CN112553546B - Preparation method and device of chopped carbon fiber reinforced amorphous composite material - Google Patents

Preparation method and device of chopped carbon fiber reinforced amorphous composite material Download PDF

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CN112553546B
CN112553546B CN202010985534.XA CN202010985534A CN112553546B CN 112553546 B CN112553546 B CN 112553546B CN 202010985534 A CN202010985534 A CN 202010985534A CN 112553546 B CN112553546 B CN 112553546B
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carbon fiber
chopped carbon
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CN112553546A (en
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王新
尹海龙
赵立臣
刘水清
崔春翔
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Hebei University of Technology
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
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    • B22D18/04—Low pressure casting, i.e. making use of pressures up to a few bars to fill the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
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    • B22D18/06—Vacuum casting, i.e. making use of vacuum to fill the mould
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C45/005—Amorphous alloys with Mg as the major constituent
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    • 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
    • C22C47/02—Pretreatment of the fibres or filaments
    • C22C47/04—Pretreatment of the fibres or filaments by coating, e.g. with a protective or activated covering
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    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
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    • C22C47/16—Making alloys containing metallic or non-metallic fibres or filaments by thermal spraying of the metal, e.g. plasma spraying
    • 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
    • C22C47/16—Making alloys containing metallic or non-metallic fibres or filaments by thermal spraying of the metal, e.g. plasma spraying
    • C22C47/18—Making alloys containing metallic or non-metallic fibres or filaments by thermal spraying of the metal, e.g. plasma spraying using a preformed structure of fibres or filaments
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    • C22C49/11—Titanium
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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Abstract

The invention discloses a preparation method and a device of a chopped carbon fiber reinforced amorphous composite material, and relates to the technical field of forming amorphous composite materials by contacting fibers with molten metal and quickly solidifying.

Description

Preparation method and device of chopped carbon fiber reinforced amorphous composite material
Technical Field
The technical scheme of the invention relates to the technical field of forming amorphous composite materials by contacting fibers with molten metal and quickly solidifying, in particular to a preparation method and a device of chopped carbon fiber reinforced amorphous composite materials.
Background
The carbon fiber reinforced metal matrix composite has high specific strength, high specific modulus and good high-temperature performance, so that the carbon fiber reinforced metal matrix composite draws wide attention in various high-technology fields of automobiles, aviation and aerospace. With the rapid development of aviation science and technology, the use proportion of various carbon fiber composite materials in the manufacturing process of novel passenger planes is higher and higher, and attractive development prospects are shown. The traditional carbon fiber reinforced metal matrix composite mainly takes alloy with low density and good plasticity, such as aluminum alloy and magnesium alloy, as a matrix, but the weak point of low strength limits the improvement range of the mechanical property of the composite. Meanwhile, due to the problems of complex preparation process, high porosity, uneven carbon fiber distribution, poor wettability between the carbon fibers and a matrix and interface combination caused by poor interface reaction, the actually measured performance index of the carbon fiber reinforced metal matrix composite material is often lower than the designed performance index. These problems are mostly related to the interface structure defects of the composite material, so that the control of interface reaction, the elimination of interface defects and the optimization of interface microstructure are key problems faced by the development of the carbon fiber reinforced metal matrix composite material.
The selection of high-strength metal as the matrix has important significance for the strengthening and toughening design of the composite material. The amorphous alloy does not have the traditional plastic deformation mechanisms such as dislocation and grain boundary in the crystal, so that the amorphous alloy is more difficult to deform, and the strength of the amorphous alloy is higher than that of the corresponding crystalline alloy. The carbon fiber composite material taking high-strength amorphous alloy as a matrix causes the international material boundaryThe importance of (1) is high. The American scholars prepared the amorphous composite material [ C.P.Kim, R.Busch, A.Masuhr, H.Choi-Yim, W.L.Johnson, Processing of carbon-fiber-reinforced Zr41.2Ti13.8Cu12.5Ni10.0Be22.5 bulk metallic composites, Applied Physics Letters,2001,79(10): 1456-.]However, there is a drawback that the carbon fiber and the matrix undergo a severe interfacial reaction and it is difficult to obtain an ideal plasticity. Short carbon fiber reinforced Zr50.5Cu36.45Ni4.05Al9 amorphous composite [ J.M.Liu, X.G.Yuan, H.M.Fu, Z.Q.Hu, Synthesis and properties of carbon short fiber reinforced ZrCuNiAl metallic matrix composite, Materials transformations, 2011,52(3): 412-.]The composite material is strengthened, but the defect that the plasticity is not obviously improved exists. Australian scholars select magnesium-based amorphous alloy with lower chemical affinity with carbon as a matrix and prepare long carbon fiber reinforced Mg65Cu25Y10 amorphous composite material [ K.F.Shamlaye, K.J.Laws, M.Ferry, Supercooled liquid fusion of carbon fiber-bulk metallic composites with super plastic composites, Scripta material 2016,111: 127-.]It is found that the matrix and the carbon fiber have no obvious interface reaction and realize the improvement of the bending strength of the composite material, but the defect that the plasticity of the composite material is not obviously improved still exists. The research reports show that for the carbon fiber reinforced amorphous composite material, the control of the interface wettability and the interface reaction is a key problem, and the selection of a proper matrix alloy and a proper carbon fiber surface modification method to regulate and control the interface tissue structure of the composite material is a feasible preparation strategy. CN101956148B discloses a double-composite high-strength and high-toughness block amorphous alloy and a preparation method thereof, wherein a quartz tube or a stainless steel tube is used as a container for reinforcing fibers, and a composite material containing an amorphous phase is obtained by adopting a quenching and water cooling method after molten metal liquid is subjected to pressure infiltration. However, this method has a low cooling rate, which is difficult to reach 100K/s or more, and cannot be applied to more amorphous materialsThe alloy system is used for preparing the composite material. CN101250677A discloses a titanium dioxide carbon coating carbon fiber reinforced magnesium-based composite material, which mainly comprises a matrix magnesium alloy and TiO2Carbon fiber composition of coating, TiO on surface of carbon fiber2The coating is prepared by a sol-gel method, and the magnesium alloy raw material is introduced with SF6And CO2Under the protection of mixed gas, heating to 700 ℃ to melt the alloy, and adding TiO2Preheating the carbon fiber of the coating to 400 ℃, placing the carbon fiber in a metal mold preheated to 200 ℃, casting the molten alloy liquid into the metal mold, and molding under pressure, wherein the extrusion pressure is 10MPa, and the pressure maintaining time is 60 seconds to obtain TiO2The coating carbon fiber reinforced magnesium-based composite material has the defects that the method is only suitable for the traditional magnesium alloy matrix, and cannot realize higher cooling speed and obtain an amorphous matrix. CN111155038A discloses a preparation method of a chopped carbon fiber reinforced magnesium-based composite material, which uses a sol-gel method to prepare an oxide coating on the surface of carbon fibers, and has the defects that the oxygen content of the alloy is high, so that the amorphization of the matrix structure of the composite material is not facilitated, the preparation process of a chopped carbon fiber preform is complicated, and the methods of extrusion casting and hot extrusion are not suitable for the preparation of an amorphous composite material requiring a rapid solidification technology. CN108385040B discloses a chopped carbon fiber reinforced magnesium-aluminum-based composite material and a preparation method thereof, wherein the chopped carbon fibers are not subjected to surface modification, so that the wettability between the carbon fibers and a metal liquid is poor, the molding of the composite material is not facilitated, and when the reaction activity of the metal liquid and the carbon fibers is high, the interface reaction is aggravated, and the interface structure and the mechanical property of the composite material are damaged. The prior art also has the defect that the amorphous composite material can not be prepared by aiming at various amorphous alloy matrixes needing vacuum melting only at the magnesium-aluminum alloy matrixes.
In a word, the prior art has the defects that the fiber aggregation phenomenon caused by uneven dispersion of the reinforcing fibers in the matrix or the interface structure of the brittle phase generated at the interface between the carbon fibers and the matrix exists, and the prior art is only suitable for the traditional magnesium alloy matrix, cannot realize higher cooling speed and obtain an amorphous matrix, and cannot design and prepare amorphous composite materials aiming at various amorphous alloys needing vacuum melting.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the preparation method and the device thereof adopt a chemical plating method to improve the wettability of carbon fibers, prepare a carbon fiber preform through a copper die, and further prepare the chopped carbon fiber reinforced amorphous composite material through a vacuum low-pressure casting method, namely a spray casting method, thereby overcoming the defects that in the prior art, the reinforcing fibers are dispersed unevenly in a matrix to cause fiber aggregation phenomenon or the carbon fibers and the matrix generate interface tissues with equal brittleness at the interface, the chopped carbon fiber reinforced amorphous composite material is only suitable for the traditional magnesium alloy matrix, can not realize higher cooling speed and obtain amorphous matrix, and can not prepare the amorphous composite material aiming at various amorphous alloy matrixes needing vacuum melting.
The technical scheme adopted by the invention for solving the technical problem is as follows: the preparation method of the chopped carbon fiber reinforced amorphous composite material adopts a chemical plating method to improve the wettability of carbon fibers, prepares a carbon fiber preform through a copper mold, and further prepares the chopped carbon fiber reinforced amorphous composite material by a vacuum low-pressure casting method, namely a spray casting method, and comprises the following specific steps:
step one, short carbon fiber chemical plating:
cutting commercial T200, T700 or T800 carbon fibers to obtain short carbon fibers with the length of 30 mu m-0.8 mm, screening by using a screen with 20-400 meshes, and carrying out chemical copper plating or nickel plating treatment on the screened short carbon fibers to obtain the chemical plating short carbon fibers which are well coated by the thin chemical plating layer;
or weaving the undersize chopped carbon fibers into short carbon fiber felt cloth, and then carrying out chemical copper plating or nickel plating treatment to obtain the chemical plating short carbon fiber felt cloth which is completely coated by the thin chemical plating layer;
thereby completing the short carbon fiber chemical plating;
step two, preparing a block amorphous alloy master alloy ingot:
weighing the components with required dosage according to the composition components of the selected base alloy, and uniformly mixing the weighed raw materials of the componentsPutting into a high vacuum induction melting furnace or a high vacuum arc furnace for melting, and before melting, firstly extracting the high vacuum induction melting furnace or the high vacuum arc furnace to the vacuum degree of-1.0 multiplied by 10-4Pa～-1.0×10-2Pa, then filling argon to the vacuum degree of-0.3 MPa to-0.6 MPa, smelting the raw materials of the components at the temperature of 900-1800 ℃, cooling the raw materials along with the furnace after the raw materials are smelted into liquid to prepare a block amorphous alloy mother alloy ingot, and crushing the mother alloy ingot into small blocks for later use;
step three, preparing a chopped carbon fiber preform:
filling the chemically plated chopped carbon fibers or chemically plated chopped carbon fiber felt cloth obtained in the first step into a copper die inner cavity, wherein the diameter of the copper die inner cavity is 2-30 mm, applying pressure through a standard balance weight of 10-50 g, and pressing by shaking a table or shaking a bed to adjust the pore size between the carbon fibers to be 50-300 mu m so as to prepare a chopped carbon fiber preform;
fourthly, preparing the chopped carbon fiber reinforced amorphous composite material:
placing the fragments of the block amorphous alloy mother alloy ingot prepared in the second step into a thick tube part of a quartz tube, wherein the lower end of the quartz tube is provided with a nozzle with the diameter of 0.5 mm-2 mm, loading the quartz tube into a high vacuum induction heating spray casting furnace with a closed furnace body, and vacuumizing the closed furnace body to-1.0 multiplied by 10-3Pa～-1.0×10-1Pa, then filling argon to the vacuum degree of-0.3 MPa to-0.5 MPa, melting the fragments of the block amorphous alloy master alloy cast ingot in the thick pipe part of the quartz pipe into a melt through a water-cooling induction heating coil, blowing the melt into the inner cavity of the copper mold filled with the prepared chopped carbon fiber preform in the third step in a negative pressure state through a nozzle at the lower end of the quartz pipe by adopting argon as a pressure source at the positive pressure of 0.2MPa to 2MPa, completely filling the melt formed by melting the fragments of the block amorphous alloy master alloy cast ingot into the pores of the chopped carbon fiber preform under the pressure infiltration, simultaneously providing the cooling speed of 400K/s to 1000K/s by the copper mold to rapidly form the chopped carbon fiber reinforced amorphous composite material, taking the amorphous composite material out after cooling, wherein the diameter of the amorphous composite material is 2mm to 30mm, and the length of the amorphous composite material is 2mm to 30mm5 mm-20 cm short carbon fiber reinforced amorphous composite round bar, and the preparation of the short carbon fiber reinforced amorphous composite is completed by adopting a vacuum low-pressure casting method, namely a spray casting method.
The preparation method of the chopped carbon fiber reinforced amorphous composite material comprises the following steps of: ti37.3Zr22.7Be25.5Fe5.5Cu9、Zr41.2Ti13.8Cu12.5Ni10.0Be22.5Or Mg59.5Cu22.9Ag6.6Gd11。
According to the preparation method of the chopped carbon fiber reinforced amorphous composite material, the chemically plated chopped carbon fibers or chemically plated short carbon fiber felt cloth which is completely coated by the thin chemical plating layer is obtained, and the thickness of the thin chemical plating layer is 100 nm-800 nm.
According to the preparation method of the chopped carbon fiber reinforced amorphous composite material, the chemically plated chopped carbon fibers or chemically plated chopped carbon fiber felt cloth obtained in the first step is filled into an inner cavity of a copper mold, and any one of complete filling, partial filling or inner surface pasting of the mold is adopted.
The raw materials and equipment used in the preparation method of the chopped carbon fiber reinforced amorphous composite material are obtained by known ways, and the operation method can be mastered by those skilled in the art.
The device used in the preparation method of the chopped carbon fiber reinforced amorphous composite material specifically comprises the following steps:
the components of the device used in the preparation method of the chopped carbon fiber reinforced amorphous composite material comprise: the device comprises an air inlet, a closed high-vacuum induction heating spray casting furnace body, a quartz tube with a nozzle with the diameter of 0.5-2 mm at the lower end of a thick tube part, a water-cooling induction heating coil, high-temperature daub, a split copper mold with the inner cavity diameter of 2-30 mm, and a valve which is used for a gas outlet and is connected with a vacuum system and arranged on one side below the closed high-vacuum induction heating spray casting furnace body; the connection mode of each component of the device is as follows: the split type copper mold is arranged in the central position inside the closed type high-vacuum induction heating spray casting furnace body, the water-cooling induction heating coil is arranged around the thick tube part of the quartz tube, the nozzle part of the quartz tube is in contact communication with the inner cavity of the split type copper mold from the top of the split type copper mold and is sealed by high-temperature cement to avoid air leakage, the top of the thick tube part of the quartz tube is provided with a cover, and the center of the cover is provided with an air inlet;
the operation method of the device used in the preparation method of the chopped carbon fiber reinforced amorphous composite material comprises the following steps: when the chopped carbon fiber reinforced amorphous composite material is prepared, a carbon fiber prefabricated body is firstly placed into an inner cavity of a split type copper mold, fragments of a block amorphous alloy master alloy cast ingot are placed into a thick tube part of a quartz tube, and a closed high-vacuum induction heating spray casting furnace body is pumped to a required vacuum degree of-1.0 multiplied by 10 through a vacuum system connected with a valve-4Pa～-1.0×10-2Pa, then filling argon to the vacuum degree of-0.3 MPa to-0.5 MPa, then melting the master alloy raw material by using a water-cooling induction heating coil to form an amorphous alloy melt, applying positive-pressure argon with the required pressure of 0.2MPa to 2MPa through an air inlet, spraying the amorphous alloy melt into an inner cavity of a split type copper die in a negative pressure state, completely filling the amorphous alloy melt into pores of the chopped carbon fiber preform under pressure infiltration, simultaneously providing a cooling speed of 400K/s to 1000K/s by the split type copper die to rapidly form the chopped carbon fiber reinforced amorphous composite material, and taking out a chopped carbon fiber reinforced amorphous composite material round bar with the diameter of 2mm to 30mm and the length of 5mm to 20cm after cooling.
The constituent parts of the apparatus used in the above-described method for producing a chopped carbon fiber-reinforced amorphous composite material are obtained by known means, and the manner of connection and the method of operation thereof will be understood by those skilled in the art.
The invention has the beneficial effects that: compared with the prior art, the invention has the following prominent substantive characteristics and remarkable progress:
(1) the invention uses chemical plating method to coat metal coating on the surface of short carbon fiber to improve the wettability of carbon fiber and matrix amorphous alloy. The chemical copper plating or nickel plating method is used for carrying out surface modification on the carbon fiber, the content of introduced oxygen is low, and the negative damage effect of the introduced copper or nickel on the amorphous forming capability of Ti-based, Zr-based and Mg-based amorphous alloys is small, so that the method is beneficial to the formation of the matrix with an amorphous structure.
(2) Compared with CN101956148B a double composite high-strength and toughness block amorphous alloy and its preparation method, the invention has the prominent substantive features and remarkable progress that: 1) the surface of the carbon fiber is modified by adopting a chemical copper plating or nickel plating method, so that the wettability of the carbon fiber and the amorphous alloy liquid is improved; 2) the invention adopts the copper mold to cool the composite material, and the cooling speed is obviously faster than that of the water quenching method involved in CN 101956148B.
(3) Compared with CN101250677A a titanium dioxide coating carbon fiber reinforced magnesium-based composite material, the invention has the prominent substantive characteristics and remarkable progress that: 1) the metal elements contained in the metal coating are all elements beneficial to the amorphous forming capability of the matrix alloy, and the TiO 101250677A in CN101250677A cannot be introduced into the amorphous alloy matrix2Such inorganic oxides, thereby destroying the amorphous forming ability of the base alloy; 2) the invention adopts vacuum melting aiming at metal liquid with high melting point and easy oxidation such as zirconium and titanium, and CN101250677A only aims at magnesium alloy with low melting point, thus the applicability is limited; 3) the invention adopts vacuum low-pressure casting, has less gas suction amount, obviously reduces gas and air holes in the composite material, and lacks a vacuum degassing process in the CN101250677A technology.
(4) Compared with the preparation method of the CN111155038A chopped carbon fiber reinforced magnesium-based composite material, the preparation method has the prominent substantive characteristics and remarkable progress that: 1) the invention adopts the chemical copper plating or nickel plating method to modify the surface of the carbon fiber, the content of the introduced oxygen is low, and the negative effect of the introduced copper and nickel on the amorphous forming capability of the titanium-based, zirconium-based and magnesium-based amorphous alloy is small, thereby being beneficial to the formation of the amorphous structure; 2) the invention adopts two chopped carbon fiber chemical plating with simpler preparation processes, one is to take the sieved chopped carbon fibers to carry out chemical copper plating or nickel plating treatment, and the other is to weave the chopped carbon fibers into short carbon fiber felt cloth and then carry out chemical copper plating or nickel plating treatment to obtain the chemical plated chopped carbon fibers or chemical plated short carbon fiber felt cloth, wherein the two preparation processes are both more simplified than the technical process published by CN 111155038A; 3) the preparation of the chopped carbon fiber reinforced amorphous composite material adopts a vacuum low-pressure casting method, and compared with the extrusion casting and hot-pressing method adopted by CN111155038A, the preparation method reduces the porosity and prevents the oxidation of metal liquid, and is more suitable for the production of amorphous alloy.
(4) Compared with CN108385040B a chopped carbon fiber reinforced magnesium-aluminum matrix composite and its preparation method, the invention has the prominent substantive features and remarkable progress that: 1) the invention adopts chemical copper plating or nickel plating, improves the wettability between the carbon fiber and the metal, avoids interface reaction while improving the wettability, and CN108385040B only enhances the wettability of the carbon fiber through the preheating treatment of the carbon fiber, so that the contact interface reaction between the metal liquid and the carbon fiber cannot be avoided; 2) according to the invention, the copper mold is used as a container of the carbon fiber preform, so that long-time contact between the metal liquid and the carbon fiber is avoided in the preparation process of the composite material, and thus complex interface reaction is avoided, while CN108385040B adopts a semi-solid stirring method, so that the contact time between the metal liquid and the carbon fiber is long, and uncontrollable interface reaction is generated; 3) the technical scheme of CN108385040B is only suitable for the traditional magnesium-aluminum alloy, but is not suitable for the amorphous alloy system which is easy to generate interface reaction, and the invention carries out technical innovation on the amorphous alloy matrix, and is particularly suitable for the preparation of amorphous composite materials.
(5) The metal plating layer prepared by the chemical plating method is uniform, the process equipment is simple, the cost is lower, and the chemical plating method is easy to control. The thickness of the plating layer is 100 nm-800 nm, the grain size is small, the plating layer is melted with the matrix alloy in the preparation process of the composite material, but the amorphous forming capability of the zirconium-based, magnesium-based and titanium-based amorphous alloy is not reduced, the wettability of the carbon fiber and the amorphous alloy matrix is effectively improved, the melting of the plating layer can ensure that the carbon fiber does not generate chemical reaction, the interface microstructure of the carbon fiber and the amorphous alloy matrix is improved, and the strength of the amorphous composite material is improved.
(6) A standard pure copper mold was used as a container for carbon fiber preforms and a mold for casting amorphous alloy matrix. The copper mold casting method is a universal casting method, and the process is simple and has good operability. The shape and size of the inner cavity of the copper die can be designed according to the requirement of the casting. The filling of the chopped carbon fiber or the short carbon fiber felt adopts the modes of complete filling, partial filling, die inner surface pasting and the like, and the preparation of the amorphous alloy member with the complex structure and the local carbon fiber composite is realized. After the chemical plating chopped carbon fibers or the chemical plating chopped carbon fiber felt cloth is filled into an inner cavity of a copper mold, the size of pores among the carbon fibers is adjusted by pressing through a heavy object with the weight of a standard balance weight of 10 g-50 g, shaking of a shaking table or vibration of a shaking bed, the method provides the cooling speed of 400K/s-1000K/s for the amorphous matrix, also ensures the uniform distribution of the carbon fibers in the composite material, and ensures the requirements of the appearance and the size of a casting.
(7) Compared with the traditional pressure infiltration-water quenching cooling method, the method has the advantages that the process is simpler, the liquid phase immersion time of the composite material is shorter, the complex and time-consuming interface reaction is completed before the preparation of the composite material is carried out, the occurrence of the interface reaction is effectively controlled, and the subsequent compression molding is carried out by heating to the amorphous alloy supercooled liquid phase region, so that the defects of high porosity and insufficient infiltration of an amorphous matrix of the prepared composite material can be overcome, and the parts with more complex shapes can be prepared.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a schematic structural diagram of an apparatus used in a method for preparing a chopped carbon fiber reinforced amorphous composite material.
FIG. 2 is a schematic view of an example of a round rod made of amorphous composite material prepared by the method of the present invention.
FIG. 3 is a comparison of XRD spectra of a short carbon fiber reinforced titanium-based amorphous composite material prepared by the method of the present invention and a titanium-based amorphous matrix alloy.
Fig. 4(a) is an SEM image of the interface between the carbon fiber and the matrix in the short carbon fiber reinforced titanium-based amorphous composite material.
Fig. 4(b) is an EDS line scan energy spectrum of the interface between the carbon fiber and the matrix in the short carbon fiber reinforced ti-based amorphous composite.
FIG. 5 is an SEM image of the interaction between the carbon fibers on the side surface of the amorphous composite round bar after compression deformation and the shear band on the surface of the amorphous composite sample prepared by the method of the invention.
FIG. 6 is a block diagram illustrating the flow of the method of the present invention.
In the figure, 1, an air inlet, 2, a closed high vacuum induction heating spray casting furnace body, 3, a quartz tube with a nozzle with the diameter of 0.5 mm-2 mm is arranged at the lower end of a thick tube part, 4, a water-cooling induction heating coil, 5, an amorphous alloy melt, 6, high-temperature daub, 7, a carbon fiber preform, 8, a split type copper mold, 9, a valve, 10, a short carbon fiber reinforced amorphous composite round bar, 11, an un-soaked carbon fiber preform, 12, a shear band on the surface of an amorphous composite sample, and 13, carbon fibers on the side face of the amorphous composite round bar after compression deformation.
Detailed Description
The embodiment shown in fig. 1 shows that the constituent components of the apparatus used in the method for preparing a chopped carbon fiber reinforced amorphous composite material include: the device comprises an air inlet 1, a closed high-vacuum induction heating spray casting furnace body 2, a quartz tube 3 with a nozzle with the diameter of 0.5-2 mm at the lower end of a thick tube part, a water-cooling induction heating coil 4, high-temperature daub 6, a split copper mold 8 with the inner cavity diameter of 2-30 mm, and a valve 9 which is used for a gas outlet and is connected with a vacuum system and arranged on one side below the closed furnace body 2; the connection mode of each component of the device is as follows: the inside central point of furnace body 2 of closed is arranged in to split type copper mould 8, and water-cooling induction heating coil 4 sets up around the thick pipe part of quartz capsule 3, and the spout part of quartz capsule 3 is from the inner chamber contact intercommunication of split type copper mould 8 top and split type copper mould 8 and use high temperature clay 6 to seal and avoid leaking gas, and the top that has the thick pipe part of quartz capsule 3 is equipped with the lid, and the central authorities of lid are equipped with air inlet 1.
The embodiment shown in fig. 2 shows that the chopped carbon fiber reinforced amorphous composite material is prepared by using a split type copper mold 8 with an inner cavity diameter of 5mm, a chopped carbon fiber reinforced amorphous composite material round bar 10 with a length of 35mm is obtained after cooling and mold opening, and the rest part is an un-infiltrated carbon fiber preform 11.
Fig. 3 shows an example of comparison between XRD spectra of the chopped carbon fiber reinforced titanium-based amorphous composite material prepared by the method of the present invention and titanium-based amorphous matrix alloy, X-ray diffraction spectra of the short carbon fiber reinforced titanium-based amorphous composite material prepared by the method of the present invention and titanium-based amorphous matrix alloy both have typical amorphous characteristics, and amorphous diffuse scattering peaks of the short carbon fiber reinforced titanium-based amorphous composite material prepared by the method of the present invention can be decomposed into two, one is a diffuse scattering peak of carbon fiber, and the other is a diffuse scattering peak of matrix amorphous alloy.
The example shown in fig. 4(a) shows that no obvious carbide exists at the interface between the carbon fiber and the matrix in the chopped carbon fiber reinforced titanium-based amorphous composite material prepared by the invention, and the shape of the carbon fiber is maintained as it is, which indicates that no interface reaction occurs.
The example shown in FIG. 4(b) shows that the content of Ti and Zr in the chopped carbon fiber reinforced Ti-based amorphous composite material prepared by the present invention is not increased at the interface, and further proves that the carbonization reaction at the interface is successfully inhibited.
The embodiment shown in fig. 5 shows that the carbon fibers 13 on the side surface of the amorphous composite round bar after the chopped carbon fiber reinforced titanium-based amorphous composite material prepared by the method is compressed and deformed form an obvious interaction with the shear band 12 on the surface of the amorphous composite material sample, and the chopped carbon fibers are proved to have the effect of improving the plastic deformation capacity of the matrix amorphous alloy.
The embodiment shown in fig. 6 shows that the process of the method of the present invention is: chemical plating of chopped carbon fibers → preparation of a chopped carbon fiber preform, preparation of a block amorphous alloy master alloy ingot → preparation of a chopped carbon fiber reinforced amorphous composite material.
Example 1
The components of the device used in the preparation method of the chopped carbon fiber reinforced amorphous composite material comprise: the device comprises an air inlet 1, a closed high-vacuum induction heating spray casting furnace body 2, a quartz tube 3 with a nozzle with the diameter of 0.5-2 mm at the lower end of a thick tube part, a water-cooling induction heating coil 4, high-temperature daub 6, a split copper mold 8 with the inner cavity diameter of 2-30 mm, and a valve 9 which is used for a gas outlet and is connected with a vacuum system and arranged on one side below the closed furnace body 2; the connection mode of each component of the device is as follows: the split type copper mold 8 is arranged in the center of the inside of the closed furnace body 2, the water-cooling induction heating coil 4 is arranged around the thick pipe part of the quartz tube 3, the nozzle part of the quartz tube 3 is communicated with the inner cavity of the split type copper mold 8 from the top of the split type copper mold 8 in a contact manner and is sealed by high-temperature cement paste 6 to avoid air leakage, the top of the thick pipe part with the quartz tube 3 is provided with a cover, and the center of the cover is provided with an air inlet 1;
the operation method of the device used in the preparation method of the chopped carbon fiber reinforced amorphous composite material comprises the following steps: when the chopped carbon fiber reinforced amorphous composite material is prepared, the short carbon fiber or short carbon fiber cloth prefabricated body 7 is firstly placed into the inner cavity of the split type copper mold 8, the fragments of the block amorphous alloy master alloy cast ingot are placed into the thick pipe part of the quartz pipe 3, and then the closed high-vacuum induction heating spray casting furnace body 2 is pumped by the vacuum system connected with the valve 9 until the required vacuum degree is-1.0 multiplied by 10-4Pa～-1.0×10-2Pa, then filling argon gas to the vacuum degree of-0.3 MPa to-0.5 MPa, then melting the master alloy raw material by using a water-cooling induction heating coil 4 to form an amorphous alloy melt 5, applying positive pressure argon gas with the required pressure of 0.2MPa to 2MPa through an air inlet 1, spraying the amorphous alloy melt 5 into an inner cavity of a split type copper mold 8 in a negative pressure state, completely filling the amorphous alloy melt 5 into pores of a carbon fiber preform 7 under pressure infiltration, simultaneously providing a cooling speed of 400K/s to 1000K/s by the split type copper mold 8 to rapidly form the chopped carbon fiber reinforced amorphous composite material, and cooling and taking out a chopped carbon fiber reinforced amorphous composite material round bar with the diameter of 2mm to 30mm and the length of 5mm to 20 cm.
In the above embodiments, the constituent elements of the apparatus used are obtained by known means, and the connection manner and operation method thereof are known to those skilled in the art.
The following examples of the method for producing a chopped carbon fiber-reinforced amorphous composite material are all the apparatuses and the methods of operation thereof shown in example 1.
Example 2
Step one, short carbon fiber chemical plating:
by usingShearing commercial T800 carbon fibers, screening by using a 400-mesh screen, taking the screened chopped carbon fibers to obtain chopped carbon fibers with the length of 30 mu m, and carrying out chemical copper plating treatment on the chopped carbon fibers, wherein the process comprises the following steps: pretreatment → sensitization, activation → reduction → plating, wherein the pretreatment uses a burning method and organic solvent soaking, the specific process is that 1h is carried out in a heating furnace at the temperature of 420 ℃, then acetone is used for soaking for 1h, then alcohol is used for ultrasonic cleaning for 15min, concentrated nitric acid is used for soaking for 1h for coarsening after drying, then clear water is used for repeatedly washing until all residual nitric acid is removed, and then alcohol is used for dehydration and drying; the sensitization and activation are implemented by putting the coarsened carbon fiber into a sensitization-activation liquid for mechanical stirring for 15min, wherein the formulation of the sensitization-activation liquid is 30g/L of stannous chloride, 60mL/L of hydrochloric acid with the weight percentage concentration of 37%, 0.5g/L of palladium chloride and 160g/L of sodium chloride; the reduction is to clean the sensitized and activated short carbon fiber, put the short carbon fiber into 30g/L sodium hypophosphite solution and stir for 15min, and reduce the PdCl residual on the surface of the carbon fiber2(ii) a The plating is to put the reduced carbon fiber into plating solution to be stirred and plated for 10min, and the formula of the plating solution is as follows: 16g/L of potassium sodium tartrate, 10mg/L of potassium ferrocyanide, 20mg/L of 2-2 bipyridine, 0.3g/L of nano-alumina, 25g/L of copper sulfate, 40mL/L of formaldehyde, 24g/L of sodium ethylenediamine and a proper amount of sodium hydroxide are used for adjusting the pH value of the plating solution to 12.1; controlling the plating temperature to be 25 ℃ by using a water bath heating device to obtain chemically plated short carbon fibers completely coated by a thin copper-plated chemical plating layer, wherein the thickness of the thin chemical plating layer is 100 nm;
thereby completing the short carbon fiber chemical plating;
second, bulk amorphous alloy Ti37.3Zr22.7Be25.5Fe5.5Cu9(at.%) preparation of master alloy ingots:
according to the selected base alloy Ti37.3Zr22.7Be25.5Fe5.5Cu9(at.%) weighing the components Ti, Zr, Be, Fe and Cu, smelting in high-vacuum arc furnace to-1.0X 10-4Pa, then filling argon to a vacuum degree of-0.5 MPaThe raw material ingredients are melted at the temperature of 1800 ℃, and the melted raw material ingredients are cooled along with the furnace after being melted into liquid to prepare the bulk amorphous alloy Ti37.3Zr22.7Be25.5Fe5.5Cu9(at.%) a master alloy ingot, which is broken into small pieces for use;
step three, preparing a chopped carbon fiber preform:
filling the chemically plated chopped carbon fibers obtained in the first step into an inner cavity of a copper die in a complete filling mode, wherein the diameter of the inner cavity of the copper die is 2mm, applying pressure by a standard balance weight of 10g, and shaking a table for pressing to adjust the size of pores among the carbon fibers to be 50 microns, so as to prepare a copper-plated chopped carbon fiber preform;
fourthly, preparing the chopped carbon fiber reinforced amorphous composite material:
the block amorphous alloy Ti prepared by the second step37.3Zr22.7Be25.5Fe5.5Cu9(at.%) fragments of mother alloy ingot are put in the thick tube of a quartz tube with a nozzle at its lower end and diameter of 0.5mm, and then the quartz tube is loaded in a high-vacuum induction heating spray casting furnace with a closed furnace body, and the vacuum degree of the closed furnace body is pumped to-1.0X 10-3Pa, then filling argon to the vacuum degree of-0.3 MPa, and leading the bulk amorphous alloy Ti in the thick tube part of the quartz tube to pass through a water-cooled induction heating coil37.3Zr22.7Be25.5Fe5.5Cu9(at.%) the broken pieces of mother alloy ingot are molten into melt, argon gas is used as pressure source, and the melt is blown into the inner cavity of copper mould containing copper-plated short carbon fibre prefabricated body in the third step in negative pressure state by means of nozzle at lower end of quartz tube under the condition of 2MPa positive pressure, and the bulk amorphous alloy Ti is formed37.3Zr22.7Be25.5Fe5.5Cu9(at.%) molten mass of the broken pieces of mother alloy ingot is filled into the pores of the copper-plated chopped carbon fibre prefabricated body under pressure infiltration, and the copper mould provides 1000K/s cooling speed to make the chopped carbon fibre reinforced amorphous composite material quickly formed, after cooling, the material is taken out, and its diameter is 2mm and length is 5mm, preparing the chopped carbon fiber reinforced amorphous composite material by adopting a vacuum low-pressure casting method, namely a spray casting method;
fifth, Performance test
And cutting the chopped carbon fiber reinforced amorphous composite round bar prepared in the fourth step into standard compressed samples with the diameter-height ratio of 1: 2 by using a diamond cutting saw, and erecting 6 samples side by side for XRD test to prove that the composite matrix is mainly in an amorphous structure. The cross section of the compressed sample is polished and then subjected to SEM observation and EDS test, which proves that serious interface reaction is not caused in the experiment. After compression testing, the composite material sample shows obvious plastic deformation capacity, the yield strength reaches 1800MPa, and the compression plasticity is 7.6%.
Example 3
Step one, short carbon fiber chemical plating:
the method comprises the following steps of shearing commercial T200 carbon fibers, screening by using a 100-mesh screen, taking the undersize chopped carbon fibers to obtain 0.2 mm-long chopped carbon fibers, and carrying out chemical nickel plating treatment on the chopped carbon fibers, wherein the basic process of the chemical nickel plating comprises the following steps: pretreatment → sensitization → activation → reduction → plating. The pretreatment comprises the steps of using a burning method and organic solvent soaking, specifically, soaking for 1h in a heating furnace at the temperature of 420 ℃, then soaking for 1h in acetone, ultrasonically cleaning for 15min in alcohol, soaking for 1h in concentrated nitric acid after drying for coarsening, then repeatedly washing with clear water until the pH value of water after washing is 6.8, and then dehydrating and drying with alcohol; the sensitization is that the coarsened chopped carbon fiber is put into a sensitization liquid prepared by stannous chloride with the component of 20g/L and hydrochloric acid with the weight percentage concentration of 37 percent of 40mL/L for mechanical stirring for 25 min; the activation is to put the sensitized carbon fiber into an activation solution prepared by 0.1g/L palladium chloride and 10mL/L hydrochloric acid and mechanically stir for 20 min; the reduction is to clean the sensitized and activated chopped carbon fibers, put the cleaned and activated chopped carbon fibers into 30g/L sodium hypophosphite solution, stir the mixture for 15min, and reduce the PdCl residual on the surfaces of the chopped carbon fibers2(ii) a The plating is to put the reduced short carbon fiber into plating solution to be stirred and plated for 20min, and the formula of the plating solution is as follows: 30g/L of nickel sulfate hexahydrate, 20g/L of sodium dihydrogen phosphate and lemon20g/L of sodium, 10g/L of sodium acetate, 20g/L of ammonium chloride and 0.1g/L of nano-alumina, and adjusting the pH to 12.5 by adopting a proper amount of sodium hydroxide; adjusting the plating temperature to 50 ℃ by using a water bath device during plating to obtain chemically plated short carbon fibers completely coated by a nickel-plated chemical plating thin plating layer, wherein the thickness of the thin chemical plating layer is 300 nm;
thereby completing the short carbon fiber chemical plating;
secondly, preparing a bulk amorphous alloy Vit1 master alloy ingot:
zr according to the composition of the selected matrix alloy Vit1 alloy41.2Ti13.8Cu12.5Ni10.0Be22.5Weighing raw materials Zr, Ti, Be, Ni and Cu at.%, weighing the components with required dosage, putting the weighed raw materials into a high-vacuum electric arc furnace for smelting, and extracting the high-vacuum electric arc furnace to the vacuum degree of-1.0 x 10 before smelting-3Pa, then filling argon to the vacuum degree of-0.4 MPa, smelting the component raw material ingredients at the temperature of 1700 ℃, cooling the liquid with the furnace to prepare a block Vit1 amorphous alloy mother alloy ingot, and crushing the mother alloy ingot into small blocks for later use;
step three, preparing a chopped carbon fiber preform:
filling the chemical plating short carbon fiber felt cloth obtained in the first step into a copper mold cavity by adopting a partial filling mode, wherein the diameter of the copper mold cavity is 20mm, applying pressure by a standard balance weight of 40g, and pressing by vibration of a vibration bed to adjust the size of pores among carbon fibers to be 200 mu m, thereby preparing a nickel plating short carbon fiber preform;
fourthly, preparing the chopped carbon fiber reinforced amorphous composite material:
placing the fragments of the bulk Vit1 amorphous alloy master alloy ingot prepared in the second step into a thick tube part of a quartz tube, wherein the lower end of the quartz tube is provided with a nozzle with the diameter of 1.2mm, loading the quartz tube into a high vacuum induction heating spray casting furnace with a closed furnace body, and vacuumizing the closed furnace body to-1.0 x 10-2Pa, then introducing argon to a vacuum of-0.4 MPa, passing the mixture through a water-cooled induction heating coilMelting fragments of a bulk Vit1 amorphous alloy master alloy ingot in a thick pipe part of a quartz pipe into a melt, blowing the melt into an inner cavity of a copper mold filled with a prepared chopped carbon fiber preform in the third step in a negative pressure state through a nozzle at the lower end of the quartz pipe by using argon as a pressure source at the positive pressure of 1.1MPa, completely filling nickel-plated holes of the chopped carbon fiber preform by the melt melted by the fragments of the bulk Vit1 amorphous alloy master alloy ingot under pressure infiltration, simultaneously providing a cooling speed of 700K/s by the copper mold to rapidly form the chopped carbon fiber reinforced amorphous composite material, cooling, taking out a chopped carbon fiber reinforced amorphous composite material round bar with the diameter of 20mm and the length of 20cm, and thus completing the preparation of the chopped carbon fiber reinforced amorphous composite material by adopting a vacuum low-pressure casting method;
fifthly, performance characterization:
and cutting the composite material round rod prepared in the fourth step into standard compressed samples with the diameter-height ratio of 1: 2 by using a diamond cutting saw, and erecting 1 sample to perform XRD (X-ray diffraction) test to prove that the composite material matrix is mainly in an amorphous structure. The cross section of the compressed sample is polished and then subjected to SEM observation and EDS test, which proves that serious interface reaction is not caused in the experiment. After compression testing, the composite material sample shows obvious plastic deformation capacity, the yield strength reaches 1750MPa, and the compression plasticity is 5.5%.
Example 4
Step one, short carbon fiber chemical plating:
the method comprises the following steps of shearing commercial T700 carbon fibers, screening by using a 20-mesh screen, taking the undersize chopped carbon fibers to obtain chopped carbon fibers with the length of 0.8mm, and carrying out chemical nickel plating treatment on the chopped carbon fibers, wherein the basic process of the chemical nickel plating comprises the following steps: pretreatment → sensitization → activation → reduction → plating. The pretreatment comprises the steps of using a burning method and organic solvent soaking, specifically, soaking for 1h in a heating furnace at the temperature of 420 ℃, then soaking for 1h in acetone, ultrasonically cleaning for 15min in alcohol, soaking for 1h in concentrated nitric acid after drying for coarsening, then repeatedly washing with clear water until the pH value of water after washing is 6.8, and then dehydrating and drying with alcohol; sensitization is carried out by putting coarsened chopped carbon fiber into the reactorThe components are stannous chloride of 20g/L and hydrochloric acid of 40mL/L with the weight percentage concentration of 37 percent, and the mixture is mechanically stirred for 30 min; the activation is to put the sensitized carbon fiber into an activation solution prepared by 0.2g/L palladium chloride and 10mL/L hydrochloric acid and mechanically stir for 30 min; the reduction is to clean the sensitized and activated chopped carbon fibers, put the cleaned and activated chopped carbon fibers into 30g/L sodium hypophosphite solution, stir the mixture for 15min, and reduce the PdCl residual on the surfaces of the chopped carbon fibers2(ii) a The plating is to put the reduced short carbon fiber into plating solution to be stirred and plated for 25min, and the formula of the plating solution is as follows: 30g/L of nickel sulfate hexahydrate, 20g/L of sodium dihydrogen phosphate, 20g/L of sodium citrate, 10g/L of sodium acetate, 20g/L of ammonium chloride and 0.1g/L of nano-alumina, and adjusting the pH to 12.5 by adopting a proper amount of sodium hydroxide; adjusting the plating temperature to 50 ℃ by using a water bath device during plating to obtain chemically plated short carbon fibers completely coated by a nickel-plated chemical plating thin plating layer, wherein the thickness of the thin chemical plating layer is 500 nm;
thereby completing the short carbon fiber chemical plating;
secondly, preparing a bulk amorphous alloy Vit1 master alloy ingot:
the specific procedure was exactly the same as the second step in example 3;
step three, preparing a chopped carbon fiber preform:
filling the chemical plating short carbon fiber felt cloth obtained in the first step into a copper mold cavity by adopting a partial filling mode, wherein the diameter of the copper mold cavity is 30mm, applying pressure by a standard balance weight of 50g, and pressing by using vibration of a vibration bed to adjust the size of pores among carbon fibers to be 300 mu m, thereby preparing a nickel plating short carbon fiber preform;
fourthly, preparing the chopped carbon fiber reinforced amorphous composite material:
placing the fragments of the bulk Vit1 amorphous alloy mother alloy ingot prepared in the second step into a thick tube part of a quartz tube, wherein the lower end of the quartz tube is provided with a nozzle with a diameter of 2mm, loading the quartz tube into a high vacuum induction heating spray casting furnace with a closed furnace body, and vacuumizing the closed furnace body to-1.0 × 10-2Pa, then filling argon to the vacuum degree of-0.6 MPa, and passing through a water-cooling induction heating coil to make the quartz tube thick tubeMelting fragments of a bulk Vit1 amorphous alloy mother alloy cast ingot in a part of the amorphous alloy mother alloy cast ingot into a melt, blowing the melt into an inner cavity of a copper mold which is filled with a prepared chopped carbon fiber preform and is in a negative pressure state in the third step by using argon as a pressure source through a nozzle at the lower end of a quartz tube under the positive pressure of 1MPa, completely filling the melt which is melted by the fragments of the bulk Vit1 amorphous alloy cast ingot into pores of the nickel-plated chopped carbon fiber preform under the pressure infiltration, simultaneously providing a cooling speed of 200K/s by the copper mold to rapidly form the chopped carbon fiber reinforced amorphous composite material, cooling, taking out a chopped carbon fiber reinforced amorphous composite material round bar with the diameter of 30mm and the length of 4cm, and thus completing the preparation of the chopped carbon fiber reinforced amorphous composite material by adopting a vacuum low-pressure casting method;
fifthly, performance characterization:
and cutting the composite material round rod prepared in the fourth step into standard compressed samples with the diameter-height ratio of 1: 2 by using a diamond cutting saw, and performing XRD (X-ray diffraction) test on 1 sample to prove that the composite material matrix is mainly in an amorphous structure. The cross section of the compressed sample is polished and then subjected to SEM observation and EDS test, which proves that serious interface reaction is not caused in the experiment. After compression testing, the composite material sample shows obvious plastic deformation capacity, the yield strength reaches 1720MPa, and the compression plasticity is 3.5%.
Example 5
Step one, short carbon fiber chemical plating:
the commercial short carbon fiber felt cloth woven by the T700 carbon fiber chopped fiber product is subjected to electroless copper plating treatment. The basic process for electroless copper plating of the short carbon fiber felt cloth comprises the following steps: pretreatment → sensitization, activation → reduction → plating. Wherein the pretreatment comprises soaking in acetone for 1h, ultrasonically cleaning with alcohol for 15min, drying, soaking in concentrated nitric acid for 1h for coarsening, repeatedly washing with clear water until the pH value of the washed water is 6.8, and dehydrating with alcohol; the sensitization and activation are to put the coarsened short carbon fiber felt cloth into a sensitization-activation liquid for soaking for 30min, and the formulation of the sensitization-activation liquid is 30g/L of stannous chloride, 60mL/L of hydrochloric acid with the weight percentage concentration of 37 percent, 0.5g/L of palladium chloride and 160g/L of sodium chloride; reduction is toCleaning the sensitized and activated short carbon fiber felt, putting the felt into 30g/L sodium hypophosphite solution, stirring for 15min, and reducing PdCl residual on the surface of the short carbon fiber felt2(ii) a The plating is to put the reduced short carbon fiber felt into plating solution to be stirred and plated for 10min to 30min, and the formula of the plating solution is as follows: 16g/L of potassium sodium tartrate, 10mg/L of potassium ferrocyanide, 20mg/L of 2-2 bipyridine, 0.3g/L of nano-alumina, 25g/L of copper sulfate, 40mL/L of formaldehyde, 24g/L of sodium ethylenediamine and a proper amount of sodium hydroxide are used for adjusting the pH value of the plating solution to 12.6; the plating temperature is adjusted to 50 ℃ by a water bath device to obtain thin chemical copper plating short carbon fiber felt cloth with good coating property, and the thickness of the thin chemical plating layer is 800 nm;
thereby completing the short carbon fiber chemical plating;
secondly, preparing a block amorphous alloy Mg-Cu-Ag-Gd master alloy ingot:
according to the composition of the selected matrix alloy, Mg59.5Cu22.9Ag6.6Gd11(at.%) weighing the needed amount of Mg, Ag, Gd and Cu, putting the weighed raw materials of Cu-Ag-Gd into a high vacuum induction smelting furnace for smelting, and before smelting, extracting the high vacuum induction smelting furnace to the vacuum degree of-1.0 x 10-2Pa, then filling argon gas to the vacuum degree of-0.6 MPa, smelting component raw material ingredients at the temperature of 900 ℃ to obtain a Cu-Ag-Gd intermediate alloy, mixing the obtained Cu-Ag-Gd intermediate alloy ingot with the weighed magnesium block, adopting argon protection, adopting a smelting process consistent with the smelting of the Cu-Ag-Gd intermediate alloy, remelting in a high-vacuum induction smelting furnace, cooling along with the furnace after smelting into liquid to obtain a bulk amorphous alloy Mg-Cu-Ag-Gd mother alloy ingot, and then crushing the mother alloy ingot into small blocks for later use;
step three, preparing a chopped carbon fiber preform:
cutting the thin electroless copper plating short carbon fiber felt cloth obtained in the first step into strips of 2.5mm multiplied by 50mm, filling the strips into an inner cavity of a copper die in a mode of pasting the inner surface of the die, wherein the diameter of the inner cavity of the copper die is 3mm, applying pressure through a standard balance weight of 30g, and shaking a table to shake and press the strips so as to adjust the size of pores among carbon fibers to be 100 mu m, thereby preparing a short carbon fiber preform;
fourthly, preparing the chopped carbon fiber reinforced amorphous composite material:
placing the fragments of the block amorphous alloy Mg-Cu-Ag-Gd mother alloy ingot prepared in the second step into a thick tube part of a quartz tube, wherein the lower end of the quartz tube is provided with a nozzle with the diameter of 2mm, loading the quartz tube into a high vacuum induction heating spray casting furnace with a closed furnace body, and vacuumizing the closed furnace body to-1.0 x 10-1Pa, then filling argon to the vacuum degree of-0.5 MPa, melting the fragments of the block amorphous alloy mother alloy cast ingot in the thick pipe part of the quartz tube into a melt by a water-cooling induction heating coil, adopting the argon as a pressure source, blowing the melt into the inner cavity of the copper mould filled with the prepared chopped carbon fiber preform in the third step in a negative pressure state through a nozzle at the lower end of a quartz tube under the positive pressure of 2MPa, completely filling the melt formed by melting the fragments of the block amorphous alloy Mg-Cu-Ag-Gd mother alloy ingot into the pores of the carbon fiber preform under the pressure infiltration, meanwhile, the copper mould provides a cooling speed of 1000K/s to rapidly form the chopped carbon fiber reinforced amorphous composite material, and after cooling, a chopped carbon fiber reinforced amorphous composite material round bar with the diameter of 3mm and the length of 12cm is taken out, therefore, the preparation of the chopped carbon fiber reinforced amorphous composite material is completed by adopting a vacuum low-pressure casting method.
Fifth, Performance test
And cutting the composite material round rod prepared in the fourth step into standard compressed samples with the diameter-height ratio of 1: 2 by using a diamond cutting saw, and erecting 5 samples side by side for XRD test to prove that the composite material matrix is mainly in an amorphous structure. The cross section of the compressed sample is polished and then subjected to SEM observation and EDS test, which proves that serious interface reaction is not caused in the experiment. After compression testing, the composite material sample shows obvious plastic deformation capacity, the yield strength reaches 850MPa, and the compression plasticity is 2.5%.
In the above examples, the raw materials and equipment used were obtained by known methods, and the operation methods were known to those skilled in the art.

Claims (5)

1. The preparation method of the chopped carbon fiber reinforced amorphous composite material is characterized by comprising the following steps of: the chemical plating method is adopted to improve the wettability of the carbon fiber, the copper mold is used to prepare a carbon fiber preform, and then the vacuum low-pressure casting method, namely the spray casting method, is used to prepare the chopped carbon fiber reinforced amorphous composite material, and the specific steps are as follows:
step one, short carbon fiber chemical plating:
cutting commercial T200, T700 or T800 carbon fibers to obtain short carbon fibers with the length of 30 mu m-0.8 mm, screening by using a screen with 20-400 meshes, and carrying out chemical copper plating or nickel plating treatment on the screened short carbon fibers to obtain the chemical plating short carbon fibers which are well coated by the thin chemical plating layer;
or weaving the undersize chopped carbon fibers into short carbon fiber felt cloth, and then carrying out chemical copper plating or nickel plating treatment to obtain the chemical plating short carbon fiber felt cloth which is completely coated by the thin chemical plating layer;
thereby completing the short carbon fiber chemical plating;
step two, preparing a block amorphous alloy master alloy ingot:
weighing the components with required dosage according to the components of the selected base alloy, putting the weighed raw materials of the components into a high-vacuum induction melting furnace or a high-vacuum electric arc furnace for melting, and before melting, firstly extracting the high-vacuum induction melting furnace or the high-vacuum electric arc furnace to the vacuum degree of-1.0 multiplied by 10-4Pa～-1.0×10-2Pa, then filling argon to the vacuum degree of-0.3 MPa to-0.6 MPa, smelting the raw materials of the components at the temperature of 900-1800 ℃, cooling the raw materials along with the furnace after the raw materials are smelted into liquid to prepare a block amorphous alloy mother alloy ingot, and crushing the mother alloy ingot into small blocks for later use; the composition of the matrix alloy components is represented by atomic percentage at.% as follows: ti37.3Zr22.7Be25.5Fe5.5Cu9、Zr41.2Ti13.8Cu12.5Ni10.0Be22.5Or Mg59.5Cu22.9Ag6.6Gd11；
Step three, preparing a chopped carbon fiber preform:
filling the chemically plated chopped carbon fibers or chemically plated chopped carbon fiber felt cloth obtained in the first step into a copper die inner cavity, wherein the diameter of the copper die inner cavity is 2-30 mm, applying pressure through a standard balance weight of 10-50 g, and pressing by shaking a table or shaking a bed to adjust the pore size between the carbon fibers to be 50-300 mu m so as to prepare a chopped carbon fiber preform;
fourthly, preparing the chopped carbon fiber reinforced amorphous composite material:
placing the fragments of the block amorphous alloy mother alloy ingot prepared in the second step into a thick tube part of a quartz tube, wherein the lower end of the quartz tube is provided with a nozzle with the diameter of 0.5 mm-2 mm, loading the quartz tube into a high vacuum induction heating spray casting furnace with a closed furnace body, and vacuumizing the closed furnace body to-1.0 multiplied by 10-3Pa～-1.0×10-1Pa, then filling argon to the vacuum degree of-0.3 MPa to-0.5 MPa, melting the fragments of the block amorphous alloy master alloy cast ingot in the thick pipe part of the quartz pipe into a melt through a water-cooling induction heating coil, blowing the melt into the inner cavity of the copper mold filled with the prepared chopped carbon fiber preform in the third step in a negative pressure state through a nozzle at the lower end of the quartz pipe by adopting argon as a pressure source at the positive pressure of 0.2MPa to 2MPa, completely filling the melt formed by melting the fragments of the block amorphous alloy master alloy cast ingot into the pores of the chopped carbon fiber preform under the pressure infiltration, simultaneously providing a cooling speed of 400K/s to 1000K/s by the copper mold to rapidly form the chopped carbon fiber reinforced amorphous composite material, and taking out a chopped carbon fiber reinforced amorphous composite material round bar with the diameter of 2mm to 30mm and the length of 5mm to 20cm after cooling, therefore, the preparation of the chopped carbon fiber reinforced amorphous composite material is finished by adopting a vacuum low-pressure casting method, namely a spray casting method.
2. The method of preparing a chopped carbon fiber reinforced amorphous composite material according to claim 1, wherein: the obtained chemically plated chopped carbon fiber or chemically plated chopped carbon fiber felt cloth is completely coated by a thin chemical plating layer, and the thickness of the thin chemical plating layer is 100 nm-800 nm.
3. The method of preparing a chopped carbon fiber reinforced amorphous composite material according to claim 1, wherein: and filling the chemically plated chopped carbon fibers or the chemically plated chopped carbon fiber felt cloth obtained in the first step into an inner cavity of a copper mold, and adopting any one of complete filling, partial filling or inner surface pasting of the mold.
4. The apparatus used in the method for preparing a chopped carbon fiber reinforced amorphous composite material according to claim 1, wherein: the concrete constitution is as follows:
the components of the device used in the preparation method of the chopped carbon fiber reinforced amorphous composite material comprise: the device comprises an air inlet, a closed high-vacuum induction heating spray casting furnace body, a quartz tube with a nozzle with the diameter of 0.5-2 mm at the lower end of a thick tube part, a water-cooling induction heating coil, high-temperature daub, a split copper mold with the inner cavity diameter of 2-30 mm, and a valve which is used for a gas outlet and is connected with a vacuum system and arranged on one side below the closed high-vacuum induction heating spray casting furnace body; the connection mode of each component of the device is as follows: the inside central point of closed high vacuum induction heating spray casting furnace body is arranged in to split type copper mould, and water-cooling induction heating coil sets up around the thick pipe part of quartz capsule, and the spout part of quartz capsule is from split type copper mould top and split type copper mould's inner chamber contact intercommunication and use high temperature clay to seal and avoid gas leakage, and the top of the thick pipe part of quartz capsule is equipped with the lid, and the central point of lid is equipped with the air inlet.
5. The apparatus for use in the method of preparing a chopped carbon fiber reinforced amorphous composite material according to claim 4, wherein: the operation method comprises the following steps: when the chopped carbon fiber reinforced amorphous composite material is prepared, a carbon fiber prefabricated body is firstly placed into an inner cavity of a split type copper mold, fragments of a block amorphous alloy master alloy cast ingot are placed into a thick tube part of a quartz tube, and a closed high-vacuum induction heating spray casting furnace body is pumped to a required vacuum degree of-1.0 multiplied by 10 through a vacuum system connected with a valve- 4Pa～-1.0×10-2Pa, then filling argon to the vacuum degree of-0.3 MPa to-0.5 MPa, then melting the master alloy raw material by using a water-cooling induction heating coil to form an amorphous alloy melt, applying positive-pressure argon with the required pressure of 0.2MPa to 2MPa through an air inlet, spraying the amorphous alloy melt into an inner cavity of a split type copper die in a negative pressure state, completely filling the amorphous alloy melt into pores of the chopped carbon fiber preform under pressure infiltration, simultaneously providing a cooling speed of 400K/s to 1000K/s by the split type copper die to rapidly form the chopped carbon fiber reinforced amorphous composite material, and taking out a chopped carbon fiber reinforced amorphous composite material round bar with the diameter of 2mm to 30mm and the length of 5mm to 20cm after cooling.
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