CN108220834B - Carbon fiber reinforced alloy composite material and preparation method thereof - Google Patents

Carbon fiber reinforced alloy composite material and preparation method thereof Download PDF

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CN108220834B
CN108220834B CN201810012041.0A CN201810012041A CN108220834B CN 108220834 B CN108220834 B CN 108220834B CN 201810012041 A CN201810012041 A CN 201810012041A CN 108220834 B CN108220834 B CN 108220834B
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carbon fiber
composite material
fiber reinforced
alloy composite
reinforced alloy
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CN108220834A (en
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张宏亮
陈天生
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China Southern Power Grid Power Technology Co Ltd
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Guangdong Electric Power Science Research Institute Energy Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • C22C49/08—Iron group metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/08—Making alloys containing metallic or non-metallic fibres or filaments by contacting the fibres or filaments with molten metal, e.g. by infiltrating the fibres or filaments placed in a mould
    • C22C47/12—Infiltration or casting under mechanical pressure
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/02—Rigid pipes of metal

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Abstract

The invention belongs to the field of metal materials, and particularly relates to a carbon fiber reinforced alloy composite material and a preparation method thereof. The invention provides a carbon fiber reinforced alloy composite material, which is prepared by taking alloy as a matrix and carbon fiber as a reinforcement; the alloy comprises: by mass percentage, Cr: 22% -24%, Al: 0.5% -2%, Ni: 2% -4%, C: 0.02% -0.08%, Ti: 0.2% -0.8% and Nb: 0.2 to 0.8 percent; the balance being iron. High-temperature corrosion kinetics tests and high-temperature oxidation kinetics tests show that the weight gain variation of the carbon fiber reinforced alloy composite material in the corrosion tests is mainly concentrated on 1.3-2.9 mg/cm2Within the range of (A), the carbon fiber reinforced alloy composite material has high-temperature potassium chloride corrosion resistance obviously superior to commercial metal materials such as TP316 and the like.

Description

Carbon fiber reinforced alloy composite material and preparation method thereof
Technical Field
The invention belongs to the field of metal materials, and particularly relates to a carbon fiber reinforced alloy composite material and a preparation method thereof.
Background
The renewable and pollution-free biomass fuel is one of the development directions of green renewable energy sources in the future, and has a wide development prospect. Compared with coal-fired power generation, biomass combustion power generation has higher requirements on corrosion resistance of equipment such as a boiler superheater tube of a power station, namely the biomass combustion power generation has the capability of resisting high-temperature corrosion of potassium, chlorine, salts and alkaline substances. At present, the commonly used alloy materials of domestic boiler superheater tubes are TP91, 304 stainless steel and the like, and the application occasions of T91 comprise a high re-outlet header, a superheater outlet safety valve tube section, a high pass tube, a screen pass tube, a high re-pass tube and a high over-outlet guide tube; the 15CrMo application occasions comprise a rear wall water-cooled wall hanging pipe, a low-pass secondary pipe group, a low-pass tertiary pipe group, a ceiling superheater pipe, a low secondary pipe group and a low secondary pipe group; SUS316 is used in high-pass, screened, high-re, high-over exit conduits.
The TP91 component is 0.1C-9Cr-1Mo, the structure is a tempered martensite structure, and the high-temperature-resistant steel has good comprehensive mechanical property and high-temperature mechanical property. C. The compound composed of Cr and Mo elements has good high-temperature stability, and the stability of mechanical properties under long-term use conditions is ensured. The corrosion resistance potential of the 304 stainless steel is improved by the Cr element with the content of 18%, and the corrosion resistance is better compared with that of TP 91. Both alloys of TP91 and 304 stainless steel have good formability and weldability.
The alloy such as TP91 is suitable for common thermal power use conditions, and has good process characteristics and service life. For biomass power generation conditions such as straw combustion and the like, the combustion atmosphere contains K+、Na+、Cl-Plasma and salts thereof, and the boiler superheater tube for thermal power are quickly scaled, corroded and oxidized, and have short service life. At high temperature and containing K+、Na+、Cl-Under the conditions of plasma, moisture and the like, the protective effect of oxides and carbides on the surface layer of the alloy is limited.
Besides the above alloys, the materials used for the foreign boiler superheater tubes also include heat-resistant steels with high alloy content such as HR 3C. HR3C is 25Cr-20Ni-Nb-N, and has high Cr content, high Ni content, excellent anticorrosive and oxidation resistance and excellent use performance in biomass power station pipe material. The alloy is an austenite structure alloy, has high price due to containing a large amount of Ni elements, has certain difficulty in processing the pipe, and has the defects of easy occurrence of pores and the like in a welding seam of the pipe due to containing N elements in the material.
For HR3C alloy, the structure is austenite, and due to the existence of high Cr content and high Ni content, the conventional high temperature corrosion resistance, high temperature oxidation resistance and high temperature K resistance are realized+、Na+、Cl-The plasma etching performance is high. The content of alkali metal sulfide in the coal ash of China is high. As for the ash generated by burning straw biomass, the straw absorbs a large amount of minerals, salts and the like in the growth process, and the ash contains a large amount of alkaliThe metal chloride contains chlorine gas, hydrogen chloride gas and the like in the combustion atmosphere, and is in contact with the superheater tube to generate corrosion action, oxygen in the oxide protective film is captured, and corrosion products are iron-containing low-melting-point chloride and iron-containing low-melting-point sulfide, so that corrosion is continuously generated.
Disclosure of Invention
The invention provides a carbon fiber reinforced alloy composite material and a preparation method thereof, which are used for solving the problem that the high-temperature corrosion resistance and the oxidation resistance of the conventional boiler superheater tube material cannot meet the requirements of the biomass power station tube in China.
The specific technical scheme is as follows:
a carbon fiber reinforced alloy composite material is prepared by taking alloy as a matrix and carbon fiber as a reinforcement;
the alloy comprises: by mass percentage, Cr: 22% -24%, Al: 0.5% -2%, Ni: 2% -4%, C: 0.02% -0.08%, Ti: 0.2% -0.8% and Nb: 0.2 to 0.8 percent; the balance being iron.
Preferably, the alloy further comprises: by mass percent, Mo: 0.1% -0.3% of Si3N4: 0.1% -0.5%, Co: 0.01-0.05%, Cu: 0.01% -0.05% and Si: 0.005-0.02 percent.
Preferably, the alloy further comprises: a rare earth element.
Preferably, the rare earth element is one or more of Nd, La, Pr, Y and V.
Preferably, the rare earth elements are Nd, La, Pr, Y and V.
Preferably, the rare earth elements include: by mass percent, Nd: 0.02% -0.08%, La: 0.0005% -0.002%, Pr: 0.002% -0.008%, Y: 0.02% -0.08% and V: 0.1 to 0.5 percent.
The invention also provides a preparation method of the carbon fiber reinforced alloy composite material, which comprises the following steps:
a) vacuum smelting the alloy to obtain a molten liquid;
b) and adding the carbon fibers into the molten liquid to obtain the carbon fiber reinforced alloy composite material.
Preferably, the temperature of the vacuum melting in the step a) is 1100-1600 ℃;
the vacuum degree of the vacuum melting in the step a) is 40-60 Pa.
Preferably, the mass of the carbon fiber is 0.02-0.08% of the mass of the carbon fiber reinforced alloy composite material.
The invention also provides an application of the carbon fiber reinforced alloy composite material in the technical scheme or the carbon fiber reinforced alloy composite material prepared by the preparation method in the technical scheme in preparation of high-temperature corrosion-resistant and oxidation-resistant pipes.
In summary, the invention provides a carbon fiber reinforced alloy composite material, which is prepared by using an alloy as a matrix and carbon fibers as a reinforcement; the alloy comprises: by mass percentage, Cr: 22% -24%, Al: 0.5% -2%, Ni: 2% -4%, C: 0.02% -0.08%, Ti: 0.2% -0.8% and Nb: 0.2 to 0.8 percent; the balance being iron. High-temperature corrosion kinetics tests and high-temperature oxidation kinetics tests show that the weight gain variation of the carbon fiber reinforced alloy composite material in the corrosion tests is mainly concentrated on 1.3-2.9 mg/cm2Within the range of (A), the carbon fiber reinforced alloy composite material has high-temperature potassium chloride corrosion resistance obviously superior to commercial metal materials such as TP316 and the like. Compared with austenitic alloys such as 304, HR3C and the like, the carbon fiber reinforced alloy composite material has the advantages of better heat conduction performance, lower thermal expansion coefficient, and excellent strength and toughness performance. In the aspect of structure, the carbon fiber reinforced alloy composite material has fine crystal grains, is a single ferrite structure, has good processing performance, and has good influence on the structure refinement and the corrosion resistance improvement of the carbon fiber reinforced alloy composite material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a metallographic micrograph of a carbon fiber reinforced alloy composite material prepared in example 1 of the present invention;
FIG. 2 is a graph showing the high temperature oxidation kinetics of the carbon fiber reinforced alloy composite material prepared in example 1 of the present invention;
FIG. 3 is a high temperature corrosion kinetics graph of the carbon fiber reinforced alloy composite material prepared in example 1 of the present invention;
FIG. 4 is an SEM representation picture (with a scale of 100 μm) of the carbon fiber reinforced alloy composite material prepared in example 1 of the present invention after being subjected to a high temperature corrosion test at 700 ℃;
FIG. 5 is an SEM representation picture (10 μm on a scale) of the carbon fiber reinforced alloy composite material prepared in example 1 of the present invention after being subjected to a high temperature corrosion test at 700 ℃;
FIG. 6 is an SEM representation picture (with a scale of 1 μm) of the carbon fiber reinforced alloy composite material prepared in example 1 of the present invention after a 700 ℃ high temperature corrosion test;
FIG. 7 is a histogram of the high temperature corrosion kinetics of the carbon fiber reinforced alloy composite material prepared in example 1 of the present invention;
fig. 8 is an energy spectrum of the carbon fiber reinforced alloy composite material prepared in example 1.
Detailed Description
The invention provides a carbon fiber reinforced alloy composite material and a preparation method thereof, which are used for solving the problem that the high-temperature corrosion resistance and the oxidation resistance of the conventional boiler superheater tube material cannot meet the requirements of the biomass power station tube in China.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A carbon fiber reinforced alloy composite material is prepared by taking alloy as a matrix and carbon fiber as a reinforcement;
the alloy comprises: the mass percentage of Cr: 22% -24%, Al: 0.5% -2%, Ni: 2% -4%, C: 0.02% -0.08%, Ti: 0.2% -0.8% and Nb: 0.2 to 0.8 percent; the balance being iron.
High-temperature corrosion kinetics tests and high-temperature oxidation kinetics tests show that the weight gain variation of the carbon fiber reinforced alloy composite material in the corrosion tests is mainly concentrated on 1.3-2.9 mg/cm2Within the range of (A), the carbon fiber reinforced alloy composite material has high-temperature potassium chloride corrosion resistance obviously superior to commercial metal materials such as TP316 and the like. Compared with austenitic alloys such as 304, HR3C and the like, the carbon fiber reinforced alloy composite material has the advantages of better heat conductivity, lower thermal expansion coefficient, good forming performance and good welding performance. In the aspect of structure, the carbon fiber reinforced alloy composite material has fine crystal grains, is a single ferrite structure, has good processing performance, and has good influence on the structure refinement and the corrosion resistance improvement of the carbon fiber reinforced alloy composite material. In addition, the carbon fiber reinforced alloy composite material has lower cost.
In the invention, Ni and Cr have good protection performance on alloy. Ni can change the crystal structure of the alloy to form an austenite crystal structure; the austenite material has very good corrosion resistance and comprehensive mechanical property, and Ni enables the material to have better oxidation resistance. Cr (chromium) component2O3The oxide film is compact, Cr enables the material to have better corrosion resistance, and the molten salt hot corrosion resistance of the alloy is improved.
Further, in percentage by mass, Cr: 23.2%, Al: 1.0%, Ni: 3.0%, C: 0.05%, Ti: 0.5% and Nb: 0.5 percent.
Further, the method also comprises the following steps: by mass percent, Mo: 0.1% -0.3% of Si3N4: 0.1% -0.5%, Co: 0.01-0.05%, Cu: 0.01% -0.05% and Si: 0.005-0.02 percent.
Further, in mass percent, Mo: 0.2% of Si3N4：0.3％、Co：0.02％、Cu：0.02% and Si: 0.01 percent.
Further, the method also comprises the following steps: a rare earth element.
In the invention, the rare earth element is one or more of Nd, La, Pr, Y and V.
In the invention, the rare earth elements are Nd, La, Pr, Y and V.
In the invention, by mass percent, Nd: 0.02% -0.08%, La: 0.0005% -0.002%, Pr: 0.002% -0.008%, Y: 0.02% -0.08% and V: 0.1 to 0.5 percent.
Further, by mass percent, the molar ratio of Nd: 0.05%, La: 0.001%, Pr: 0.005%, Y: 0.05% and V: 0.3 percent.
In the invention, the mass percentage of the carbon fiber in the carbon fiber reinforced alloy composite material is 0.05%.
In the present invention, the carbon fiber reinforced alloy composite material further includes: p, S and Mn, wherein P is less than 0.045%, S is less than 0.03%, and Mn is less than 2.0% in mass percentage.
According to the invention, Mo, Co, Nb, Ti, Cu and Si elements are simultaneously added into the carbon fiber reinforced alloy composite material to form a Mo-Co-Nb-Ti-Cu-Si multi-element reinforced phase, so that the alkali metal and chlorine corrosion resistance of the carbon fiber reinforced alloy composite material is improved through synergistic reinforcement. The Ni element can prevent the austenitic material from generating pitting corrosion and crevice corrosion; the Ni-Mo-Co interacts to form a compact rust layer to prevent chloride ions from invading, so that the pitting corrosion resistance effect is stronger; nb and Ti are carbide stabilizing elements and can reduce intercrystalline corrosion of the carbon fiber reinforced alloy composite material; cu can improve the corrosion resistance of the carbon fiber reinforced alloy composite material in an acid environment, and a compact sulfide film or insoluble salt is formed on the surface of the material to prevent the pitting corrosion from being amplified to the inside of the material; si can improve the stress corrosion cracking resistance of the carbon fiber reinforced alloy composite material.
According to the carbon fiber reinforced alloy composite material, the rare earth element is added, the corrosion resistance of the carbon fiber reinforced alloy composite material is improved by cooperatively adding the rare earth element, and the ductility and toughness of the carbon fiber reinforced alloy composite material are improved by controlling the form of the inclusion. The neodymium and the lanthanum can improve the high-temperature performance and the corrosion resistance of the carbon fiber reinforced alloy composite material; pr obviously improves the oxidation resistance and the mechanical property of the carbon fiber reinforced alloy composite material; y can enhance the oxidation resistance and the ductility of the carbon fiber reinforced alloy composite material; v is an excellent deoxidizer of the carbon fiber reinforced alloy composite material, vanadium is added into the carbon fiber reinforced alloy composite material to refine structure grains and improve the strength and toughness, and sulfide formed by V and sulfur can improve the hydrogen corrosion resistance under high temperature and high pressure. V can perform a complex reaction with other components in the invention to improve the material capability, for example, when Ti-V is added in a complex way, in order to play a role of precipitation strengthening of V, it is required to say that the content of Ti is not too high. The toughness of the carbon fiber reinforced alloy composite material is reduced due to the excessively high Ti content, and the Ti content is 0.5 percent; the Nb-V composite addition has higher strength than that of the single addition of Nb, and can further refine austenite grains, so that ferrite grains after cooling are finer, and the strength and toughness of the carbon fiber reinforced alloy composite material are finally improved.
The carbon fiber reinforced alloy composite material is formed by using the alloy as a substrate and adopting carbon (graphite) fibers as a reinforcement, so that the specific strength and specific modulus of the carbon fiber reinforced alloy composite material are obviously improved, the carbon fiber reinforced alloy composite material has high strength, toughness and impact resistance, and the alkali metal and chlorine corrosion resistance of the carbon fiber reinforced alloy composite material is greatly improved. The composite material is a multi-body material formed by combining two or more substances with different physical and chemical properties. In composite materials, one phase is usually a continuous phase, which is the matrix; the other phase is the dispersed phase, called reinforcement. While the components of the composite remain relatively independent, the properties of the composite are not simply the sum of the properties of the constituent materials, but rather are a significant improvement. The components of the composite material can make up for deficiencies of each other and have synergistic effect, so that the defect of a single material is overcome.
The invention also provides a preparation method of the carbon fiber reinforced alloy composite material in the technical scheme, which comprises the following steps:
a) vacuum smelting the alloy to obtain a molten liquid;
b) and (3) adding carbon fibers into the molten liquid by hot extrusion to obtain the carbon fiber reinforced alloy composite material.
In the invention, the temperature of the vacuum melting in the step a) is 1100-1600 ℃;
the vacuum degree of the vacuum melting in the step a) is 40-60 Pa.
The mass of the carbon fiber is 0.02-0.08% of the mass of the carbon fiber reinforced alloy composite material.
In the present invention, a master alloy may be used as the element such as Cr or Mo in the alloy. The vacuum smelting is vacuum induction smelting, the carbon fiber is added into the molten liquid in the step b), then a hot extrusion process is adopted to obtain the carbon fiber reinforced alloy composite material, and the alloy is sequentially subjected to hot working, cold working and annealing to obtain the carbon fiber reinforced alloy composite material with uniform ferrite structure grains.
According to the preparation method of the carbon fiber reinforced alloy composite material, the alloy is used as a matrix, the reinforcement is carbon fiber, the carbon fiber reinforced alloy composite material has high specific strength, high modulus, high temperature performance, high and low thermal expansion and the like, and the carbon fiber reinforced alloy composite material is matched with matrix metal to obtain excellent comprehensive performance of the material. The reinforcement also has good chemical stability, good wettability and compatibility with the base metal. The interface of the metal matrix composite is formed by a diffusion-permeation mode, namely, the reinforcement body diffuses to the matrix, and the matrix diffuses to the surface of the reinforcement body, permeates and mutually dissolves. When carbon fibers are contained, the carbon fibers are gradually broken and arranged in parallel along the extrusion axis during the extrusion. The extrusion temperature is higher, and the strain rate reduces, and then the fracture degree of carbon fiber will reduce, is favorable to keeping the major diameter ratio of carbon fiber.
The invention also provides application of the carbon fiber reinforced alloy composite material prepared by the technical scheme or the carbon fiber reinforced alloy composite material prepared by the preparation method of the technical scheme in preparation of high-temperature corrosion-resistant and oxidation-resistant pipes.
Example 1
707.94g of pure iron ingot, 232g of chromium ingot, 2g of molybdenum alloy, 10g of pure aluminum ingot, 30g of pure nickel ingot, 5g of pure titanium ingot, 5g of pure niobium ingot and 3g of silicon nitride (Si)3N4) 0.2g pure cobalt, 0.2g pure copper block, 0.1g pure silicon powder and 4.06g rare earth (including 0.5g neodymium, 0.01g lanthanum, 0.05g praseodymium, 0.5g yttrium, 3g vanadium) And (4) preparing materials.
And smelting the metal raw materials in the prepared materials, wherein the smelting method is vacuum induction smelting. After the metal raw materials are fed into the furnace, vacuumizing the whole hearth to ensure that the smelting process is carried out under vacuum; heating the hearth to 1100-1600 ℃, and properly stirring to ensure that the metal raw materials are completely melted and all components are uniformly distributed; it should be noted that the possibility of oxidation of the metal material can be reduced by adding the metal material in batches according to the properties of each metal.
After the metal raw materials in the furnace are melted into a uniformly distributed molten liquid state, 0.5g of graphite fiber is added, the graphite fiber is placed into a fiber casting, molten metal is pressurized to enter the fiber casting, and then the carbon fiber composite molten liquid is cast into a fully preheated metal mold casting die or sand mold casting die to be solidified into a casting. The carbon fiber composite casting is subjected to hot working, cold working and annealing treatment to obtain the carbon fiber reinforced alloy composite material with uniform ferrite structure grains.
Example 2
Microscopic examination is carried out on the carbon fiber reinforced alloy composite material prepared in the example 1, and as shown in fig. 1, the microscopic examination is a metallographic microscopic picture of the carbon fiber reinforced alloy composite material prepared in the example 1 of the invention.
As shown in fig. 1, although the carbon fiber reinforced alloy composite material of the present invention contains more kinds of elements and has higher content of elements, the structure has more substructures, but still is a ferrite alloy. The Nb and Ti are added into the carbon fiber reinforced alloy composite material, so that the structure is refined, and the carbon fiber reinforced alloy composite material has good mechanical properties. Chromium is the most basic element of the heat-resistant steel and can form a compact oxidation film, so that the carbon fiber reinforced alloy composite material has high corrosion resistance and high oxidation resistance. The nickel is added into the carbon fiber reinforced alloy composite material to dissolve solid solution, so that the mechanical property of the carbon fiber reinforced alloy composite material is obviously improved, and the oxidation resistance of the carbon fiber reinforced alloy composite material can be improved. The addition of aluminum and silicon into the carbon fiber reinforced alloy composite material can form a protective oxide film, and the oxidation resistance of the carbon fiber reinforced alloy composite material is improved. Vanadium, niobium and titanium are added into the carbon fiber reinforced alloy composite material, so that stable carbide can be formed, and the strength and the hot hardness of the carbon fiber reinforced alloy composite material are improved.
The performance test of the carbon fiber reinforced alloy composite material, T316, T91, 15CrMo and HR3C shows that the carbon fiber reinforced alloy composite material has better heat conductivity, lower thermal expansion coefficient and excellent strength and toughness compared with the carbon fiber reinforced alloy composite material, T316, T91, 15CrMo and HR3C shown in Table 1.
TABLE 1 Performance parameters of the carbon fiber reinforced alloy composite material of the present invention
Figure BDA0001540643280000081
Example 3
The carbon fiber reinforced alloy composite material prepared in the example 1 is subjected to a high temperature oxidation test, the corrosion resistance of the carbon fiber reinforced alloy composite material is detected, a test piece of the carbon fiber reinforced alloy composite material is pretreated and then placed in a box type resistance furnace to be heated, the temperature of the high temperature oxidation test is 700 ℃, and the period of the high temperature oxidation test is 30 hours. The high-temperature oxidation test is carried out according to HB5258-2000 method for measuring and testing the oxidation resistance of steel and high-temperature alloy. Referring to fig. 2, a graph of the high temperature oxidation kinetics of the carbon fiber reinforced alloy composite material prepared in example 1 of the present invention is compared with the high temperature oxidation kinetics of the commercial metal material at 700 ℃, wherein the abscissa of the graph is the testing time of the high temperature oxidation test, the ordinate of the graph is the weight change per unit area measured after the test piece material is taken out, and each curve of the graph represents a metal material. As can be seen from fig. 2: the weight change quantity (delta W) of the carbon fiber reinforced alloy composite material in unit area is not large in the high-temperature oxidation process at 700 ℃, and is basically 0.2mg/cm2The results show that the carbon fiber reinforced alloy composite material has good high-temperature oxidation performance, and other commercial metal materials have high delta W in the high-temperature oxidation process at 700 DEG CThe total concentration of the active ingredients is 0.2-1.2 mg/cm2And negative value (namely showing that the weight-gaining materials are obviously fallen off) appears, and the change range of delta W is-12Meanwhile, the high-temperature oxidation effect is not ideal, and weight-increasing substances with poor adhesion are generated, so that a weight-increasing negative value is generated.
Example 4
The carbon fiber reinforced alloy composite material prepared in example 1 was subjected to a high temperature corrosion test to test the corrosion resistance of the carbon fiber reinforced alloy composite material of the present invention, and the corrosion amount of the test piece was measured by a weight-increasing method and a weight-loss method, respectively, and a corrosion kinetics curve was drawn. High temperature corrosion test the KCl medium is added on the basis of the high temperature oxidation test, and the medium can evaporate at higher temperature to form corrosive steam, thereby forming the test condition of high temperature corrosion. The temperature of the high-temperature corrosion test is 700 ℃, and the time period of the high-temperature corrosion test is 30 h. Referring to fig. 3, a high temperature corrosion kinetics curve of the carbon fiber reinforced alloy composite material prepared in example 1 of the present invention is shown, which is compared with a high temperature corrosion kinetics curve of a commercial metal material at 700 ℃, wherein the abscissa of the graph is the testing time of the high temperature corrosion test, and the ordinate of the graph is the weight change per unit area measured after the test piece material is taken out; each curve of the figure represents a test material. As can be seen from fig. 3: the weight change quantity (delta W) of each time point of the carbon fiber reinforced alloy composite material at 700 ℃ under the potassium chloride medium condition is greatly increased compared with the high-temperature oxidation test, and the delta W value is 4.0mg/cm2Within. The large delta W value fluctuation of other commercial metal materials at each time point under the medium conditions of 700 ℃ and potassium chloride indicates that the corrosion resistance of the carbon fiber reinforced alloy composite material is superior to that of the commercial metal materials under the medium conditions of 700 ℃ and potassium chloride.
Example 5
Referring to fig. 4 to 6, SEM characterization pictures of the carbon fiber reinforced alloy composite material prepared in example 1 of the present invention after being subjected to the 700 ℃ high temperature corrosion test include 3 pictures, and the scales in fig. 4 to 6 are 100 μm, 10 μm, and 1 μm in sequence. As can be seen from fig. 4 to 6: the surface of the test piece is relatively uniform in the different magnification pictures. Although there is a sharp interface in fig. 4, its further microstructure shows a uniform densification, especially in fig. 5, the surface of the carbon fiber reinforced alloy composite material of the present invention shows a high degree of uniformity.
Example 6
Referring to fig. 7, a histogram of the high temperature corrosion kinetics of the carbon fiber reinforced alloy composite material prepared in example 1 of the present invention is compared with a histogram of the high temperature corrosion kinetics of a conventional superheater tube at 700 ℃, where the abscissa of the histogram is the test time of the high temperature corrosion test, and the ordinate of the histogram is the weight change (Δ W) per unit area measured after the test piece material is taken out. As can be seen from fig. 7: the carbon fiber reinforced alloy composite material has excellent corrosion resistance, the TP316 material shows lower corrosion weight gain when the test time is 0-7 h under the conditions of 700 ℃ and KCl, after the test time exceeds 10h, the corrosion resistance of the TP316 material is rapidly reduced, nonadherent corrosion products are rapidly formed, the TP316 material cannot be tested to the time point of 30h, and the corrosion products of the HR3C material are rapidly increased after the test time is 20 h.
Example 7
Referring to fig. 8, which is a graph of an energy spectrum of the carbon fiber reinforced alloy composite material prepared in example 1, the abscissa of fig. 8 is an energy value of emitted electrons in keV; the ordinate is the reflection intensity of the carbon fiber reinforced alloy composite material of the invention under the emission energy. As can be seen from fig. 8: the carbon fiber reinforced alloy composite material has stronger high-temperature corrosion resistance, and the high chromium content enables the material to form a chromium oxide adhesion layer with very high strength, and the adhesion layer can resist the corrosion of high-temperature potassium chloride. In addition, the adhesion layer is firm and hard, and the integral integrity of the carbon fiber reinforced alloy composite material is effectively protected.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (4)

1. The carbon fiber reinforced alloy composite material is characterized in that the carbon fiber reinforced alloy composite material is prepared by taking alloy as a matrix and carbon fiber as a reinforcement;
the alloy comprises: by mass percentage, Cr: 22% -24%, Al: 0.5% -2%, Ni: 2% -4%, C: 0.02% -0.08%, Ti: 0.2% -0.8%, Nb: 0.2% -0.8%, Mo: 0.1% -0.3% of Si3N4: 0.1% -0.5%, Co: 0.01% -0.05%, Cu: 0.01% -0.05%, Si: 0.005% -0.02%, Nd: 0.02% -0.08%, La: 0.0005% -0.002%, Pr: 0.002% -0.008%, Y: 0.02% -0.08% and V: 0.1% -0.5% of iron, and the balance of iron;
the mass of the carbon fiber is 0.02-0.08% of the mass of the carbon fiber reinforced alloy composite material.
2. The method for producing a carbon fiber-reinforced alloy composite material according to claim 1, comprising:
a) vacuum smelting the alloy to obtain a molten liquid;
b) and hot extruding the molten liquid to add the carbon fibers to obtain the carbon fiber reinforced alloy composite material.
3. The preparation method according to claim 2, wherein the temperature of the vacuum melting in the step a) is 1100-1600 ℃;
the vacuum degree of the vacuum melting in the step a) is 40-60 Pa.
4. Use of the carbon fiber reinforced alloy composite material according to claim 1 or the carbon fiber reinforced alloy composite material prepared by the preparation method according to any one of claims 2 to 3 for preparing a high temperature corrosion and oxidation resistant pipe.
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CN103266277A (en) * 2013-06-14 2013-08-28 兰州理工大学 High-alumina 2205 stainless steel and preparation method thereof
CN105441833A (en) * 2015-11-24 2016-03-30 宁波市鸿博机械制造有限公司 Pump shaft and preparation method thereof

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JP2833042B2 (en) * 1989-08-31 1998-12-09 大同特殊鋼株式会社 Manufacturing method of metal expansion anchor

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103266277A (en) * 2013-06-14 2013-08-28 兰州理工大学 High-alumina 2205 stainless steel and preparation method thereof
CN105441833A (en) * 2015-11-24 2016-03-30 宁波市鸿博机械制造有限公司 Pump shaft and preparation method thereof

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