesium alloy sacrificial anode material |
| CN106609372A (en) * | 2016-10-21 | 2017-05-03 | 洛阳理工学院 | Magnesium alloy sacrificial anode containing Sm and Sb |
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2017
- 2017-05-04 CN CN201710309376.4A patent/CN107130249B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105734375A (en) * | 2016-04-12 | 2016-07-06 | 洛阳理工学院 | Sb-containing magnesium alloy sacrificial anode material |
| CN106609372A (en) * | 2016-10-21 | 2017-05-03 | 洛阳理工学院 | Magnesium alloy sacrificial anode containing Sm and Sb |
Non-Patent Citations (2)
| Title |
|---|
| Y对心血管支架用Mg-Zn-Ca-Y合金的腐蚀性能的影响;李利等;《中国铸造装备与技术》;20161231(第4期);39-42页 |
| 合金化及热处理工艺对镁阳极性能影响的研究进展;张万友等;《腐蚀科学与防护技术》;20160331;第28卷(第2期);179-183页 |
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