CN1292363A - Production method of carborundum whiskers high-toughened silicon nitride base ceramic roll material - Google Patents
Production method of carborundum whiskers high-toughened silicon nitride base ceramic roll material Download PDFInfo
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- CN1292363A CN1292363A CN 00129948 CN00129948A CN1292363A CN 1292363 A CN1292363 A CN 1292363A CN 00129948 CN00129948 CN 00129948 CN 00129948 A CN00129948 A CN 00129948A CN 1292363 A CN1292363 A CN 1292363A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 78
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 69
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000000463 material Substances 0.000 title abstract description 50
- 229910010271 silicon carbide Inorganic materials 0.000 title description 37
- 238000005245 sintering Methods 0.000 claims abstract description 83
- 239000000843 powder Substances 0.000 claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 4
- 239000010439 graphite Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000395 magnesium oxide Substances 0.000 claims description 13
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 8
- 238000005299 abrasion Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
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- 229920001778 nylon Polymers 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 19
- 238000007254 oxidation reaction Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 12
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 238000005096 rolling process Methods 0.000 abstract description 9
- 238000011049 filling Methods 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract 3
- 238000001914 filtration Methods 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 31
- 239000013078 crystal Substances 0.000 description 26
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 description 16
- 239000010955 niobium Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 12
- 229910052758 niobium Inorganic materials 0.000 description 11
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000002131 composite material Substances 0.000 description 8
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- 238000006243 chemical reaction Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 7
- 230000003245 working effect Effects 0.000 description 7
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 5
- 229940075624 ytterbium oxide Drugs 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 235000006708 antioxidants Nutrition 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 4
- 239000005543 nano-size silicon particle Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000001133 acceleration Effects 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000003064 anti-oxidating effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
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- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 3
- 230000004584 weight gain Effects 0.000 description 3
- 235000019786 weight gain Nutrition 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 150000002822 niobium compounds Chemical class 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000008698 shear stress Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910002795 Si–Al–O–N Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
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- 238000013001 point bending Methods 0.000 description 1
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- -1 rare earth silicon nitride Chemical class 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
The preparation method of silicon nitride base ceramic roll includes the following steps: firstly, using silicon nitride ball or aluminium oxide ball as ball-grinding medium, adding anhydrous ethanol and silicon nitride ball or aluminium oxide ball in ball-grinding mill, ball-grinding, pumping and filtering to separate powder material from liquid medium, seiving and granulating, then filling the above-mentioned material into graphite mould and high-temp. sintering so as to obtain the invented product. Said invention ceramic material features resisting high temp., high strength, high toughness, high oxidation resistance and high wearability, can be used for making roll. In the course of high-speed rolling metal wire material it can attain the effects of prolonging its service life and obtaining high-quality wire material.
Description
The present invention relates to a kind of manufacture method of carborundum whiskers high-toughened silicon nitride base ceramic roll material, the roll ceramic new material that belongs to the rolling processing usefulness of metal wire, the roll for hot-rolling material that uses when soon metals such as iron, copper at high temperature are pressed into wire rod has high abrasion resistance and keeps the ganoid characteristics of converted products.
The major cause of existing superhard alloy roll quality defective, be superhard alloy aspect hot hardness and high-temperature oxidation resistance, have serious weakness.Although Hardmetal materials at room temperature has very high intensity and hardness, but performances such as its intensity and hardness can raise and decline rapidly along with temperature, and the wire rod processing conditions is the high temperature of 700-1000 ℃ of degree, under such high temperature, when the performance of Wimet itself descended, its surface and the high temperature wire rod contact site generation oxidizing reaction of passing through at a high speed produced oxide particles such as rust staining, be shed on the contact surface, aggravated surperficial abrasion.In addition, because the high-temperature behavior of Wimet phase descends obviously, for the stability that guarantees high temperature bottom roll shape and the quality of wire rod, superhard alloy can not add too many mutually, hardness is also not enough, resistance to heat shocks is also not enough, at high temperature and during the water-cooled thermal shock is operated repeatedly, forms microcrack and be full of cracks easily on the surface.
In order to overcome the deficiency of superhard alloy roller performance, at the mid-80, people have taked the way at the ceramic coated layer of metal roller surface, and expectation forms one deck high-hardness ceramic layer.But owing to metal is bigger with the thermal expansivity gap of pottery, under high temperature rolling and water spray refrigerative environment, the delamination between ceramic layer and the metal mother metal is peeled off phenomenon and is difficult to obtain the essence solution.Split away off fine potsherd from the metal roll and also wire rod may be ground disconnected, cause quality problems.The technology of ceramic coating does not obtain real practicability on the high temperature wire roll.Enter after the nineties, Japan has proposed the imagination of full ceramic roll, and the patented technology of several enforcements has been arranged in order further to improve the quality of wire rod working (machining) efficiency and processing wire rod.
It is stupalith that Japanese Patent in 1984 has proposed the oxide-nitride thing sosoloid with sial, makes the imagination of ceramic roll, still, and the rolling requirement that all do not reach a high temperature of its intensity and toughness.There was a patent (spy opens flat 5-337518) to propose to make roll to increase the technology of heat-shock resistance in 1993 again with Si-Al-O-N (Sialon); Patent (spy opens flat 9-278529) in 1997 has proposed to disperse Cr at the deficiency of silicon nitride ceramics wear resistance in silicon nitride ceramics
2The N particle is to increase the technology of roll wear resistant; The special permission communique has proposed in silicon nitride ceramics dispersed carbon silicon carbide particle for No. 2920138 to increase the technology of wear resistant; Another patent of Japan in 1998 has proposed to add the design (spy opens flat 10-101436) of high heat conductance AlN at the heat-shock resistance problem of pottery, has proposed to use Si
3N
4-Y
2O
3The technology of-MgO-AlN ceramic sintered bodies manufacturing revolution processing component; Hot strength at stupalith, the flat 10-81566 of patent EP0726236A2 and Te Kai has proposed to add Y and Yb element in silicon nitride, through sintering again 1100-1300 ℃ of tempering heat treatment to form the technology of crystal boundary J phase, to increase the hot strength of roll material.But these patents all are the improvement at the some aspect of performances of material, and the over-all properties of ceramic roll is the restriction that is subjected to the many aspects performance, and effect is unsatisfactory.
Find that after deliberation for the roll of high temperature and high speed wire rod processing, its material requirements is very strict, must have following characteristics: 1, hot hardness height; 2, good in oxidation resistance; 3, and be rolled between the material (iron, iron alloy, copper, copper alloy etc.) and do not react; 4, high wear resistant (comprising anti-surface roughening ability); 5, good thermal shock; 6, hot-pressing strength height; 7, ability of anti-deformation strong (high-temperature elastic modulus is big).
Compare with Wimet, stupalith all has superiority on the 1st, 2,3,4,5,7.In addition, since the density of ceramic roll, half of not enough Wimet, and when changing roll, ceramic roll also has the effect that reduces labor intensity.In stupalith, can be at the normal material that uses of more than 1000 degree, and have both above-mentioned performance, have only the material of silicon nitride series.Thereby people focus mostly on the research silicon nitride-based material as roll material.
Present silicon nitride base ceramic roll technology can than the long 2-5 of superhard alloy doubly originally be replaced at interval its work-ing life in 4 hours, use ceramic roll instead after, can extend to more than 15 hour.But, from theoretical calculate, the 8-20 that can further bring up to superhard alloy roll campaign work-ing life doubly, the someone thinks the possibility that reaches more than 300 hours the work-ing life of ceramic roll.Analyze the Breakage Mechanism of present ceramic roll, but find wherein to also have improvements, be that mainly the toughness of pottery is not enough, oxidation-resistance is not enough, the high temperature resistance shearing resistance is not enough.If stupalith has obvious improvement aspect above-mentioned three, then will inevitably further improve the work-ing life of ceramic roll.The starting point of this research, three aspect characteristics at present ceramic roll improve exactly.
Studies confirm that, the oxidising process of silicon nitride ceramic material under the high temperature, mainly be Sauerstoffatom along crystal boundary to internal divergence, Sauerstoffatom is at the crystal boundary oxidation material of some easy oxidation wherein optionally, and forms new crystal boundary phase.Crystal boundary is generally siliceous nitrogen oxide glass phase mutually, forms silica glass after oxidation, and this glass has very strong crystallization ability, separates out and volumetric shrinkage takes place in the crystal boundary crystallization, causes the formation of grain-boundary crack.The formation of grain-boundary crack becomes the passage of oxygen to internal divergence again conversely, has quickened oxygen and has goed deep into to the infiltration of inside.So, the failure mechanisms of silicon nitride ceramics under the high temperature, be crystal boundary phase oxidation-formation grain-boundary crack-grain-boundary crack polymerization form check surface or hair shape crackle-oxygen along grain-boundary crack fast to the material internal infiltration deeply-material deep crystal boundary is mutually oxidized.This is that a grain boundary oxidation-microcrack development interacts catalytic each other process.Take measures to stop any one catalysis link in this process, just can effectively delay the breakdown speed of ceramic roll, prolong roll campaign.
Silicon nitride ceramic material at high temperature working order is when applying big squeeze, high speed rotating.Shear strength under the high temperature of roll is the important symbol of roll quality.Silicon nitride ceramics itself has good ultimate compression strength, and still, its shear strength is not high, mainly is the not high cause of its toughness.If can obviously improve the fracture toughness property of stupalith, then can improve its shearing resistance, increase the working strength (squeeze and velocity of rotation) of roll.
Silicon nitride ceramic material itself has reasonable hot strength, and still, because the existence of crystal boundary glassy phase, its high temperature creep property is still waiting to improve.Method commonly used has: the one, reduce sintering agent content, to reduce the content of crystal boundary glassy phase; The 2nd, after sintering circuit was finished, annealed thermal treatment made the sintering agent crystallization form dystectic crystal boundary phase; The 3rd, increase the bonding strength of crystal boundary and principal crystalline phase.Extremely reduce the method for agglutinant, cause the sintering ununiformity of member easily, for large size ceramic parts and improper; The method of anneal crystallization, it is the common method that improves silicon nitride ceramic material intensity, but, because the ununiformity that annealing can cause the silicon nitride material internal crystallization to be separated out, for composite ceramic material, can cause the inappropriate reduction of interface binding power, cause the reduction of fracture toughness property on the macroscopic view.
The objective of the invention is to propose a kind of manufacture method of carborundum whiskers high-toughened silicon nitride base ceramic roll material, with the silicon nitride ceramic material is main raw material, carrying out highly malleablized with silicon carbide whisker handles, with densification of rare earth oxide acceleration of sintering and raising high-temperature behavior, the compound that adds the transition metal niobium forms the high temperature self-adaption anti oxidation layer and fills and leads up the roller surface crackle voluntarily to reach, to improve silicon nitride ceramic material oxidation-resistance at high temperature, fracture toughness property, intensity, and then the work-ing life and the result of use of raising silicon nitride base ceramic roll, improve quality and the dimensional precision and the production efficiency of institute's rolled wire, and reduce working strength of workers.
The present invention be directed to ceramic roll under the high temperature and high speed environment for use, the mutual catalytic process that the shear-stress of suffered harshness and grain boundary oxidation and tiny crack form proposes.This is a kind of novel material synthetic technology and member manufacturing method thereof of clearly using object that have.
High abrasion resistance silicon nitride base ceramic roll of the present invention, its composition is as follows:
Si
3N
4(technical pure) 60.0～90.0wt%
SiC whisker 3.0～30.0wt%
Niobide 0.1～10.0wt%
Magnesium oxide 0.5～4.5wt%
Aluminum oxide 0.7～6.0wt%
Yttrium oxide 0.5～6.0wt%
Lanthanum trioxide 0.0～3.0wt%
Ytterbium oxide 0.0～2.0wt%
Added single-crystal silicon carbide body fiber-silicon carbide whisker in ceramic roll, purpose is silicon nitride base ceramic roll to be carried out highly malleablized handle.Silicon carbide whisker, English is Silicon carbide crystal whisker, is that diameter is 0.5-2.0 micron, the length monocrystalline build silicon carbide at the 5-30 micron.Because this single crystal fibre defective is few, intensity all has good toughened and reinforced effect substantially near theoretical strength for metal, polymer and various stupalith.The addition of silicon carbide whisker is relevant with multiple factor, comprises the content of sintering agent, the environment that product is on active service, production cost etc.In this invention, the weight percent of silicon carbide whisker is 3.0-30.0%.Be less than 3.0%, toughening effect is not obvious; More than 30.0%, then whisker easy cotton-shaped caking in silicon nitride material causes cavity and defective, reduces the toughness and the intensity of material on the contrary.
The adding of silicon carbide whisker, in silicon nitride matrix stupalith, formed tridimensional network, ceramic intensity and toughness have not only been improved, needle-like whisker forms staggered reticulated structure in pottery, the particle on all right stationary roll surface, microcosmic ground, prevent that the individual ceramic particulate from coming off, help keeping surface smooth smooth of roll parts.The adding of whisker can reach the toughness that increases silicon nitride ceramics, increases ceramic roll and resist shear-stress destructive ability when high speed rotating; The hardness of silicon carbide whisker and wear resistance are also far better than nitride silicon based material, and the adding of silicon carbide whisker also helps the hardness that increases stupalith, increases its wear resistant.Silicon carbide whisker oxidation-resistance at high temperature is also superior than silicon nitride, and the adding of whisker also helps the high-temperature oxidation resistance that improves roll material.So the adding of silicon carbide whisker is many-sided for the improved performance of silicon nitride ceramics roll.
The adding mode of silicon carbide whisker can be the whisker of having grown in the direct interpolation of batch mixing stage, also can be the raw material that adds whisker growth, the whisker of growing and forming voluntarily in high-temperature sintering process.The latter can form more satisfactory network-like structure, but strict to processing requirement, makes the products production cost improve.The former must first homodisperseization and pre-treatment in early stage before silicon carbide whisker adds body material.The purpose of homodisperseization is, prevents the cotton-shaped caking of silicon carbide whisker, causes discontinuity of material.Pre-treatment in early stage purpose is to improve the bonding properties at whisker and interface, is preferably formed as oxide compound or carbonaceous thin layer, just more helps the performance of toughness effect.
In body material, add the niobium nitride nano particle, reached the purpose that increases the high-temperature oxidation resistance of silicon nitride ceramics roll material greatly.Niobium is a kind of valence variation element, under different environment, can form different valence states: 0 ,+2 ,+3 ,+4 ,+5, its oxide compound can be compound or its mixture, for example NbO of above various valence states
2, Nb
2O
5Deng, still, when at high temperature forming, form the glass coating of the very big densification of viscosity easily.After the nitride-niobium nitride (NbN) with the niobium of+3 valencys joins in the silicon nitride ceramics, the nano silicon nitride niobium that is positioned at crystal boundary can preferentially react with the Sauerstoffatom that diffuses into, form niobium oxides glass, thereby not only absorb and consumed the Sauerstoffatom that diffuses into, reduced the oxidized probability of silicon nitride principal crystalline phase, and, because the oxygen diffusion passage of crystal boundary is stopped up in the easy filling of full-bodied niobium oxides glass, stop the mutual katalysis of high temperature oxidation-crystal boundary microcrack development, increased silicon nitride ceramics roll resistance of oxidation at high temperature.The ability of this prevention oxidation of niobium nitride is found back (Li Jianbao etc., the 1219th page of Chinese science circular volume o. 11th June the 43rd in 1998) by the inventor, and the oxidation-resistance ability that is applied to ceramic roll for the first time strengthens.At high temperature this, difference along with well-oxygenated environment, form the phenomenon of the zone of oxidation that contends with voluntarily, be called as self-adaptation anti oxidation layer (Self-diagnosis layer of anti-oxidation), be similar to the reconditioning layer that the back forms in the crack that breaks of ice cube on the water surface in winter, perhaps the surface alumina oxide high rigidity compact film that forms in use of metallic aluminium goods.Have this anti-oxidant adaptation layer and form machine-processed material, reduced intelligent material (Smart materials).
Compound with niobium of high-temperature oxidation resistant adaptivity except that niobium nitride, also has niobium carbide (NbC), niobium (Nb) boride (NbB
2) and other contain niobium compound.But the niobium nitride with lower valency is more effective.The form of niobium nitride can be particle, needle-like crystal or tabular crystal, but the most effective with nano particle.Because nano grain surface is long-pending big, easier reaction to diffusing into the Sauerstoffatom of crystal boundary under the high temperature, has reaction response more rapidly.The adding of niobide has improved the high-temperature oxidation resistance of member, but has sacrificed a small amount of other performance, as hardness, shock-resistance etc.In the present invention, the weight percent of niobide is 0.1-10.0%, should decide on the member Service Environment.
The adding of magnesium oxide, aluminum oxide, rare earth oxide composite sintering agent, one side has improved the speed of sintering reaction, and the adding of rare earth oxide has limited the negative influence of sintering agent to material property on the other hand, has improved the hot strength of material.Because the adding of silicon carbide whisker, the sintering difficulty of silicon nitride increases.For this carborundum whiskers high-toughened silicon nitride ceramic composite, the acceleration of sintering densification, (MgO) is necessary as the agglutinant component with magnesium oxide.Because the eutectoid point glassy phase that it forms under sintering temperature, the surface of easier moistening silicon carbide whisker reaches acceleration of sintering and the effect of improving whisker interface bonding state.Aluminum oxide (Al
2O
3) and rare earth oxide-yttrium oxide (Y
2O
3), in sintering process, certain solid solution reaction takes place with the silicon nitride principal crystalline phase in part, forms the more intense transition crystal boundary of bonding force easily.At this matrix material, add a spot of rare earth oxide-lanthanum trioxide (La
2O
5) and ytterbium oxide (Yb
2O
3), at high temperature the liquid phase viscosity of Xing Chenging is big, prevents that silicon nitride grain from growing up unusually, and this is in cool down, and partial crystallizationization forms high temperature resistant, high-intensity crystal boundary phase easily, helps improving the hot strength of silicon nitride ceramics matrix material.
Add sintering agent in the silicon nitride ceramics roll, main purpose is to improve sintering efficient, reaches the complete densification of product, and reduces production costs.Suitable sintering agent content can make the sintering process quicken greatly, under relatively low temperature, with fast speeds, base substrate is reached approach 100% density.It is the 1.7-18.0% weight ratio that composite sintering agent adds total amount.Add very fewly, do not reach above-mentioned effect, add too much, can reduce the content of principal crystalline phase relatively, thereby reduce the overall performance of silicon nitride ceramics roll, but to add 4.0-12.0wt% for well; In the present invention, magnesium oxide and makes its content must consider sintering temperature, factors such as sintering time because of there being the problem of vaporization at high temperature in the sintering agent.
The preparation method of high abrasion resistance silicon nitride base ceramic roll of the present invention comprises following each step:
1: raw material mixes.This operation is with silicon carbide whisker toughner, magnesium oxide and aluminum oxide sintering agent, rare earth oxide high temperature crystal boundary antioxidant such as material, niobide mutually, after the weighing, joins in the technical pure silicon nitride ceramics powder to scale.Silicon carbide whisker need carry out homodisperseization and pre-treatment in early stage before adding body material.Make blending agent with acetone or industrial alcohol, make ball-milling medium with silicon nitride ball or alumina balls, add dehydrated alcohol in adding 110～120 ml volumes ratios in the above-mentioned mixed powder of per 100 grams, by the silicon nitride ball or the alumina balls that add 200～250 gram weight ratio in the 100 gram powders, pour in the nylon jar ball milling 24～30 hours into.Through suction filtration sharp separation powder and liquid medium, oven dry then, and in 110～120 ℃ of baking ovens, be incubated 6～8 hours, to remove adsorbed moisture.
2: powder is handled.Powder with after the oven dry carries out 200 mesh sieve and sieves, carry out granulation operations such as (1～5 μ m) again after, take by weighing the powder of corresponding weight by the actual fabrication dimension of roller.
3: sintering process.Step 2 gained powder packed in special graphite jig, is put into the High Temperature High Pressure sintering oven again and calcined.When adopting hot pressed sintering, sintering temperature is chosen between 1650-1850 ℃, and pressure is chosen between the 15-40MPa.When rising to 1100～1200 ℃, the sintering oven temperature begins to pressurize gradually.After pressure reaches specified requirement, continue to heat up again and reach the sintering temperature of final regulation.Insulation is 1.0-5.0 hour under the sintering temperature of regulation, makes sintering reaction that time enough be arranged.After reaching the sintering time of regulation, sintering oven is with certain speed cooling, and cooling rate is per hour between 400-800 ℃.After cooling, be silicon nitride base ceramic roll of the present invention.
Adopting pressurized high-temperature agglomerating method to make ceramic roll, is the necessary method that realizes the complete densification of goods.For the ceramic roll that makes whiskers high-toughenedization rare earth silicon nitride composite material reaches densification completely, the method of pressure sintering be must adopt, hot pressed sintering (Hot-pressing sintering), HIP sintering (HIP-High temperatureIsostatic pressing Sintering) and air pressure sintering process (Gas Pressure Sintering) comprised.Sintering temperature must be more than 1600 ℃.Be lower than this temperature, sintering is insufficient, inaccessible complete densification.Pressurization total pressure during sintering can not be less than 10MPa or 20 normal atmosphere.Less than this pressure, the silicon nitride ceramics that contains whisker is with regard to inaccessible densification.The sintering reaction time is 1.0～5.0 hours.Be no less than 1.0 hours, sintering reaction is not thorough, burns not thoroughly, and material structure is inhomogeneous.Sintering time was longer than 5.0 hours, can cause too growing up of silicon nitride grain, also can cause the volatilization of niobium compound.Sintering temperature, sintering time are all relevant with the content of sintering agent.Should take all factors into consideration quality product, on the basis of production efficiency, adjust corresponding prescription and sintering process.
The silicon carbide whisker of enhancing usefulness can (step 1) adds, and also can add the whisker growth raw material in step 1, allows whisker generate voluntarily when high temperature sintering in the batch mixing stage.
With the ceramic roll of the inventive method preparation, after it was carried out surface finish, proofreaies and correct circularity and accuracy correction, goods were through check, can be to produce to use after up-to-standard.
The silicon nitride ceramic material of the roll shape that makes with method of the present invention, have characteristics such as high temperature resistant, high strength, high tenacity, high antioxidant, high abrasion resistance, be used to be made into roll, in the high speed hot rolling processing of metal wire, can reach the high effect of wire product quality that prolong, process work-ing life.Room temperature strength reaches more than the 800MPa, and fracture toughness property reaches 7.5MPam
1/2More than, HRA reaches more than 90, and 800 ℃ hot strength remains to more than the 500MPa.Be applied in the actual production, ceramic roll improves 3～5 times than superhard alloy roll wear resistant, improve 2～3 times work-ing life, and the production cost of ceramic roll is low slightly than the superhard alloy roll, has the very high ratio of performance to price.In addition, the density of ceramic roll has only 30% of superhard alloy, and quality alleviates greatly, has reduced operator's labour intensity.
Introduce embodiments of the invention below.
The roll profile diameter of actual measurement check usefulness is 160 (mm), internal diameter 86 (mm), and height 65 (mm), groove curvature is R6 (mm).
The intensity of the ceramic composite of made and toughness adopt general three-point bending method, and the strength test sample is of a size of 3 * 4 * 36mm, and the specimen size of toughness test is 4 * 6 * 36mm, and kerf width is 0.18mm.
Embodiment 1:
Will be through decentralized, pretreated silicon carbide whisker, niobium nitride, sintering agent (magnesium oxide, aluminum oxide and rare earth oxide), press the formula rate weighing of table 1 after, join in the technical pure silicon nitride ceramics powder.Make blending agent with industrial alcohol, make ball-milling medium with alumina balls, add dehydrated alcohol in adding 110 ml volumes ratios in the above-mentioned mixed powder of per 100 grams, by the alumina balls that add 250 gram weight ratio in the 100 gram powders, pour in the nylon jar ball milling 24 hours into.Through suction filtration, oven dry, insulation is 6 hours in 110 ℃ of baking ovens.Powder with after the oven dry carries out that 200 mesh sieve sieve, granulation, by the required powder that takes by weighing corresponding weight of reality.Powder packed in graphite jig, is put into hot-pressed sintering furnace again and carried out hot pressed sintering.Sintering temperature is selected 1650 ℃, and pressure is 15MPa.When furnace temperature rises to 1100 ℃, begin pressurization, after pressure reaches specified requirement, continue to be warming up to sintering temperature again.Be incubated cooling after 1.5 hours, cooling rate is about per hour 800 ℃.The ceramic block material of gained is carried out Performance Detection, and the result is as shown in table 1.
Table 1: silicon carbide whisker content breaker roll effect of material performance
* above data are test mean value.
From table 1, be not difficult to find, if niobide, sintering agent content remains unchanged substantially, and (silicon carbide whisker content improves, niobide content is corresponding also will to be increased to some extent, to guarantee quality of item, interact owing to exist between the multiple additives, thereby exist a kind of composition to change, other composition may need the phenomenon that adjusts slightly, but this is unlikely to influence the explanation to problem, following examples are similar), the adding of silicon carbide whisker is favourable to the raising of ceramic material property, improves particularly evident to flexible.Addition surpasses at 20% o'clock, and pore increases in the ceramic composite, and the strength of materials can obviously descend.
Embodiment 2:
Press the prescription shown in the table 2, strict preparation technology with reference to embodiment 1, the performance of detection sintering block materials, the result is as shown in table 2.
Table 2: niobide content is to Effect on Performance
| Numbering | ?1 | ?2 | ?3 | ?4 | ?5 | ?6 | ?7 |
| Niobium nitride wt% | ?0 | ?0.1 | ?0.5 | ?2.0 | ?5.0 | ?7.0 | ?10.0 |
| Silicon carbide whisker wt% | ?10.0 | ?10.0 | ?10.0 | ?10.0 | ?10.0 | ?10.0 | ?10.0 |
| Magnesium oxide wt% | ?1.5 | ?1.5 | ?1.8 | ?1.8 | ?2.0 | ?2.0 | ?2.0 |
| Aluminum oxide wt% | ?6.0 | ?6.0 | ?6.0 | ?6.0 | ?6.5 | ?6.5 | ?6.5 |
| Yttrium oxide wt% | ?5.5 | ?5.5 | ?5.5 | ?5.5 | ?5.0 | ?5.0 | ?5.0 |
| Lanthanum trioxide wt% | ?2.0 | ?2.0 | ?2.0 | ?2.0 | ?2.5 | ?2.5 | ?2.5 |
| Ytterbium oxide wt% | ?1.0 | ?1.0 | ?1.0 | ?1.0 | ?0.5 | ?0.5 | ?0.5 |
| Vickers' hardness HRA | ?86 | ?85 | ?85 | ?84 | ?83 | ?83 | ?83 |
| Room temperature strength Mpa | ?880 | ?870 | ?850 | ?840 | ?830 | ?820 | ?800 |
| Hot strength (800 ℃) MPa | ?490 | ?500 | ?520 | ?530 | ?530 | ?520 | ?520 |
| Fracture toughness property MPam 1/2 | ?8.1 | ?7.9 | ?7.6 | ?7.4 | ?7.1 | ?7.0 | ?6.8 |
| 1100 ℃ of oxidation weight gain mg/cm 2 | ?0.80 | ?0.78 | ?0.42 | ?0.20 | ?0.22 | ?0.23 | ?0.30 |
* above data are test mean value.
The purpose that adds niobide in the silicon nitride ceramics roll is to improve the high-temperature oxidation resistance of member.Alternative niobide has niobium nitride, niobium carbide, niobium (Nb) boride etc.In this example, having selected nano silicon nitride niobium particle for use is additive.Can find out that from table 2 though intensity, toughness have decline slightly, oxidation weight gain reduces, promptly oxidation-resistance improves.The interpolation of niobium nitride nanopowder has increased ceramic antioxidant property, and 1100 ℃ anti-oxidant weightening finish is 0.2mg/cm when adding the 2wt% niobium nitride
2, and do not add the equivalent material of niobium nitride, but reach 0.8mg/cm
2, improved about 4 times.
Embodiment 3:
Press the prescription shown in the table 3, strict preparation technology with reference to embodiment 1, the performance of detection sintering block materials, the result is as shown in table 3.
Table 3: niobium nitride, niobium carbide and niobium (Nb) boride additive are relatively
| Numbering | 1 (selecting the nano silicon nitride niobium) | 2 (selecting the nano silicon carbide niobium) | 3 (selecting the nanometer niobium (Nb) boride) |
| Niobide wt% | ?5.0 | ?5.0 | ?5.0 |
| Silicon carbide whisker wt% | ?10.0 | ?10.0 | ?10.0 |
| Magnesium oxide wt% | ?2.0 | ?2.0 | ?2.0 |
| Aluminum oxide wt% | ?6.5 | ?6.5 | ?6.5 |
| Yttrium oxide wt% | ?7.6 | ?7.6 | ?7.6 |
| Lanthanum trioxide wt% | ?6.0 | ?6.0 | ?6.0 |
| Ytterbium oxide wt% | ?1.5 | ?1.5 | ?1.5 |
| Vickers' hardness HRA | ?83 | ?86 | ?85 |
| Room temperature strength Mpa | ?830 | ?820 | ?820 |
| Hot strength (800 ℃) Mpa | ?530 | ?520 | ?510 |
| Fracture toughness property Mpam 1／2 | 7．1 | 6．9 | 7．0 |
| 1100 ℃ of oxidation weight gain mg/cm 2 | 0．22 | 0．26 | 0．26 |
* above data are test mean value.
Know that from the contrast of last table three kinds of niobides all can significantly improve the high-temperature oxidation resistance of roll member, difference is also little.And the niobium nitride cost is relatively low, can be used as first-selected niobide additive generally speaking.
Embodiment 4:
Press the prescription shown in the table 4, strict preparation technology with reference to embodiment 1, the performance of detection sintering block materials, the result is as shown in table 4.
Table 4: sintering agent content is to Effect on Performance
| Numbering | ?1 | ?2 | ?3 | ?4 | ?5 | ?6 |
| Magnesium oxide wt% | ?1.0 | ?1.0 | ?1.0 | ?2.0 | ?2.0 | ?2.0 |
| Aluminum oxide wt% | ?2.0 | ?2.0 | ?2.0 | ?3.0 | ?3.0 | ?3.0 |
| Yttrium oxide wt% | ?2.0 | ?4.0 | ?6.0 | ?2.0 | ?4.0 | ?6.0 |
| Lanthanum trioxide wt% | ?1.0 | ?2.0 | ?3.0 | ?1.0 | ?2.0 | ?3.0 |
| Ytterbium oxide wt% | ?0 | ?0 | ?1.0 | ?0 | ?0 | ?1.0 |
| Silicon carbide whisker wt% | ?12.0 | ?12.0 | ?12.0 | ?12.0 | ?12.0 | ?12.0 |
| Niobium nitride wt% | ?3.0 | ?3.0 | ?3.0 | ?3.0 | ?3.0 | ?3.0 |
| Vickers' hardness HRA | ?88 | ?87 | ?86 | ?85 | ?85 | ?84 |
| Room temperature strength MPa | ?980 | ?940 | ?890 | ?860 | ?830 | ?820 |
| Hot strength (800 ℃) MPa | ?520 | ?530 | ?520 | ?540 | ?510 | ?500 |
| Fracture toughness property MPam 1/2 | ?9.1 | ?8.4 | ?8.2 | ?7.9 | ?7.6 | ?7.1 |
* above data are test mean value.Sintering temperature is between 1650～1850 ℃, and the resulting product density reaches more than 99.5%.
Add sintering agent in the silicon nitride ceramics roll, purpose is to improve sintering efficient, reduces production costs, and improves the material at high temperature performance.Similar with niobide, sintering agent content increases, and toughness, hardness have decline slightly.Total sintering agent weight percent can not surpass 30%.The interpolation of rare earth oxide has clear improvement for the hot strength of material.High temperature test result at 1100 ℃ shows that when the interpolation total amount was 10% left and right sides, the hot strength of ceramic composite was best.The more interpolation causes crystal boundary thickness excessive, reduced the direct contact of silicon nitride ceramics crystal grain, reduced ceramic hot strength.
Embodiment 5:
With treated silicon carbide whisker, niobium nitride, sintering agent (magnesium oxide, aluminum oxide and rare earth oxide), press the formula rate weighing of table 5 after, join in the technical pure silicon nitride ceramics powder.Make blending agent with industrial alcohol, make ball-milling medium with alumina balls, add dehydrated alcohol in adding 110 ml volumes ratios in the above-mentioned mixed powder of per 100 grams, by the alumina balls that add 220 gram weight ratio in the 100 gram powders, pour in the nylon jar ball milling 36 hours into.Through suction filtration, oven dry, insulation is 6 hours in 110 ℃ of baking ovens.Powder with after the oven dry carries out that 200 mesh sieve sieve, granulation, by the required powder that takes by weighing corresponding weight of reality.Powder packed in special mould, is put into sintering oven again and carried out hot pressed sintering.Prescription 1 and prescription 2 adopt hot pressed sintering, and sintering temperature is selected 1680 ℃, and pressure is 15MPa; Begin pressurization when furnace temperature rises to 1100 ℃, after pressure reaches specified requirement, continue to be warming up to sintering temperature again, be incubated cooling after 1.5 hours, cooling rate is about per hour 600 ℃; Prescription 3 adopts HIP sintering, and ceramic body is through 1600 ℃ of pre-burnings after 0.5 hour, and in the HIP sintering stove 1750 ℃, 5MPa, sintering 1.5 hours, cooling is with prescription 1,2; Prescription 4 adopts the gas pressure sintering method, and sintering temperature is 1850 ℃, and 25 normal atmosphere are incubated 1.5 hours.The ceramic roll (totally 8 pairs, corresponding two rolls of each prescription) of gained is carried out surface finish, proofreaies and correct circularity and accuracy correction.On the simultaneous test production line, the performance of silicon nitride base ceramic roll and tungsten carbide roll is more as shown in table 6.
Table 5: silicon nitride base ceramic roll comparison test prescription
| Formula number | Prescription 1 | Prescription 2 | Prescription 3 | Prescription 4 |
| Silicon nitride matrix wt% | ～88.0 | ?～78.3 | ?～71.0 | ?～67.0 |
| Silicon carbide whisker wt% | 5.0 | ?10.0 | ?14.0 | ?18.0 |
| Niobium nitride wt% | 3.0 | ?4.0 | ?4.0 | ?5.0 |
| Magnesium oxide wt% | 2.0 | ?1.0 | ?1.5 | ?1.0 |
| Aluminum oxide wt% | 5.0 | ?2.0 | ?2.5 | ?2.0 |
| Yttrium oxide wt% | 4.0 | ?4.0 | ?3.0 | ?2.5 |
| Lanthanum trioxide wt% | 2.5 | ?1.5 | ?3.0 | ?3.0 |
| Ytterbium oxide wt% | 0.5 | ?0.2 | ?1.0 | ?1.5 |
Table 6: silicon nitride base ceramic roll and tungsten carbide roll performance comparison
| Roll material | Density g/cm 3 | Wear resistant (mm) | Average steel rolling amount (ton/to) | Active time (hour) |
| The crystal whisker toughening silicon nitride base matrix material | 3．5～4．2 | 0．6～1．0 | 7．0～8．5 | 16～20 |
| Tungsten carbide material | ～13．2 | ＞3．2 | 1．3～2．0 | 3．0～5．0 |
* above data are test mean value.SUS series iron alloy is adopted in roll actual measurement check, and rolling temperature is 800～950 ℃, is 20m/s by rolling line material transfer rate, and the wear resistant evaluation index adopts the wear loss of roll groove behind the similar wire rod of rolling 1000t.When rolling wire size precision is lower than production standard, looks this roll and complete the term of service.
From the silicon nitride base ceramic roll of table 6 the present invention preparation contrasts with existing wolfram varbide superhard alloy roll production performance as can be known, from cost, benefit angle contrast sees that the ceramic roll of the present invention's development has the bigger ratio of performance to price, is one to have the invention achievement of applications well potentiality.
Claims (2)
1, a kind of high abrasion resistance silicon nitride base ceramic roll is characterized in that, the composition of this ceramic roll is as follows:
Si
3N
4??????????????60．0～90．0wt％
SiC whisker 3.0～30.0wt%
Niobide 0.1～10.0wt%
Magnesium oxide 0.5～4.5wt%
Aluminum oxide 0.7～6.0wt%
Yttrium oxide 0.5～6.0wt%
Lanthanum trioxide 0.0～3.0wt%
2, a kind of preparation method of high abrasion resistance silicon nitride base ceramic roll is characterized in that, this method comprises following each step:
(1) makes blending agent with acetone or industrial alcohol, make ball-milling medium with silicon nitride ball or alumina balls, add dehydrated alcohol in adding 110～120 ml volumes ratios in the above-mentioned mixed powder of per 100 grams, by the silicon nitride ball or the alumina balls that add 200～250 gram weight ratio in the 100 gram powders, pour in the nylon jar ball milling 24～30 hours into, through suction filtration sharp separation powder and liquid medium, oven dry then, and in 110～120 ℃ of baking ovens, be incubated 6～8 hours, to remove adsorbed moisture;
(2) powder after will drying carries out 200 mesh sieve and sieves, and carries out granulation again, and granularity is 1～5 μ m, takes by weighing the powder of corresponding weight by the actual fabrication dimension of roller;
(3) with step 2 gained powder packed in graphite jig, putting into the High Temperature High Pressure sintering oven again calcines, when adopting hot pressed sintering, sintering temperature is 1650-1850 ℃, pressure is 15-40Mpa, is incubated 1.0-5.0 hour, is per hour cooling between 400-800 ℃ in cooling rate, after the cooling, be silicon nitride base ceramic roll of the present invention.
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| CN 00129948 CN1292363A (en) | 2000-10-20 | 2000-10-20 | Production method of carborundum whiskers high-toughened silicon nitride base ceramic roll material |
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|---|---|---|---|
| CN 00129948 CN1292363A (en) | 2000-10-20 | 2000-10-20 | Production method of carborundum whiskers high-toughened silicon nitride base ceramic roll material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100390101C (en) * | 2005-10-21 | 2008-05-28 | 清华大学 | Self toughening silion nitride ceramic guide and guard roller and its preparing method |
| CN100448798C (en) * | 2007-04-29 | 2009-01-07 | 北京科技大学 | Method for preparing carborundum whisker reinforced carborundum composite material element |
| CN105016738A (en) * | 2014-04-30 | 2015-11-04 | 广东工业大学 | Silicon nitride ceramic and preparation method thereof |
| CN109516814A (en) * | 2018-11-28 | 2019-03-26 | 中国科学院上海硅酸盐研究所 | A kind of Si3N4/ SiC diphase ceramic material and preparation method thereof |
| CN111187072A (en) * | 2020-01-09 | 2020-05-22 | 中国科学院上海硅酸盐研究所 | Porous silicon nitride ceramic with excellent high-temperature performance and preparation method thereof |
| CN112876270A (en) * | 2021-01-26 | 2021-06-01 | 山东丁鼎科技发展有限公司 | Microwave dielectric ceramic injection feed, microwave dielectric ceramic and preparation method thereof |
-
2000
- 2000-10-20 CN CN 00129948 patent/CN1292363A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100390101C (en) * | 2005-10-21 | 2008-05-28 | 清华大学 | Self toughening silion nitride ceramic guide and guard roller and its preparing method |
| CN100448798C (en) * | 2007-04-29 | 2009-01-07 | 北京科技大学 | Method for preparing carborundum whisker reinforced carborundum composite material element |
| CN105016738A (en) * | 2014-04-30 | 2015-11-04 | 广东工业大学 | Silicon nitride ceramic and preparation method thereof |
| CN105016738B (en) * | 2014-04-30 | 2017-07-14 | 广东工业大学 | Silicon nitride ceramics and preparation method thereof |
| CN109516814A (en) * | 2018-11-28 | 2019-03-26 | 中国科学院上海硅酸盐研究所 | A kind of Si3N4/ SiC diphase ceramic material and preparation method thereof |
| CN111187072A (en) * | 2020-01-09 | 2020-05-22 | 中国科学院上海硅酸盐研究所 | Porous silicon nitride ceramic with excellent high-temperature performance and preparation method thereof |
| CN112876270A (en) * | 2021-01-26 | 2021-06-01 | 山东丁鼎科技发展有限公司 | Microwave dielectric ceramic injection feed, microwave dielectric ceramic and preparation method thereof |
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