CN101914704B - Cr-containing creep-resisting extruded zinc alloy and preparation method thereof - Google Patents
Cr-containing creep-resisting extruded zinc alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Cr-containing creep-resisting extruded zinc alloy, belonging to the technical field of metal material manufacture. The alloy comprises the following components by mass percent: 0.05-3.0% of Cr, 0.5-2.5% of Cu, 0.1-0.3% of Ti and the balance of Zn and impurities which accounts for no more than 0.05% of the total amount. The alloy also can comprise 0.1-1.0% of Al by mass. The preparation method is implemented as follows: smelting by adopting a coverage protective method at the temperature of 630-720 DEG C, adding the alloy elements respectively in a form of pure Zn, pure Al and intermediate alloys of Cu-Cr, Zn-Cu and Zn-Ti, casting at the temperature of 450-500 DEG C after the alloy solution is mixed evenly, homogenizing ingots for 6-10h at the temperature of 360-380 DEG C, performing extrusion forming at the temperature of 240-320 DEG C with the extrusion ratio of 15-38, and annealing for 1-3h at the temperature of 180-220 DEG C. The invention has reasonable component proportioning, and the prepared zinc alloy is a deformation zinc alloy suitable for extrusion and has excellent creep resistance and combination properties.
Description
Technical field
The invention discloses a kind of zinc alloy and preparation method thereof, be meant creep-resisting extruded zinc alloy of a kind of Cr of containing and preparation method thereof especially; Belong to metal alloy compositions manufacturing technology field.
Background technology
Lower creep resistance is one of main bottleneck of applying of restrained deformation zinc alloy.For improving the creep resisting ability of zinc alloy, abroad some investigator has carried out certain research to the aspects such as deformation mechanism, alloying and processing condition of zinc alloy.Deformation zinc alloy is after getting into the sixties in last century; Because the progress of smelting, processing technology; Improving the research work progress of zinc alloy physicals and over-all properties accelerates; Especially the grasp of high-strength creep resistant zinc alloy melting technology, complete processing, having broken zinc alloy can not be as the restriction of structured material use.The later stage nineties in last century; Japan has carried out a series of research to cold forging, heat-resisting and cast zinc alloy; On the intensity of material and creep-resistant property, obtained certain progress, but comprehensive performance is still waiting to improve, the research of particularly doing at the extruded zinc alloy this respect seldom.
Domestic zinc-copper is that the research of alloy is almost blank, and since the end of the nineties in last century, Guangzhou Institute of Metallurgical Technology, Central South University etc. are that alloy has carried out preliminary study to zinc-copper, but research contents is narrow, studies not enough system and gos deep into.Guangdong emtallurgy research in 1999 the Guangzhou zinc metal sheet factory continuous casting and rolling production line of doing has been manufactured experimently the zinc-copper-titanium alloy product of several trades mark, and its creep-resistant property increases, but remarkable inadequately.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art and a kind of reasonable mixture ratio of components is provided contain creep-resisting extruded zinc alloy of Cr and preparation method thereof; Prepared zinc alloy is a kind of deformation zinc alloy of suitable extruding, has excellent creep-resistant property and over-all properties.
The objective of the invention is to realize in the following manner:
A kind of creep-resisting extruded zinc alloy that contains Cr, form by following component by mass percentage:
Chromium 0.05～3.0%;
Copper 0.5～2.5%;
Titanium 0.1～0.3%;
All the other are zinc and unavoidable impurities, and the total content of impurity is not more than 0.05%.
As preferably, the mass percent of each component of alloy is:
Chromium 0.1～2.8%;
Copper 0.6～2.2%;
Titanium 0.15～0.25%;
All the other are zinc and unavoidable impurities, and the total content of impurity is not more than 0.05%.
A kind of creep-resisting extruded zinc alloy that contains Cr, form by following component by mass percentage:
Chromium 0.05～3.0%;
Copper 0.5～2.5%;
Titanium 0.1～0.3%;
Aluminium 0.1～1.0%;
All the other are zinc and unavoidable impurities, and the total content of impurity is not more than 0.05%.
As preferably, the mass percent of each component of alloy is:
Chromium 0.05～3.0%;
Copper 0.5～2.5%;
Titanium 0.1～0.3%;
Aluminium 0.25～0.8%;
All the other are zinc and unavoidable impurities, and the total content of impurity is not more than 0.05%.
Preferred as further, the mass percent of each component of alloy is:
Chromium 0.1～2.8%;
Copper 0.6～2.2%;
Titanium 0.15～0.25%;
Aluminium 0.25～0.8%;
All the other are zinc and unavoidable impurities, and the total content of impurity is not more than 0.05%.
The preparation method of the creep-resisting extruded zinc alloy of the said Cr of containing is: alloy adopts the covering protection method to carry out melting; Chromium, copper, titanium add with Cu-Cr, Zn-Cu, Zn-Ti master alloy form respectively; Zinc, aluminium then add with pure zinc, fine aluminium form respectively; Smelting temperature is 630～720 ℃, treat that the alloy liquation mixes after, be cast into ingot casting at 450～500 ℃; Ingot casting is after 360～380 ℃ of homogenizing are handled 6～10h, and at 240～320 ℃ of extrusion moldings, extrusion ratio is 15～38; The extruding back is at 180～220 ℃ of annealing 1～3h.
The preparation method of said Zn-Ti master alloy is: the pure Ti that will account for Zn-Ti master alloy total mass 4～8% adds melting in the Zn liquation, 830～920 ℃ of smelting temperatures, treat that Ti all melts and mixes after, be incubated 25～35 minutes, be cast into ingot casting then.
The preparation method of the creep-resisting extruded zinc alloy of a kind of Cr of containing of the present invention: described melting is in medium-frequency induction furnace, to carry out.
The present invention makes copper, chromium and zinc form CuZn owing to adopt said components and preparation method
4And CrZn
17Intermetallic compound second phase, this intermetallic compound second phase fusing point is high, and hardness is high, and stability is strong, is distributed in the crystal boundary place more, in creep process, stablizes crystal boundary and hinders dislocation motion, improves the creep resistance of alloy, reaches creep resisting effect.Secondly, Ti also can generate hard TiZn with zinc
15Second phase, disperse is distributed in matrix, improves the creep-resistant property of alloy.Second is broken mutually in the process of under 240～320 ℃ of temperature, pushing, and makes these second be on good terms more tiny and disperse distributes, and can effectively improve alloy creep-resistant property and over-all properties.Simultaneously added Al again, crystal grain thinning impels the second phase uniform particles to distribute simultaneously, has reduced gathering partially of detrimental impurity, thereby has effectively suppressed the fragility tendency and the corrosion tendency of material, has improved creep-resistant property, mechanical property and the corrosion resistance nature of alloy.In addition,, improved the recrystallization temperature of alloy, effectively suppressed growing up of alloy recrystallization crystal grain, further improved the creep-resistant property of alloy owing to the adding of alloying elements such as Cu, Cr and Ti.The mechanism of action of each component in alloy is specified in down:
Cr is dissolved in zinc at normal temperatures hardly, Cr ability crystal grain thinning, and reinforced alloys, chromium and zinc can generate hard and stable intermetallic compound CrZn
17Be distributed in the crystal boundary place, in creep process, stablize crystal boundary and hinder dislocation motion, improve the creep resistance of alloy, reach creep resisting effect; Cr has improved the recrystallization temperature of alloy, has effectively suppressed growing up of alloy recrystallization crystal grain, has further improved the creep-resistant property of alloy.Experiment showed, that the too low grain refining of Cr content is not obvious, and almost do not have CrZn
17Generate, little to improving the creep-resistant property effect; But content (massfraction %) surpasses at 3.0% o'clock, intermetallic compound CrZn
17Too much gather partially in crystal boundary, the plasticity of alloy reduces greatly.Therefore we fix on to Cr content (massfraction %) at 0.05～3.0% o'clock, and the creep-resistant property and the over-all properties of alloy are best.
The effect of Cu mainly shows the following aspects: the one, and the Cu solid solution produces solution strengthening in the Zn matrix, and the 2nd,, form intermetallic compound ε phase (CuZn
4), produce second and strengthen mutually.The solid solubility of Cu in zinc is very little under the normal temperature, can be known by phasor, and when copper content (massfraction %) surpassed 1.25%, copper can generate ε (CuZn mutually with zinc
4) be distributed in crystal boundary, make alloy have excellent creep-resistant property and good comprehensive performances; When copper content is too low, the alloy strengthening DeGrain, and can not generate ε phase (CuZn
4) or generate very little, therefore to almost not influence of creep-resistant property; When the copper too high levels, the ε phase (CuZn that the crystal boundary place generates
4) cause alloy plasticity sharply to descend too much, through a large amount of analysis of experimentss, fix on copper content (massfraction %) between 0.5～2.5% at last, could guarantee the over-all properties that alloy also can obtain like this when having good creep-resistant property.Also find in the test, when crystal boundary ε is too much mutually, can impel intergranular corrosion, make the etch resistant properties variation of alloy.
Al can crystal grain thinning, also plays the effect of solution strengthening, and tensile strength of alloys and creep strength are obviously improved, and the corrosion resistance nature that improves alloy is also had certain effect.Alloy is in fusion process, and Al can improve the flowability of zinc liquid largely, thereby improves its castability; And aluminium forms one deck compact oxide at molten surface; And the ability slag making, can prevent alloy oxidation, the castability that improves alloy there is very big benefit.The addition of Al in the alloy of the present invention (massfraction %) is: 0.1～1.0%.
Ti can generate intermetallic compound TiZn with the zinc reaction
15, be distributed in the crystal boundary place, the creep-resistant property that improves alloy there is good supplementary function; In addition, Ti adds as a kind of alterant, mainly is the basic phase of refinement, and improves frangible compounds, impurity and be mingled with the form and the distribution of grade in an imperial examination two-phase.The addition of Ti of the present invention (massfraction %) is: 0.1～0.3%.
In sum; Reasonable mixture ratio of components of the present invention; Prepared zinc alloy is a kind of deformation zinc alloy of suitable extruding, has excellent creep-resistant property and over-all properties, is specially adapted to the bathroom hot-water heating; Fields such as five metals and automobile industry's component are a kind of materials that have very much application prospect.
Embodiment
1-9 does further explain to the present invention below in conjunction with specific embodiment.
The technological process of production that contains the Cr creep-resisting extruded zinc alloy in the embodiment of the invention is following:
Starting material are prepared and batching, and------------------------------------checked finished product to alloy casting to the preparation master alloy in annealing in the ingot casting extruding in the homogenizing processing.
Specifically can explain as follows: adopt covering protection method melting creep resistance zinc alloy in medium-frequency induction furnace; Chromium, copper, titanium add with Cu-Cr, Zn-Cu, Zn-Ti master alloy form respectively; Zinc, aluminium then add with simple substance form respectively; Smelting temperature is 630～720 ℃, makes chromium, copper, titanium and aluminium after the zinc liquation melts fast and mixes, and under 450～500 ℃, is cast as the zinc alloy ingot casting.Ingot casting is handled 6～10h through 360～380 ℃ of homogenizing, under 240～320 ℃, is squeezed into pole then, and extrusion ratio is 15～38, and finished product is checked at last at 180～220 ℃ of annealing 1～3h in the extruding back.Wherein the preparation method of Zn-Ti master alloy is: the pure Ti that will account for Zn-Ti master alloy total mass 4～8% adds melting in the Zn liquation; Smelting temperature is 830～920 ℃; After treating that Ti all melts and mixes, be incubated 30 minutes, alloy is melting in medium-frequency induction furnace; The preparation method of Cu-Cr master alloy is: the pure Cr that will account for Cu-Cr master alloy total mass 3～7% adds melting in the Cu liquation, and smelting temperature is 1150～1250 ℃, and alloy is melting in medium-frequency induction furnace.
The creep-resisting extruded zinc alloy composition such as the table 1 that contain Cr of embodiment of the invention 1-9 melt into ingot casting and are squeezed into pole by the alloy of process method of the present invention with embodiment 1-9, concrete preparation technology parameter such as table 2; In addition, routine as a comparison with the Zn-Cu-Ti alloy, concrete composition of Comparative Examples alloy such as table 1, alloy preparation technology parameter such as table 2.
Embodiment and Comparative Examples alloy are carried out creep property and room-temperature mechanical property detection.Test is carried out on RWS50 electronics creep relaxation trier, sample is placed in the process furnace that keeps constant temperature (attemperation automatically), guarantee the three sections temperature fluctuations in upper, middle and lower be controlled at ± 1 ℃, realize the constant temperature loading.Trier regulate to keep dead load through electronically controlled, before intensification, sample is applied the starting force that is no more than total test force 10%, and trier is not more than in use range internal force value relative error ± and 1%, indicating value relative variability degree is not more than 1.0%.Strain-gauging is adopted and is fixed on the special lazy-tongs that draws on the test specimen; The end of anchor clamps is drawn from stove; Adopt the displacement of two axial extensometer bilateral measured material then; Check the quality that is installed of extensometer before the test with the power of suitable increment, in case of necessity extensometer is adjusted, make the difference of MV and the either side reading of both sides reading be not more than 15% divided by the per-cent of MV.Entire test is controlled and data gathering real time record axle power, distortion etc. with computingmachine.Creep loading stress is 70Mpa, and temperature is 25 ℃ of room temperatures.Alloy and the Comparative Examples alloy property index such as the table 3 of embodiment 1-9 preparation.
Table 1 embodiment and Comparative Examples alloy composition (massfraction %)
| Embodiment and Comparative Examples alloy | Cr | Cu | Ti | Al | Zn |
| Embodiment 1:Zn-Cr-Cu-Ti | 0.05 | 2.50 | 0.10 | - | Surplus |
| Embodiment 2:Zn-Cr-Cu-Ti | 0.56 | 2.20 | 0.15 | - | Surplus |
| Embodiment 3:Zn-Cr-Cu-Ti | 1.0 | 1.50 | 0.12 | - | Surplus |
| Embodiment 4:Zn-Cr-Cu-Ti | 1.92 | 1.55 | 0.30 | - | Surplus |
| Embodiment 5:Zn-Cr-Cu-Ti | 3.0 | 0.5 | 0.16 | - | Surplus |
| Embodiment 6:Zn-Cr-Cu-Ti | 0.10 | 1.00 | 0.20 | - | Surplus |
| Embodiment 7:Zn-Cr-Cu-Ti-Al | 1.07 | 1.00 | 0.18 | 0.10 | Surplus |
| Embodiment 8:Zn-Cr-Cu-Ti-Al | 1.12 | 1.45 | 0.20 | 0.55 | Surplus |
| Embodiment 9:Zn-Cr-Cu-Ti-Al | 0.62 | 2.05 | 0.30 | 1.00 | Surplus |
| Comparative Examples: Zn-Cu-Ti | - | 1.25 | 0.2 | - | Surplus |
Table 2 alloy preparation technology parameter
Table 3 alloy property detected result
The performance test results of comparison sheet 3 embodiment of the invention 1-9 and Comparative Examples alloy can be found out, the creep-resisting extruded zinc alloy that the present invention contains Cr has excellent more creep-resistant property and over-all properties than Comparative Examples Zn-Cu-Ti alloy.This shows reasonable mixture ratio of components of the present invention; Prepared zinc alloy is a kind of deformation zinc alloy of suitable extruding, has excellent creep-resistant property and over-all properties, is specially adapted to the bathroom hot-water heating; Fields such as five metals and automobile industry's component are a kind of materials that have very much application prospect.
Claims (9)
1. one kind contains the Cr creep-resisting extruded zinc alloy, is made up of following component by mass percentage:
Chromium 0.05～3.0%;
Copper 0.5～2.5%;
Titanium 0.1～0.3%;
All the other are zinc and unavoidable impurities, and the total content of impurity is not more than 0.05%, and its preparation method comprises the steps:
(1) alloy adopts the covering protection method to carry out melting; Chromium, copper, titanium add with Cu-Cr, Zn-Cu, Zn-Ti master alloy form respectively, and zinc then adds with pure zinc form, and smelting temperature is 630～720 ℃; After treating that the alloy liquation mixes, be cast into ingot casting at 450～500 ℃;
(2) ingot casting is after 360～380 ℃ of homogenizing are handled 6～10h, and at 240～320 ℃ of extrusion moldings, extrusion ratio is 15～38;
(3) after the extruding, at 180～220 ℃ of annealing 1～3h.
2. the Cr creep-resisting extruded zinc alloy that contains according to claim 1 is characterized in that each component is by mass percentage:
Chromium 0.1～2.8%;
Copper 0.6～2.2%;
Titanium 0.15～0.25%;
All the other are zinc and unavoidable impurities, and the total content of impurity is not more than 0.05%.
3. one kind contains the Cr creep-resisting extruded zinc alloy, is made up of following component by mass percentage:
Chromium 0.05～3.0%;
Copper 0.5～2.5%;
Titanium 0.1～0.3%;
Aluminium 0.1～1.0%;
All the other are zinc and unavoidable impurities, and the total content of impurity is not more than 0.05%, and its preparation method comprises the steps:
(1) alloy adopts the covering protection method to carry out melting; Chromium, copper, titanium add with Cu-Cr, Zn-Cu, Zn-Ti master alloy form respectively; Zinc, aluminium then add with pure zinc, fine aluminium form respectively; Smelting temperature is 630～720 ℃, treat that the alloy liquation mixes after, be cast into ingot casting at 450～500 ℃;
(2) ingot casting is after 360～380 ℃ of homogenizing are handled 6～10h, and at 240～320 ℃ of extrusion moldings, extrusion ratio is 15～38;
(3) after the extruding, at 180～220 ℃ of annealing 1～3h.
4. the Cr creep-resisting extruded zinc alloy that contains according to claim 3 is characterized in that each component is by mass percentage:
Chromium 0.05～3.0%;
Copper 0.5～2.5%;
Titanium 0.1～0.3%;
Aluminium 0.25～0.8%;
All the other are zinc and unavoidable impurities, and the total content of impurity is not more than 0.05%.
5. the Cr creep-resisting extruded zinc alloy that contains according to claim 3 is characterized in that each component is by mass percentage:
Chromium 0.1～2.8%;
Copper 0.6～2.2%;
Titanium 0.15～0.25%;
Aluminium 0.25～0.8%;
All the other are zinc and unavoidable impurities, and the total content of impurity is not more than 0.05%.
6. a preparation method who contains the Cr creep-resisting extruded zinc alloy as claimed in claim 1 comprises the steps:
(1) alloy adopts the covering protection method to carry out melting; Chromium, copper, titanium add with Cu-Cr, Zn-Cu, Zn-Ti master alloy form respectively, and zinc then adds with pure zinc form, and smelting temperature is 630～720 ℃; After treating that the alloy liquation mixes, be cast into ingot casting at 450～500 ℃;
(2) ingot casting is after 360～380 ℃ of homogenizing are handled 6～10h, and at 240～320 ℃ of extrusion moldings, extrusion ratio is 15～38;
(3) after the extruding, at 180～220 ℃ of annealing 1～3h.
7. a preparation method who contains the Cr creep-resisting extruded zinc alloy as claimed in claim 3 comprises the steps:
(1) alloy adopts the covering protection method to carry out melting; Chromium, copper, titanium add with Cu-Cr, Zn-Cu, Zn-Ti master alloy form respectively; Zinc, aluminium then add with pure zinc, fine aluminium form respectively; Smelting temperature is 630～720 ℃, treat that the alloy liquation mixes after, be cast into ingot casting at 450～500 ℃;
(2) ingot casting is after 360～380 ℃ of homogenizing are handled 6～10h, and at 240～320 ℃ of extrusion moldings, extrusion ratio is 15～38;
(3) after the extruding, at 180～220 ℃ of annealing 1～3h.
8. according to claim 6 or the 7 described preparing methods that contain the Cr creep-resisting extruded zinc alloy; It is characterized in that: said Zn-Ti master alloy is that the pure Ti that accounts for Zn-Ti master alloy total mass 4～8% is added melting in the Zn liquation; 830～920 ℃ of smelting temperatures; After treating that Ti all melts and mixes, be incubated 25～35 minutes, be cast into ingot casting again.
9. according to right 6 or the 7 described preparing methods that contain the Cr creep-resisting extruded zinc alloy, it is characterized in that: said melting is in medium-frequency induction furnace, to carry out.
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| CN103361516A (en) * | 2012-03-28 | 2013-10-23 | 广东中实金属有限公司 | Zinc-based nickel-cobalt alloy metal spraying material and preparation method thereof |
| CN102808116A (en) * | 2012-06-08 | 2012-12-05 | 常州大学 | Method for preparing high-performance die casting zinc alloys |
| CN102994805B (en) * | 2012-12-17 | 2015-04-08 | 宁波香豪莱宝金属工业有限公司 | Extruded zinc alloy and preparation method thereof |
| CN105543562A (en) * | 2016-01-20 | 2016-05-04 | 广西丛欣实业有限公司 | Zinc alloy for burglary-resisting window |
| CN114732944B (en) * | 2022-04-07 | 2023-01-13 | 北京大学 | Zinc-based bar with composite structure and preparation method thereof |
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| US3006758A (en) * | 1960-01-05 | 1961-10-31 | Hydrometals Inc | Zinc alloy |
| GB1184282A (en) * | 1968-02-15 | 1970-03-11 | British Non Ferrous Metals Res | Zinc-Base Alloys |
| JPS6338551A (en) * | 1986-08-01 | 1988-02-19 | Sekisui Chem Co Ltd | Zinc alloy containing rare earth element |
| CN1053930C (en) * | 1996-11-19 | 2000-06-28 | 山东省科学院新材料研究所 | Zinc base alloy material for making pressure reducer parts and mfg. method thereof |
| JP4000339B2 (en) * | 2003-08-11 | 2007-10-31 | Ｄｏｗａメタルマイン株式会社 | Zn alloy for die casting and Zn alloy die casting product |
| CN101514410A (en) * | 2009-04-03 | 2009-08-26 | 中南大学 | Lead-free free-cutting magnesium-stibium brass alloy |
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