CN117887999A - Free-cutting iron bronze alloy and preparation method thereof - Google Patents
Free-cutting iron bronze alloy and preparation method thereof Download PDFInfo
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- CN117887999A CN117887999A CN202410017491.4A CN202410017491A CN117887999A CN 117887999 A CN117887999 A CN 117887999A CN 202410017491 A CN202410017491 A CN 202410017491A CN 117887999 A CN117887999 A CN 117887999A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 238000005520 cutting process Methods 0.000 title claims abstract description 93
- 229910000906 Bronze Inorganic materials 0.000 title claims abstract description 67
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 238000001125 extrusion Methods 0.000 claims description 36
- 239000006104 solid solution Substances 0.000 claims description 36
- 230000032683 aging Effects 0.000 claims description 31
- 238000005266 casting Methods 0.000 claims description 31
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 30
- 239000010974 bronze Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000003723 Smelting Methods 0.000 claims description 20
- 238000005728 strengthening Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 14
- 229910000859 α-Fe Inorganic materials 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000009749 continuous casting Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012071 phase Substances 0.000 description 111
- 239000000956 alloy Substances 0.000 description 57
- 229910045601 alloy Inorganic materials 0.000 description 56
- 239000010949 copper Substances 0.000 description 31
- 229910052802 copper Inorganic materials 0.000 description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 28
- 238000012545 processing Methods 0.000 description 27
- 230000000694 effects Effects 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 239000000498 cooling water Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 21
- 239000011572 manganese Substances 0.000 description 15
- 239000011701 zinc Substances 0.000 description 11
- 229910052748 manganese Inorganic materials 0.000 description 9
- 229910000881 Cu alloy Inorganic materials 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 229910001369 Brass Inorganic materials 0.000 description 4
- 239000010951 brass Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910017888 Cu—P Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000001192 hot extrusion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 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 2
- 238000002844 melting Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- -1 iron bronze series Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
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Abstract
The invention discloses a free-cutting iron bronze alloy, which comprises the following components in percentage by mass: 2-3wt% of Pb, 0.1-0.5wt% of Zn, 0.1-0.3wt% of Ni:0.1-0.4wt%, mn:0.05-0.25wt%, S:0.02-0.1wt%, P:0.01-0.05wt%, the balance being Cu and unavoidable impurities. The iron bronze alloy has high mechanical property and good machinability. The invention also discloses a preparation method of the free-cutting iron bronze alloy.
Description
Technical Field
The invention belongs to the technical field of copper alloy materials and processes, and particularly relates to a free-cutting iron bronze alloy and a preparation method thereof.
Background
The iron bronze is bronze with Fe as a main element. The national standard QFE2.5 is a representative copper alloy in the iron bronze series alloy, and the alloy comprises the following components: 2.1-2.6%, P:0.015-0.15%, zn:0.05-0.20%, and the balance copper, wherein the Fe phase is separated out during heat treatment, so that the strength of the alloy is improved, the tensile strength in a hard state can reach more than 450MPa, the hardness HV reaches more than 145, the elongation A11.3 is not lower than 4%, the conductivity can reach more than 60% IACS, and the alloy is suitable for occasions with higher requirements on conductivity and strength, and has wide application, such as: contact springs, electrical clamps, terminals, washers, plugs, screws, etc.
The Chinese patent with publication number of CN114990377A discloses a high-strength and high-conductivity bronze alloy for an electric connector and a preparation method thereof, wherein the alloy comprises the following components in percentage by mass: the proposal provided by the patent searches the mixing amount ratio of iron, zinc, phosphorus and the like to magnesium, chromium and rare earth elements through a great deal of experiments, and the processing procedures of hot-rolled ingot casting, solid solution treatment, secondary aging and three-time cold rolling are matched under the component amount ratio relation, so that the tensile strength, the electrical conductivity and the like of the bronze alloy are greatly improved. Although the high-strength and high-conductivity bronze alloy for an electrical connector disclosed in the patent has higher strength and higher conductivity, the cutting effect is poor when the bronze alloy is prepared.
QFE2.5 is excellent in strength and conductivity, but QFE2.5 alloy is difficult to cut and process, is difficult to break, is spiral, is extremely easy to wind on a cutter and a workpiece, and has to be stopped frequently to manually clean the copper scraps, and in addition, fine copper scraps are easy to adhere to the surface of the cutter, so that the frictional resistance between the cutter and the workpiece is large, and the cutter is rapid in abrasion.
The most common method for improving the cutting performance of copper alloys is to add elements which are subject to chip breakage, such as Pb, bi, S, te, etc., and have a common feature that the solubility in copper is extremely low and the elements exist in the alloy in the form of simple substances or brittle compounds, thereby improving the cutting performance of copper alloys. However, after the elements are added, the continuity of the original structure of the copper alloy is broken, so that the strength of the alloy is greatly reduced and the conductivity of the alloy is damaged to a certain extent.
Therefore, how to improve the cutting performance of the iron bronze QFE2.5 on the premise of meeting the mechanical property and the electrical property of the material is a technical problem encountered at present.
Disclosure of Invention
The invention provides the free-cutting iron bronze alloy which has higher mechanical property and better free-cutting property.
The embodiment of the invention provides a free-cutting iron bronze alloy, which comprises the following components in percentage by mass: 2-3wt% of Pb, 0.1-0.5wt% of Zn, 0.05-0.3wt% of Ni:0.1-0.4wt%, mn:0.05-0.25wt%, S:0.02-0.1wt%, P:0.01-0.05wt%, the balance being Cu and unavoidable impurities.
The solubility of Fe in copper is greatly changed, the solubility is 3.5% at 1050 ℃, but the solubility is reduced to 1.5% at 635 ℃ and is only 0.3% at normal temperature, so that Fe is precipitated from solid solution in the form of dispersed particles along with the reduction of temperature, and if P exists, fine Fe can be generated 3 The P compound is separated out from the copper matrix, the alloy has strengthening effect, and the Fe content is controlled to be 2-3wt% according to the solubility change of Fe in copper and the strengthening effect of Fe on the alloy.
The P provided by the invention has positive influence on the mechanical property of copper, and if the addition amount of the P is too high during smelting, the redundant P is combined with Fe to form Fe 3 The P compound is easily precipitated as coarse particles. Fe (Fe) 3 The P phase has higher hardness and has certain strengthening effect on the alloy, but Fe 3 The P phase is precipitated in a large quantity, so that the quantity of alpha-Fe dispersion phases playing a main role in strengthening in the subsequent aging process is reduced, the strength of the material is reduced, and the addition quantity of P is as low as possible on the premise of meeting the requirements of deoxidation and hydrogen embrittlement, so that the P content is controlled to be 0.01-0.05wt% in the invention.
Pb provided by the invention exists in an independent phase in the alloy, and the Pb has no obvious influence on the conductivity of copper, but reduces the strength, hardness and elongation of the alloy. Free Pb particles play a role in lubrication and can disintegrate the chips during cutting, so that the machinability of copper is greatly improved. Pb is in liquid phase at the hot working temperature, so that the high-temperature plasticity of copper is seriously reduced, and the Pb-containing high-copper alloy is extremely easy to crack during hot working. In the present invention, pb content as an improvement in cutting action is in the range of 0.1 to 0.5wt%, less than 0.1wt%, and the effect of improving cutting is poor; after the weight percentage exceeds 0.5 percent, the mechanical property of the material is difficult to reach the standard.
The Zn provided by the invention has two functions: firstly, the casting performance of the alloy can be improved, and the problem of poor casting performance caused by the reduction of the P content is solved; secondly, the hot brittleness of Pb during hot working of the alloy can be reduced. The Zn content is improved, the effect of improving the alloy strength is not obvious, but after the Zn content exceeds 0.3 weight percent, the influence on the conductivity is large, so that the Zn content is controlled to be 0.05-0.3 weight percent.
The Ni provided by the invention can refine Pb distribution, further improves the cutting performance of the alloy, but has insignificant refining effect when the Ni content is lower than 0.1%; since Ni is completely dissolved in Cu and has a large influence on the conductivity of the alloy, the Ni content should be controlled to be 0.1-0.4wt%.
The Mn provided by the invention has little damage to the conductivity of the alloy, but can improve the strength of the alloy, the content exceeds 0.25wt%, the influence on the conductivity is larger, the main effect of Mn in the alloy and S form a brittle compound MnS to improve the cutting performance of the alloy, and the Mn content in the alloy is controlled to be 0.05-0.25%.
Because Mn is more active than Cu, S provided by the invention preferentially forms MnS brittle compounds with Mn in the invention, and can separate the continuity of a matrix, so that chips are easy to brittle fracture, but the S content exceeds 0.1%, the alloy hot brittleness is increased, and the hot working is easy to crack, so that the S content is limited to be within the range of 0.1%, the S content is less than 0.02wt% and cannot form MnS phase, and the MnS phase is obtained after a proper amount of Mn is matched with a proper amount of S, so that the cutting performance of the iron bronze alloy is improved.
Further, the microstructure of the free-cutting iron bronze alloy provided by the invention comprises a matrix phase, a reinforced phase, a soft phase and a brittle phase, wherein the matrix phase is an alpha phase, and the reinforced phase is alpha-Fe and Fe 3 And P, wherein the soft phase is Pb, and the brittle phase is MnS.
Further, the area ratio of the alpha-Fe phase in the microstructure of the free-cutting iron bronze alloy is 15-20%, fe 3 The area ratio of the P phase in the microstructure of the free-cutting iron bronze alloy is less than 0.1 percent.
The precipitation strengthening effect of alpha-Fe phase is superior to that of Fe 3 The area ratio of the alpha-Fe phase should be increased as much as possible to be not less than 15%, so as to avoid the deterioration of the strengthening effect caused by the fact that the Fe phase is excessively high and easily aggregated and grown during heat treatment, so that the area ratio of the alpha-Fe phase should not exceed 20%; fe (Fe) 3 The P-phase area ratio is < 0.1% because of Fe 3 P is present under conditions that the P content is excessive, which leads to a decrease in the conductivity of the alloy, and secondly, fe 3 The P phase area ratio is increased, fe 3 The P phase is liable to appear in a block shape, and the strengthening effect is deteriorated.
Further, the alpha-Fe phase has a size of < 15nm. The smaller-sized alpha-Fe phase can play a better role in dispersion strengthening.
Further, the Fe 3 The P phase is short bar-shaped Fe 3 P-phase and bulk Fe 3 P phase, the short rod-shaped Fe 3 The P phase quantity is Fe 3 The P phase is more than 90%, and the short rod-shaped Fe 3 The length of the P phase in the long axis direction is less than 20nm, and the length of the P phase in the short axis direction is less than 10nm. Suitable amount of short rod-like Fe 3 The P phase can improve the precipitation strengthening effect and avoid coarse blocky Fe 3 Effect of P on alloy deformation strengthening.
Further, the area ratio of Pb phase to microstructure of the free-cutting iron bronze alloy is 0.1-0.5%, and the area ratio of MnS phase to microstructure of the free-cutting iron bronze alloy is 0.01-0.2%. The invention improves the cutting performance of the alloy by providing a proper amount of Pb phase and MnS phase under the condition of not weakening the alloy strength of the free-cutting iron bronze alloy provided by the invention.
Further, the Pb phase size is less than 2 mu m, and the Pb distribution quantity is more than or equal to 4000pic/mm 3 . Since the smaller the size of the Pb phase is, the larger the number of Pb distributions per unit volume is under the condition that the Pb mass fraction is relatively fixed, the better the machinability of the iron bronze provided by the present invention is.
Further, the MnS phase size is < 100nm. The finer the MnS phase size, the more dispersed the distribution, and the more desirable the cutting effect is improved.
It is further preferred that the grain size (alpha phase) average size of the free-cutting iron bronze provided by the present invention is 5 to 20 μm because: firstly, the iron bronze provided by the invention mainly depends on Pb phase and brittle phase MnS to realize easy chip breaking, and during aging heat treatment, the easy chip breaking phases are preferentially separated out from a crystal boundary, so that the chip breaking effect can be further improved by increasing the area of the crystal boundary, the smaller the grain size is, the more the number of crystal grains on a unit area is, the larger the total area of the crystal boundary is, the more uniform the distribution of Pb phase and brittle phase MnS is, and the better the chip breaking effect is; secondly, negative influences of Pb phase and brittle phase MnS on the strength of the material are compensated by fine grain strengthening, but if the grain size is smaller than 5 mu m, the Pb phase and the MnS phase are added to play a role in brittleness of grain boundaries, so that the part is easy to crack in the process of service stress.
Furthermore, the tensile strength Rm of the free-cutting iron bronze alloy is more than or equal to 500MPa, the hardness HV5 is more than or equal to 160, the elongation A11.3 is more than or equal to 4%, the conductivity is more than or equal to 55% IACS, and the relative cutting index reaches more than 60% of the free-cutting brass HPb 63-3.
The invention also provides a preparation method of the free-cutting iron bronze alloy, which comprises the following process flows: batching, smelting, semi-continuous casting, water seal extrusion, first-pass disc stretching, online solid solution, second-pass disc stretching, aging annealing and combined drawing;
wherein, the batching is to batching the raw materials according to the mass percent of the free-cutting iron bronze alloy;
in the semi-continuous casting process, the length of an ingot casting red ingot zone at the outlet of the crystallizer is 80-150mm;
the aging annealing temperature is 330-400 ℃, the heating time is 1-2h, and the heat preservation time is 2-4h.
In the semi-continuous casting process provided by the invention, the length of the ingot casting red ingot zone at the outlet of the crystallizer is controlled to be 80-150mm, and more second phases are separated out because of the slow cooling speed of the red ingot zone, and the second phases are alpha-Fe phase and Fe phase 3 The uniform distribution of the P phase and the MnS phase can prevent the movement and the redistribution of dislocation, and simultaneously has a pinning effect on grain boundaries, so that grains are not obviously grown; if the length of the red ingot zone is too short, the cooling speed of the ingot is too high, the precipitated second phase is in dendritic segregation distribution, the precipitated phase is uneven in subsequent heat treatment, the aging strengthening effect is poor, and scale-shaped cracks are easy to appear on the surface of an extrusion blank during hot extrusion; if the length of the ingot red ingot zone is too long, the ingot cooling speed is low, the precipitated second phase stays at high temperature for a long time to form a coarse second phase, and the second phase is still remained even after hot extrusion and subsequent processing, so that the second phase in the final product is unevenly distributed, and the strength and cutting performance of the alloy are affected.
The alloy of the invention needs to adopt a low-temperature aging process, the aging temperature is 330-400 ℃ and the heat preservation time is 2-4 hours, because the melting point of Pb is only 327.46 ℃, the aging temperature is too high, pb particles are melted and aggregated, pb phases grow up, pb distribution quantity is reduced, the cutting performance of the alloy is poor, and if the temperature is too low, the aging effect cannot be achieved. As aging time is prolonged, the growth trend of precipitated phases is increased, so that the coarsening of the precipitated phases is caused, the tensile strength of the alloy is obviously reduced, and therefore, the heat preservation time does not exceed 4 hours, and therefore, by providing proper aging temperature and heat preservation time, pb is tiny and more in distribution quantity, thereby achieving higher cutting performance, and the solid-solution alpha-Fe phase and Fe phase can be enabled to be in solid solution 3 The P phase is separated out from the structure, second phase particles which are dispersed and distributed obstruct dislocation movement, the strength of the alloy is improved, the finer the second phase particles are, the more dispersed the second phase particles are, and the higher the strength of the alloy is. Further, the temperature rise time is 1-2h.
Further, smelting raw materials after proportioning, wherein the raw materials comprise electrolytic copper, pure iron, lead ingots, electrolytic nickel, zinc ingots, cu-S intermediate alloy, cu-P intermediate alloy and electrolytic manganese, and the feeding sequence in the smelting process comprises electrolytic copper, pure iron, electrolytic nickel, zinc ingots, lead ingots, electrolytic manganese, cu-P intermediate alloy and Cu-S intermediate alloy, and the smelting temperature is 1080-1300 ℃.
In the smelting process, the smelting furnace provided by the invention is an electromagnetic induction electric furnace, the feeding sequence of the invention follows the principle that main element metal is firstly added, refractory metal is firstly added, low-melting metal is added in the middle, and metal which is easy to burn is finally added, and all raw materials are uniformly stirred after being melted, sampled and tested, and the copper liquid components are regulated until the copper liquid components are qualified.
Further, the technological parameters of the semi-continuous casting are as follows: the casting temperature is 1150-1230 ℃, the water inlet temperature of cooling water is 15-38 ℃, the cooling water pressure is 300-500kpa, and the primary cooling water flow is 10-16m 3 The flow rate of secondary cooling water is 5-10m 3 and/L, the casting speed is 50-90mm/min.
Further, the process parameters of the water seal extrusion are as follows: the extrusion temperature is 870-950 ℃, the extrusion ratio is 30-160, the extrusion speed is 7-11mm/s, the surface solid solution temperature of the extrusion blank when the extrusion blank is just extruded from the die is controlled to be 700-800 ℃, and the extrusion blank is immediately fed into a water seal groove for solid solution, and the water temperature is less than 50 ℃. If the solid solution temperature is below 700 ℃, fe is not sufficiently solid-dissolved, the subsequent aging precipitated phases are few and uneven, the solid solution temperature exceeds 800 ℃, and the solid solution is sufficient, but the grains are coarse.
Further, the total processing rate of the first-pass disc stretching is 30-60%. The extruded blank is stretched and reduced in multiple passes through an inverted wire drawing machine, if the processing rate is lower than 30%, the crystal grains are not sufficiently broken, the subsequent solid solution treatment structure is uneven, if the processing rate exceeds 60%, the processing hardening effect leads to high material strength, the diameter of the wire blank in the processing procedure is larger, and the wire blank is easy to break under the action of shearing stress when the wire rod is wound.
Further, the online solid solution temperature is 700-780 ℃, the online solid solution time is 2-8min, and the water temperature of the cooling water tank is less than 50 ℃. The online solid solution temperature is lower than 700 ℃, the solid solution time is short, the situation of insufficient solid solution exists, the online solid solution temperature exceeds 780 ℃, the solid solution time is short, the grain size after solid solution is larger, and the solid solution effect is poor if the cooling water temperature is higher.
Furthermore, the second disc type stretching should adopt a large processing rate, the total processing rate of the second disc type stretching is controlled to be 60-80%, because the large processing rate stretching can increase dislocation density in the alloy, so that larger deformation energy is stored in the crystal lattice, the precipitated phase has larger precipitation power, the precipitation speed is higher, the tensile strength of the alloy can reach a peak value in a short time, and conditions are created for the completion of aging of the alloy at a lower temperature.
Further, the total processing rate of the combined drawing is 3-12%. The aged hard wire blank is stretched, straightened and cut to a certain length by a fixed-length saw on a combined drawing machine set at a small processing rate, the straightness is not more than 0.5mm/m, the total drawing processing rate is required to be controlled at 3-12%, and the wire blank has high strength and poor plasticity due to the combined action of deformation strengthening and precipitation strengthening after the wire blank is subjected to the former-stage large processing rate disc drawing and ageing treatment in the working procedure, so that the material starts to embrittle after the processing rate is more than 12%, and the strength is not increased but is reduced.
The preparation method of the free-cutting iron bronze alloy provided by the invention further comprises the following steps of: and detecting indexes such as tensile strength, elongation, straightness and surface quality of the finished bar.
Compared with the prior art, the invention has the beneficial effects that:
in the design of alloy components, proper Pb, mn and S elements are added to obtain soft Pb phase and brittle MnS phase, the cutting performance of the iron bronze is improved under the synergistic effect, pb distribution is refined by adding Ni element, the quantity of Pb phase in unit volume is increased, and the effect of improving the cutting performance of the iron bronze by the Pb phase is further improved.
In the preparation process, the uniformity of precipitated phases is improved by controlling the length of a cast red ingot zone, aggregation growth of low-melting-point Pb phases is avoided and cutting performance is poor by low-temperature aging treatment, and a bronze structure is rendered by regulation measures: the alpha-Fe phase of the main strengthening phase is fine and has high proportion, and the Fe phase of the secondary strengthening phase 3 The P phase is mainly in a short bar shape, the soft Pb phase is tiny and numerous, the brittle MnS phase is tiny and is in dispersion distribution, and the balance of strength and cutting performance is obtained.
Drawings
FIG. 1 is a metallographic photograph of a free-cutting iron bronze bar made in example 1 of the present invention;
FIG. 2 is a metallographic photograph of a commercially available iron bronze bar of comparative example 1 of the present invention;
FIG. 3 is a photograph showing the morphology of copper scraps in the cutting process of the free-cutting iron bronze bar material prepared in the embodiment 1 of the present invention;
fig. 4 is a photograph of the morphology of the iron bronze bar cutting process of the present invention as purchased in comparative example 1.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
The invention provides 3 examples and 1 comparative example, the specific composition is shown in table 1.
Example 1
The embodiment provides a specification ofThe preparation method of the high-strength free-cutting iron bronze bar comprises the following steps:
1) Smelting: raw materials are electrolytic copper, pure iron, lead ingots, electrolytic nickel, zinc ingots, cu-S intermediate alloy and Cu-P intermediate alloy, electrolytic manganese is prepared according to the required components of the alloy, and the raw materials are added into a smelting furnace for smelting, wherein the smelting temperature is 1100-1270 ℃.
2) Semi-continuous casting: the casting temperature is 1180-1230 ℃, the water inlet temperature of cooling water is 21 ℃, the cooling water pressure is 410kpa, and the primary cooling water flow is 15m 3 The flow rate of secondary cooling water is 7m 3 L, draw casting speed: when in casting, 75mm/min, the length of the red ingot zone of the ingot casting at the outlet of the crystallizer is controlled to be 100-130mm, and the specification of the ingot casting is phi 195mm multiplied by 600mm.
3) And (3) water seal extrusion: the extrusion temperature is 910 ℃, the specification of an extrusion blank is phi 18mm, the extrusion ratio is 148, the extrusion speed is 9mm/s, the surface temperature of the extrusion blank is 720-780 ℃ when the extrusion blank is just extruded from a die, and the extrusion blank is immediately fed into a water seal groove for on-line solid solution, and the water temperature is 24-50 ℃.
4) First-pass disc stretching: the phi 18mm extruded blank is stretched to phi 12mm through multiple passes, and the total processing rate is 43.7%.
5) On-line solid solution: the online solid solution temperature of the phi 12mm wire blank is 740 ℃, the solid solution time is 4.5min, and the water temperature of the cooling water tank is 21-35 ℃.
6) Second disc stretching: the phi 12mm wire blank after solution treatment is stretched to phi 6.6mm through multiple passes, and the total processing rate is 69.7%.
7) Aging annealing: the ageing temperature of phi 6.6mm is 370 ℃, the heating time is 1h, the heat preservation time is 3h, and the steel is discharged after being cooled to below 60 ℃.
8) And (3) joint drawing: the aged phi 6.6mm hard wire blank is subjected to drawing, straightening and sizing sawing on a combined drawing machine set to form a phi 6.39mm multiplied by 2500mm copper bar, the total drawing processing rate is 6.3%, and the straightness of the bar is 0.2mm/m.
9) And (3) checking: and detecting indexes such as tensile strength, elongation, straightness and surface quality of the finished bar, and the obtained golden phase diagram is shown in figure 1.
Example 2
The embodiment provides a specification ofThe preparation method of the high-strength free-cutting iron bronze bar comprises the following steps:
1) Smelting: raw materials are electrolytic copper, pure iron, lead ingots, electrolytic nickel, zinc ingots, cu-S intermediate alloy and Cu-P intermediate alloy, electrolytic manganese is prepared according to the required components of the alloy, and the raw materials are added into a smelting furnace for smelting, wherein the smelting temperature is 1115-1245 ℃.
2) Semi-continuous casting: casting temperature is 1190-1230 ℃, cooling water inlet temperature is 26 ℃, cooling water pressure is 345kpa, primary cooling water flow rate is 12m3/L, secondary cooling water flow rate is 5m3/L, and casting speed is high: during the casting, the length of the red ingot zone of the ingot casting at the outlet of the crystallizer is controlled to be 85-110mm, and the specification of the ingot casting is phi 145mm multiplied by 500mm.
3) And (3) water seal extrusion: the extrusion temperature is 890 ℃, the specification of an extrusion blank is phi 14mm, the extrusion ratio is 107, the extrusion speed is 10.2mm/s, the surface temperature of the extrusion blank is 700-770 ℃ when the extrusion blank is just extruded from a die, and the extrusion blank immediately enters a water seal groove to be in solid solution on line, and the water temperature is 24-50 ℃.
4) First-pass disc stretching: the phi 14mm extruded blank is stretched to phi 9mm through multiple passes, and the total processing rate is 58.7%.
5) On-line solid solution: the online solid solution temperature of the phi 9mm wire blank is 720 ℃, the solid solution time is 4min, and the water temperature of the cooling water tank is 23-33 ℃.
6) Second disc stretching: the phi 9mm wire blank after solution treatment is stretched to phi 4.2mm through multiple passes, and the total processing rate is 78.2%.
7) Aging annealing: the ageing temperature of phi 4.2mm is 340 ℃, the heating time is 1h, the heat preservation time is 3.5h, and the steel is discharged after the temperature is reduced to below 60 ℃.
8) And (3) joint drawing: the aged phi 4.2mm hard wire blank is subjected to drawing, straightening and sizing sawing on a combined drawing machine set to form a phi 4mm multiplied by 2000mm copper bar, the total drawing processing rate is 9.3%, and the straightness of the bar is 0.15mm/m.
9) And (3) checking: and detecting indexes such as tensile strength, elongation, straightness and surface quality of the finished bar.
Example 3
The embodiment provides a specification ofThe preparation method of the high-strength free-cutting iron bronze bar comprises the following steps:
1) Smelting: raw materials are electrolytic copper, pure iron, lead ingots, electrolytic nickel, zinc ingots, cu-S intermediate alloy and Cu-P intermediate alloy, electrolytic manganese is prepared according to the required components of the alloy, and the raw materials are added into a smelting furnace for smelting, wherein the smelting temperature is 1130-1300 ℃.
2) Semi-continuous casting: casting temperature is 1170-1220 ℃, cooling water inlet temperature is 27 ℃, cooling water pressure is 450kpa, primary cooling water flow is 16m3/L, secondary cooling water flow is 9m3/L, and casting speed is high: during the casting, the length of the red ingot zone of the ingot casting at the outlet of the crystallizer is controlled to be 100-140mm, and the specification of the ingot casting is phi 245mm multiplied by 700mm.
3) And (3) water seal extrusion: the extrusion temperature is 930 ℃, the specification of an extrusion blank is phi 32mm, the extrusion ratio is 58.6, the extrusion speed is 6.5mm/s, the surface temperature of the extrusion blank is 740-800 ℃ when the extrusion blank is just extruded from a die, the extrusion blank immediately enters a water seal groove for online solid solution, and the water temperature is 28-50 ℃.
4) First-pass disc stretching: the phi 32mm extruded blank is stretched to phi 26mm through multiple passes, and the total processing rate is 34%.
5) On-line solid solution: the online solid solution temperature of the phi 26mm wire blank is 770 ℃, the solid solution time is 6min, and the water temperature of the cooling water tank is 30-45 ℃.
6) Second disc stretching: the phi 26mm wire blank after solution treatment is stretched to phi 16.3mm through multiple passes, and the total processing rate is 60.7%.
7) Aging annealing: the ageing temperature of phi 16.3mm is 370 ℃, the heating time is 1h, the heat preservation time is 3h, and the product is discharged after the temperature is reduced to below 60 ℃.
8) And (3) joint drawing: the aged phi 16.3mm hard wire blank is subjected to drawing, straightening and sizing sawing on a combined drawing machine set to form a phi 16mm multiplied by 3000mm copper bar, the total drawing processing rate is 3.6%, and the straightness of the bar is 0.35mm/m.
9) And (3) checking: and detecting indexes such as tensile strength, elongation, straightness and surface quality of the finished bar.
Comparative example 1
The commercial alloy mark is QFE2.5, and the specification isThe alloy compositions of the iron bronze bars are shown in Table 1, and the processed copper scraps of the bars are shown in FIG. 4.
Comparative example 2
Pb was not added, and the other components were the same as in example 1, except that the effect of addition of Pb on machinability of the bronze was compared, and Pb was an impurity in Table 1.
Comparative example 3
Mn and S elements were not added, and the other elements were the same as in example 1, in order to compare the influence of addition of Mn and S elements on the machinability of the iron bronze, and Mn and S elements in Table 1 were impurities.
Comparative example 4
The other elements were the same as in example 1 except that no Ni element was added, and the effect of the addition of Ni element on the machinability of the iron bronze was compared, and in table 1, ni element was an impurity.
Comparative example 5
In the case of drawing casting, the length of the ingot casting red ingot zone at the outlet of the crystallizer is less than 10mm, and the rest is the same as in example 1, so as to compare the influence on the mechanical property and the cutting processability of the iron bronze when the red ingot zone hardly appears in casting.
Comparative example 6
During the drawing casting, the length of the ingot casting red ingot zone at the outlet of the crystallizer reaches more than 500mm, and the rest is the same as the embodiment 1, so as to compare the influence of the casting time on the mechanical property and the cutting processing property of the iron bronze.
Comparative example 7
The second disc drawing had a total working ratio of 30% and the rest was the same as in example 1, with the aim of comparing the effect of the working ratio on the mechanical properties and machinability of the bronze before aging.
Comparative example 8
The aging temperature was 450 ℃, and the rest was the same as in example 1, in order to compare the influence of the working ratio before aging on the mechanical properties and machinability of the bronze.
Comparative example 9
The total machining rate of combined drawing is 18%, and the purpose is to compare the influence of the finished drawing machining rate after aging on the mechanical property and the cutting machining property of the iron bronze.
The phase area ratio, phase size, and number of phase distributions in the microstructures of 3 examples and 9 comparative examples are recorded in table 2; the tensile strength, elongation, hardness and conductivity were measured and the results are shown in table 3.
Phase ratio, size, number: observing under a scanning electron microscope.
Tensile strength Rm, elongation a11.3: according to GB/T228.1-2021 section 1 Metal tensile test: room temperature test method.
Hardness HV5: according to GB/T4340.1-2009 Vickers hardness test of Metal materials part 1: test methods.
Conductivity of: measured according to GB/T351-2019 method for measuring resistivity of metallic materials.
Cutting performance: through copper scrapsMorphology and cutting index. Copper scraps are collected through a cutting process, the cutting performance is better and worse through the morphology comparison of the copper scraps, C-shaped scraps do not wind a cutter and a workpiece, spiral scraps are easy to wind the cutter and the workpiece, the longer the spiral rolls are, the easier the spiral rolls are wound, and the C-shaped scraps show that the cutting performance is better. As can be seen from fig. 2 and 3, the copper scraps of example 1 were C-type scraps, the copper scraps of qfe2.5 were long spiral scraps, and the cutting force calculated from the cutting force tester was compared with HPb63-3, and then according to the formula:the cutting performance index was obtained and the specific data are shown in table 3.
Table 1 chemical compositions of examples and comparative examples
Table 2 size, number and ratio of each phase of examples and comparative examples
Table 3 tensile strength Rm, hardness HV5, elongation a11.3, conductivity, relative cutting index of examples and comparative examples
As can be seen from table 3:
1) Comparative example 1 is a bar of QFe phi 6.39mm x 2500mm which is commercially available, and although the mechanical properties and the electrical properties meet the index requirements, the relative cutting index is only 25% of the free-cutting brass HPb63-3, which indicates that the existing iron bronze bar in the market has poor cutting processability.
2) Comparative example 2 was free of Pb element, and even though brittle MnS phase was present, the relative cutting index was only 36% of free cutting brass HPb63-3, indicating that the cutting performance of iron bronze was improved by adding only Mn and S elements, but not Pb element, but the relative cutting index was much lower than 60%, and the cutting performance of the material was still poor.
3) Comparative example 3 was free of added Mn and S elements, even though Pb phase was present, the relative cutting index was only 52% of free-cutting brass HPb63-3, indicating that addition of only 0.1-0.5wt% Pb element, without addition of Mn and S elements, forms brittle phase, and the machinability of iron bronze was greatly improved, but the relative cutting index was less than 60%, and the machinability of the material was still poor.
4) Comparative example 4 was free from Ni element, and as apparent from Table 2, since Ni had the effect of refining Pb phase, the Pb phase had a size of 2.8 μm and exceeding 2. Mu.m, and the Pb phase amount was 3722pic/mm in the case where Ni element was not added 3 Below 4000pic/mm 3 As is clear from Table 3, the relative cutting index was 58%, and it was slightly lower than 60%, indicating that Ni element further improved the cutting performance of the material by refining Pb phase.
5) In comparative example 5, the length of the ingot casting red ingot zone at the outlet of the crystallizer is less than 10mm, the precipitated second phase is in dendritic segregation distribution, the precipitated phase is not uniform in subsequent heat treatment, the data in table 2 can be verified that the aging strengthening effect is poor, the tensile strength of the material is 441Mpa, the tensile strength is not up to 450Mpa, the hardness HV5 is 136, and the hardness is not up to 145, which indicates that the length of the ingot casting red ingot zone is too small, and the material strength is not up to the standard.
6) In comparative example 6, the length of the ingot red ingot zone at the outlet of the crystallizer reaches more than 500mm, coarse second phase is easy to form, so that the second phase in the final product is unevenly distributed, the data in table 2 can verify that the strength and cutting performance of the alloy are affected, the tensile strength of the material is 428Mpa, the tensile strength of the material is not 450Mpa, the hardness HV5 is 140 and is not 145, the relative cutting index is only 50 percent and is lower than 60 percent, the length of the ingot red ingot zone is overlong, the strength of the material is not up to the standard, and the cutting performance is poor.
7) In comparative example 7, the total second-pass disc drawing processing rate is 30% or less than 60%, and the data in table 2 shows that the size of the precipitated phase is increased after aging treatment of the material, the reinforcing effect of the precipitated phase is poor, the tensile strength of the material is only 382Mpa, the tensile strength of the material is far less than 450Mpa, the hardness HV5 is 125, the tensile strength is far less than 145, the conductivity is 54.6% or less than 60%, which indicates that the total second-pass disc drawing processing rate is less than 60% and the properties of the material are not up to standard.
8) In comparative example 8, the aging temperature was 450 ℃, the data in Table 2 revealed that the size of the precipitated phase increased, but the number of Pb phases was 2534 only, and less than 4000pic/mm3, and the relative cutting index was 44%, less than 60%, indicating that after the aging temperature exceeded 400 ℃, the Pb phases began to melt and aggregate, the Pb phases grew, the number of Pb distributions decreased, and the machinability of the alloy was deteriorated.
9) In comparative example 9, the joint drawing ratio was 18%, more than 12%, the tensile strength of the material was 430Mpa, not reaching 450Mpa, and the hardness HV5 was 157, more than 145, indicating that after the joint drawing ratio exceeded 12%, the material began to embrittle, and the strength did not rise but rather decreased.
Claims (10)
1. The free-cutting iron bronze alloy is characterized by comprising the following components in percentage by mass: 2-3wt% of Pb, 0.1-0.5wt% of Zn, 0.05-0.3wt% of Ni:0.1-0.4wt%, mn:0.05-0.25wt%, S:0.02-0.1wt%, P:0.01-0.05wt%, the balance being Cu and unavoidable impurities.
2. The free-cutting iron bronze alloy according to claim 1, wherein the microstructure of the free-cutting iron bronze alloy comprises a matrix phase, a strengthening phase, a soft phase and a brittle phase, the matrix phase being an alpha phase, the strengthening phase being alpha-Fe and Fe 3 And P, wherein the soft phase is Pb, and the brittle phase is MnS.
3. The free-cutting iron bronze alloy according to claim 2, wherein the alpha-Fe phase is in the micro-scale of the free-cutting iron bronze alloyThe area ratio of the microstructure is 15-20%, and the Fe 3 The area ratio of the P phase in the microstructure of the free-cutting iron bronze alloy is less than 0.1 percent.
4. The free-cutting iron bronze alloy according to claim 2, wherein the α -Fe phase has a size of < 15nm; the Fe is 3 The P phase is short bar-shaped Fe 3 P-phase and bulk Fe 3 P phase, the short rod-shaped Fe 3 The P phase quantity is Fe 3 The P phase is more than 90%, and the short rod-shaped Fe 3 The length of the P phase in the long axis direction is less than 20nm, and the length of the P phase in the short axis direction is less than 10nm.
5. The free-cutting iron bronze alloy according to claim 2, wherein the area ratio of the Pb phase to the microstructure of the free-cutting iron bronze alloy is 0.1-0.5%, and the area ratio of the MnS phase to the microstructure of the free-cutting iron bronze alloy is 0.01-0.2%.
6. The free-cutting iron bronze alloy according to claim 2, wherein the Pb phase has a size of less than 2. Mu.m, and the Pb distribution amount is not less than 4000pic/mm 3 。
7. The free-cutting iron bronze alloy according to claim 2, characterized in that the MnS phase size is < 100nm.
8. The free-cutting iron bronze alloy according to claim 1, wherein the average grain size of the free-cutting iron bronze according to the present invention is 20 μm or less.
9. A method of producing a free-cutting iron bronze alloy as claimed in any one of claims 1 to 8, characterised in that the process flow comprises: batching, smelting, semi-continuous casting, water seal extrusion, first-pass disc stretching, online solid solution, second-pass disc stretching, aging annealing and combined drawing;
wherein, the batching is to batching the raw materials according to the mass percent of the free-cutting iron bronze alloy;
in the semi-continuous casting process, the length of an ingot casting red ingot zone at the outlet of the crystallizer is 80-150mm;
the aging annealing temperature is 330-400 ℃, the heating time is 1-2h, and the heat preservation time is 2-4h.
10. The method for producing a free-cutting iron bronze alloy according to claim 9, wherein the water seal extrusion is followed by solid solution, the surface solid solution temperature of the extruded blank after the water seal extrusion is 700-800 ℃, and the water temperature at the solid solution is < 50 ℃.
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