CN103553637A - Cubic boron nitride glomerocryst composite with surface coating structure and preparation method thereof - Google Patents
Cubic boron nitride glomerocryst composite with surface coating structure and preparation method thereof Download PDFInfo
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- CN103553637A CN103553637A CN201310544306.9A CN201310544306A CN103553637A CN 103553637 A CN103553637 A CN 103553637A CN 201310544306 A CN201310544306 A CN 201310544306A CN 103553637 A CN103553637 A CN 103553637A
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- 229910052582 BN Inorganic materials 0.000 title claims abstract description 121
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 9
- 239000011248 coating agent Substances 0.000 title abstract description 6
- 238000000576 coating method Methods 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 39
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 238000012360 testing method Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 230000032683 aging Effects 0.000 claims abstract description 14
- 238000001879 gelation Methods 0.000 claims abstract description 11
- 230000005540 biological transmission Effects 0.000 claims abstract description 5
- -1 boron nitride compound Chemical class 0.000 claims description 27
- 239000003595 mist Substances 0.000 claims description 26
- 238000005245 sintering Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 238000003483 aging Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000002210 silicon-based material Substances 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000008141 laxative Substances 0.000 claims description 8
- 230000002475 laxative effect Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- 229910017083 AlN Inorganic materials 0.000 claims description 3
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract 1
- 229910052796 boron Inorganic materials 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 14
- 239000011159 matrix material Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000000748 compression moulding Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 7
- 239000012141 concentrate Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 238000002955 isolation Methods 0.000 description 7
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 239000011733 molybdenum Substances 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 238000013001 point bending Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 229910008947 W—Co Inorganic materials 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
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Abstract
本发明属于切削加工材料技术领域，特别涉及一种具有表面包覆结构的立方氮化硼聚晶复合材料及其制备方法。所述材料通过下法得到：先制备莫来石前驱体溶胶，溶胶陈化浓缩后加入立方氮化硼粉体中进行原位溶胶化和凝胶化，干燥后获得具有表面包覆的立方氮化硼；将其与粘结剂混合后压制试块，再与传压介质装配成合成块，之后烧结得到具有表面包覆结构的立方氮化硼聚晶复合材料。本发明具有表面包覆结构的立方氮化硼聚晶复合材料的制备方法使立方氮化硼表面包覆一层莫来石化学成分的物质，改善了立方氮化硼的表面化学结构和组成，提高了烧结的聚晶立方氮化硼复合材料的抗冲击韧性和切削效率。The invention belongs to the technical field of cutting materials, in particular to a cubic boron nitride polycrystalline composite material with a surface coating structure and a preparation method thereof. The material is obtained by the following method: first prepare the mullite precursor sol, add the sol to cubic boron nitride powder after aging and concentration for in-situ sol and gelation, and obtain cubic nitrogen with surface coating after drying boron; mix it with a binder, press the test block, and then assemble it with a pressure transmission medium to form a composite block, and then sinter to obtain a cubic boron nitride polycrystalline composite material with a surface coating structure. The preparation method of the cubic boron nitride polycrystalline composite material with a surface coating structure of the present invention makes the surface of the cubic boron nitride coated with a layer of mullite chemical composition, which improves the surface chemical structure and composition of the cubic boron nitride, Improved impact toughness and cutting efficiency of sintered polycrystalline cubic boron nitride composites.
Description
Technical field
The invention belongs to machining material technology field, particularly a kind of polycrystalline cubic boron nitride compound material with full-package structure and preparation method thereof.
Background technology
Utilize bonding agent the small single crystal particle of cubic boron nitride (cBN) can be bondd under High Temperature High Pressure and prepare the PcBN(polycrystalline cubic boron nitride that becomes block), because polycrystalline cubic boron nitride has high rigidity, high-wearing feature, high heat transfer efficiency and the excellent advantages such as high-temperature behavior, therefore, polycrystalline cubic boron nitride cutter can be used to make the cutter material of the difficult-to-machine metals such as quenched steel, cold hard cast-iron, superstrength iron group alloy, titanium alloy.
For improving durability and the working (machining) efficiency of cutter, adopting the alternative inserted tool of polycrystalline cubic boron nitride cutter and sintex is the trend of superhard cutting tool development.Progress along with Materials science, requirement to the hardness of cutter material, wear resistance, toughness and intensity is had higher requirement, desirable cutter material should both have high hardness, wear resistance, be conducive to improve stock-removing efficiency, extend tool life, the toughness having had again, makes it can bear large cutting force simultaneously.If, easily there is " collapsing cutter " phenomenon in use procedure in poor toughness, not only destroy workpiece to be machined, even there is the injury accident to the infringement of equipment or operator, must stop the course of processing, the blade more renewing, causes production cost obviously to increase.
In order to overcome this deficiency, people start to improve the toughness of polycrystalline cubic boron nitride cutter material.The disclosed patent WO2004040029 of Britain Element Six company, the core that adopts the mixture of various carbide and nitride to form a kind of complexity is scattered in matrix, in matrix, be surrounded by superhard material cubic boron nitride and diamond, and bonding agent, through the synthetic polycrystalline cubic boron nitride with a kind of polynuclear plane of high pressure-temperature, there is good intensity and fracture toughness property.Chinese patent CN201010542237.4 discloses a kind of plating nickel on surface Si
3n
4the preparation method of crystal whisker toughened polycrystalline cubic boron nitride compound sheets, adopts Si
3n
4the Si of whisker and coating surface nano nickel
3n
4the introducing of whisker increases the toughness of polycrystalline cubic boron nitride compound sheets, has improved the impact resistance of cutter, thereby realizes its turning continuously for a long time, improves the work-ing life of cutter and the production efficiency of enterprise.Chinese patent 201010615047.0 also discloses the powdery binder that a kind of polycrystalline cubic boron nitride compound sheets is used, and includes TiN, AlN, Si
3n4, Co and SiO
2, can strengthen the shock resistance of composite sheet.Chinese patent 201110325539.0 is by utilizing the high tenacity of body material W-Co kind Wimet, glomerocryst layer chemical gradient at polycrystalline cubic boron nitride sexually revises the powder content of high tenacity W-Co kind hard alloy substrate, and adopts the crystal whisker reinforced and toughened overall flexibility that improves sintered polycrystalline cubic boron nitride composite piece of inorganic non-metallic.
Summary of the invention
The object of this invention is to provide a kind of new thinking, by cubic boron nitride, be coated, thereby polycrystalline cubic boron nitride matrix material of a kind of high tenacity and preparation method thereof is provided.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of polycrystalline cubic boron nitride compound material with full-package structure, by laxative remedy, obtain: first prepare mullite precursor colloidal sol, after colloidal sol ageing is concentrated, add in cubic boron nitride powder and carry out original position solation and gelation, dry rear acquisition has surface coated cubic boron nitride; Compacting test block after it is mixed with binding agent, then be assembled into synthetic piece with transmission medium, sintering obtains having the polycrystalline cubic boron nitride compound material of full-package structure afterwards.
The method of preparing mullite precursor colloidal sol is as follows: by aluminum contained compound, silicon-containing compound and catalyzer with water mixes and carry out polyreaction, obtain described mullite precursor colloidal sol.
Aluminum contained compound and silicon-containing compound are according to mullite chemical composition 3Al
2o
32SiO
2stoichiometric equation is set the proportioning add, the amount of substance that water adds be aluminum contained compound, both amount of substance summations of silicon-containing compound 5-16 doubly, the amount that catalyzer adds take that to adjust pH value be 2 ~ 3.
Aluminum contained compound is selected from one or more the mixture in aluminium powder, aluminum isopropylate, aluminum chloride and aluminum nitrate; Described silicon-containing compound is tetraethoxy; The preferred hydrochloric acid of described catalyzer or acetic acid.
Wherein, aluminum contained compound is aluminium source, and silicon-containing compound is silicon source.The condition of polyreaction is as follows: time 2-72h, 30～60 ℃ of temperature of reaction.
Mullite precursor colloidal sol is 50～60
othe ageing that C carries out 10～24 hours concentrates, and while adding in cubic boron nitride powder, in cubic boron nitride powder and colloidal sol, the mass ratio of solid matter is 40～60:60-40.
When colloidal sol ageing is concentrated, temperature can have upper and lower 1 ℃ floating.
Original position solation process temperature is 60～65 ℃, and the time is controlled at 2～8 hours; Gelling temperature is 65～120 ℃, and the time is controlled at 4～12 hours.Solation and gelling temperature can have upper and lower 1-2 ℃ floating.
Described cubic boron nitride powder is comprised of the cubic boron nitride micro mist of the size distribution of following mass percent: 1-4 μ m accounts for 42～45%, 7-10 μ m and accounts for 35～50%, 12-15 μ m and account for 5～20%.
When having surface coated cubic boron nitride and mixing with binding agent, both mass fractions are as follows: have surface coated cubic boron nitride 25-90 part, binding agent 2-25 part; Be preferably and there is surface coated cubic boron nitride 75-83 part, binding agent 17-25 part.
Described binding agent is one or more the mixture in metal cobalt powder, metal nickel powder, titanium nitride, aluminium nitride, titanium carbide, wolfram varbide.
The mixture of binding agent preferable alloy cobalt powder and titanium nitride.Both ratios are preferably 6-12 part: 7-14 part.
The best purity of binding agent is all greater than 99%, and particle diameter is not more than 10 μ m.
The test block of compression moulding is put in the molybdenum cup of salt tube shield layer isolation, then puts the salt pipe installing into graphite jig, finally packs agalmatolite cavity into, and end socket, is assembled into synthetic piece.
Composite material by adopting cubic pressure machine equipment synthesizes, and pressure is 4.6～7.0 GPa, 1300～1600 ℃ of temperature, generated time 6～35 minutes.
Concrete, step prepared by material of the present invention is as follows:
1) proportioning that provides the aluminum contained compound in aluminium source, the silicon-containing compound that silicon source is provided and catalyzer to set according to reaction is mixed in water medium, join in polymerization reaction kettle and at 30-60 ℃ reactive polymeric 2～72 hours, obtain transparent mullite precursor colloidal sol.
2) the mullite precursor colloidal sol in step 1) is carried out to ageing at 50～60 ℃ concentrated, then add the cubic boron nitride powder after purifying treatment, through original position solation process and gelation, dry the cubic boron nitride that obtains the coated one deck mullite chemical composition in surface again.
3) by step 2) in the cubic boron nitride that obtains and binding agent according to different massfraction ratios, mix respectively, be pressed into test block.
4) test block of step 3) compression moulding and transmission medium are assembled into synthetic piece, by high pressure high temperature sintering, obtain polycrystalline cubic boron nitride.
The present invention adopts sol-gel method technique, sol-gel method in-situ polymerization can make cubic boron nitride powder dispersed and be blended in liquid phase, can make at low temperatures the effectively coated one deck mullite Chemical Composition in surface, surface chemical structure and the composition of cubic boron nitride have been improved, the toughness and the stock-removing efficiency that have improved the PcBN of preparation, extended work-ing life.
The cutter being processed into is for processing following material: workpiece material more than main workhardness HRC45, as, the workpiece material that the high rigidity such as various graphitic cast iron, quenched steel, superalloy, high-cobalt hart metal, surface spraying material, black powder sintering metal, titanium alloy, pure nickel, pure tungsten, wear-resisting etc. are difficult to process with universal cutter.
Compared with prior art, tool has the following advantages in the present invention:
The preparation method that the present invention has the polycrystalline cubic boron nitride compound material of full-package structure makes cubic boron nitride surface be coated the material of one deck mullite chemical composition, improve surface chemical structure and the composition of cubic boron nitride, improved toughness and the stock-removing efficiency of the polycrystalline cubic boron nitride matrix material of sintering.
Embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited to this:
Embodiment 1
A polycrystalline cubic boron nitride compound material with full-package structure, obtains by laxative remedy:
(1) metering takes containing 0.30 mole of the aluminum nitrate of 9 crystal water, 0.30 mole of aluminum isopropylate, 0.2 mole of tetraethoxy, add 12.4 moles, water, adding catalyzer hydrochloric acid to adjust pH value is 2, under the temperature condition of 60 ± 1 ℃, react, polymerization 22 hours, obtains transparent mullite precursor colloidal sol;
(2), by the mullite precursor colloidal sol in step (1), warp is 60 ± 1
othe ageing that C carries out 10 hours concentrates.Select the admixed finepowder of three kinds of particle diameter cubic boron nitrides, massfraction ratio in each comfortable admixed finepowder of the cubic boron nitride of different-grain diameter is: 1 micron accounts for 42% to 4 micrometer ranges, 7 microns of accounting for 45%, 12 micron and account for 13% to 15 micrometer ranges to 10 micrometer ranges.Above-mentioned cubic boron nitride powder after purifying treatment is joined in precursor sol, in cubic boron nitride powder and colloidal sol, the mass ratio of solid matter is 40/60, again through original position solation process and gelation, the insulation of original position solation process is at 60 ± 1 ℃, time is controlled at 5 hours, gelling temperature is at 95 ± 2 ℃, and the time is controlled at 8 hours, obtains the cubic boron nitride of the coated one deck mullite chemical composition in surface after oven dry.
(3) to account for the massfraction ratio of raw material micro mist be 83% to cubic boron nitride micro mist, and the massfraction ratio that cementing metal cobalt powder and titanium nitride account for respectively raw material micro mist is 10% and 7%.Above-mentioned raw materials micro mist is mixed by preset proportion, and be pressed into test block.
(4) test block of compression moulding is put in the molybdenum cup of salt tube shield layer isolation, then put the salt pipe installing into graphite jig, finally pack agalmatolite cavity into, end socket, be assembled into synthetic piece, dry in baking oven, then obtain polycrystalline cubic boron nitride by high pressure high temperature sintering.The actual conditions of sintering is to adopt cubic pressure machine equipment to synthesize, and pressure is 5.6 GPa, 1450 ℃ of temperature, generated time 6 minutes.
The polycrystalline cubic boron nitride matrix material microhardness that aforesaid method prepares is HV7410, and impelling strength is 722 times, and three-point bending method test bending strength is 781MPa.
Embodiment 2
A polycrystalline cubic boron nitride compound material with full-package structure, obtains by laxative remedy:
(1) metering takes containing 0.30 mole of the aluminum nitrate of 9 crystal water, 0.30 mole of aluminum isopropylate, and 0.2 mole of tetraethoxy, adds 12.4 moles, water, and adding catalyzer hydrochloric acid to adjust pH value is 2.5,60 ± 1
ounder the temperature condition of C, react, polymerization 25 hours, obtains transparent mullite precursor colloidal sol;
(2), by the mullite precursor colloidal sol in step (1), warp is 60 ± 1
othe ageing that C carries out 10 hours concentrates.Select the admixed finepowder of three kinds of particle diameter cubic boron nitrides, massfraction ratio in each comfortable admixed finepowder of the cubic boron nitride of different-grain diameter is: 1 micron accounts for 45% to 4 micrometer ranges, 7 microns of accounting for 40%, 12 micron and account for 15% to 15 micrometer ranges to 10 micrometer ranges.Above-mentioned cubic boron nitride powder after purifying treatment is joined in precursor sol, in cubic boron nitride powder and colloidal sol, the mass ratio of solid matter is 40/60, again through original position solation process and gelation, the insulation of original position solation process is at 60 ± 1 ℃, time is controlled at 5 hours, gelling temperature is at 90 ± 2 ℃, and the time is controlled at 10 hours, obtains the cubic boron nitride of the coated one deck mullite chemical composition in surface after oven dry.
(3) to account for the massfraction ratio of raw material micro mist be 83% to cubic boron nitride micro mist, and the massfraction ratio that cementing metal cobalt powder and titanium nitride account for respectively raw material micro mist is 6% and 11%.Above-mentioned raw materials micro mist is mixed by preset proportion, and be pressed into test block.
(4) test block of compression moulding is put in the molybdenum cup of salt tube shield layer isolation, then put the salt pipe installing into graphite jig, finally pack agalmatolite cavity into, end socket, be assembled into synthetic piece, dry in baking oven, then obtain polycrystalline cubic boron nitride by high pressure high temperature sintering.The actual conditions of sintering is to adopt cubic pressure machine equipment to synthesize, and pressure is 5.3 GPa, 1500 ℃ of temperature, generated time 8 minutes.
The polycrystalline cubic boron nitride matrix material microhardness that aforesaid method prepares is HV7230, and impelling strength is 732 times, and three-point bending method test bending strength is 805MPa.
Embodiment 3
A polycrystalline cubic boron nitride compound material with full-package structure, obtains by laxative remedy:
(1) metering takes containing 0.30 mole of the aluminum nitrate of 9 crystal water, 0.30 mole of aluminum isopropylate, 0.2 mole of tetraethoxy, add 12.4 moles, water, adding catalyzer hydrochloric acid to adjust pH value is 2, under the temperature condition of 60 ± 1 ℃, react, polymerization 22 hours, obtains transparent mullite precursor colloidal sol;
(2), by the mullite precursor colloidal sol in step (1), warp is 60 ± 1
othe ageing that C carries out 10 hours concentrates.Select the admixed finepowder of three kinds of particle diameter cubic boron nitrides, massfraction ratio in each comfortable admixed finepowder of the cubic boron nitride of different-grain diameter is: 1 micron accounts for 42% to 4 micrometer ranges, 7 microns of accounting for 45%, 12 micron and account for 13% to 15 micrometer ranges to 10 micrometer ranges.Above-mentioned cubic boron nitride powder after purifying treatment is joined in precursor sol, and in cubic boron nitride powder and colloidal sol, the mass ratio of solid matter is 50/50, then through original position solation process and gelation, original position solation process is incubated 65 ± 1
oc, the time is controlled at 5 hours, and gelling temperature is 90 ± 2
oc, the time is controlled at 10 hours, obtains the cubic boron nitride of the coated one deck mullite chemical composition in surface after oven dry.
(3) to account for the massfraction ratio of raw material micro mist be 75% to cubic boron nitride micro mist, and the massfraction ratio that cementing metal cobalt powder and titanium nitride account for respectively raw material micro mist is 11% and 14%.Above-mentioned raw materials micro mist is mixed by preset proportion, and be pressed into test block.
(4) test block of compression moulding is put in the molybdenum cup of salt tube shield layer isolation, then put the salt pipe installing into graphite jig, finally pack agalmatolite cavity into, end socket, be assembled into synthetic piece, dry in baking oven, then obtain polycrystalline cubic boron nitride by high pressure high temperature sintering.The actual conditions of sintering is to adopt cubic pressure machine equipment to synthesize, and pressure is 5.3 GPa, 1500 ℃ of temperature, generated time 8 minutes.
The polycrystalline cubic boron nitride matrix material microhardness that aforesaid method prepares is HV7160, and impelling strength is 783 times, and three-point bending method test bending strength is 825MPa.
Embodiment 4
A polycrystalline cubic boron nitride compound material with full-package structure, obtains by laxative remedy:
(1) metering takes 0.30 mole of aluminium powder, containing 0.08 mole of the aluminum nitrate of 9 crystal water, 0.076 mole of tetraethoxy, add 5.5 moles, water, adding catalyzer hydrochloric acid to adjust pH value is 2, under the temperature condition of 55 ± 1 ℃, react, polyase 13 0 hour, obtains transparent mullite precursor colloidal sol;
(2), by the mullite precursor colloidal sol in step (1), warp is 60 ± 1
othe ageing that C carries out 15 hours concentrates.Select the admixed finepowder of three kinds of particle diameter cubic boron nitrides, massfraction ratio in each comfortable admixed finepowder of the cubic boron nitride of different-grain diameter is: 1 micron accounts for 45% to 4 micrometer ranges, 7 microns of accounting for 48%, 12 micron and account for 7% to 15 micrometer ranges to 10 micrometer ranges.Cubic boron nitride powder after purifying treatment is joined in precursor sol, and in cubic boron nitride powder and colloidal sol, the mass ratio of solid matter is 40/60, then through original position solation process and gelation, the above-mentioned solation process insulation of original position is 65 ± 1
oc, the time is controlled at 5 hours, and gelling temperature is 100 ± 2
oc, the time is controlled at 8 hours, obtains the cubic boron nitride of the coated one deck mullite chemical composition in surface after oven dry.
(3) to account for the massfraction ratio of raw material micro mist be 83% to cubic boron nitride micro mist, and the massfraction ratio that cementing metal cobalt powder and titanium nitride account for respectively raw material micro mist is 6% and 11%.Above-mentioned raw materials micro mist is mixed by preset proportion, and be pressed into test block.
(4) test block of compression moulding is put in the molybdenum cup of salt tube shield layer isolation, then put the salt pipe installing into graphite jig, finally pack agalmatolite cavity into, end socket, be assembled into synthetic piece, dry in baking oven, then obtain polycrystalline cubic boron nitride by high pressure high temperature sintering.The actual conditions of sintering is to adopt cubic pressure machine equipment to synthesize, and pressure is 5.3 GPa, 1500 ℃ of temperature, generated time 8 minutes.
The polycrystalline cubic boron nitride matrix material microhardness that aforesaid method prepares is HV7580, and impelling strength is 764 times, and three-point bending method test bending strength is 891MPa.
Embodiment 5
A polycrystalline cubic boron nitride compound material with full-package structure, obtains by laxative remedy:
(1) metering takes 0.38 mole of aluminium powder, and containing 0.10 mole, the aluminum chloride of 6 crystal water, 0.056 mole of tetraethoxy, adds 5.5 moles, water, and adding catalyzer hydrochloric acid to adjust pH value is 2.5,50 ± 1
ounder the temperature condition of C, react, polyase 13 5 hours, obtains transparent mullite precursor colloidal sol;
(2), by the mullite precursor colloidal sol in step (1), warp is 60 ± 1
othe ageing that C carries out 15 hours concentrates.Select the admixed finepowder of three kinds of particle diameter cubic boron nitrides, massfraction ratio in each comfortable admixed finepowder of the cubic boron nitride of different-grain diameter is: 1 micron accounts for 42% to 4 micrometer ranges, 7 microns of accounting for 45%, 12 micron and account for 13% to 15 micrometer ranges to 10 micrometer ranges.Above-mentioned cubic boron nitride powder after purifying treatment is joined in precursor sol, and in cubic boron nitride powder and colloidal sol, the mass ratio of solid matter is 50/50, then through original position solation process and gelation, original position solation process is incubated 60 ± 1
oc, the time is controlled at 5 hours, and gelling temperature is 100 ± 2
oc, the time is controlled at 8 hours, obtains the cubic boron nitride of the coated one deck mullite chemical composition in surface after oven dry.
(3) to account for the massfraction ratio of raw material micro mist be 83% to cubic boron nitride micro mist, and the massfraction ratio that cementing metal cobalt powder and titanium nitride account for respectively raw material micro mist is 10% and 7%.Above-mentioned raw materials micro mist is mixed by preset proportion, and be pressed into test block.
(4) test block of compression moulding is put in the molybdenum cup of salt tube shield layer isolation, then put the salt pipe installing into graphite jig, finally pack agalmatolite cavity into, end socket, be assembled into synthetic piece, dry in baking oven, then obtain polycrystalline cubic boron nitride by high pressure high temperature sintering.The actual conditions of sintering is to adopt cubic pressure machine equipment to synthesize, and pressure is 5.3 GPa, 1500 ℃ of temperature, generated time 6 minutes.
The polycrystalline cubic boron nitride matrix material microhardness that aforesaid method prepares is HV7260, and impelling strength is 747 times, and three-point bending method test bending strength is 832MPa.
Embodiment 6
A polycrystalline cubic boron nitride compound material with full-package structure, obtains by laxative remedy:
(1) metering takes 0.38 mole of aluminium powder, and containing 0.10 mole, the aluminum chloride of 6 crystal water, 0.056 mole of tetraethoxy, adds 5.5 moles, water, and adding catalyzer hydrochloric acid to adjust pH value is 2,55 ± 1
ounder the temperature condition of C, react, polyase 13 0 hour, obtains transparent mullite precursor colloidal sol;
(2), by the mullite precursor colloidal sol in step (1), warp is 60 ± 1
othe ageing that C carries out 10 hours concentrates.Select the admixed finepowder of three kinds of particle diameter cubic boron nitrides, massfraction ratio in each comfortable admixed finepowder of the cubic boron nitride of different-grain diameter is: 1 micron accounts for 42% to 4 micrometer ranges, 7 microns of accounting for 40%, 12 micron and account for 18% to 15 micrometer ranges to 10 micrometer ranges.Above-mentioned cubic boron nitride powder after purifying treatment is joined in precursor sol, and in cubic boron nitride powder and colloidal sol, the mass ratio of solid matter is 40/60, then through original position solation process and gelation, original position solation process is incubated 65 ± 1
oc, the time is controlled at 6 hours, and gelling temperature is 90 ± 2
oc, the time is controlled at 10 hours, obtains the cubic boron nitride of the coated one deck mullite chemical composition in surface after oven dry.
(3) to account for the massfraction ratio of raw material micro mist be 75% to cubic boron nitride micro mist, and the massfraction ratio that cementing metal cobalt powder and titanium nitride account for respectively raw material micro mist is 12% and 13%.Above-mentioned raw materials micro mist is mixed by preset proportion, and be pressed into test block.
(4) test block of compression moulding is put in the molybdenum cup of salt tube shield layer isolation, then put the salt pipe installing into graphite jig, finally pack agalmatolite cavity into, end socket, be assembled into synthetic piece, dry in baking oven, then obtain polycrystalline cubic boron nitride by high pressure high temperature sintering.The actual conditions of sintering is to adopt cubic pressure machine equipment to synthesize, and pressure is 5.6 GPa, 1450 ℃ of temperature, generated time 6 minutes.
The polycrystalline cubic boron nitride matrix material microhardness that aforesaid method prepares is HV7060, and impelling strength is 689 times, and three-point bending method test bending strength is 843MPa.
Claims (10)
1. a polycrystalline cubic boron nitride compound material with full-package structure, it is characterized in that, by laxative remedy, obtain: first prepare mullite precursor colloidal sol, after colloidal sol ageing is concentrated, add in cubic boron nitride powder and carry out original position solation and gelation, dry rear acquisition has surface coated cubic boron nitride; Compacting test block after it is mixed with binding agent, then be assembled into synthetic piece with transmission medium, sintering obtains having the polycrystalline cubic boron nitride compound material of full-package structure afterwards.
2. a preparation method with the polycrystalline cubic boron nitride compound material of full-package structure, it is characterized in that, first prepare mullite precursor colloidal sol, after colloidal sol ageing is concentrated, add in cubic boron nitride powder and carry out original position solation and gelation, dry rear acquisition has surface coated cubic boron nitride; Compacting test block after it is mixed with binding agent, then be assembled into synthetic piece with transmission medium, sintering obtains having the polycrystalline cubic boron nitride compound material of full-package structure afterwards.
3. a kind of preparation method with the polycrystalline cubic boron nitride compound material of full-package structure as claimed in claim 2, it is characterized in that, the method for preparing mullite precursor colloidal sol is as follows: be incorporated in 30-60 ℃ of polyreaction 2-72h and obtain described mullite precursor colloidal sol aluminum contained compound, silicon-containing compound and catalyzer and water are mixed; The amount of substance that water adds is aluminum contained compound, both amount of substance summations of silicon-containing compound 5-16 times.
4. a kind of preparation method with the polycrystalline cubic boron nitride compound material of full-package structure as claimed in claim 3, is characterized in that, aluminum contained compound is selected from one or more the mixture in aluminium powder, aluminum isopropylate, aluminum chloride and aluminum nitrate; Described silicon-containing compound is tetraethoxy; Described catalyzer is hydrochloric acid or acetic acid.
5. a kind of preparation method with the polycrystalline cubic boron nitride compound material of full-package structure as claimed in claim 2, it is characterized in that, mullite precursor colloidal sol is at the concentrated 10-24h of 50～60 ℃ of ageings, and while adding in cubic boron nitride powder, in cubic boron nitride powder and colloidal sol, the mass ratio of solid matter is 40～60:60-40.
6. a kind of preparation method with the polycrystalline cubic boron nitride compound material of full-package structure as claimed in claim 5, it is characterized in that, original position solation process temperature is 60～65 ℃, and the time is controlled at 2～8 hours, gelling temperature is 65～120 ℃, and the time is controlled at 4～12 hours.
7. a kind of preparation method with the polycrystalline cubic boron nitride compound material of full-package structure as claimed in claim 5, it is characterized in that, described cubic boron nitride powder is comprised of the cubic boron nitride micro mist of the size distribution of following mass percent: 1-4 μ m accounts for 42～45%, 7-10 μ m accounts for 35～50%, 12-15 μ m and accounts for 5～20%.
8. a kind of preparation method with the polycrystalline cubic boron nitride compound material of full-package structure as claimed in claim 2, it is characterized in that, when thering is surface coated cubic boron nitride and mixing with binding agent, both mass fractions are as follows: have surface coated cubic boron nitride 25-90 part, binding agent 2-25 part.
9. a kind of preparation method with the polycrystalline cubic boron nitride compound material of full-package structure as claimed in claim 8, it is characterized in that, described binding agent is one or more the mixture in metal cobalt powder, metal nickel powder, titanium nitride, aluminium nitride, titanium carbide, wolfram varbide.
10. a kind of preparation method with the polycrystalline cubic boron nitride compound material of full-package structure as claimed in claim 2, it is characterized in that, composite material by adopting cubic pressure machine equipment synthesizes, and pressure is 4.6～7.0 GPa, 1300～1600 ℃ of temperature, generated time 6～35 minutes.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789596A (en) * | 2014-02-26 | 2014-05-14 | 中原工学院 | Polycrystalline cubic boron nitride cutter material and preparation method thereof |
| CN104892002A (en) * | 2015-05-20 | 2015-09-09 | 中原工学院 | Method for preparing ceramic matrix cubic boron nitride composite material by employing conversion of organosilicon |
| WO2016023200A1 (en) * | 2014-08-11 | 2016-02-18 | 河海大学 | Preparation method for high-density hexagonal boron nitride ceramic material |
| CN106623908A (en) * | 2017-02-27 | 2017-05-10 | 齐鲁工业大学 | Preparation method of nickel-coated hexagonal boron nitride composite powder |
| CN107759227A (en) * | 2017-10-09 | 2018-03-06 | 中原工学院 | A kind of method that PcBN cutter materials are prepared using membrane by accelerant process |
| CN108913095A (en) * | 2018-07-19 | 2018-11-30 | 江苏华东砂轮有限公司 | Modified cubic boron nitride abrasive materials and preparation method thereof |
| CN109158591A (en) * | 2018-09-30 | 2019-01-08 | 桂林理工大学 | A kind of metallic aluminium cladding cubic boron nitride and preparation method thereof |
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| CN114276151A (en) * | 2021-12-21 | 2022-04-05 | 富耐克超硬材料股份有限公司 | PCBN composite material and preparation method thereof |
| CN114774068A (en) * | 2022-04-25 | 2022-07-22 | 无锡腾跃特种钢管有限公司 | Wear-resistant perforating roller and processing method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4353714A (en) * | 1981-10-26 | 1982-10-12 | General Electric Company | Polycrystalline silicon-bonded cubic boron nitride body and method |
| US5320988A (en) * | 1988-11-10 | 1994-06-14 | General Electric Company | Process for preparing polycrystalline CBN ceramic masses and resulting product |
| CN1986487A (en) * | 2005-12-22 | 2007-06-27 | 三菱麻铁里亚尔株式会社 | Cutting tool made of surface-coated cubic boron nitride-based ultrahigh pressure sintered material |
| CN102505090A (en) * | 2011-10-21 | 2012-06-20 | 中原工学院 | Preparation method of high-toughness polycrystalline cubic boron nitride compound sheets |
| CN103304240A (en) * | 2012-03-08 | 2013-09-18 | 三菱综合材料株式会社 | CBN sintered body cutting tool with excellent toughness |
-
2013
- 2013-11-06 CN CN201310544306.9A patent/CN103553637B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4353714A (en) * | 1981-10-26 | 1982-10-12 | General Electric Company | Polycrystalline silicon-bonded cubic boron nitride body and method |
| US5320988A (en) * | 1988-11-10 | 1994-06-14 | General Electric Company | Process for preparing polycrystalline CBN ceramic masses and resulting product |
| CN1986487A (en) * | 2005-12-22 | 2007-06-27 | 三菱麻铁里亚尔株式会社 | Cutting tool made of surface-coated cubic boron nitride-based ultrahigh pressure sintered material |
| CN102505090A (en) * | 2011-10-21 | 2012-06-20 | 中原工学院 | Preparation method of high-toughness polycrystalline cubic boron nitride compound sheets |
| CN103304240A (en) * | 2012-03-08 | 2013-09-18 | 三菱综合材料株式会社 | CBN sintered body cutting tool with excellent toughness |
Non-Patent Citations (2)
| Title |
|---|
| MALIK ADEEL UMER.ETAL.: "Polycrystalline cubic boron nitride sintered compacts prepared from nanocrystalline TiN coated cBN powder", 《MATERIALS SCIENCE AND ENGINEERING A》, 1 June 2012 (2012-06-01), pages 151 - 156 * |
| 亓曾笃: "多晶立方氮化硼复合材料研究进展", 《金刚石与磨料磨具工程》, vol. 172, no. 4, 31 August 2009 (2009-08-31), pages 15 - 17 * |
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|---|---|---|---|---|
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| CN103789596B (en) * | 2014-02-26 | 2015-11-04 | 中原工学院 | A kind of polycrystalline cubic boron nitride tool material and preparation method thereof |
| WO2016023200A1 (en) * | 2014-08-11 | 2016-02-18 | 河海大学 | Preparation method for high-density hexagonal boron nitride ceramic material |
| GB2534530A (en) * | 2014-08-11 | 2016-07-27 | Univ Hohai | Preparation method for high-density hexagonal boron nitride ceramic material |
| GB2534530B (en) * | 2014-08-11 | 2017-01-25 | Univ Hohai | Method for preparing high-density hexagonal boron nitride ceramic material |
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| CN107759227B (en) * | 2017-10-09 | 2020-03-31 | 中原工学院 | Method for preparing PcBN cutter material by catalyst method |
| CN108913095A (en) * | 2018-07-19 | 2018-11-30 | 江苏华东砂轮有限公司 | Modified cubic boron nitride abrasive materials and preparation method thereof |
| CN108913095B (en) * | 2018-07-19 | 2020-10-16 | 江苏华东砂轮有限公司 | Modified cubic boron nitride abrasive and preparation method thereof |
| CN109158591A (en) * | 2018-09-30 | 2019-01-08 | 桂林理工大学 | A kind of metallic aluminium cladding cubic boron nitride and preparation method thereof |
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