CN103114221A - Lead-free free-cutting silicon brass alloy and preparation method thereof - Google Patents
Lead-free free-cutting silicon brass alloy and preparation method thereof Download PDFInfo
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- CN103114221A CN103114221A CN2013100664794A CN201310066479A CN103114221A CN 103114221 A CN103114221 A CN 103114221A CN 2013100664794 A CN2013100664794 A CN 2013100664794A CN 201310066479 A CN201310066479 A CN 201310066479A CN 103114221 A CN103114221 A CN 103114221A
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Abstract
The invention discloses a lead-free free-cutting silicon brass alloy and a preparation method thereof. The silicon brass alloy comprises the following components and contents: 28-34wt% of zinc, 2.2-3.5wt% of silicon, 0.5-1.8wt% of zinc sulfide and the balance of copper. The lead-free free-cutting silicon brass alloy has the beneficial effects that the copper content in brass alloy is less than 70%, and the free-cutting performance of brass alloy is improved through adjusting the contents of zinc, silicon and zinc sulfide added in brass alloy; the obtained free-cutting brass alloy is low in cost; and zinc sulfide is introduced in silicon brass by using an in-situ synthesis technology and is brittle, so that the effect of improving the cutting performance of brass is achieved.
Description
Technical field
The present invention relates to the easily-cut silicon brass alloy field, particularly a kind of lead-free free-cutting silicon brass and preparation method thereof.
Background technology
Because the Application Areas of brass alloys is very extensive, so its cutting ability directly has influence on the yield rate of material machinofacture, production cost and production efficiency.Existing free-cutting brass mainly comprises leaded brass, because that leaded casting yellow copper alloy has excellent cutting ability and castability and production cost is lower, so be widely applied to various fields.Yet, development along with industrialization society, plumbous harm to ecotope manifests day by day, so developed country is devoted to the research of easy-cutting lead-free brass always, easy-cutting lead-free brass is exactly by the Composition Design in the improvement brass, the element substitution that suitably adds other a small amount of toxicological harmlesss is plumbous, is formed with to be beneficial to the cenotype of improving the brass cutting ability in alloy, reaches free machining purpose.These substitute plumbous element mainly is bismuth, silicon, antimony, tellurium, graphite and magnesium etc.From practical angle, what dropped into application both at home and abroad at present mainly is bismuth brass and silicon brass.In the silicon brass of having developed, can form product and what drop into to use mainly is unleaded silicon brass series product by the exploitation of Japanese Triratna company.The principal character of Triratna series product is that copper content is very high, generally all is higher than 70%, so this class silicon brass cost is higher than general brass product, is difficult to be accepted by the user, thereby has limited applying of it.
Summary of the invention
The purpose of this invention is to provide a kind of castability, forgeability excellence, cutting ability, good mechanical performance, the relatively low easily-cut silicon brass alloy of required raw metal cost.
According to an aspect of the present invention, provide the lead-free free-cutting silicon brass alloy, its component and content
Comprise:
In some embodiments, inevitable foreign matter content≤0.8wt% in the alloy.
In some embodiments, the content of zinc is 30～31wt%, and the content of silicon is 2.5～3wt%, and the content of zinc sulphide is 1～1.5wt%, and surplus is copper.
In some embodiments, the content of zinc is 31wt%, and the content of silicon is 3wt%, and the content of zinc sulphide is 1wt%, and surplus is copper.
Another aspect of the present invention has also related to a kind of preparation method of lead-free free-cutting silicon brass alloy, may further comprise the steps:
Step 1, alloying constituent proportion design: zinc 28～34wt%, silicon 2.2～3.5wt%, zinc sulphide 0.5～1.8wt%, surplus is copper;
Step 2, preparation prefabricated section: copper powder, sulfuration copper powder, zinc powder are fully mixed rear compacting with the ratio of 4:3:3 form prefabricated section;
Step 3, melting: at first electrolytic copper is added smelting furnace and melt with stove, with Control for Kiln Temperature at 1040～1100 ℃, then add prefabricated section and silicon, can be by the high temperature generation reaction in－situ of copper liquid after prefabricated section adds, after question response fully carries out, cool to 450～500 ℃ with the furnace, add pure zinc and stirring, then be incubated 5～15 minutes;
Step 4, copper alloy liquid watered cast from swage and obtain the silicon brass alloy ingot casting.
In some embodiments, described silicon brass alloy ingot casting is heated to 700～750 ℃ and carries out the hot extrusion finished product.
The factor that affects the brass material cutting ability is main relevant with alloy structure and mechanical property.If the α phase that the brass tissue is single, this phase matter is soft, and its plasticity is good, adds the long bits that are easy to get man-hour continuously, entwines at cutter and workpiece, and is unfavorable to cutting.If having other intensity, hardness, plasticity and α to differ larger other at α phase matrix exists mutually, especially there are β phase, γ phase time, because γ phase matter is hard and be fragility, these fragility are easily broken mutually under action of pulling stress so, these fragility phase constitutions have just destroyed the preferably continuity of α phase matrix of plasticity, have the effect of chip breaking, thereby be conducive to improve the cutting ability of brass alloys.
Zinc is the main alloy element in the brass, and the variation of its content is larger on the impact of brass alloys.Among the present invention, the content of zinc is 28～34wt%, zinc content is during less than 28wt%, the γ phase volume fraction is less, effect to the cutting ability of brass alloys is little, and along with zinc content raises, the α phase volume fraction in the brass alloys reduces, and the volume fraction of β phase, γ phase increases, and the cutting ability of brass alloys increases.
The variation of silicone content is also larger to the performance impact of brass alloys.Among the present invention, the content of silicon is 2.2～3.5wt%, and silicone content is during less than 2wt%, cutting ability does not reach satisfied effect, when silicone content is higher than 3.5wt%, although the cutting ability of brass alloys is improved, but the tensile strength of brass alloys is lower, and the application of brass alloys is exerted an influence.
Zinc sulphide improves the cutting ability of brass mutually mainly as chip breaking in brass alloys.The existence of zinc sulphide can be considered and occurs some small holes in the alloy substrate, wherein filled the zns particle of fragility, these holes have destroyed the continuity of matrix, become stress raiser, consist of many reduction microcells, breeding and motion in that these zones produce stress concentration and dislocation easily produce notched effect, realize chip breaking under the effect of shearing stress.The content of zinc sulphide is 0.5～1.8wt% among the present invention, when the content of zinc sulphide during less than 0.5wt%, cutting ability impact on brass alloys is not obvious, along with increasing of the content of zinc sulphide, the cutting ability of brass alloys is better improved, but consider the factor of the over-all properties of cost and brass alloys, so the content of control zinc sulphide is not more than 1.8wt%.
The present invention compared with prior art, its beneficial effect is, copper content improves the free cutting property of brass alloys less than 70% by the content of adjusting the zinc, silicon and the zinc sulphide that add in the brass in the brass alloys, the free machining brass alloys cost of gained is lower.Because the viscosity of brass alloys metal melt is very high, the particle diameter of the zinc sulphide that adds is very little, density also is lower than the density of copper liquid, after zinc sulphide joins the metal of melting, be subject to capillary effect, float over the metal melt surface, the feasibility that the surface tension that makes these particles overcome metallic solution is distributed in melt equably is very little, so the method that the present invention relates to is that the employing cupric sulfide is starting material, adopt the original position synthesis technique in silicon brass, to introduce zinc sulphide, zinc sulphide is fragility, thereby reaches the effect of improving the brass cutting ability.
Description of drawings
Fig. 1 is the cutting ability chip shape of the lead-free free-cutting silicon brass of the embodiment of the invention 1;
Fig. 2 is the cutting ability chip shape of the lead-free free-cutting silicon brass of the embodiment of the invention 2;
Fig. 3 is the cutting ability chip shape of the lead-free free-cutting silicon brass of the embodiment of the invention 3;
Fig. 4 is the cutting ability chip shape of the lead-free free-cutting silicon brass of the embodiment of the invention 4;
Fig. 5 is the figure of SEM tissue topography of the lead-free free-cutting silicon brass of the embodiment of the invention 1.
Embodiment
The present invention is further detailed explanation below in conjunction with embodiment.
One, the preparation method of lead-free free-cutting silicon brass, its concrete technology is:
Step 1, design alloying constituent proportioning, namely the component in the alloy and content comprise: copper 62～68wt%, zinc 28～34wt%, silicon 2.2～3.5wt%, zinc sulphide 0.5～1.8wt%, surplus is copper;
Step 2, preparation prefabricated section: copper powder, sulfuration copper powder, zinc powder are fully mixed rear compacting with the ratio of 4:3:3 form prefabricated section, the copper powder, sulfuration copper powder, the zinc powder that prepare are in proportion evenly mixed on mixed powder machine, with mixed powder briquetting on oil press.
Step 3, melting: at first electrolytic copper is added smelting furnace and melt with stove, with Control for Kiln Temperature at 1040～1100 ℃, then add prefabricated section and silicon, can be by the high temperature generation reaction in－situ of copper liquid after prefabricated section adds, question response cools to 450～500 ℃ with the furnace after fully carrying out, and adds pure zinc, fully stir and make its homogeneous chemical composition, be incubated 5～15 minutes; Wherein reaction in－situ is: CuS+Zn → ZnS+Cu, thus be implemented in the purpose of introducing zinc sulphide in the brass alloys solution; Wherein, the melting of brass alloys is that the frequency induction melting furnace carries out in a vacuum.
In the thermodynamic (al) theory of classics, usually judge that according to Gibbs function criterion can a reaction spontaneously carry out.The process that system's Gibbs function reduces can spontaneously be carried out, and is in equilibrium state when Gibbs function is constant, namely wants keeping system to stablize and must satisfy △ G≤0.
According to the second law of thermodynamics, under the isothermal and isobaric condition, have:
In the formula, on be designated as standard atmospheric pressure,
Be the standard Gibbs free energy variation of reaction,
Be the Standard Enthalpies variation of reaction,
Be the standard entropy variation of reaction, T is absolute temperature.In the formula
Function for temperature is respectively:
△ C in two formulas
pPoor for the thermal capacitance of resultant and reactant, the thermal capacitance of material is the function of a temperature, i.e. following formula:
C
p=A
1+A
2×10
-3T+A
3×10
5T
-2+A
4×10
-6T
2+A
5×10
8T
-3
A in the formula
1, A
2, A
3, A
4, A
5Be the constant that is obtained by the experimental data recurrence,
Can get thus:
△C
p=△A
1+△A
2×10
-3T+△A
3×10
5T
-2+△A
4×10
-6T
2+△A
5×10
8T
-3
Each reactant and resultant
A
1, A
2, A
3, A
4, A
5Value all can obtain by searching the thermodynamic data handbook, by calculating the reaction front and back gibbs free energy change value that just can obtain under the assigned temperature
Thereby can use the gibbs criterion
Judge the feasibility of reacting under this temperature.Sulfide original position synthesis technique described in the invention designs according to this thermodynamic criterion, this reaction process: CuS+Zn → ZnS+Cu, and each thermodynamic data that relates to is listed among the table a.Can calculate according to data in the table
Relation function with T.Under the smelting temperature of the present invention, the Gibbs free energy of this reaction shows that less than 0 this reaction of design can spontaneously be carried out.
Table a is the thermodynamic data of used each material
Step 4, copper alloy liquid watered cast from swage and obtain the silicon brass alloy ingot casting;
Step 5, the silicon brass alloy ingot casting is heated to 700～750 ℃, and with mould and die preheating to 150～200 ℃, carries out the hot extrusion finished product take extrusion ratio as 9:1.
Embodiment 1
By table 1 design alloying constituent and after preparing prefabricated section, first electrolytic copper is joined in the smelting furnace and melt with stove, then Control for Kiln Temperature adds prefabricated section and silicon at 1040 ℃, can be by the high temperature generation reaction in－situ of copper liquid after prefabricated section adds, after question response fully carries out, cool to 450 ℃ with the furnace, add pure zinc, fully stir and make its homogeneous chemical composition, be incubated 5 minutes, copper alloy liquid is watered cast from swage and obtain the silicon brass alloy ingot casting; The silicon brass alloy ingot casting is heated to 700 ℃, and with mould and die preheating to 150 ℃, carries out the hot extrusion finished product take extrusion ratio as 9:1.
Table 1 is brass alloys composition of the present invention (wt%)
| Alloying element | Copper | Zinc | Silicon | Zinc sulphide | Component in the prefabricated block quality proportioning |
| Content | Surplus | 28 | 2.2 | 1.8 | Copper: cupric sulfide: zinc=4:3:3 |
Embodiment 2
By table 2 design alloying constituent and after preparing prefabricated section, first electrolytic copper is joined in the smelting furnace and melt with stove, then Control for Kiln Temperature adds prefabricated section and silicon at 1050 ℃, can be by the high temperature generation reaction in－situ of copper liquid after prefabricated section adds, after question response fully carries out, cool to 450 ℃ with the furnace, add pure zinc, fully stir and make its homogeneous chemical composition, be incubated 8 minutes, copper alloy liquid is watered cast from swage and obtain the silicon brass alloy ingot casting; The silicon brass alloy ingot casting is heated to 750 ℃, and with mould and die preheating to 150 ℃, carries out the hot extrusion finished product take extrusion ratio as 9:1.
Table 2 is brass alloys composition of the present invention (wt%)
| Alloying element | Copper | Zinc | Silicon | Zinc sulphide | Component in the prefabricated block quality proportioning |
| Content | Surplus | 30 | 2.5 | 1.5 | Copper: cupric sulfide: zinc=4:3:3 |
Embodiment 3
By table 3 design alloying constituent and after preparing prefabricated section, first electrolytic copper is joined in the smelting furnace and melt with stove, then Control for Kiln Temperature adds prefabricated section and silicon at 1100 ℃, can be by the high temperature generation reaction in－situ of copper liquid after prefabricated section adds, after question response fully carries out, cool to 500 ℃ with the furnace, add pure zinc, fully stir and make its homogeneous chemical composition, be incubated 15 minutes, copper alloy liquid is watered cast from swage and obtain the silicon brass alloy ingot casting; The silicon brass alloy ingot casting is heated to 700 ℃, and with mould and die preheating to 150 ℃, carries out the hot extrusion finished product take extrusion ratio as 9:1.
Table 3 is brass alloys composition of the present invention (wt%)
| Alloying element | Copper | Zinc | Silicon | Zinc sulphide | Component in the prefabricated block quality proportioning |
| Content | Surplus | 31 | 3 | 1 | Copper: cupric sulfide: zinc=4:3:3 |
Embodiment 4
By table 4 design alloying constituent and after preparing prefabricated section, first electrolytic copper is joined in the smelting furnace and melt with stove, then Control for Kiln Temperature adds prefabricated section and silicon at 1100 ℃, can be by the high temperature generation reaction in－situ of copper liquid after prefabricated section adds, after question response fully carries out, cool to 500 ℃ with the furnace, add pure zinc, fully stir and make its homogeneous chemical composition, be incubated 15 minutes, copper alloy liquid is watered cast from swage and obtain the silicon brass alloy ingot casting; The silicon brass alloy ingot casting is heated to 720 ℃, and with mould and die preheating to 150 ℃, carries out the hot extrusion finished product take extrusion ratio as 9:1.
Table 4 is brass alloys composition of the present invention (wt%)
| Alloying element | Copper | Zinc | Silicon | Zinc sulphide | Component in the prefabricated block quality proportioning |
| Content | Surplus | 34 | 3.5 | 0.5 | Copper: cupric sulfide: zinc=4:3:3 |
In above-mentioned all embodiments, all there is inevitable impurity in silicon brass alloy, this inevitable foreign matter content≤0.8wt%.
Comparative example
With the HPb59-1 leaded brass as a comparative example, its composition is copper 57.0～60.0wt%, plumbous 0.8～1.9wt%, aluminium≤0.2, iron≤0.5, antimony≤0.01, bismuth≤0.003, phosphorus≤0.02, and surplus is zinc.
Two, the performance test of the brass alloys of each embodiment and comparative example
Get the alloy of the embodiment of the invention and the alloy of comparative example and carry out under the same conditions performance test, relate generally to the test of tensile strength, unit elongation, Brinell hardness and machinability index.
The test of machinability rating is to adopt the external cutting test, the deliberated index of machinability mainly adopts the difficulty or ease of chip breaking: adopt the GSK928TC-2 digital controlled lathe to carry out cutting test, cutter material YG8, main shaft rotating speed 1000r/min, back engagement of the cutting edge 2mm, speed of feed 0.15mm/r.
(composition is as copper 57.0～60.0wt%, plumbous 0.8～1.9wt%, aluminium≤0.2, iron≤0.5, antimony≤0.01, bismuth≤0.003, phosphorus≤0.02 take the HPb59-1 leaded brass, surplus is zinc) cutting ability be 80%, estimate the cutting ability of other brass of each embodiment of the present invention with this standard.
Table 5 is tensile strength, unit elongation and Brinell hardness and the machinability index of each embodiment and comparative example
The chip shape of the lead-free free-cutting silicon brass alloy of each embodiment of the present invention such as Fig. 1～shown in Figure 4.As can be seen from the figure, smear metal is light and collapses the short bits of broken C type, illustrates that the cutting ability of alloy is good.
The displaing micro tissue topography of the embodiment of the invention 1 lead-free free-cutting silicon brass alloy as shown in Figure 5.SEM photo from figure can find out, except matrix phase, also has the micropore hole of particulate state and strip at intracrystalline and grain boundaries in the lead-free free-cutting silicon brass alloy.The inboard remaining part of hole has been carried out the energy spectrum analysis judgement mutually, and these holes are vestiges that the ZnS particle detachment stays.The reason that comes off is that compound ZnS is fragility, and with the matrix phase bonding force a little less than, in the process of metallographic sample pre-grinding preparation, easily come off.According to form and the distribution at these hole places, can learn in the alloy structure at matrix phase crystal boundary and intracrystalline to have more ZnS particle that metallic sulfide is introduced and achieved success in the test.
As can be seen from Table 5, lead-free free-cutting silicon brass alloy over-all properties of the present invention is good, and the machinability index of the leaded brass in its machinability index and the Comparative Examples is approaching, has good cutting ability.
In sum, copper content is less than 70% in the brass alloys of the present invention, improve the cutting ability of brass alloys by the content of adjusting the zinc, silicon and the zinc sulphide that add in the brass, gained brass alloys mechanical property and cutting ability are good, product cost is lower simultaneously, is conducive to the practical application of brass alloys.
Claims (6)
1. a lead-free free-cutting silicon brass alloy is characterized in that, its component and content comprise:
2. a kind of lead-free free-cutting silicon brass alloy according to claim 1 is characterized in that, inevitable foreign matter content≤0.8wt% in the alloy.
3. a kind of lead-free free-cutting silicon brass alloy according to claim 1 is characterized in that, the content of zinc is 30～31wt%, and the content of silicon is 2.5～3wt%, and the content of zinc sulphide is 1～1.5wt%, and surplus is copper.
4. a kind of lead-free free-cutting silicon brass alloy according to claim 1 is characterized in that, the content of zinc is 31wt%, and the content of silicon is 3wt%, and the content of zinc sulphide is 1wt%, and surplus is copper.
5. a preparation method who prepares such as each described lead-free free-cutting silicon brass alloy among the claim 1-4 is characterized in that, adopts take cupric sulfide and introduces zinc sulphide in as raw-material in-situ synthesis to brass alloys, specifically may further comprise the steps:
Step 1, design alloying constituent proportioning: zinc 28～34wt%, silicon 2.2～3.5wt%, zinc sulphide 0.5～1.8wt%, surplus is copper;
Step 2, preparation prefabricated section: copper powder, sulfuration copper powder, zinc powder are fully mixed rear compacting with the weight ratio of 4:3:3 form prefabricated section;
Step 3, melting: at first electrolytic copper is added smelting furnace and melt with stove, with Control for Kiln Temperature at 1040～1100 ℃, then add prefabricated section and silicon, can be by the high temperature generation reaction in－situ of copper liquid after prefabricated section adds, after question response fully carries out, cool to 450～500 ℃ with the furnace, add pure zinc and stirring, then be incubated 5～15 minutes;
Step 4, copper alloy liquid watered to cast from obtain the silicon brass alloy ingot casting in the mold.
6. the preparation method of lead-free free-cutting silicon brass alloy according to claim 5 is characterized in that, and is further comprising the steps of:
Described silicon brass alloy ingot casting is heated to 700～750 ℃ carries out the hot extrusion finished product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020037759A1 (en) * | 2018-08-22 | 2020-02-27 | 华南理工大学 | Micro-textured cutter based on silicon brass structure and processing method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53147609A (en) * | 1977-05-31 | 1978-12-22 | Mitsubishi Metal Corp | Cu-based sintered alloy for brush material |
| JP2005240136A (en) * | 2004-02-27 | 2005-09-08 | Nikko Metal Manufacturing Co Ltd | Nickel silver strip having excellent heating discoloration resistance |
| CN101476056A (en) * | 2008-12-10 | 2009-07-08 | 宋长洪 | Leadless free-cutting silicon-phosphorous-copper alloy |
| CN101633987A (en) * | 2009-06-19 | 2010-01-27 | 浙江天申铜业有限公司 | Lead-free environmental silicon brass alloy bar or alloy ingot and preparation method thereof |
| JP2012241202A (en) * | 2011-05-16 | 2012-12-10 | Joetsu Bronz1 Corp | Lead-free brass alloy for hot working |
-
2013
- 2013-03-01 CN CN201310066479.4A patent/CN103114221B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53147609A (en) * | 1977-05-31 | 1978-12-22 | Mitsubishi Metal Corp | Cu-based sintered alloy for brush material |
| JP2005240136A (en) * | 2004-02-27 | 2005-09-08 | Nikko Metal Manufacturing Co Ltd | Nickel silver strip having excellent heating discoloration resistance |
| CN101476056A (en) * | 2008-12-10 | 2009-07-08 | 宋长洪 | Leadless free-cutting silicon-phosphorous-copper alloy |
| CN101633987A (en) * | 2009-06-19 | 2010-01-27 | 浙江天申铜业有限公司 | Lead-free environmental silicon brass alloy bar or alloy ingot and preparation method thereof |
| JP2012241202A (en) * | 2011-05-16 | 2012-12-10 | Joetsu Bronz1 Corp | Lead-free brass alloy for hot working |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020037759A1 (en) * | 2018-08-22 | 2020-02-27 | 华南理工大学 | Micro-textured cutter based on silicon brass structure and processing method and application thereof |
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