CN1303236C - Zinc bismuth multicomponent alloy used for hot dip galvanizing of steel and iron members and hot dip galvanizing method therefor - Google Patents
Zinc bismuth multicomponent alloy used for hot dip galvanizing of steel and iron members and hot dip galvanizing method therefor Download PDFInfo
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- CN1303236C CN1303236C CNB200510031270XA CN200510031270A CN1303236C CN 1303236 C CN1303236 C CN 1303236C CN B200510031270X A CNB200510031270X A CN B200510031270XA CN 200510031270 A CN200510031270 A CN 200510031270A CN 1303236 C CN1303236 C CN 1303236C
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Abstract
The present invention relates to a zinc alloy and a hot dipping galvanizing method. The present invention has the technical scheme that a zinc bismuth multi-component alloy A containing bismuth and used for galvanizing a hot dipping steel component is composed of 0.05 to 0.1 wt% of Bi, 0.05 to 0.09 wt% of Al, 0.01 to 0.05 wt% of rare earth metal RE, 0 to 0.05 wt% of Ni and zinc and unavoidable impurities as the rest, wherein the rare earth metal RE is a mixture of at least two of lanthanum (La), cerium (Ce) and praseodymium (Pr). A hot dipping galvanizing method for a steel product containing Si and/or P adopts the zinc and bismuth multi-component alloy of the components as a zinc bath. The present invention reasonably controls the content of the aluminum, the nickel and the rare earth (the rare earth metal RE), and simultaneously adds a bismuth element to the alloy so that the flowing property of the zinc bath is obviously improved. The thickness of a plating layer is properly reduced when the anticorrosive performance and the mechanical performance of the plating layer are ensured.
Description
Technical field
The present invention relates to a kind of zinc alloy, this alloy is used to make steel and iron member zinc-plated under heating condition.
Background technology
The used zinc of galvanizing industry is bathed substantially and is improved to zinc alloy baths by pure zinc bath both at home and abroad at present, made significant headway in aspects such as the etch resistant properties of latter's gained coating, surface quality, bonding force, but at present used various zinc alloy baths exist that fluidity of molten is poor, zinc stream, list edge, burr is many, and coating surface smooth finish is owed the problem of difference.Though various improved alloys have solved some problems wherein to a certain extent, but still have defective, improvement produces effect very much to the coating luminance brightness as Zn-Al alloy, and the melt segregation is big, and zinc is bathed and is clamminess; Zn-Al-rare earth metal RE alloy can improve the wetting property of steel and zinc well, but the composition fluctuation is big, and melting loss of elements is serious; Sheng Delin phenomenon when Zn-Ni alloy can solve active steel galvanizing ideally, but narrower to the scope that suppresses active steel Sheng Delin effect.In sum, present various zinc alloy baths need further to improve.
Summary of the invention
The object of the present invention is to provide a kind of zinc bismuth multicomponent alloy and method thereof that is used for hot dip galvanizing of steel and iron members, the mobile obviously improvement that it can make zinc bathe suitably reduces thickness of coating in etch resistant properties that ensures coating and mechanical property.
Another object of the present invention is to provide a kind of new hot dip galvanizing method, and this method is that zinc is bathed with the zinc bismuth multicomponent alloy, solves that the existing fluidity of molten of galvanizing is poor, problems such as zinc stream, list edge, burr are many, coating surface smooth finish difference.
Technical scheme of the present invention is: a kind of galvanized, bismuthiferous zinc bismuth multicomponent alloy of hot dipping steel and iron member that is used for, and it consists of 0.05～0.1% (wt) Bi; The Al of～0.09% 0.05 (wt); 0.01 the rare earth metal RE of～0.05% (wt); The Ni of 0～0.05% (wt); All the other are zinc and unavoidable impurities, and described rare earth metal RE is at least two kinds a mixture among lanthanum (La), cerium (Ce), the praseodymium (Pr).
As to further improvement of the present invention, described rare earth metal RE is the wantonly two kinds equal amount of mixture of lanthanum (La), cerium (Ce), praseodymium (Pr).
As to further improvement of the present invention, described rare earth metal RE is the mixture of lanthanum (La), cerium (Ce), praseodymium (Pr), and the mixed weight ratio is: lanthanum (La): cerium (Ce): praseodymium (Pr)=2: 2: 1.
A kind of hot dip galvanizing method that contains the steel work of Si and/or P adopts the zinc bismuth multicomponent alloy of said components to bathe as zinc.
Beneficial effect
The present invention rationally controls the content of Aluminum in Alloy, nickel, rare earth metal RE, adds bismuth element simultaneously in alloy, and the flowing property that zinc is bathed is obviously improved, and suitably reduces thickness of coating in etch resistant properties that ensures coating and mechanical property.The disclosed mould of mobile available Chinese patent ZL03248893.9 of products obtained therefrom of the present invention detects, and detection method and result are as follows:
1, the mobile simultaneous test of the present invention and other zinc alloys
(1) spoon casting fluidity test
Test method: adopt the disclosed snakelike mould of Chinese patent ZL03248893.9, after the fusing of zinc bismuth alloy, be warming up to 500 ℃, pour in the same manner in the snakelike mould with a certain amount of liquid metal of iron bale-out, allow liquid metal flow, when liquid metal no longer flows in the mould, stop in snakelike mould, to fall molten metal.After treating that metal cools is solidified in the snakelike mould, measure the length of metal flow.Repeat this test, test-results is averaged.Choose pure zinc and bi content and be respectively the test of 0.01%, 0.06%, 0.1%, 0.16% and 0.2% zinc bismuth alloy.
(2) luxuriant good fortune constant temperature resistance furnace test
Test method: adopt the disclosed snakelike mould of Chinese patent ZL03248893.9, soaking time is 3 hours, utilize alloy melting after liquid metal nature mobile character do this kind test.When treating that liquid alloy no longer flows, stop constant temperature, the furnace cooling solidified superalloy.Alloy natural mobile length under the liquid state in snakelike mould is measured in the back of coming out of the stove, and repeats this test, its results averaged.
Take by weighing identical weight, bi content is 0.02%, 0.04%, 0.06%, 0.08%, 0.1%, 0.12%, 0.14%, 0.16%, 0.18%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% and 1% zinc bismuth alloy, put into constant temperature and be 460 ℃ luxuriant good fortune constant temperature resistance furnace and test.
Draw bi content shown in Figure 1 and its alloy flowability graph of a relation according to above-mentioned test gained result.
As can be seen from Figure 1, contain Bi amount in the multicomponent alloy 0.1% when following, the alloy flow performance is along with the increase of Bi content, presenting parabola rule increases, and reach at 0.1% o'clock and a peak value occurs, be 0.1%～0.15% o'clock at Bi content, presenting parabola rule with the increase of Bi content reduces, bi content is greater than after 0.2%, and the flowability of alloy is increase trend with the increase of bi content, but cost increases; Therefore gained zinc bismuth alloy flowability of the present invention is fine, the cost performance optimum.
2, thickness of coating check of the present invention:
The contriver uses Zn-Ni alloy bath, Zn-Al-rare earth metal RE alloy baths, alloy baths of the present invention to carry out the hot dip process test in the processing condition of laboratory simulation hot dip producer, and hot dip process test technology and condition are as follows:
Technical process: chlorohydric acid pickling → wash → help plating → oven dry → hot dip process → cooling → following process → finished product
Chlorohydric acid pickling: adopt 8%～20% concentration of hydrochloric acid, room temperature pickling 5～10 minutes;
Washing: a large amount of tap water is washed acid residual on the plating piece and molysite off;
Help plating: adopt conventional plating assistant agent, i.e. 100g/l NH
4Cl+480g/l ZnCl
2, NH
4Cl and ZnCl
2Concentration can according to the doing of different areas, humidity are different can appropriate change, the plating assistant agent temperature helps 0.5～1 minute plating time more than 80 ℃.
Oven dry: adopt 100 ℃～200 ℃ bake out temperature, do not get final product to there being free water
Hot dip process: adopt 450 ℃～490 ℃ zinc-plated, 30 seconds to 5 minutes immersion plating time
Cooling: divide air cooling, water cooling and first air cooling three kinds of modes of water cooling again
The testing data of products obtained therefrom as shown in Figure 2.The thickness of coating of three kinds of alloys of gained as shown in Figure 2, on behalf of Zn-Ni alloy, a bathe among Fig. 2, b represents Zn-Al-rare earth metal RE alloy baths, c represents Zn-Bi-Al-rare earth metal RE alloy baths.As shown in Figure 2, the thickness of coating minimum of the present invention of c representative.
Etch resistant properties:
Choose pure zinc and the bismuth-containing amount is respectively 0.01%, 0.06%, 0.1%, 0.16%, Al content is about 0.05%, rare earth metal RE content is about 0.05%, and the use Galvanized Steel Strip of the present invention that the hot dip process time was respectively 30 seconds, 3 minutes is done corrosion test.Test method: GB6458-86NSS neutral salt acid corrosion proofing box, testing installation: HK-1 type hcl corrosion proofing box.
Test conditions: salt fog sedimentation velocity (80cm
2) 1～2ml, corrosion system is the NaCl solution of 50 ± g/ml, pH value is 6.5～7.2, test temperature: 35 ℃ ± 2 ℃, the test period: the discontinuity spraying stopped 96 hours total times 16 hours in 8 hours.Test-results is as shown in table 1.
Numbering 1# is that pure zinc, 2# are that Zn-0.01%Bi alloy, 3# are that Zn-0.1%Bi alloy, 4# are that Zn-0.1%Al-0.03% rare earth metal RE alloy, 5# are that Zn-0.1%Bi-0.05%Al-0.05% rare earth metal RE alloy is that product of the present invention, 6# are that Zn-0.1%Bi-0.1% rare earth metal RE-0.1%Ni alloy, 7# are the Zn-0.1%Ni alloy in the table.
Gained is the result show, increases with bi content, and the corrosion speed value reduces, and the alloy erosion resistance strengthens.
Mechanical property:
1, hot-dip galvanized alloy coating snappiness detects test
Detection method: bending method
Test set: snappiness multiaxis rod tester
Detected object: A3 steel zn alloy coating
Statutory standards: coating has reticulate pattern, and it is defective that crackle and peeling off is
Choose in 430～470 ℃ of scopes hot dip A in Zn-Ni, Zn-Al rare earth metal RE, Zn-Bi multicomponent alloy are bathed
3In every kind of alloy layer thin slice under the steel thin slice, differing temps, randomly draw 3 and make snappiness multiaxis rod and test the detection snappiness, viewing test found that per sample (p.s.) coating integrity degree is good, and no reticulate pattern, crackle and breakoff phenomenon such as peel off are up-to-standard.The present invention is better than other result.
2, Zn Alloy Hot Dipped Coating sticking power detects test
Detection method: draw the circle method
Test set: adherometer
Detected object: A
3The steel zn alloy coating
Evaluation criteria: according to seven grade standard samples evaluation cut coating integrated degree
Choose 430 ℃～470 ℃ temperature ranges, hot dip process A in Zn-Ni, Zn-Al-rare earth metal RE, Zn-Bi multicomponent alloy are bathed
3Alloy layer thin slice under the steel disc, differing temps is randomly drawed three and is done sticking power detection test, averages.The result shows: per sample (p.s.) coating integrity degree is good, and test control all reaches seven grades.
The present invention is better than other result
3, the Zn Alloy Hot Dipped Coating impact detects test
Detection method: ballistic method
Test set: shock-testing machine
Detected object: A
3The steel zn alloy coating
Evaluation criteria: coating crackle, wrinkle are arranged and peel off be defective
In 430 ℃～470 ℃ scopes of picked at random, hot dip Zn-Ni, Zn-Al rare earth metal RE, Zn-Bi polybasic A
3Each 3 of steel discs carry out shock test, and test-results shows: A
3The alloy layer quality is good on the steel disc.The present invention is better than other result.
Description of drawings
Below in conjunction with accompanying drawing invention is further described:
Fig. 1 bi content and its alloy flowability graph of a relation
The graph of a relation of Fig. 2 the present invention and other two kinds of alloy hot dip time and thickness
Embodiment
A kind of galvanized, bismuthiferous zinc bismuth multicomponent alloy A of hot dipping steel and iron member that is used for, it consists of 0.05% (wt) Bi; The Al of 0.09% (wt); The rare earth metal RE of 0.01% (wt); The Ni of 0.05% (wt); All the other are zinc and unavoidable impurities, and rare earth metal RE is lanthanum (La): the mixture of cerium (Ce)=1: 1.
Embodiment 2
A kind of galvanized, bismuthiferous zinc bismuth multicomponent alloy A of hot dipping steel and iron member that is used for, it consists of 0.1% (wt) Bi; The Al of 0.09% (wt); The rare earth metal RE of 0.01% (wt); The Ni of 0.05% (wt); All the other are zinc and unavoidable impurities, and described rare earth metal RE is lanthanum (La): cerium (Ce): the mixture of praseodymium (Pr)=2: 2: 1.
Embodiment 3
A kind of galvanized, bismuthiferous zinc bismuth multicomponent alloy A of hot dipping steel and iron member that is used for, it consists of 0.05% (wt) Bi; The Al of 0.05% (wt); The rare earth metal RE of 0.05% (wt); The Ni of 0.05% (wt); All the other are zinc and unavoidable impurities, and described rare earth metal RE is lanthanum (La): the mixture of cerium (Ce)=1: 1.
Embodiment 4
A kind of galvanized, bismuthiferous zinc bismuth multicomponent alloy A of hot dipping steel and iron member that is used for, it consists of 0.1% (wt) Bi; The Al of 0.09% (wt); The rare earth metal RE of 0.05% (wt); The Ni of 0% (wt); All the other are zinc and unavoidable impurities, and described rare earth metal RE is cerium (Ce): the mixture of praseodymium (Pr)=1: 1.
Table 1 salt spray corrosion test result
| Numbering | Sample size/mm | Before the W/g | Behind the W/g | Corrosion rate/g/m2·h | Immersion plating time/S |
| 1-1 | 4.5×3.1×1.58 | 14.973 | 14.928 | 10.03 | 300 |
| 1-2 | 2×3.1×1.58 | 21.769 | 21.692 | 11.06 | 180 |
| 2-1 | 5×3.1×1.58 | 17.958 | 17.915 | 9.20 | 30 |
| 2-2 | 5×3.1×1.58 | 20.466 | 20.420 | 8.47 | 180 |
| 3-1 | 5×3.1×1.58 | 16.222 | 16.199 | 5.52 | 30 |
| 3-2 | 6×3.1×1.58 | 17.785 | 17.759 | 4.74 | 180 |
| 4-1 | 5×3.1×1.58 | 13.153 | 13.126 | 5.84 | 30 |
| 4-2 | 4×3.1×1.58 | 14.027 | 14.002 | 5.51 | 180 |
| 5-1 | 5×3.1×1.58 | 16.450 | 16.390 | 1.00 | 30 |
| 5-2 | 5×3.1×1.58 | 19.605 | 19.550-650 | 0.849 | 60 |
| 5-3 | 8×3.1×1.58 | 27.575 | 27.570 | 1.23 | 120 |
| 5-4 | 8×3.1×1.58 | 32.695 | 32.689 | 1.23 | 180 |
| 6-1 | 8×3.1×1.58 | 24.806 | 24.788 | 2.46 | 30 |
| 6-2 | 8×3.1×1.58 | 26.706 | 26.692 | 2.46 | 60 |
| 6-3 | 5×3.1×1.58 | 23.320 | 23.304 | 2.944 | 120 |
| 6-4 | 5×3.1×1.58 | 22.393 | 22.380 | 2.87 | 180 |
| 7-1 | 8×3.1×1.58 | 37.744 | 34.723 | 3.69 | 30 |
| 7-2 | 8×3.1×1.58 | 26.809 | 26.782 | 3.61 | 60 |
| 7-3 | 8×3.1×1.58 | 23.989 | 23.969 | 3.42 | 120 |
| 7-4 | 6×3.1×1.58 | 20.363 | 20.337 | 4.106 | 180 |
Claims (4)
1, a kind of galvanized, bismuthiferous zinc bismuth multicomponent alloy of hot dipping steel and iron member that is used for, it is characterized in that: it consists of 0.05～0.1% (wt) Bi; The Al of～0.09% 0.05 (wt); 0.01 the rare earth metal RE of～0.05% (wt); The Ni of 0～0.05% (wt); All the other are zinc and unavoidable impurities, and described rare earth metal RE is at least two kinds a mixture among lanthanum (La), cerium (Ce), the praseodymium (Pr).
2, galvanized, the bismuthiferous zinc bismuth multicomponent alloy of hot dipping steel and iron member that is used for according to claim 1, it is characterized in that: described rare earth metal RE is the wantonly two kinds equal amount of mixture of lanthanum (La), cerium (Ce), praseodymium (Pr).
3, galvanized, the bismuthiferous zinc bismuth multicomponent alloy of hot dipping steel and iron member that is used for according to claim 1, it is characterized in that: described rare earth metal RE is the mixture of lanthanum (La), cerium (Ce), praseodymium (Pr), and the mixed weight ratio is: lanthanum (La): cerium (Ce): praseodymium (Pr)=2: 2: 1.
4, a kind of hot dip galvanizing method that optionally contains the steel work of Si and/or P is characterized in that: adopt the zinc bismuth multicomponent alloy of claim 1-3 component described in each to bathe as zinc.
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| CN1303236C true CN1303236C (en) | 2007-03-07 |
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| CN102816984A (en) * | 2012-07-21 | 2012-12-12 | 靖江市大通标准件厂 | Hot dip galvanizing additive |
| CN111719072A (en) * | 2020-07-28 | 2020-09-29 | 惠博新型材料有限公司 | Zn-Al-Si-Mn-Bi-Ti-Ce alloy for hot dip coating and use method thereof |
| CN115852288A (en) * | 2022-12-28 | 2023-03-28 | 江苏电力装备有限公司 | Alloy-added hot galvanizing solution |
Citations (6)
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|---|---|---|---|---|
| US5330712A (en) * | 1993-04-22 | 1994-07-19 | Federalloy, Inc. | Copper-bismuth alloys |
| CN1257553A (en) * | 1997-05-23 | 2000-06-21 | 联合矿业有限公司 | Alloy and process for galvanizing steel |
| WO2000050658A1 (en) * | 1999-02-22 | 2000-08-31 | Nippon Steel Corporation | High strength galvanized steel plate excellent in adhesion of plated metal and formability in press working and high strength alloy galvanized steel plate and method for production thereof |
| CN1271783A (en) * | 2000-05-12 | 2000-11-01 | 朴永华 | Hot-dipping galvanized alloy and its preparing process |
| CN1390672A (en) * | 2002-05-10 | 2003-01-15 | 大连理工大学 | Leadfree SnZn-base alloy solder containing rare-earth elements |
| CN1483090A (en) * | 2000-12-29 | 2004-03-17 | �ձ�������ʽ���� | High-strength molten-zinc-plated steel plate excellent in deposit adhesion and suitability for press forming and process for producing the same |
-
2005
- 2005-02-07 CN CNB200510031270XA patent/CN1303236C/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5330712A (en) * | 1993-04-22 | 1994-07-19 | Federalloy, Inc. | Copper-bismuth alloys |
| CN1257553A (en) * | 1997-05-23 | 2000-06-21 | 联合矿业有限公司 | Alloy and process for galvanizing steel |
| WO2000050658A1 (en) * | 1999-02-22 | 2000-08-31 | Nippon Steel Corporation | High strength galvanized steel plate excellent in adhesion of plated metal and formability in press working and high strength alloy galvanized steel plate and method for production thereof |
| CN1271783A (en) * | 2000-05-12 | 2000-11-01 | 朴永华 | Hot-dipping galvanized alloy and its preparing process |
| CN1483090A (en) * | 2000-12-29 | 2004-03-17 | �ձ�������ʽ���� | High-strength molten-zinc-plated steel plate excellent in deposit adhesion and suitability for press forming and process for producing the same |
| CN1390672A (en) * | 2002-05-10 | 2003-01-15 | 大连理工大学 | Leadfree SnZn-base alloy solder containing rare-earth elements |
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