CN1219087C - Graphite spheroidizing process for ternary Ni-Cu-graphite alloy - Google Patents
Graphite spheroidizing process for ternary Ni-Cu-graphite alloy Download PDFInfo
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- CN1219087C CN1219087C CN 03125266 CN03125266A CN1219087C CN 1219087 C CN1219087 C CN 1219087C CN 03125266 CN03125266 CN 03125266 CN 03125266 A CN03125266 A CN 03125266A CN 1219087 C CN1219087 C CN 1219087C
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Abstract
The present invention discloses a spheroidizing process for graphite in a ternary Ni-Cu-graphite alloy. A smelting process is adopted to prepare a solid self-lubricating material in ternary Ni-Cu-graphite series, which has high elongation rate and plasticity and is molded by processing, and a traditional rare earth-magnesium spheroidizing agent for industrial service is used to realize the spheroidization of graphite in a ternary Ni-Cu-graphite alloy; research indicates that the spheroidized graphite is round and fine, and is uniformly distributed in an alloy basal body; when worn by the dry friction of No. 45 annealed steel and GCr15 bearing steel, a spheroidized material has more stable frictional property than a material which is not spheroidized, and has greater reduction in the friction coefficient of wear by dry friction than soft No. 45 annealed steel; after being spheroidized, the Ni-Cu-graphite alloy has high elongation rate and reduced resistivity, and the elongation rate of a profile tensile specimen reaches 10.3 to 20.2%; in addition, the spheroidized Ni-Cu-graphite alloy can be pressed into a V shape without brittle fracture in a three point bending test.
Description
Technical field: the present invention relates to the nodulizing process of graphite in a kind of Ni-Cu-graphite ternary alloy, be applicable to chemical machinary material and high-temperature engine material in the self-lubricating bearing material of in high temperature oxidation and corrosive environment, working, conduction sliding material, pyrometallurgy mechanical material, the corrosive environment.
Technical background: for a long time, people have done a large amount of research work to the spheroidizing of graphite in the cast iron, have obtained the nodular cast iron alloy of excellent property.Graphite owing to weakened the flake graphite tip to the isolating and stress concentration effect of material matrix, makes the toughness of cast iron to be improved after spheroidizing, is widely used in the every field in the industrial production.Cast iron is being carried out in the research of spheroidizing, rare earth element (as Ce etc.), metal M g, Ca have been found and by multiple elementary composition mishmetal magnesium alloy, can make cast iron in process of setting, make flake graphite crystalline transition glomeration graphite crystallization wherein.Ni-Cu-graphite high temperature self-lubricating composite be the present invention develop a kind of new type high temperature self-lubricating material, under common curing condition, graphite pattern substantially in the form of sheets in its tissue, though originally discover in the Ni-Cu-graphite alloy increase along with constituent element Cu content, graphite has the trend of nodularization gradually, but the form of graphite still is based on sheet or sheet and spherically mixes coexistence, be form and the distribution that further improves graphite, the refinement graphite structure, further improve its self-lubricating property, it is target of the present invention that graphite is carried out spheroidizing.
The objective of the invention is Ni-Cu-graphite high temperature self-lubricating composite to be carried out the spheroidizing of graphite with rare earth magnesium nodularizer, make the flake graphite form in the casting alloy change the globular graphite form into, and the refinement graphite structure, to reach the self-lubricating property that improves material.Employing is used for the rare earth magnesium nodularizer of cast iron any report is not seen in the spheroidizing that graphite in the Ni-Cu-graphite alloy carries out in the process of setting at present.
Summary of the invention the invention provides a kind of spheroidization of graphite treatment process of high temperature Ni-Cu-graphite self-lubricating material to achieve these goals, it is characterized in that: 1. the material component proportioning is Ni-(0～50) wt%Cu-3.5wt%C.2. adopt rare earth magnesium nodularizer that the graphite in solidifying is carried out spheroidizing, the composition proportion of rare earth magnesium nodularizer sees Table 1.3. adopt smelting process to be prepared, its step is as follows: 1. adopt vacuum Medium frequency induction melting method, heating crucible is a plumbago crucible in the stove, 2. the adding method of raw material is as follows: will claim the Graphite Powder 99 for preparing to be positioned over the bottom of smelting pot earlier, the Ni piece for preparing is placed on it, the Cu piece for preparing is placed on respectively in the different feed hoppers with rare earth magnesium nodularizer, to be added.3. first to extracting rough vacuum to 1.25 * 10 in the stove before melting
-1Pa; charging into argon gas to 1 normal atmosphere then protects; 4. heat smelting temperature and be higher than 1650 ℃; to temperature back insulation 5-10 minute; from feed hopper, metal Cu piece is added in the molten metal, to temperature back insulation 3 ~ 10 minutes, treat that 5. the gentle boil phenomenon appears in molten metal after; to claim the rare earth magnesium nodularizer for preparing to pour into the liquid metal liquid from loading hopper, the add-on of nodulizing agent be the 0.75wt% of alloy gross weight.Behind 0.8 ~ 1.5 minute spheroidizing reacion, 6. powered-down, treat the metal calmness after, immediately liquid alloy is poured in the casting mold.
The composition of table 1 rare earth magnesium nodularizer and massfraction
| Element | Massfraction (wt%) | Element | Massfraction (wt%) |
| Mg Al Si Ca Mn | 21.6 2.1 47.2 2.4 0.4 | Fe Cu Ba Ce | 24.2 0.2 1.2 0.7 |
After adopting above-mentioned spheriodizing technique to handle, the graphite rounding is tiny to be distributed in the matrix, the mean diameter of graphite pebbles is 20-30 μ m, the Ni-Cu-graphite alloy has high stretch percentage elongation after spheroidizing, unit elongation has reached 10.3～20.2%, reached for example stretch percentage elongation of steel of industrial structured material, and the common graphitiferous material for preparing with powder metallurgic method is fragility, the all material of being developed is through three point bending test, all can be pressed into V-shape and brittle rupture does not take place, and shows high plasticity, graphite is after spheroidizing, material and softer 45# annealed steel (HRC=28) are to mill, and frictional coefficient significantly reduces, and the resistivity of material decreases.
Description of drawings
Fig. 1. with the Ni-3.5wt% Graphite Binary alloy structure pattern of smelting method for preparing, without spheroidizing, graphite is pattern in the form of sheets.
Fig. 2. use the Ni-3.5wt% Graphite Binary alloy structure pattern of smelting method for preparing equally, the rare earth magnesium nodularizer with 0.75wt% before the casting has carried out spheroidizing.Graphite is spherical pattern.
Fig. 3. use the tissue topography of the Ni-20wt%Cu-3.5wt% graphite ternary alloy of smelting method for preparing, without spheroidizing, graphite is short sheet type looks,
Fig. 4. with the Ni-20wt%Cu-3.5wt% graphite ternary alloy tissue topography of smelting method for preparing, the rare earth magnesium nodularizer with 0.75wt% before the casting has carried out spheroidizing.Graphite is spherical pattern.
The mirco structure pattern of Fig. 5 .Ni-20wt%Cu-3.5wt% graphite ternary alloy after spheroidizing, graphite pebbles rounding and uniform distribution.
Fig. 6. with the tissue topography of the Ni-34wt%Cu-3.5wt% graphite ternary alloy of smelting method for preparing, without spheroidizing, except that flake graphite, part graphite because of the increase that adds the copper amount by nodularization.
Fig. 7. use the tissue topography of the Ni-34wt%Cu-3.5wt% graphite ternary alloy of smelting method for preparing, the rare earth magnesium nodularizer with 0.75wt% before the casting has carried out spheroidizing.Graphite is spherical pattern.
Fig. 8. use the tissue topography of the Ni-50wt%Cu-3.5wt% graphite ternary alloy of smelting method for preparing, without spheroidizing, except that flake graphite, because the further increase of copper content, globular graphite quantity further increases.
Fig. 9. use the tissue topography of the Ni-50wt%Cu-3.5wt% graphite ternary alloy of smelting method for preparing, the graphite mould cast, the rare earth magnesium nodularizer with 0.75wt% before the casting has carried out spheroidizing.Graphite is spherical pattern.
The outward appearance type looks of sample after the plate shape tension specimen stretch broken of Figure 10 .Ni-3.5wt% graphite, Ni-20wt%Cu-3.5wt% graphite, Ni-34wt%Cu-3.5wt% graphite, Ni-50wt%Cu-3.5wt% graphite alloy, unit elongation ε reaches 10.3-20.2%, because deflection is big, the surface is tangible concavo-convex fluctuating shape, show that this material after spheroidizing, has good plasticity.
The high power type looks of Figure 11 .Ni-34wt%Cu-3.5wt% graphite alloy tension specimen surface deformation.Unit elongation is up to 20.2%, and specimen surface has produced significant concavo-convex fluctuating because of a large amount of plastic flows, and plasticity is fine.
Figure 12 .Ni-20wt%Cu-3.5wt% graphite, Ni-34wt%Cu-3.5wt% graphite, Ni-50wt%Cu-3.5wt% graphite alloy are behind the three-point bending performance test, and the distortion pattern of sample all can bend into V-shape and brittle rupture does not take place.
Figure 13. the frictional coefficient curve during with 45# annealed steel dry friction and wear.Curve 1 is the frictional coefficient curve of Ni-20wt%Cu-3.5wt% graphite alloy; Curve 2 is frictional coefficient curves of Ni-3.5wt% graphite alloy; Curve 3 is frictional coefficient curves of Ni-34wt%Cu-3.5wt% graphite alloy; Curve 4 is frictional coefficient curves of Ni-50wt%Cu-3.5wt% graphite alloy.
Figure 14. the friction curve during with GGr15 bearing steel (HRC=58) dry friction and wear.Curve 1 is the frictional coefficient curve of Ni-20wt%Cu-3.5wt% graphite alloy; Curve 2 is frictional coefficient curves of Ni-34wt%Cu-3.5wt% graphite alloy; Curve 3 is frictional coefficient curves of Ni-3.5wt% graphite alloy; Curve 4 is frictional coefficient curves of Ni-50wt%Cu-3.5wt% graphite alloy.
The invention will be further described by embodiment and comparative example below in conjunction with accompanying drawing for embodiment.
The spheroidization of graphite of embodiment 1.Ni-3.5wt% graphite alloy, with the Ni-3.5wt% Graphite Binary alloy structure pattern of described smelting method for preparing, the rare earth magnesium nodularizer with 0.75wt% before the casting has carried out spheroidizing, and graphite is spherical pattern, sees Fig. 2; And, see Fig. 1 without the graphite form in the form of sheets of spheroidizing.
The spheroidization of graphite of embodiment 2.Ni-20wt%Cu-3.5wt% graphite alloy, Fig. 4, Fig. 5 are the Ni-20wt%Cu-3.5wt% graphite ternary alloy tissue topographies with described smelting method for preparing, rare earth magnesium nodularizer with 0.75wt% before the casting has carried out spheroidizing, and graphite is evenly tiny spherical pattern.And, see Fig. 3 without the graphite form in the form of sheets of spheroidizing.
The spheroidization of graphite of embodiment 3.Ni-34wt%Cu-3.5wt% graphite alloy, Fig. 7 is the tissue topography with the Ni-34wt%Cu-3.5wt% graphite ternary alloy of described smelting method for preparing, rare earth magnesium nodularizer with 0.75wt% before the casting has carried out spheroidizing, and graphite is evenly tiny spherical pattern.And, see Fig. 6 without the mainly graphite form in the form of sheets of spheroidizing.
The spheroidization of graphite of embodiment 4.Ni-50wt%Cu-3.5wt% graphite alloy, Fig. 9 is the tissue topography with the Ni-50wt%Cu-3.5wt% graphite ternary alloy of described smelting method for preparing, the graphite mould cast, rare earth magnesium nodularizer with 0.75wt% before the casting has carried out spheroidizing, and graphite is evenly tiny spherical pattern.And without the graphite in the form of sheets and the globular graphite mixed style of spheroidizing, the globular graphite form is also imperfect, sees Fig. 8.
Comparative example
(1) friction and wear behavior.Graphite is after spheroidizing, material and softer 45# annealed steel (HRC=28) are to mill, the frictional coefficient ratio not Ni-Cu-graphite alloy of nodularization significantly reduces, wherein the Ni-3.5wt%C alloy has reduced by 44%, the Ni-20wt%Cu-3.5wt% graphite alloy has reduced by 45%, the Ni-34wt%Cu-3.5wt% graphite alloy has reduced by 11%, and the Ni-50wt%Cu-3.5wt% graphite alloy has reduced by 37%.With harder GCr15 bearing steel the mill frictional coefficient is changed little (see Table 2, table 3 data) than the Ni-Cu-graphite alloy of not nodularization is overall.This mainly be with softer material to when mill, the adhesive wear of storeroom is serious, graphite is more evenly distributed after spheroidizing, and is more tiny, density increases, flour milling is more even, thereby adhesive wear is alleviated.
(2) tensile property.Graphite is after spheroidizing, material of the present invention shows good unit elongation and intensity under stretching condition, the unit elongation of material has reached 10.3～20.2% (seeing Table 2), shows high plasticity, reached of the requirement of industrial structured material, possessed the ability of plastic working moulding plasticity.Figure 10 is that Ni-3.5wt%C, Ni-20wt%Cu-3.5wt% graphite, Ni-34wt%Cu-3.5wt% graphite, Ni-50wt%Cu-3.5wt% graphite alloy are after spheroidizing, outward appearance type looks after its plate shape tension specimen tension fracture, because deflection is big, the surface is tangible deformation of unevenness vestige, this is the sign that has experienced moderate finite deformation, shows that this material has good plasticity.Figure 11 is the high power type looks of Ni-34wt%Cu-3.5wt% graphite alloy tension specimen surface deformation.Unit elongation is up to 20.2%, and plasticity is fine.This mainly be graphite after spheroidizing, weakened the flake graphite tip to the isolating and stress concentration effect of material matrix, make the further distortion of matrix to be guaranteed.Owing to the tiny uniform distribution of graphite after the nodularization, prevented growing up of matrix metal crystal grain simultaneously, the plasticity of material is further improved.All material is through three point bending test, all can be pressed into V-shape and brittle rupture (seeing Figure 12) does not take place, and the mmaterial of common graphitiferous phase and graphitiferous cast iron alloy all is tangible fragility.
(3) conductivity.Graphite is after spheroidizing, the mixed and disorderly flake graphite that distributes becomes the waveform obstruction of globular graphite to electric current to the fold-type obstruction of electric current, the resistivity of material is decreased (see Table 2, table 3), thereby conductivity improve after the nodularization, is more suitable for being used for the electroconductibility self-lubricating material.
Table 2. Ni-Cu-graphite alloy is without the physical parameter of spheroidizing
| Ni-3.5wt% graphite | Ni-20wt%Cu-3.5wt% graphite | Ni-34wt%Cu-3.5wt% graphite | Ni-50wt%Cu-3.5wt% graphite | |
| Electricalresistivity (density (the g/cm of Ω/mm-2m) 3) area percent % hardness (HB) the impelling strength a of graphite k(J/cm 2) three-point bending strength σ bb(MPa) | 2.4 8.25 22.35 90.0 121.8 49. 2 | 5.8 8.47 23.62 97.3 117.5 50.8 | 7.1 8.61 19.37 98.6 110.2 52.5 | 5.3 8.77 15.84 113.6 102.6 65.1 |
The physical parameter of table 3. Ni-Cu-graphite alloy after spheroidizing
| Ni-3.5wt% graphite | Ni-20wt%Cu-3.5wt% graphite | Ni-34wt%Cu-3.5wt% graphite | Ni-50wt%Cu-3.5wt% graphite | |
| Electricalresistivity (Ω/mm -2M) density (g/cm 3) area percent % hardness (HB) tensile strength sigma of graphite b(MPa) unit elongation ε (%) | 2.1 8.25 24.21 89.6 259.5 12.7 | 4.7 8.05 26.09 93.8 225.8 10.33 | 6.8 8.47 22.84 102.8 337.3 20.2 | 5.0 8.64 18.69 98.8 304.5 16.0 |
Table 4. Ni-Cu-graphite series alloy is without the dry friction and wear performance of spheroidizing
| Material | With the frictional coefficient of 45# steel to mill | Frictional coefficient with the GCr15 bearing steel |
| Ni-3.5wt% graphite | 0.25 | 0.15 |
| Ni-20wt%Cu-3.5wt% graphite | 0.20 | 0.12 |
| Ni-34wt%Cu-3.5wt% graphite | 0.18 | 0.16 |
| Ni-50wt%Cu-3.5wt% graphite | 0.35 | 0.25 |
The dry friction and wear performance of table 5. Ni-Cu-graphite series alloy after spheroidizing
| Material | With the frictional coefficient of 45# steel to mill | Frictional coefficient with the GCr15 bearing steel |
| Ni-3.5wt% graphite (nodularization) | 0.14 | 0.15 |
| Ni-20wt%Cu-3.5wt% graphite (nodularization) | 0.11 | 0.13 |
| Ni-34wt%Cu-3.5wt% graphite (nodularization) | 0.16 | 0.14 |
| Ni-50wt%Cu-3.5wt% graphite (nodularization) | 0.22 | 0.22 |
Although the present invention has done detailed explanation and has exemplified out some object lessons; but the present invention is not limited to these scopes, and every employing rare earth magnesium nodularizer is handled the spheroidization of graphite of the Ni-Cu-graphite self-lubricating material of smelting method for preparing and all belonged to protection scope of the present invention.
Claims (1)
1, the nodulizing process of graphite in a kind of Ni-Cu-graphite ternary alloy is characterized in that: the alloy material set of dispense is than being Ni-0～50wt%Cu-3.5wt%C, and nodulizing agent adopts rare earth magnesium nodularizer, and its composition proportion is: 21.6wt%Mg; 2.1wt%Al; 47.2wt%Si; 2.4wt%Ca; 0.4wt%Mn; 24.2wt%Fe; 0.2wt%Cu; 1.2wt%Ba; 0.7wt%Ce, performing step is as follows: 1. adopt vacuum medium frequency induction furnace, heating crucible is a plumbago crucible in the stove; 2. earlier with claiming the Graphite Powder 99 for preparing to be positioned over the bottom of smelting pot, the Ni piece for preparing is placed on it; 3. the Cu piece for preparing is placed on respectively in the different feed hoppers with rare earth magnesium nodularizer, to be added; 4. first to extracting rough vacuum to 1.25 * 10 in the stove before melting
-1Pa charges into argon gas to 1 normal atmosphere then and protects; 5. heat smelting temperature and be higher than 1650 ℃, to temperature back insulation 5-10 minute, from feed hopper, metal Cu piece is added in the molten metal, to temperature back insulation 3～10 minutes; 6. after treating that the gentle boil phenomenon appears in molten metal, will claim the rare earth magnesium nodularizer for preparing to pour into the liquid metal liquid from loading hopper, the add-on of nodulizing agent be the 0.75wt% of alloy gross weight, behind 0.8～1.5 minute spheroidizing reacion; 7. powered-down, treat the metal calmness after, immediately liquid alloy is poured in the casting mold.
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