CN117966083A - Surface boronizing method for mirror symmetry double-gradient laminated composite material - Google Patents
Surface boronizing method for mirror symmetry double-gradient laminated composite material Download PDFInfo
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- CN117966083A CN117966083A CN202410389449.5A CN202410389449A CN117966083A CN 117966083 A CN117966083 A CN 117966083A CN 202410389449 A CN202410389449 A CN 202410389449A CN 117966083 A CN117966083 A CN 117966083A
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- 238000005271 boronizing Methods 0.000 title claims abstract description 101
- 239000002131 composite material Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 63
- 239000010439 graphite Substances 0.000 claims abstract description 63
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 62
- 229910001060 Gray iron Inorganic materials 0.000 claims abstract description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 238000005245 sintering Methods 0.000 claims abstract description 32
- 238000005488 sandblasting Methods 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007731 hot pressing Methods 0.000 claims abstract description 13
- 238000005520 cutting process Methods 0.000 claims abstract description 12
- 238000007781 pre-processing Methods 0.000 claims abstract description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 19
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 18
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 17
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 16
- 239000001099 ammonium carbonate Substances 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 16
- 229910052746 lanthanum Inorganic materials 0.000 claims description 16
- -1 lanthanum aluminate Chemical class 0.000 claims description 16
- 229910052700 potassium Inorganic materials 0.000 claims description 16
- 239000011591 potassium Substances 0.000 claims description 16
- 235000013024 sodium fluoride Nutrition 0.000 claims description 16
- 239000011775 sodium fluoride Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 229910021538 borax Inorganic materials 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 239000004328 sodium tetraborate Substances 0.000 claims description 11
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 11
- 239000012190 activator Substances 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 9
- 230000000737 periodic effect Effects 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 6
- 229910000592 Ferroniobium Inorganic materials 0.000 claims description 5
- 235000013877 carbamide Nutrition 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- ZFGFKQDDQUAJQP-UHFFFAOYSA-N iron niobium Chemical compound [Fe].[Fe].[Nb] ZFGFKQDDQUAJQP-UHFFFAOYSA-N 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims 3
- 238000003475 lamination Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000001976 improved effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 244000137852 Petrea volubilis Species 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
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- Laminated Bodies (AREA)
Abstract
The invention discloses a surface boriding method of a mirror symmetry double-gradient laminated composite material, which comprises the following steps of: cutting the gray cast iron plate and the Nb metal plate by using a wire electric discharge machine, and preprocessing a sample; step 2: placing the sample laminate pretreated in the step 1, and placing the sample laminate in a graphite die for hot-pressing sintering to obtain the mirror symmetry double-gradient laminate composite material. The mirror symmetry double gradient lamination composite material is boronized, sand blasting is carried out between two boronizing steps, nickel powder is added into a second boronizing agent, the boronizing temperature is obviously reduced, meanwhile, the content of Fe 2 B phase is obviously increased, and compared with the traditional boronizing process, the boronizing temperature is reduced to 750 ℃ from 1000 ℃, but the performance can reach a comparable level.
Description
Technical Field
The invention belongs to the technical field of metal surface treatment, and relates to a mirror symmetry double-gradient laminated composite material surface boronizing method.
Background
In industrial production, metal components are in service in severe environments, and failure phenomena such as abrasion, corrosion, fatigue, fracture and the like can occur. Economic losses due to metal component damage are also rising year by year, which is an urgent need to prepare new wear resistant materials that are economical, energy efficient and practical to meet increasingly severe service conditions. Inspired by the strong and tough matching of a natural biological laminated structure (such as a shell), the manufactured micro-nano lamellar structure can effectively solve the problem of inverted strong and tough properties of the metal matrix composite material by alternately superposing different components together; the reinforcing phase particles generated by the in-situ method are tiny, submicron or even nano-scale can be achieved, and the bonding strength of the micro-phase interface of the reinforcing phase and the matrix can be effectively improved. Compared with a uniform layered structure, the mirror symmetry double-gradient laminated composite material has the advantages that the strength is improved, the toughness is improved, the current increasingly severe service conditions are better met, and the wear resistance is difficult to meet the use requirements.
The boronizing can effectively improve the wear resistance of the material, and the boronizing layer obtained by the conventional boronizing process at present mainly comprises Fe 2 B, feB two phases, wherein the FeB phase is relatively brittle and easy to crack, the bonding strength is relatively poor, the hardness of the Fe 2 B phase is slightly low, but the toughness is relatively good, and the requirements of the toughness can be met simultaneously, so that the comprehensive performance is relatively good, and the Fe 2 B phase is preferably obtained.
Disclosure of Invention
The invention combines a mirror symmetry double-gradient laminated composite material and a boronizing process, and provides a surface boronizing method of the mirror symmetry double-gradient laminated composite material; after combining a specific boronizing process, the surface hardness and the wear resistance are obviously improved.
The technical scheme adopted by the invention is that the surface boronizing method of the mirror symmetry double-gradient laminated composite material is implemented according to the following steps:
S1: preparing a first boronizing agent and a second boronizing agent, wherein the first boronizing agent comprises the following components in parts by mass: 10 to 40 parts by weight of boron donor, 10 to 40 parts by weight of activator and 30 to 70 parts by weight of filler; the second boronizing agent comprises the following components in parts by mass: 10-40 parts of boron donor, 10-40 parts of activator, 30-70 parts of filler and 3-6 parts of nickel powder;
S2: cleaning the surface of the mirror symmetry double-gradient laminated composite material;
S3: filling the cleaned composite material and the first boronizing agent into a graphite mold, embedding the composite material into the first boronizing agent, sealing the graphite mold, putting the graphite mold into a resistance furnace for heating boronizing, heating to 600-650 ℃, preserving heat for 1-5h, and cooling the furnace to room temperature;
S4: carrying out sand blasting treatment on the composite material, wherein the sand grain is silicon carbide, the sand blasting pressure is 0.1-0.7MPa, and the sand blasting treatment time is 5-15min;
s5: filling the sand-blasted composite material and the second boronizing agent into a graphite mold, embedding the composite material into the second boronizing agent, sealing the graphite mold, putting the graphite mold into a resistance furnace for heating and boronizing, heating to 700-750 ℃, preserving heat for 1-5h, and cooling the furnace to room temperature;
The mirror symmetry double-gradient laminated composite material is a ferroniobium composite material, and the mirror symmetry axis can be: unreacted Nb layer center line or Fe layer center line; in cross section, it appears that:
(1) When the center line of the unreacted Nb layer is taken as a symmetry axis, the direction of the Fe layer is along the normal line of the unreacted Nb layer: the volume fraction gradient of NbC is reduced, and the particle size gradient of the particles is increased, namely mirror symmetry double gradient;
(2) When the center line of the Fe layer is taken as a symmetry axis, the direction of the Nb layer is along the normal line of the Fe layer: the volume fraction gradient of NbC is increased, and the particle size gradient of the particles is reduced, namely mirror symmetry double gradient;
the structure is characterized by being generally in a layered, periodic structure and periodic unit, and is composed of a Fe layer, a NbC/Fe composite layer and a Nb layer.
The invention is also characterized in that:
The thickness of each characteristic layer in the periodic unit is controllable, the thickness of the Nb layer is 0.1mm-5mm, the thickness of the Fe-NbC composite layer is 5 mu m-3mm, the thickness of the Fe layer is 0.1mm-10mm, the composite layer is compounded by NbC and Fe, and the NbC is generated in situ by Nb and C atoms in an iron matrix.
The preparation method of the mirror symmetry double-gradient laminated composite material comprises the following steps:
Step 1: cutting the gray cast iron plate and the Nb metal plate by using a wire electric discharge machine, and preprocessing a sample;
step 2: placing the sample laminate pretreated in the step 1, and placing the sample laminate in a graphite die for hot-pressing sintering to obtain an NbC/Fe mirror symmetry double-gradient laminate composite material;
The step 2 is specifically as follows: the pretreated Nb plates and gray cast iron plates are overlapped in a crossing way, and are placed in the central position inside a sintering furnace, the furnace cover of the hot press furnace is closed, and the sintering atmosphere is under the protection of argon; wherein the sintering process firstly heats up to 750-900 ℃ at the speed of 10-15 ℃/min and keeps the temperature for 0.5-2 h under the pressure of 20-50 MPa; then heating to 1100-1300 ℃ at the speed of 5-9 ℃/min, preserving heat for 3-8 h under the pressure of 60-80 MPa, and cooling to room temperature along with a furnace to obtain the NbC/Fe mirror symmetry double-gradient laminated composite material.
The boron donor is one of borax, boric acid or ferroboron.
The filler is one of silicon carbide, graphite and aluminum oxide.
The activator is a mixture of potassium fluoborate, ammonium carbonate, urea, sodium fluoride and lanthanum aluminate, and the mass ratio of the potassium fluoborate, the ammonium carbonate, the urea, the sodium fluoride and the lanthanum aluminate is 8-10:7-9:4-6:4-6:1-2.
The beneficial effects of the invention are as follows:
(1) The mirror symmetry double-gradient laminated composite material prepared by the method has the advantages that the strength is greatly improved by 4-5 times, nb reacts with C in an iron matrix, reinforcing particles NbC are generated in situ, so that alloy interfaces of a plurality of NbC particles and the matrix and interfaces among the NbC particles are generated in the material, dislocation movement is hindered by the interfaces, dislocation product is generated, the deformation resistance of the material is increased, and the macroscopic appearance is improved in hardness and elastic modulus; the impact toughness is improved by 2-3 times, and the particles of the carbide are tiny (100 nm-2 mu m), the cycle is symmetrical and the gradient distribution thereof leads the crack initiation and the crack expansion to be blocked;
(2) After the specific boronizing process is combined, the surface hardness and the wear resistance of the material are obviously improved. According to the method, the boronizing process is optimized, sand blasting is carried out between two boronizing steps, meanwhile, nickel powder is added into the second boronizing agent, the boronizing temperature is obviously reduced, and meanwhile, the content of Fe 2 B phase is obviously increased. Compared with the traditional boronizing process, the boronizing temperature is reduced from 1000 ℃ to 750 ℃, but the performance can reach a comparable level;
(3) The method takes potassium fluoborate, ammonium carbonate, urea, sodium fluoride and lanthanum aluminate as activating agents, fully exerts the advantages of the boron supplying agents, remarkably improves the boronizing capacity and boronizing speed, and ensures that the potassium fluoborate is an excellent activating agent, continuous boron potential and compact permeable layer; the boronizing ability is greatly improved after the use of ammonium carbonate, urea, sodium fluoride and lanthanum aluminate. Compared with the prior art, the activator has obvious effects of improving the depth of the boronizing layer and improving the hardness and the wear resistance.
Drawings
FIG. 1 is a schematic structural view of a composite material of the present invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The invention relates to a surface boronizing method of a mirror symmetry double-gradient laminated composite material, wherein the composite material is a ferrocolumbium laminated composite material, the structure of the ferrocolumbium laminated composite material is shown in figure 1, and the mirror symmetry axis of the ferrocolumbium laminated composite material can be as follows: unreacted Nb layer center line or Fe layer center line. In cross section, it appears that: (1) When the center line of the unreacted Nb layer is taken as a symmetry axis, the direction of the Fe layer is along the normal line of the unreacted Nb layer: the volume fraction gradient of NbC is reduced, and the particle size gradient of the particles is increased, namely mirror symmetry double gradient; (2) When the center line of the Fe layer is taken as a symmetry axis, the direction of the Nb layer is along the normal line of the Fe layer: the volume fraction gradient of NbC is increased, and the particle size gradient of the particles is reduced, namely the mirror symmetry double gradient. The structure is generally in a layered, periodic structure and periodic unit, and mainly comprises a Fe layer, a NbC/Fe composite layer and a Nb layer.
The thickness of each characteristic layer in the periodic unit is controllable, the thickness of the Nb layer is 0.1mm-5mm, the thickness of the Fe-NbC composite layer is 5 mu m-3mm, the thickness of the Fe layer is 0.1mm-10mm, and in particular, the composite layer contains NbC and Fe, and the NbC is generated in situ by the Nb and C atoms in an iron matrix.
As shown in fig. 1, the Nb layer diffuses into the Fe layer, and the NbC size gradient increases and the volume fraction gradient decreases, and can be divided into two regions: the NbC compact ceramic region with the micro-nano structure has fine and uniform NbC particles and tight connection, and the volume fraction is more than 95%; compared with the micro-nano structure NbC compact ceramic region, the micro-nano structure NbC ceramic region has the advantages that NbC particles grow up, the regular square sugar shape is shown, the volume fraction is 90% -95%, and a small amount of ferrite exists in the structure.
The invention discloses a surface boronizing method of a mirror symmetry double-gradient laminated composite material, which is implemented according to the following steps:
Step 1: the gray cast iron plate and the Nb metal plate were cut using a wire electric discharge machine, and the samples were pretreated. The method comprises the following steps:
Firstly, a wire electric discharge machine is used for cutting a gray cast iron plate with the size of 10 multiplied by 2mm and a Nb metal plate with the size of 10 multiplied by 1mm respectively, then, the surfaces of the Nb metal plate and the gray cast iron plate are subjected to step-by-step polishing treatment, and the specification of sand paper is 400 meshes to 2000 meshes so as to remove an oxide layer on the surfaces of the Nb metal plate and the gray cast iron plate. Finally, the Nb metal plates and the gray cast iron plates are ultrasonically cleaned by adopting an ethanol solution, and the temperature is kept at 25 ℃ in the cleaning process, so that the oxidation reaction of the Nb metal plates and the gray cast iron plates caused by the overhigh temperature in the cleaning process is avoided. And then drying the raw materials subjected to ultrasonic cleaning for later use.
Step 2: and (3) placing the sample laminate pretreated in the step (1), and placing the sample laminate in a graphite die for hot-pressing sintering to obtain the NbC/Fe mirror symmetry double-gradient laminate composite material. The method comprises the following steps:
And (3) overlapping the pretreated Nb plates and gray cast iron plates in a crossed manner, wrapping the Nb plates and the gray cast iron plates by adopting refractory paper, putting the Nb plates and the gray cast iron plates into a graphite mold, putting the graphite mold into the central position inside a sintering furnace, closing the furnace cover of the hot-pressing furnace, and protecting the sintering atmosphere by argon. Wherein the sintering process firstly heats up to 750-900 ℃ at the speed of 10-15 ℃/min and keeps the temperature for 0.5-2 h under the pressure of 20-50 MPa; then heating to 1100-1300 ℃ at the speed of 5-9 ℃/min, preserving heat for 3-8 h under the pressure of 60-80 MPa, and cooling to room temperature along with a furnace to obtain the NbC/Fe mirror symmetry double-gradient laminated composite material.
Step 3: the boronizing process specifically comprises the following steps:
S1: preparing a first boronizing agent and a second boronizing agent, wherein the first boronizing agent comprises the following components in parts by mass: 10 to 40 parts of boron donor, 10 to 40 parts of activator and 30 to 70 parts of filler. The second boronizing agent comprises the following components in parts by mass: 10-40 parts of boron donor, 10-40 parts of activator, 30-70 parts of filler and 3-6 parts of nickel powder.
The boron donor is one of borax, boric acid or ferroboron.
The activator is a mixture of potassium fluoborate, ammonium carbonate, urea, sodium fluoride and lanthanum aluminate, and the mass ratio of the potassium fluoborate, the ammonium carbonate, the urea, the sodium fluoride and the lanthanum aluminate is 8-10:7-9:4-6:4-6:1-2.
The filler is one of silicon carbide, graphite and aluminum oxide.
S2: cleaning the surface of the mirror symmetry double-gradient laminated composite material;
S3: filling the cleaned composite material and the first boronizing agent into a graphite mold, embedding the composite material into the first boronizing agent, sealing the graphite mold, putting the graphite mold into a resistance furnace for heating boronizing, heating to 600-650 ℃, preserving heat for 1-5h, and cooling the furnace to room temperature;
s4: performing sand blasting treatment, wherein the sand is silicon carbide, the sand blasting pressure is 0.1-0.7MPa, and the sand blasting treatment time is 5-15min;
S5: filling the sand-blasted composite material and the second boronizing agent into a graphite mold, embedding the composite material into the second boronizing agent, sealing the graphite mold, heating and boronizing the graphite mold in a resistance furnace, heating to 700-750 ℃, preserving heat for 1-5h, and cooling the furnace to room temperature.
Example 1
Step 1: firstly, cutting and processing gray cast iron plates and Nb metal plates by using a wire electric discharge machine, and carrying out sample pretreatment:
the specific implementation mode of the step 1 is as follows: firstly, a wire electric discharge machine is used for cutting a gray cast iron plate with the size of 10 multiplied by 2mm and a Nb metal plate with the size of 10 multiplied by 1mm respectively, then, the surfaces of the Nb metal plate and the gray cast iron plate are subjected to step-by-step polishing treatment, and the specification of sand paper is 400 meshes to 2000 meshes so as to remove an oxide layer on the surfaces of the Nb metal plate and the gray cast iron plate. Finally, the Nb metal plates and the gray cast iron plates are ultrasonically cleaned by adopting an ethanol solution, and the temperature is kept at 25 ℃ in the cleaning process, so that the oxidation reaction of the Nb metal plates and the gray cast iron plates caused by the overhigh temperature in the cleaning process is avoided. And then drying the raw materials subjected to ultrasonic cleaning for later use.
Step 2: placing the sample laminate pretreated in the step 1, and placing the sample laminate in a graphite die for hot-pressing sintering to obtain the NbC/Fe mirror symmetry double-gradient laminate composite material:
The specific implementation mode of the step 2 is as follows: and (3) overlapping the pretreated Nb plates and gray cast iron plates in a crossed manner, wrapping the Nb plates and the gray cast iron plates by adopting refractory paper, putting the Nb plates and the gray cast iron plates into a graphite mold, putting the graphite mold into the central position inside a sintering furnace, closing the furnace cover of the hot-pressing furnace, and protecting the sintering atmosphere by argon. Wherein the sintering process is firstly to raise the temperature to 800 ℃ at the speed of 10 ℃/min, and to keep the temperature at the pressure of 30MPa for 1h, then to raise the temperature to 1200 ℃ at the speed of 7 ℃/min, and to keep the temperature at the pressure of 70MPa for 5h, and then to cool to room temperature along with the furnace to obtain the mirror symmetry double gradient laminated composite material.
Step 3: surface boronizing process:
S1: preparing a boronizing agent, wherein the first boronizing agent is as follows: 5000g of borax, 1000g of potassium fluoborate, 800g of ammonium carbonate, 600g of urea, 500g of sodium fluoride, 100g of lanthanum aluminate and 6000g of silicon carbide. Second boriding agent: 5000g of borax, 1000g of potassium fluoborate, 800g of ammonium carbonate, 600g of urea, 500g of sodium fluoride, 100g of lanthanum aluminate, 6000g of silicon carbide and 600g of nickel powder; s2: cleaning the surface of the mirror symmetry double-gradient laminated composite material; s3: filling the cleaned composite material and the first boronizing agent into a graphite mold, embedding the composite material into the first boronizing agent, sealing the graphite mold, putting the graphite mold into a resistance furnace, heating and boronizing, heating to 620 ℃, preserving heat for 3h, and cooling the furnace to room temperature; s4: performing sand blasting treatment, wherein the sand is silicon carbide, the sand blasting pressure is 0.5MPa, and the sand blasting treatment time is 10min; s5: filling the sand-blasted composite material and the second boronizing agent into a graphite mold, embedding the composite material into the second boronizing agent, sealing the graphite mold, heating and boronizing the graphite mold in a resistance furnace, heating to 720 ℃, preserving heat for 3h, and cooling the furnace to room temperature.
Example 2
Step 1: firstly, cutting and processing gray cast iron plates and Nb metal plates by using a wire electric discharge machine, and carrying out sample pretreatment:
the specific implementation mode of the step 1 is as follows: firstly, a wire electric discharge machine is used for cutting a gray cast iron plate with the size of 10 multiplied by 2mm and a Nb metal plate with the size of 10 multiplied by 1mm respectively, then, the surfaces of the Nb metal plate and the gray cast iron plate are subjected to step-by-step polishing treatment, and the specification of sand paper is 400 meshes to 2000 meshes so as to remove an oxide layer on the surfaces of the Nb metal plate and the gray cast iron plate. Finally, the Nb metal plates and the gray cast iron plates are ultrasonically cleaned by adopting an ethanol solution, and the temperature is kept at 25 ℃ in the cleaning process, so that the oxidation reaction of the Nb metal plates and the gray cast iron plates caused by the overhigh temperature in the cleaning process is avoided. And then drying the raw materials subjected to ultrasonic cleaning for later use.
Step 2: placing the sample laminate pretreated in the step 1, and placing the sample laminate in a graphite die for hot-pressing sintering to obtain the NbC/Fe mirror symmetry double-gradient laminate composite material:
The specific implementation mode of the step 2 is as follows: and (3) overlapping the pretreated Nb plates and gray cast iron plates in a crossed manner, wrapping the Nb plates and the gray cast iron plates by adopting refractory paper, putting the Nb plates and the gray cast iron plates into a graphite mold, putting the graphite mold into the central position inside a sintering furnace, closing the furnace cover of the hot-pressing furnace, and protecting the sintering atmosphere by argon. Wherein the sintering process is firstly to heat up to 900 ℃ at the speed of 10 ℃/min, and to heat up for 1h under the pressure of 30MPa, then to heat up to 1200 ℃ at the speed of 7 ℃/min, and to heat up for 5h under the pressure of 70MPa, and then to cool down to room temperature along with the furnace to prepare the mirror symmetry double gradient laminated composite material.
Step 3: surface boronizing process:
S1: preparing a boronizing agent, wherein the first boronizing agent is as follows: 5000g of borax, 1000g of potassium fluoborate, 800g of ammonium carbonate, 500g of urea, 500g of sodium fluoride, 200g of lanthanum aluminate and 6000g of silicon carbide. Second boriding agent: 5000g of borax, 1000g of potassium fluoborate, 800g of ammonium carbonate, 500g of urea, 500g of sodium fluoride, 200g of lanthanum aluminate, 6000g of silicon carbide and 600g of nickel powder; s2: cleaning the surface of the mirror symmetry double-gradient laminated composite material; s3: filling the cleaned composite material and the first boronizing agent into a graphite mold, embedding the composite material into the first boronizing agent, sealing the graphite mold, putting the graphite mold into a resistance furnace, heating and boronizing, heating to 620 ℃, preserving heat for 3h, and cooling the furnace to room temperature; s4: performing sand blasting treatment, wherein the sand is silicon carbide, the sand blasting pressure is 0.5MPa, and the sand blasting treatment time is 10min; s5: filling the sand-blasted composite material and the second boronizing agent into a graphite mold, embedding the composite material into the second boronizing agent, sealing the graphite mold, heating and boronizing the graphite mold in a resistance furnace, heating to 720 ℃, preserving heat for 3h, and cooling the furnace to room temperature.
Example 3
Step 1: firstly, cutting and processing gray cast iron plates and Nb metal plates by using a wire electric discharge machine, and carrying out sample pretreatment:
the specific implementation mode of the step 1 is as follows: firstly, a wire electric discharge machine is used for cutting a gray cast iron plate with the size of 10 multiplied by 2mm and a Nb metal plate with the size of 10 multiplied by 1mm respectively, then, the surfaces of the Nb metal plate and the gray cast iron plate are subjected to step-by-step polishing treatment, and the specification of sand paper is 400 meshes to 2000 meshes so as to remove an oxide layer on the surfaces of the Nb metal plate and the gray cast iron plate. Finally, the Nb metal plates and the gray cast iron plates are ultrasonically cleaned by adopting an ethanol solution, and the temperature is kept at 25 ℃ in the cleaning process, so that the oxidation reaction of the Nb metal plates and the gray cast iron plates caused by the overhigh temperature in the cleaning process is avoided. And then drying the raw materials subjected to ultrasonic cleaning for later use.
Step 2: placing the sample laminate pretreated in the step 1, and placing the sample laminate in a graphite die for hot-pressing sintering to obtain the NbC/Fe mirror symmetry double-gradient laminate composite material:
the specific implementation mode of the step 2 is as follows: and (3) overlapping the pretreated Nb plates and gray cast iron plates in a crossed manner, wrapping the Nb plates and the gray cast iron plates by adopting refractory paper, putting the Nb plates and the gray cast iron plates into a graphite mold, putting the graphite mold into the central position inside a sintering furnace, closing the furnace cover of the hot-pressing furnace, and protecting the sintering atmosphere by argon. Wherein the sintering process is firstly to heat up to 900 ℃ at the speed of 10 ℃/min, and to heat up for 1h under the pressure of 30MPa, then to heat up to 1250 ℃ at the speed of 7 ℃/min, and to heat up for 5h under the pressure of 70MPa, and then to cool down to room temperature along with the furnace to prepare the mirror symmetry double gradient laminated composite material.
Step 3: surface boronizing process: s1: preparing a boronizing agent, wherein the first boronizing agent is as follows: 5000g of borax, 800g of potassium fluoborate, 900g of ammonium carbonate, 600g of urea, 600g of sodium fluoride, 100g of lanthanum aluminate and 6000g of silicon carbide. Second boriding agent: 5000g of borax, 900g of potassium fluoborate, 700g of ammonium carbonate, 600g of urea, 600g of sodium fluoride, 200g of lanthanum aluminate, 6000g of silicon carbide and 600g of nickel powder; s2: cleaning the surface of the mirror symmetry double-gradient laminated composite material; s3: filling the cleaned composite material and the first boronizing agent into a graphite mold, embedding the composite material into the first boronizing agent, sealing the graphite mold, putting the graphite mold into a resistance furnace, heating and boronizing, heating to 620 ℃, preserving heat for 3h, and cooling the furnace to room temperature; s4: then carrying out sand blasting treatment, wherein the sand is silicon carbide, the sand blasting pressure is 0.5MPa, and the sand blasting treatment time is 10min; s5: filling the sand-blasted composite material and the second boronizing agent into a graphite mold, embedding the composite material into the second boronizing agent, sealing the graphite mold, heating and boronizing the graphite mold in a resistance furnace, heating to 720 ℃, preserving heat for 3h, and cooling the furnace to room temperature.
Example 4
Step 1: firstly, cutting and processing gray cast iron plates and Nb metal plates by using a wire electric discharge machine, and carrying out sample pretreatment:
the specific implementation mode of the step 1 is as follows: firstly, a wire electric discharge machine is used for cutting a gray cast iron plate with the size of 10 multiplied by 2mm and a Nb metal plate with the size of 10 multiplied by 1mm respectively, then, the surfaces of the Nb metal plate and the gray cast iron plate are subjected to step-by-step polishing treatment, and the specification of sand paper is 400 meshes to 2000 meshes so as to remove an oxide layer on the surfaces of the Nb metal plate and the gray cast iron plate. Finally, the Nb metal plates and the gray cast iron plates are ultrasonically cleaned by adopting an ethanol solution, and the temperature is kept at 25 ℃ in the cleaning process, so that the oxidation reaction of the Nb metal plates and the gray cast iron plates caused by the overhigh temperature in the cleaning process is avoided. And then drying the raw materials subjected to ultrasonic cleaning for later use.
Step 2: placing the sample laminate pretreated in the step 1, and placing the sample laminate in a graphite die for hot-pressing sintering to obtain the NbC/Fe mirror symmetry double-gradient laminate composite material:
the specific implementation mode of the step 2 is as follows: and (3) overlapping the pretreated Nb plates and gray cast iron plates in a crossed manner, wrapping the Nb plates and the gray cast iron plates by adopting refractory paper, putting the Nb plates and the gray cast iron plates into a graphite mold, putting the graphite mold into the central position inside a sintering furnace, closing the furnace cover of the hot-pressing furnace, and protecting the sintering atmosphere by argon. Wherein the sintering process is firstly to heat up to 900 ℃ at a speed of 15 ℃/min, and to heat up for 2 hours under a pressure of 50MPa, then to heat up to 1300 ℃ at a speed of 9 ℃/min, and to heat up for 6 hours under a pressure of 80MPa, and then to cool down to room temperature along with the furnace to prepare the mirror symmetry double gradient laminated composite material.
Step 3: surface boronizing process: s1: preparing a boronizing agent, wherein the first boronizing agent is as follows: 5000g of borax, 1000g of potassium fluoborate, 900g of ammonium carbonate, 400g of urea, 500g of sodium fluoride, 200g of lanthanum aluminate and 6000g of silicon carbide. Second boriding agent: 5000g of borax, 1000g of potassium fluoborate, 900g of ammonium carbonate, 400g of urea, 500g of sodium fluoride, 200g of lanthanum aluminate, 6000g of silicon carbide and 600g of nickel powder; s2: cleaning the surface of the mirror symmetry double-gradient laminated composite material; s3: filling the cleaned composite material and the first boronizing agent into a graphite mold, embedding the composite material into the first boronizing agent, sealing the graphite mold, putting the graphite mold into a resistance furnace, heating and boronizing, heating to 620 ℃, preserving heat for 3h, and cooling the furnace to room temperature; s4: performing sand blasting treatment, wherein the sand is silicon carbide, the sand blasting pressure is 0.5MPa, and the sand blasting treatment time is 10min; s5: filling the sand-blasted composite material and the second boronizing agent into a graphite mold, embedding the composite material into the second boronizing agent, sealing the graphite mold, heating and boronizing the graphite mold in a resistance furnace, heating to 720 ℃, preserving heat for 3h, and cooling the furnace to room temperature.
Comparative example 1
Substantially the same as in example 1, except that the sintering process of step 2 was first heated to 700℃at a rate of 10℃per minute and heat-preserved for 1 hour at a pressure of 30MPa, then heated to 1200℃at a rate of 7℃per minute and heat-preserved for 5 hours at a pressure of 70 MPa.
Comparative example 2
Substantially the same as in example 1, except that the sintering process of step 2 was first heated to 900℃at a rate of 10℃per minute and held at a pressure of 30MPa for 1 hour, then heated to 1000℃at a rate of 7℃per minute and held at a pressure of 70MPa for 5 hours.
Comparative example 3
Substantially the same as in example 1, except that the sintering process of step 2 was first heated to 700℃at a rate of 10℃per minute and heat-preserved for 1 hour at a pressure of 30MPa, then heated to 1000℃at a rate of 7℃per minute and heat-preserved for 5 hours at a pressure of 70 MPa.
Comparative example 4
Substantially the same as in example 1, except that sand blasting was not performed.
Comparative example 5
Substantially the same as in example 1, except that the first boriding agent and the second boriding agent each contain no nickel.
Comparative example 6
Substantially the same as in example 1, except that the first boronizing agent contained nickel and the second boronizing agent contained no nickel.
Table 1 shows the results of the performance tests of the materials prepared in examples 1 to 4 and comparative examples 1 to 6:
TABLE 1 Performance test results
As can be seen from the table 1, the hardness and toughness of the Fe-based composite material treated by the method are improved, the NbC reinforcing layer thickness is reduced due to the lower temperature, the boronizing depth is affected, and the problem of inversion of toughness is effectively solved by the surface boronizing method of the dual-gradient laminated composite material.
Claims (6)
1. The surface boronizing method of the mirror symmetry double-gradient laminated composite material is characterized by comprising the following steps of:
S1: preparing a first boronizing agent and a second boronizing agent, wherein the first boronizing agent comprises the following components in parts by mass: 10 to 40 parts by weight of boron donor, 10 to 40 parts by weight of activator and 30 to 70 parts by weight of filler; the second boronizing agent comprises the following components in parts by mass: 10-40 parts of boron donor, 10-40 parts of activator, 30-70 parts of filler and 3-6 parts of nickel powder;
S2: cleaning the surface of the mirror symmetry double-gradient laminated composite material;
S3: filling the cleaned composite material and the first boronizing agent into a graphite mold, embedding the composite material into the first boronizing agent, sealing the graphite mold, putting the graphite mold into a resistance furnace for heating boronizing, heating to 600-650 ℃, preserving heat for 1-5h, and cooling the furnace to room temperature;
S4: carrying out sand blasting treatment on the composite material, wherein the sand grain is silicon carbide, the sand blasting pressure is 0.1-0.7MPa, and the sand blasting treatment time is 5-15min;
s5: filling the sand-blasted composite material and the second boronizing agent into a graphite mold, embedding the composite material into the second boronizing agent, sealing the graphite mold, putting the graphite mold into a resistance furnace for heating and boronizing, heating to 700-750 ℃, preserving heat for 1-5h, and cooling the furnace to room temperature;
The mirror symmetry double-gradient laminated composite material is a ferroniobium composite material, and the mirror symmetry axis is as follows: unreacted Nb layer center line or Fe layer center line; in cross section, it appears that:
(1) When the center line of the unreacted Nb layer is taken as a symmetry axis, the direction of the Fe layer is along the normal line of the unreacted Nb layer: the volume fraction gradient of NbC is reduced, and the particle size gradient of the particles is increased, namely mirror symmetry double gradient;
(2) When the center line of the Fe layer is taken as a symmetry axis, the direction of the Nb layer is along the normal line of the Fe layer: the volume fraction gradient of NbC is increased, and the particle size gradient of the particles is reduced, namely mirror symmetry double gradient;
the structure is characterized by being generally in a layered, periodic structure and periodic unit, and is composed of a Fe layer, a NbC/Fe composite layer and a Nb layer.
2. The method of claim 1, wherein each of the feature layers in the periodic element has a controllable thickness, the Nb layer has a thickness of 0.1mm to 5mm, the Fe-NbC composite layer has a thickness of 5 μm to 3mm, the Fe layer has a thickness of 0.1mm to 10mm, the NbC is formed in situ from Nb and C atoms in the iron matrix.
3. The method for surface boriding of a mirror-symmetrical dual gradient laminate composite according to claim 1, wherein the method for preparing the mirror-symmetrical dual gradient laminate composite comprises the steps of:
Step 1: cutting the gray cast iron plate and the Nb metal plate by using a wire electric discharge machine, and preprocessing a sample;
step 2: placing the sample laminate pretreated in the step 1, and placing the sample laminate in a graphite die for hot-pressing sintering to obtain an NbC/Fe mirror symmetry double-gradient laminate composite material;
The step 2 is specifically as follows: the pretreated Nb plates and gray cast iron plates are overlapped in a crossing way, and are placed in the central position inside a sintering furnace, the furnace cover of the hot press furnace is closed, and the sintering atmosphere is under the protection of argon; wherein the sintering process firstly heats up to 750-900 ℃ at the speed of 10-15 ℃/min and keeps the temperature for 0.5-2 h under the pressure of 20-50 MPa; then heating to 1100-1300 ℃ at the speed of 5-9 ℃/min, preserving heat for 3-8 h under the pressure of 60-80 MPa, and cooling to room temperature along with a furnace to obtain the NbC/Fe mirror symmetry double-gradient laminated composite material.
4. The method for surface boriding of a mirror-symmetrical dual gradient laminate composite according to claim 1, wherein the boron donor is one of borax, boric acid or ferroboron.
5. The method of claim 1, wherein the filler is one of silicon carbide, graphite, and aluminum oxide.
6. The method for boronizing the surface of the mirror symmetry double-gradient laminated composite material according to claim 1, wherein the activating agent is a mixture of potassium fluoborate, ammonium carbonate, urea, sodium fluoride and lanthanum aluminate, and the mass ratio of the potassium fluoborate, the ammonium carbonate, the urea, the sodium fluoride and the lanthanum aluminate is 8-10:7-9:4-6:4-6:1-2.
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