CN108796357B - Preparation method of composite material containing nodular cast iron - Google Patents
Preparation method of composite material containing nodular cast iron Download PDFInfo
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- CN108796357B CN108796357B CN201810765252.1A CN201810765252A CN108796357B CN 108796357 B CN108796357 B CN 108796357B CN 201810765252 A CN201810765252 A CN 201810765252A CN 108796357 B CN108796357 B CN 108796357B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C37/00—Cast-iron alloys
- C22C37/10—Cast-iron alloys containing aluminium or silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/006—Making ferrous alloys compositions used for making ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/08—Making cast-iron alloys
- C22C33/10—Making cast-iron alloys including procedures for adding magnesium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C37/00—Cast-iron alloys
- C22C37/04—Cast-iron alloys containing spheroidal graphite
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
- C23C4/11—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/129—Flame spraying
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
Abstract
The invention discloses a preparation method of a composite material containing nodular cast iron, which comprises the following steps: designing components of an oxide mixed raw material; grinding the mixed oxide raw material to respectively prepare a fine-grain oxide raw material and a coarse-grain oxide raw material; designing chemical components of the nodular cast iron; and step four, mixing the raw materials of the nodular cast iron, smelting by using an induction furnace to prepare a nodular cast iron part, spraying the coarse-grained oxide raw material and the fine-grained oxide raw material to the surface of the nodular cast iron in sequence by using supersonic flame spraying when the part is molded and cooled to 500-600 ℃, preserving heat for 0.5-1h, and sintering at 950-980 ℃ for 2-4h to obtain the required composite material. According to the invention, the composition of the raw material of the oxide protective layer and the chemical composition of the nodular cast iron are improved, so that the oxide protective layer and the nodular cast iron can form a tightly combined composite material, the grade of surface protection of the nodular cast iron is improved, and the service life of the nodular cast iron is greatly prolonged.
Description
Technical Field
The invention belongs to the field of metal composite materials, and particularly relates to a preparation method of a composite material containing nodular cast iron.
Background
The cast iron is an iron-carbon alloy and is characterized by high carbon content, more than 2% of carbon element by mass and more impurity elements such as silicon, manganese, phosphorus, sulfur and the like. Carbon is present in cast iron mostly as carbides or free graphite, and a very small amount thereof is dissolved in ferrite. The graphite lattice type in the cast iron is a simple hexagonal lattice, the atomic distance in the basal plane is 0.142nm, the bonding force is strong, but the surface distance between the two basal planes is 0.340nm, the bonding force is weak, so the basal plane of the graphite is easy to slide, the strength, the hardness, the plasticity and the toughness are extremely low, and the graphite often exists in a sheet shape. The graphite in the nodular cast iron is spherical, the strength and the toughness of the nodular cast iron are higher than those of other cast irons such as gray cast iron, the nodular cast iron has excellent castability, high damping performance and good machinability, and compared with steel with similar performance, the nodular cast iron has relatively low price, so that the nodular cast iron is widely applied to industry, wear-resistant parts such as crankshafts, camshafts, hot rolls and the like are usually made of the nodular cast iron, and the dosage of the nodular cast iron is the second place of all metal materials in the manufacturing industry. Ductile iron, also known as ductile iron, has graphite that acts as a crack stopper, giving it excellent properties of human and ductility. The diversity of the nodular cast iron makes the nodular cast iron suitable for more applications and is considered as a substitute of steel, but the strength of the iron matrix is discontinuous because the spheroidal graphite is embedded in the iron matrix, and the spheroidal graphite is a crack source under impact load, so that the matrix is easy to crack.
Although the nodular cast iron material has corresponding advantages and disadvantages, the nodular cast iron material has outstanding advantages of iron nature, steel performance, excellent corrosion resistance and good ductility, still obtains very wide application in the industrial field, is the first choice of metal material superior to plastic pipelines particularly in the pipeline transportation field, and has superior cost performance from the aspects of installation convenience and maintenance cost. Ductile iron materials also have the common disadvantage of ferrous materials-the surface is gradually eroded as the service life progresses. At present, the cement mortar coating or the high-molecular protective coating is mostly used for corrosion prevention of ductile iron pipeline materials. Although the protection methods in the prior art are applied more frequently, the problems of the binding force between the protective layer and the nodular iron castings and the reduction of the protective capability of the protective layer along with the use time still exist, and no effective method for solving the problems exists so far.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a method for protecting the surface of a nodular cast iron product by using an oxide protective layer, and provides a preparation method of a composite material containing nodular cast iron. The technical effect to be achieved by the invention is realized by the following scheme:
the preparation method of the composite material containing the nodular cast iron comprises the following steps:
designing the components and mass percentages of the oxide mixed raw materials as follows: ZrO (ZrO)215-18%、HfO23-5%、Cr2O31-2%、SiO214-16%、MnO23-7%, BaO0.5-0.9%, CuO0.1-0.3%, and the restIs Al2O3；
Grinding the mixed oxide raw material to respectively prepare a fine-grain oxide raw material with the average grain size of 0.05-0.1 mu m and a coarse-grain oxide raw material with the average grain size of 1-2 mu m;
step three, designing the ductile cast iron to have the following chemical components in percentage by mass: 3.85-3.92% of C, 1.5-1.7% of Si, 0.55-0.60% of Mn, less than or equal to 0.02% of P, less than or equal to 0.02% of S, less than or equal to 0.02% of Cr, 0.015-0.023% of B, 0.3-0.5% of Mo0.3, 0.7-0.9% of Cu0.02-0.03% of Mg, 1.0-1.15% of Ni1.03, 0.03-0.045% of V, and the balance of Fe and inevitable impurities; the raw materials of the nodular cast iron mainly adopt pig iron and scrap steel, and the rest raw materials adopt ferromolybdenum, red copper, ferrochromium, ferromanganese and ferrovanadium;
and step four, mixing the raw materials of the nodular cast iron, smelting by using an induction furnace to prepare a nodular cast iron part, spraying the coarse-grained oxide raw material and the fine-grained oxide raw material to the surface of the nodular cast iron in sequence by using supersonic flame spraying when the part is molded and cooled to 500-600 ℃, preserving heat for 0.5-1h, and sintering at 950-980 ℃ for 2-4h to obtain the required composite material.
The technical route of the invention is as follows: the nodular cast iron with high surface energy is designed, and then the oxide protective layer is sprayed on the surface of the nodular cast iron material, so that the nodular cast iron material and the oxide protective layer are tightly combined to form a new composite material. The oxide composition used in the present invention is Al2O3Mainly of mixed oxides of Al only2O3The raw material as the oxide protective layer has been proved in practice to have poor adhesion to the surface of the nodular cast iron and high sintering temperature, and the change of the internal structure of the nodular cast iron is easily caused during the sintering of the oxide layer to cause adverse effects. In the present invention, Al is contained in2O3On the basis of the mixed solution, ZrO with higher transparency is added2And HfO adapted thereto2Zr and Hf are elements of the same group and have similar atomic structures, and atoms can be mutually filled to form a close-packed structure in the oxide sintering process to improve the compactness of an oxide layer. At the same time, Cr2O3、MnO2Can effectively reduce the sintering temperature, SiO2Not only does BaO and CuO be mixed and addedThe sintering temperature can be reduced and the oxide layer can be more tightly adhered to the surface of the nodular cast iron. It should be noted that the composition and amount of the oxide layer should be strictly controlled, and that no single component or multiple component changes can bring about the technical effects of the present invention.
The invention also improves the chemical components of the nodular cast iron, so that the nodular cast iron material is more corrosion-resistant and has higher surface energy, and can be more suitable for being used as a raw material in a composite material. Firstly, components of the nodular cast iron are adaptively blended. In order to obtain a suitable ductile iron structure, it is necessary to select and add suitable elements. In the invention, Si, Mn, Mo, Cu and Ni are selected as main alloy addition elements, and a small amount of B, Mg and V are doped at the same time, and further, the content of P, S, Cr is controlled. In the main alloy additive elements, proper amount of Si and Ni can jointly influence the graphitization process in the nodular cast iron smelting process, the critical temperature of austenite transformation can be reduced, the austenite area is enlarged, the carbon content of a eutectoid point can be reduced, and the effects of strong stability and pearlite refinement are achieved. The Cu can promote graphitization during eutectic transformation, the critical temperature of austenite transformation is reduced, the formation of pearlite is promoted, the formation of free cementite is reduced or eliminated, the toughness of the nodular cast iron is improved, the pearlite can be obviously refined by the Mo, the strength and the hardenability of the nodular cast iron are improved, and the pearlite and ferrite in the pearlite can be simultaneously strengthened and refined by the cooperation of the Cu and the Mo, so that the strength and the hardness of the nodular cast iron are obviously improved. It is obvious from actual production that B, Mg and V are solid-dissolved in the microstructure of the nodular cast iron to improve the wear resistance and hardenability of the nodular cast iron, but the addition amount is not excessive, especially the content of B is strictly controlled within the range of 0.015-0.023%, otherwise, the comprehensive mechanical property of the nodular cast iron is adversely affected, and the macroscopic toughness is reduced in a cliff-off manner.
Further, in the second step, the particles having a particle size of 0.05 to 0.08 μm in the fine-grained oxide raw material account for 95% or more of the total amount of the fine-grained oxide raw material.
Further, in the second step, the coarse oxide raw material contains particles having a particle size of 1.5 to 1.8 μm in an amount of 95% or more of the total amount of the coarse oxide raw material.
The invention adopts a supersonic flame spraying process to coat an oxide layer on the surface of the nodular cast iron to form the composite material. Different from one-time spraying in the prior art, the method adopts a two-time spraying process, and the oxide raw material particles sprayed twice are arranged differently, the coarse-grain oxide raw material is firstly coated on the surface of the nodular cast iron, the fine-grain oxide raw material is coated on the surface of the nodular cast iron to fill the gap in the coarse-grain oxide layer, two oxide layers form a compact oxide protective layer, and the coating force in the spraying process of the second oxide layer effectively deepens the degree of the combination of the oxide material contacted with the nodular cast iron and the oxide material.
Further, in the third step, the nodulizer used for smelting the nodular cast iron is FeSiMg8Re7, and the adding method of the nodulizer is an impact method.
Furthermore, the addition amount of the nodulizer is 1.5-1.7% of the mass of the nodular cast iron raw material.
Further, in the fourth step, the smelting temperature of the nodular cast iron is 1480-1500 ℃.
Further, in the fourth step, the thickness of the oxide sintered layer is 500-.
Further, in the fourth step, the amount of the fine oxide raw material is 1.1 to 1.2 times the amount of the coarse oxide raw material. The proportion of the amount of the fine-grained oxide raw material to the amount of the coarse-grained oxide raw material is preferably controlled to be 1.1-1.2, and the most compact oxide protective layer can be prepared.
The invention has the following advantages:
the invention provides a method for protecting the surface of a nodular cast iron product by using an oxide protective layer, and provides a preparation method of a composite material containing nodular cast iron. According to the invention, the composition of the raw material of the oxide protective layer and the chemical composition of the nodular cast iron are improved, so that the oxide protective layer and the nodular cast iron can form a tightly combined composite material, the grade of surface protection of the nodular cast iron is improved, the service life of the nodular cast iron is greatly prolonged, and the composite material containing the nodular cast iron is particularly suitable for the anti-corrosion design of an industrial infusion pipeline.
Detailed Description
The present invention will be described in detail with reference to examples.
Firstly, preparing nodular cast iron, namely, utilizing pig iron and scrap steel, and adopting ferromolybdenum, red copper, ferrochromium, ferromanganese and ferrovanadium to cast the rest, wherein the raw materials are all commercially available materials, and the mass ratio of the pig iron to the scrap steel is 8: 1.
the casting method of the nodular cast iron part comprises the following steps:
selecting corresponding raw materials according to component design, smelting the raw materials by using a medium-frequency induction furnace, and smelting the raw materials into molten liquid at the temperature of 1480-1500 ℃ (in the embodiment of the invention, a 50kg medium-sized smelting furnace is adopted, induction furnaces of different models can be correspondingly adopted for smelting in production or other tests, and the temperature control is within the smelting temperature range); the casting ladle is dried by adopting a flushing method, a FeSiMg8Re7 nodulizer is put into the casting ladle, the adding amount of the nodulizer is 1.7 percent of the mass of the nodular cast iron raw material, then ferrosilicon FeSi90Al1.5 powder with the average particle size of 1mm is covered on the surface of the casting ladle, after the smelting is finished, when the temperature test result of the raw material melt exceeds 1480 ℃, 80 percent of the melt is flushed into the casting ladle immediately, and the rest raw material melt is flushed after the spheroidization reaction is finished.
In this step, other commercially available and compatible nodulizers can be used as the nodulizer, and the addition amount can be adaptively adjusted according to the change of the actual situation. The type and amount of the covering agent ferrosilicon alloy can be adjusted adaptively according to actual conditions, and preferably one or more of FeSi90Al1.5, FeSi75Al0.5-A, FeSi75Al0.5-B, FeSi75Al1.5-A, FeSi75Al1.5-B, FeSi65 and FeSi 45. After the steps are finished, adding CBSALLOY inoculant accounting for 0.6 percent of the mass of the raw materials for primary inoculation, discharging from a furnace at 1460 ℃ for pouring, wherein the pouring temperature is 1420 ℃, and preparing the nodular cast iron finished piece. The inoculant particle size used in this step was 0.1 mm. In the manufacturing method of the nodular cast iron, the process steps provided by professional terms are taken as the prior art, such as the 'punching method' and inoculation in the nodular cast iron casting process are all descriptions of cast iron processing processes in the prior art, and the prior art is not taken as the invention point of the invention, so that the detailed description is omitted, but the basis for the lack of necessary technical characteristic description in the invention is not taken as the basis.
The casting method is utilized to prepare 10 batches of nodular cast iron pipe fittings, the length of each pipe fitting is 20cm, the outer diameter of each pipe fitting is 4.5cm, and the inner diameter of each pipe fitting is 3 cm. The measurement results of the element content by using an oxygen-nitrogen analyzer and an ICP emission spectrometer are as follows (the test results are the mass percentages of the corresponding elements):
and spraying an oxide layer on the obtained nodular cast iron pipe fitting, and specifically comprises the following steps:
① the component and mass percentage of the mixed raw material of the designed oxide are ZrO216.4%、HfO24.2%、Cr2O31.6%、SiO215%、MnO25%, BaO0.8%, CuO0.22%, and the balance of Al2O3。
② grinding the mixed raw material of oxides to produce a fine raw material of oxides having an average particle size of 0.06 μm and a coarse raw material of oxides having an average particle size of 1.4 μm, wherein particles having a particle size of 0.05 to 0.08 μm in the fine raw material of oxides account for more than 95% of the total amount of the fine raw material of oxides and particles having a particle size of 1.5 to 1.8 μm in the coarse raw material of oxides account for more than 95% of the total amount of the coarse raw material of oxides.
After the casting of the nodular cast iron pipe fitting is finished, when the pipe fitting is molded and cooled to 550 ℃, the coarse-grained oxide raw material and the fine-grained oxide raw material are sequentially sprayed on the surface of the nodular cast iron by supersonic flame spraying, the temperature is kept for 1h, and the whole body is sintered for 2.5h at 962 ℃ to obtain the required composite material. In this step, the amount of the fine oxide raw material was 1.2 times the amount of the coarse oxide raw material, and the thickness of the oxide sintered layer was 1000 μm. The prepared oxide layer is compact and is tightly attached to the nodular cast iron pipe fitting. The composite materials prepared from the 10 batches of pipe fittings are randomly extracted for each batch, 10PCS in total are 100 PSCs, and the PSCs are placed in a salt spray test box for neutral salt spray test, wherein the test result is as follows: after the test is over 10000h, the nodular cast iron with the oxide protective layer has no change, and the nodular cast iron matrix and the oxide layer have no separation phenomenon, but the nodular cast iron pipe fittings which are obtained in the embodiment which is compared with the nodular cast iron pipe fittings and are not protected by the oxide layer have obvious corrosion signs, the corrosion rate reaches 0.24 mm/year, and the corrosion rate of a comparison group which adopts the commercially available nodular cast iron pipe fittings is higher than 1.21 mm/year.
According to the embodiment, the composition of the raw materials of the oxide protective layer and the chemical composition of the nodular cast iron are improved, so that the raw materials and the chemical composition of the nodular cast iron can form a tightly combined composite material, the grade of surface protection of the nodular cast iron is improved, the service life of the nodular cast iron is greatly prolonged, and the composite material containing the nodular cast iron is particularly suitable for the anti-corrosion design of an industrial infusion pipeline.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the embodiments of the present invention and not for limiting the same, and although the embodiments of the present invention are described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the embodiments of the present invention, and these modifications or equivalent substitutions cannot make the modified technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. A preparation method of a composite material containing nodular cast iron is characterized by comprising the following steps:
designing the components and mass percentages of the oxide mixed raw materials as follows: ZrO (ZrO)215-18%、HfO23-5%、Cr2O31-2%、SiO214-16%、MnO23-7%, BaO0.5-0.9%, CuO0.1-0.3%, and the rest isAl2O3；
Grinding the mixed oxide raw material to respectively prepare a fine-grain oxide raw material with the average grain size of 0.05-0.1 mu m and a coarse-grain oxide raw material with the average grain size of 1-2 mu m;
step three, designing the ductile cast iron to have the following chemical components in percentage by mass: 3.85-3.92% of C, 1.5-1.7% of Si, 0.55-0.60% of Mn, less than or equal to 0.02% of P, less than or equal to 0.02% of S, less than or equal to 0.02% of Cr, 0.015-0.023% of B, 0.3-0.5% of Mo0.3, 0.7-0.9% of Cu0.02-0.03% of Mg, 1.0-1.15% of Ni1.03, 0.03-0.045% of V, and the balance of Fe and inevitable impurities; the raw materials of the nodular cast iron mainly adopt pig iron and scrap steel, and the rest raw materials adopt ferromolybdenum, red copper, ferrochromium, ferromanganese and ferrovanadium;
and step four, mixing the raw materials of the nodular cast iron, smelting by using an induction furnace to prepare a nodular cast iron part, spraying the coarse-grained oxide raw material and the fine-grained oxide raw material to the surface of the nodular cast iron in sequence by using supersonic flame spraying when the part is molded and cooled to 500-600 ℃, preserving heat for 0.5-1h, and sintering at 950-980 ℃ for 2-4h to obtain the required composite material.
2. The method of preparing a composite material comprising ductile iron according to claim 1, wherein: in the second step, the fine oxide raw material contains particles having a particle size of 0.05 to 0.08 μm in an amount of 95% or more of the total amount of the fine oxide raw material.
3. The method of preparing a composite material comprising ductile iron according to claim 1, wherein: in the second step, the coarse-grained oxide raw material contains particles with a particle size of 1.5-1.8 μm accounting for more than 95% of the total amount of the coarse-grained oxide raw material.
4. The method of preparing a composite material comprising ductile iron according to claim 1, wherein: in the fourth step, the nodulizer used for smelting the nodular cast iron is FeSiMg8Re7, and the adding method of the nodulizer is a flushing method.
5. The method of preparing a composite material comprising ductile iron according to claim 4, wherein: the addition amount of the nodulizer is 1.5-1.7 percent of the mass of the nodular cast iron raw material.
6. The method of preparing a composite material comprising ductile iron according to claim 1, wherein: in the fourth step, the smelting temperature of the nodular cast iron is 1480-1500 ℃.
7. The method of preparing a composite material comprising ductile iron according to claim 1, wherein: in the fourth step, the thickness of the oxide sintered layer is 500-2000 μm.
8. The method of preparing a composite material comprising ductile iron according to claim 1, wherein: in the fourth step, the dosage of the fine-grained oxide raw material is 1.1-1.2 times of the dosage of the coarse-grained oxide raw material.
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