CN108220755A - A kind of method for preparing zirconium oxide-zirconium carbide particle enhancing gray cast iron - Google Patents
A kind of method for preparing zirconium oxide-zirconium carbide particle enhancing gray cast iron Download PDFInfo
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- CN108220755A CN108220755A CN201810066851.4A CN201810066851A CN108220755A CN 108220755 A CN108220755 A CN 108220755A CN 201810066851 A CN201810066851 A CN 201810066851A CN 108220755 A CN108220755 A CN 108220755A
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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
- C22C37/06—Cast-iron alloys containing chromium
- C22C37/08—Cast-iron alloys containing chromium with nickel
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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
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Abstract
The invention belongs to cast iron materials field, particularly a kind of method for preparing zirconium oxide zirconium carbide particle enhancing gray cast iron.The mixed-powder in activated carbon, graphite, Zirconium oxide powder, petroleum coke (or coal tar), zirconium powder is blown into gray cast iron melt by the mixed gas of carbon dioxide, methane, argon gas and oxygen, enhancing particle is generated by reacting, the present invention is being that generation is reacted in gray cast iron melt because enhancing particle to be, solves the problems such as additional particle is poor with matrix alloy wetability, easily generation interfacial reaction and structure stability is poor.Particle enhancing gray cast iron material can play the advantage of gray cast iron matrix and reinforced phase simultaneously, significantly improve intensity, elasticity modulus, hardness and the wearability of gray cast iron.Particle enhances gray cast iron material because its is of low cost simultaneously, and intensity, rigidity are high, formerly has wide practical use into modern industrial process fields such as manufactures.
Description
Technical field
The present invention relates to a kind of cast iron materials fields, enhance ash more particularly to a kind of zirconium oxide-zirconium carbide particle for preparing
The method of cast iron.
Background technology
Iron-carbon alloy of the phosphorus content more than 2.11% is known as cast iron, and the carbon in gray cast iron is largely or entirely with free state
Flake graphite form, fracture gray has certain mechanical property and good is cut processing performance, extensive use
In industrial production.In order to improve gray cast iron, industrial quarters usually uses inoculation more for improving Mechanical Properties of Grey Cast Iron at present
Come obtain with fine pearlite matrix and fine uniform distribution flake graphite structure, the inoculation cast iron of acquisition can be in gray cast iron
High-strength cast iron is obtained on the basis of existing mechanical property.Recently as the requirement for developing high-end electronic product, to cast iron
The requirement needs of mechanical property further improve, and particle enhancing gray cast iron material can play gray cast iron matrix and reinforced phase simultaneously
Advantage, significantly improve intensity, elasticity modulus, hardness and the wearability of gray cast iron.Particle enhances gray cast iron material because of it simultaneously
Of low cost, intensity, rigidity are high, formerly have wide practical use into modern industrial process fields such as manufactures.
For gray cast iron material, under the premise of high intensity, high rigidity is required；Gray cast iron is required to still maintain fine simultaneously
Damping performance, certain toughness, high hardness and wearability, this for gray cast iron material industrial production extensively using to close
It is important.But the rigidity of gray cast iron material, intensity, hardness and wearability needs further improve at present, so as to reach higher
Intensity and wearability, while further expand gray cast iron application field.
Based on above-mentioned purpose, enhance ash using nontoxic, free of contamination zirconium oxide-zirconium carbide particle is added in gray cast iron
The method of the intensity of cast iron materials, good toughness and hardness.The chemical composition of gray cast iron basis material of the present invention and weight hundred
Point ratio is：C：2.6-3.0, Mn：0.8-1.3, Ni：1-1.5, Cr：0.2-0.4, P：0.01-0.05, S：0.03-0.15, ZrO：
0.2-0.8, Sn：0.01-0.1.The existing gray cast iron in China is 201210329569.3 Hes in number of patent application at present
In 201210404904.1, propose in casting process using the elements such as inoculation or addition rare earth, ash casting can be improved
Toughness, hardness and the wearability of iron material, but to reach higher intensity and wearability, it needs further to be studied.This
Invention proposes a kind of stable processing technology, low production cost, non-pollution discharge, can be produced in conventional melting condition undertissue
Zirconium oxide-zirconium carbide particle enhancing gray cast iron material preparation method, it is the intensity of more traditional gray cast iron material, toughness, hard
Degree and wearability are substantially improved.Therefore, reach enhancing gray cast iron material by adding zirconium oxide-zirconium carbide particle in the present invention
The purpose of mechanical property.
Invention content
The purpose of the present invention is：It is to overcome the above-mentioned prior art insufficient, a kind of stable processing technology, production cost is provided
Cheap, non-pollution discharge, the zirconium oxide-zirconium carbide particle that can be produced in conventional melting condition undertissue enhance gray cast iron material
Preparation method, intensity, toughness, hardness and the wearability of more traditional gray cast iron material are substantially improved.
The technical solution of patent of the present invention is：The present invention is a kind of zirconium oxide-zirconium carbide particle enhancing gray cast iron material
Preparation method is mixed the precursor of zirconium oxide-zirconium carbide particle by the mixed gas of carbon dioxide, methane, argon gas and oxygen
It closes powder to be blown into gray cast iron melt, self-propagating combustion synthetic reaction is generated during being blown into, it is ultra-fine by reacting generation
Zirconium oxide-zirconium carbide enhancing particle, silver powder and copper powders are pressed with the heat-resisting gray cast iron melt of tungsten carbide-SiC particles reinforced
Mass percent is 1:99 ratio is added melting, using mechanization mixing, Metamorphism treatment, refining, cast, obtains
It obtains ingot casting and the zirconium oxide with anti-microbial property-zirconium carbide particle enhancing heat-resistance high-strength is obtained by high pressure torsion severe plastic deformation
Spend gray cast iron material.
Zirconium oxide powder is handled using adding in absolute ethyl alcohol and stirring evenly by sonic oscillation in above-mentioned preparation method
5 minutes-after ten minutes, the active carbon powder of nano-scale is then added in, continues to turn after sonic oscillation is handled -50 minutes 10 minutes
Move on in crucible, then in a vacuum furnace under 1550-1800 DEG C of high-temperature calcination and keep the temperature 3 hours, furnace cooling then grind;Most
The superfine zirconia powder and zirconium carbide mixed-powder particle that average particle size is 40 nanometers -100 nanometers are obtained afterwards.
ZrO2+3C=（Electric furnace）ZrC+2CO↑
The volume proportion of each component is methane in each mixed gas in above-mentioned preparation method（8-45）：Argon gas（8-35）：Oxygen（8-
35）：Carbon dioxide（8-70）；The pressure of mixed gas is 0.05-0.3MPa, gas flow 0.02-0.15m3/min.Dioxy
Change carbon for providing C element, carbon dioxide and oxygen is used to provide O elements.Argon gas is diluent, for reaction speed and
Particle growth rate.
The preparation method of zirconium oxide-zirconium carbide particle enhancing gray cast iron material, 700-800 DEG C of the temperature of gray cast iron melt.
The time of reaction generation enhancing particle is 10-60 minutes, and the time of the higher reaction generation enhancing particle of granule content requirement is longer.
（1）Increased response is mutually the ZrC and ZrO synthesized under melt state2Particle mainly occurs as follows under melt state
Reaction：
CO2+Zr=ZrO2+2[C]
CO2+Zr=ZrC+2[O]
ZrO2+3[C]=ZrC+2CO↑
O2+Zr=ZrO2
C+Zr=ZrC
CH4+Zr=ZrC+2H2
And the reaction of two kinds of products also has decomposition and further reaction between each other, is one and promotes and decompose mutually
Equilibrium process, so as to reach final balanced reaction speed.The size for enhancing particle is 0.1-1 μm.By to reaction time, anti-
Composition of temperature, mixed gas etc. is answered to carry out associated adjustment, the composition of reaction generation enhancing particle can be controlled（ZrC and ZrO2
Ratio）, particle size, quantity and distribution, so as to meet the requirement of different parts.Activated carbon and graphite are used to provide carbon
Element, Zirconium oxide powder are used to provide zirconium carbide and zr element.
The precursor mixing preparation method of zirconium oxide-zirconium carbide particle：By the Zirconium oxide powder of nano-scale, absolute ethyl alcohol
Stirred evenly with the active carbon powder of nano-scale, by sonic oscillation handle -50 minutes 5 minutes after, after be transferred in crucible,
Then in a vacuum furnace under 1550-1800 DEG C of high-temperature calcination and keep the temperature 3 hours, furnace cooling then grind;It finally obtains average
Superfine zirconia powder and the zirconium carbide precursor powder that granularity is 40 nanometers -100 nanometers.Superfine zirconia powder and carbonization
The precursor powder addition of zirconium particle is the 5% of alloy melt weight；
The present invention matrix be using the chemical composition and weight percent of alloy：C：2.6-3.0, Mn：0.8-1.3, Ni：1-
1.5, Cr：0.2-0.4, P：0.01-0.05, S：0.03-0.15, Cu：0.2-0.8, Sn：0.01-0.1.Can by it is above-mentioned into
Divide and alloy melting is required to carry out melting offer.In the melting in resistance heating crucible furnace of gray cast iron basis material, to hot gray cast iron
The silver powder and copper powders added in melt be by the average particle degree that mechanization ball-milling method 24 hours obtains for 40 nanometers-
100 nanometers of particle；Into melting zirconium oxide-zirconium carbide particle enhance added again in heat-resisting gray cast iron material melt silver powder and
The adding proportion of copper powders, wherein silver powder and copper powders is is 50：50, silver powder and copper powders are in zirconium oxide-zirconium carbide
The mass content that grain enhances in heat-resisting gray cast iron material is 1%, and silver powder and copper powders are enhanced with zirconium oxide-zirconium carbide particle
Heat-resisting gray cast iron material melt is 1 by mass percentage:99 ratio is added melting, is mixed, becomes by mechanization
Matter processing, refining, cast obtain zirconium oxide-zirconium carbide particle enhancing gray cast iron material ingot casting.Ingot casting is obtained in 400-500
It DEG C is deformed by high pressure torsion, high pressure torsion machined parameters are：The rotating speed of pressure head is 600rpm, lower pressure is 1.2GPa, test
Show that obtained zirconium oxide-zirconium carbide particle enhances heat-resisting gray cast iron and has high-strength tenacity.Can finally obtain intensity, toughness and
The gray cast iron material that hardness is substantially improved.
The zirconium oxide-zirconium carbide particle enhances gray cast iron material without special equipment（Without vacuum melting furnace, high temperature
The equipment such as high pressure）, can organize to produce in conventional gray cast irons factory, the molten cast iron after melting directly be poured into well prepared in advance
In casting mold, artificial tooth is made after cooling, small investment of the present invention is quick, and can quickly recoup capital outlay cost.
Compared with existing gray cast iron technology, the preparation method of zirconium oxide-zirconium carbide particle enhancing gray cast iron material has such as
Lower advantage：
（1）Wearability, intensity and property significantly improve, and the poor mechanical property for being spaced 2 hours cast samples is less than 6%, this is beneficial to
In high volume, the steady production of small-size materials.It is tiny to enhance particle size, is evenly distributed, structure stability is high, and surface is without dirt
Dye, with being well combined in gray cast iron matrix.The room-temperature mechanical property and wear-resisting property of material significantly improve, and are particularly suitable for material
The application of material, aerospace key components and parts etc..
（2）Structure of cast iron stability is good, will not decompose toxic gas or dissolved matter, is beneficial to the health of customer,
The present invention is being that generation is reacted in gray cast iron melt because enhancing particle to be, solves additional particle and cast iron matrix wetability
The problems such as interfacial reaction and structure stability are poor easily occurs for difference.Because the particle size of generation is small, caused by the difference in specific gravity on
Floating/subsidence velocity is small, is not easy to be segregated, and the technology stability of production is high.
(2) copper and silver metal in zirconium oxide-heat-resisting gray cast iron material of zirconium carbide particle enhancing is obtained to combine and resist with wide spectrum
Pseudomonas property increases the application range of the material.
Description of the drawings
Here is that specific embodiments of the present invention are described in detail in conjunction with the accompanying drawings and embodiments.
Fig. 1 obtains the optics microstructure photo of the sample of zirconium oxide-zirconium carbide particle enhancing gray cast iron material；
Fig. 2 obtains the true stress and strain curve of the sample of zirconium oxide-zirconium carbide particle enhancing gray cast iron material.
Evengranular point of ZrC is can be seen that from zirconium oxide shown in FIG. 1-zirconium carbide particle enhancing gray cast iron optical photograph
Cloth can greatly improve the mechanical property of gray cast iron in sample, including uniform ZrC particles in the matrix of gray cast iron.
Stretch true stress-true strain curve from zirconium oxide shown in Fig. 2-zirconium carbide particle enhancing gray cast iron sample, it can be seen that intensity compared with
Conventional specimen improves 180.6%.
Specific embodiment
Highly preferred embodiment of the present invention is given below：According to chemical composition ranges, the melting sheet in resistance heating crucible furnace
Invent heat-resisting gray cast iron.The chemical composition and weight percent of gray cast iron basis material of the present invention be：C：2.6-3.0, Mn：0.8-
1.3, Ni：1-1.5, Cr：0.2-0.4, P：0.01-0.05, S：0.03-0.15, Cu：0.2-0.8, Sn：0.01-0.1.By metal
Melt is heated to 1520 DEG C, alloy melting is required to carry out melting offer by mentioned component.In gray cast iron basis material in resistance
Melting in heating crucible stove, by the mixed gas of carbon dioxide, methane, argon gas and oxygen by zirconium oxide-zirconium carbide particle
Precursor mixed-powder is blown into gray cast iron melt, and self-propagating combustion synthetic reaction is generated during being blown into, passes through reaction
Superfine zirconia-zirconium carbide enhancing particle is generated, is blown into molten cast iron, gas pressure 0.1Mpa, 0.05 m of gas flow3/
Min, 10 minutes time, mixed powder addition are the 5% of molten cast iron weight, and into melting, zirconium oxide-zirconium carbide particle enhancing is resistance to
Silver powder and copper powders are added in hot gray cast iron material melt again, wherein the adding proportion of silver powder and copper powders is is 50：
50, the mass content of silver powder and copper powders in the heat-resisting gray cast iron material of tungsten carbide-SiC particles reinforced is 1%, by silver powder
End and copper powders and the heat-resisting gray cast iron material melt of tungsten carbide-SiC particles reinforced are 1 by mass percentage:99 ratio into
Row addition melting, the silver powder and copper powders added into gray cast iron melt are obtained within 24 hours by mechanization ball-milling method
Average particle degree is 40 nanometers -100 nanometers of particle；Metamorphism treatment and refining treatment, running castings are carried out again, then are kept the temperature, and
Respectively at 20 points, 80 points of cast castings by mechanization mixing, Metamorphism treatment, refining, cast, that is, obtain tungsten carbide-carbonization
Silicon particle enhances heat-resisting gray cast iron material ingot casting, obtains ingot casting and is deformed at 400-500 DEG C by high pressure torsion, high pressure torsion processing
Parameter is：The rotating speed of pressure head is 600rpm, lower pressure is 1.2GPa, type.Then T6 processing is carried out, and is tested for the property.It is real
It tests the result shows that zirconium oxide-zirconium carbide particle enhancing gray cast iron material tensile strength is 452.5Mpa, Brinell hardness 292 is corroded
Performance：Weightless ratio is 0.01761%, and cost is 2.8 yuan/Kg.432.7 Mpa of room temperature tensile strength, cloth after such as keeping the temperature 80 minutes
Family name's hardness 281, corrosive nature：Weightless ratio is 0.01783%, and cost is 2.8 yuan/Kg.It can be seen that present invention oxidation simultaneously
Although the price of zirconium-zirconium carbide particle enhancing gray cast iron material is slightly above traditional gray cast iron, the tension of material of the present invention is strong
Degree, wearability, especially hardness and structure stability all significantly improve, and stable processing technique is good, convenient for producing in enormous quantities.
Claims (6)
1. in a kind of method for preparing zirconium oxide-zirconium carbide particle enhancing gray cast iron, it is characterized in that by carbon dioxide, methane,
The precursor mixed-powder of zirconium oxide-zirconium carbide particle is blown into gray cast iron melt by the mixed gas of argon gas and oxygen, is being blown
Self-propagating combustion synthetic reaction is generated during entering, generating superfine zirconia-zirconium carbide by reaction enhances particle, by silver powder
End and copper powders and the heat-resisting gray cast iron melt of tungsten carbide-SiC particles reinforced are 1 by mass percentage:99 ratio is added
Add melting, using mechanization mixing, Metamorphism treatment, refining, cast, obtain ingot casting and become by the violent plasticity of high pressure torsion
Shape obtains the zirconium oxide with anti-microbial property-zirconium carbide particle enhancing heat-resistant high-strength gray cast iron material；
（a）The chemical composition and weight percent of gray cast iron basis material be for：C：2.6-3.0, Mn：0.8-1.3, Ni：1-
1.5, Cr：0.2-0.4, P：0.01-0.05, S：0.03-0.15, Cu：0.2-0.8, Sn：0.01-0.1；
（b）The volume proportion of each component is methane in mixed gas（8-45）：Argon gas（8-35）：Oxygen（8-35）：Carbon dioxide
（8-70）；The pressure of mixed gas is 0.05-0.3MPa, gas flow 0.02-0.15m3/min；
（c）The precursor mixing preparation method of zirconium oxide-zirconium carbide particle：By the Zirconium oxide powder of nano-scale, absolute ethyl alcohol
Stirred evenly with the active carbon powder of nano-scale, by sonic oscillation handle -50 minutes 5 minutes after, after be transferred in crucible,
Then in a vacuum furnace under 1550-1800 DEG C of high-temperature calcination and keep the temperature 3 hours, furnace cooling then grind;It finally obtains average
Superfine zirconia powder and the zirconium carbide precursor powder that granularity is 40 nanometers -100 nanometers；
（d）The precursor powder addition of superfine zirconia powder and zirconium carbide particle is the 5% of alloy melt weight；
（e）The silver powder and copper powders added into hot gray cast iron melt are put down by what mechanization ball-milling method obtained for 24 hours
The particle that equal graininess is 40 nanometers -100 nanometers.
2. a kind of method for preparing zirconium oxide-zirconium carbide particle enhancing gray cast iron according to claim 1, it is characterized in that grey
Cast iron matrix material melt contains the C element that weight percent is 2.6-3.0, Mn elements that weight percent is 0.8-1.3, again
Measure the Mn elements that percentage is 1-1.5,1480-1560 DEG C of the temperature of gray cast iron melt.
3. according to a kind of method for preparing zirconium oxide-zirconium carbide particle enhancing gray cast iron of claim 1, it is characterized in that：Reaction life
Time into enhancing particle is 15-60 minutes, and the time of the higher reaction generation enhancing particle of granule content requirement is longer.
4. a kind of method for preparing zirconium oxide-zirconium carbide particle enhancing gray cast iron according to claim 1, it is characterized in that：
Into melting, zirconium oxide-zirconium carbide particle enhances in heat-resisting gray cast iron material melt adds silver powder and copper powders again, wherein silver
The adding proportion of powder and copper powders is is 50：50, silver powder and copper powders enhance heat-resisting ash in zirconium oxide-zirconium carbide particle
Mass content in cast iron materials is 1%, and silver powder and copper powders are enhanced heat-resisting gray cast iron material with zirconium oxide-zirconium carbide particle
It is 1 by mass percentage to expect melt:99 ratio is added melting, by mechanization mixing, Metamorphism treatment, refining,
Cast obtains zirconium oxide-zirconium carbide particle enhancing gray cast iron material ingot casting.
5. a kind of method for preparing zirconium oxide-zirconium carbide particle enhancing gray cast iron according to claim 1, it is characterized in that：
It obtains ingot casting to deform by high pressure torsion at 400-500 DEG C, high pressure torsion machined parameters are：The rotating speed of pressure head for 600rpm, under
Pressure is 1.2GPa, and test shows that obtained zirconium oxide-zirconium carbide particle enhances heat-resisting gray cast iron and has high-strength tenacity.
6. a kind of method for preparing zirconium oxide-zirconium carbide particle enhancing gray cast iron according to claim 1, it is characterized in that：
Obtaining copper and silver metal in zirconium oxide-heat-resisting gray cast iron material of zirconium carbide particle enhancing and combining has broad-spectrum antiseptic attribute, increase
The application range of the material.
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| CN110157975A (en) * | 2019-06-28 | 2019-08-23 | 含山县兴达球墨铸铁厂 | A kind of preparation method of high-strength thin-walled gray iron casting |
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| CN110157975A (en) * | 2019-06-28 | 2019-08-23 | 含山县兴达球墨铸铁厂 | A kind of preparation method of high-strength thin-walled gray iron casting |
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Application publication date: 20180629 |