CN1017422B - Nitride-based ceramic material - Google Patents
Nitride-based ceramic materialInfo
- Publication number
- CN1017422B CN1017422B CN 85101384 CN85101384A CN1017422B CN 1017422 B CN1017422 B CN 1017422B CN 85101384 CN85101384 CN 85101384 CN 85101384 A CN85101384 A CN 85101384A CN 1017422 B CN1017422 B CN 1017422B
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- stupalith
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- 150000004767 nitrides Chemical class 0.000 title abstract description 18
- 229910010293 ceramic material Inorganic materials 0.000 title description 3
- 238000005245 sintering Methods 0.000 claims abstract description 36
- 229910002795 Si–Al–O–N Inorganic materials 0.000 claims description 85
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 229910017083 AlN Inorganic materials 0.000 claims 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 114
- 238000005520 cutting process Methods 0.000 abstract description 66
- 238000000034 method Methods 0.000 abstract description 16
- 239000000919 ceramic Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- 239000012071 phase Substances 0.000 description 120
- 239000000203 mixture Substances 0.000 description 36
- 229910052751 metal Inorganic materials 0.000 description 22
- 239000002184 metal Substances 0.000 description 22
- 230000008859 change Effects 0.000 description 21
- 238000003754 machining Methods 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 14
- 229910052727 yttrium Inorganic materials 0.000 description 14
- 239000002671 adjuvant Substances 0.000 description 13
- 239000004411 aluminium Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- 239000011777 magnesium Substances 0.000 description 12
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910001018 Cast iron Inorganic materials 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 9
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 241000209094 Oryza Species 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- 229910052790 beryllium Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 235000009566 rice Nutrition 0.000 description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000002223 garnet Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 229910052984 zinc sulfide Inorganic materials 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910017109 AlON Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052706 scandium Inorganic materials 0.000 description 3
- 229910018514 Al—O—N Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910001141 Ductile iron Inorganic materials 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- 150000002738 metalloids Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 230000007704 transition Effects 0.000 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 description 2
- 238000007514 turning Methods 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000145 adjuvantlike effect Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- Ceramic Products (AREA)
Abstract
The present invention relates to sintering nitride-based ceramic, wherein a polytype Si-AI-O-N phase, a beta type Si-AI-O-N phase and (or) alpha type Si-AI-O-N phase are used as maim components, the present invention also contains an intercrystalline phase, and then the components are compounded and crystallized into AIN or AI-[2]O-[3]. The properties of the present invention, such as wear resistance, toughness, etc., can be improved through adding hard high temperature-resistance elements and (or) beard-shaped materials. A hard, inert and wear-resistant coating method is the other improving method. The sintering nitride-based ceramic is suitable for occasions with the requirements of thermal-shock resistance, high mechanical strength and high heat conduction and is especially suitable for cutting tools, engine components, wear-resistance member and heat exchangers or being used as substrate materials of electronic industries.
Description
The present invention discusses a kind of ultrahigh-temperature characteristic that has, the unusual good nitride-based ceramic material of thermal-shock resistance height and heat conductivility.This kind material is specially adapted to as cutting tool material.The present invention relates to Si-Al-O-N type one class nitride ceramics, wherein, the polytype settling of dispersive gives the character of this kind stupalith with active influence.
Existing many articles and patent are described to Si-Al-O-N system (for example " nitrogen base pottery progress " book, F.L.Riley edit, the nineteen eighty-three publication of Martinus Nijhoff press) and added Y
2O
3And so on the facies relationship behind certain oxide compound.Generally consist of Si
6-ZAl
ZO
ZN
8-ZThe hexagonal crystal phase, 0＜Z≤4.2 wherein, known is β-Si-Al-O-N, the crystalline structure of this material and β-Si
3N
4Identical.The general composition M of another kind of hexagonal crystal phase
X(Si, Al)
12(O, N)
16, wherein 0＜X＜2 and the mixture of M=yttrium or other LiCaMg one metalloid and lanthanide or these metals.Other metals with suitable ionic radius are steady its α phase also.Main structure and the α-Si of α type Si-Al-O-N
3N
4Identical.But find,, be difficult to make it to become the part of α type Si-Al-O-N because as if the ionic radius of La and Ce excessive.
Many in Si-Al-O-N system or the M-Si-Al-O-N system have a class formation that can be described as the wurtzite superstructure mutually, in the sort of superstructure, the AlN crystallization.Letter M represents one or more metals, for example Y, Mg, Be, Li or Sc as in the previous paragraph.May comprise that also other have the metal of suitable ionic radius.These phases are many types of as everyone knows, and they come across in the Si-Al-O-N system in high Al and the determined quadrant of high N content, promptly approach the AlN angle.Above-mentioned one or more are generally provided by " many types of " mark later mutually.Multi-structure what belong to good the arrangement, and can return be aforesaid wurtzite basic structure (for example, can referring to above-mentioned that this book).This kind is many types of to have hexagonal or the rhombohedral structure cell mutually, and they are 8H, 15R, 12H, 21R, 27R and 2H by so-called Ramsdell denotational description.In the document, this type of is many types of mutually often according to these denotational descriptions, and for example, note is made the many types of material of 12H etc.
The basic phase analysis of Si-Al-O-N and many M-Si-Al-O-N system already this century the seventies carry out, and existing a large amount of resemble aforementioned that class book.Also had the patent of some application β type Si-Al-O-N at the seventies initial stage, wherein will should be mentioned that for example United States Patent (USP) 3991166 of Toshiba (for example United States Patent (USP) 3969125), Toyota (for example United States Patent (USP) 3903230) and Lucas(especially).Relevant one piece of article the earliest that forms a kind of α type Si-Al-O-N with Li was delivered in 1972, and many other articles are then arranged.Already certainly, the Yt that is related to cutting tool material, formed above-mentioned Si-Al-O-N phase (SHampshire, HKPark, DPThompson and KHJack Nature, Vol 274,1978, P880-882), and pointed out very early that α type Si-Al-O-N brought interests might for technology department.For example, just now three authors (Science, Vo are l.10 at " α type sialon ", 1980, P251-256, HHausnlr chief editor) literary composition, and then in English Patent 2118927A, be described to, the Si-Al-O-N of α type and β type may make by some composition.This patent relate to have α type Si-Al-O-N phase, β type Si-Al-O-N mutually and a kind of glassy phase, the ceramic cutting material of sial oxynitrides type.Many advantages of this material, the advantage in cutting for example according to the present invention, is unexpectedly found to be present in the Si-Al-O-N material that contains multiple crystal formation, and this is never to report in the past and proposed.
Above-described this Si-Al-O-N material can obtain by following technology in some cases, i.e. sintering Si under non-pressurized condition
3N
4And a certain amount of silicon-dioxide, (normally) a spot of Al is arranged in its surface
2O
3With metal oxide, nitride or oxynitride as small amounts of additives.For example oxide compound, nitride or the oxynitride of Y, Ca, Mg, Be and lanthanon etc. or their mixture.This class additive plays a part sintering adjuvant, and and SiO
2(or) Al
2O
3Together, under the sintering temperature of this stupalith, form the molten glassy phase of a kind of height in intergranular.In addition, metal of using of other similar molding glass and so on also can be used as sintering adjuvant like compound.Typical example is to form high molten and high-strength glass thus by the Zr and the Hf of oxide compound, oxynitride or nitride form interpolation.Also have, be easy to heating in nitrogen atmosphere and form the metal of nitride, can be used as a kind of component of sintering adjuvant, for example the quantity of Si, Mg and Cre glassy phase will enough be used for the starting materials of sintered ceramic naturally.In order to make a kind of stupalith have (for example) best cutting character, the quantity of glassy phase must be very little, but can not be little of making this material lose its toughness.
Know that also some metal is the softening temperature of meeting attenuating glassy phases such as Ca, Mg, Fe for example.In order to obtain to have the glassy phase of best high temperature properties, so the content of this dvielement in glassy phase must little arriving, this kind Si-Al-O-N material can not lost its advantageous property, especially used as cutting tool material the time.
Should emphasize that whole compositions of above-mentioned glassy phase no matter be to the densification process of stupalith or to the character of agglomerated material, all can have remarkably influenced.Thereby importantly, considering the working conditions of this stupalith, carefully select sintering adjuvant (or their mixture).For example, add this composition of Mg, will obtain to be easy to handle and can be used as the stupalith of wear parts.But such material will lack good high-temperature character.For a task after finishing, must employing can provide dvielements such as Y, the Zr of Gao Rong, high-strength glass and lanthanon.The various systems of M-Si-Al-O-N phase at last,, can control the formation of other crystalline phases, because it seems and be inequality according to desirable direction by selecting sintering adjuvant.If adopt the mixture of different elements, just can obtain various possibilities.For example, in sintering mix, adopt La and Ce one dvielement, just can have influence on the formation of α type Si-Al-O-N.
Except above-mentioned glassy phase, also can form other intergranular phases, wherein exist metal from sintering adjuvant.In general, these are the silicate or the aluminosilicate of (for example) yttrium mutually, or also contain the similar structures of nitrogen, for example YAG(yttrium aluminium garnet), N-YAM or YAM(yttrium aluminium melilith), b phase (a kind of distortion form of YAG), and the structure phase identical with phosphatic rock.Similarly also come across mutually in the other system that is different from Y-Si-Al-O-N, for example have in the corresponding system of Ca and Be.When other metals are arranged in sintering adjuvant, just other crystalline phases may occur, they have and are different from above-mentioned other types structure.
This rich metallographic phase of sintering adjuvant can continue so that (for example thermal treatment makes its big part change crystalline phase into from glassy phase.Utilize this method, glassy phase is significantly reduced.Existing report in the aforementioned documents, in the metallic aluminium oriental garnet, take this make method that glassy phase changes crystallization phases into reduce the quantity of glassy phase after, can make this material might make high temperature and use, for example as engine parts.In the situation of yttrium, this type of oriental garnet is YAG or b phase.In the Si-Al-O-N material, when planning as cutting tool then always favourable, this is not because the ductile failure of material.
Other character of above-mentioned glassy phase, for example microhardness also can be added the Y of common employing to owing to oxide compound, oxynitride or the nitride with rare earth metal or beryllium
2O
3In and change.This processing is particularly conducive to the high temperature properties of this kind stupalith.
With Si
3N
4With Si-Al-O-N be the material on basis, for example,, the people is paid attention to as aspect the cutting tool material of metal cutting.Si-Al-O-N material as the cutting element material on the market can be divided into two kinds of main types: β type Si-Al-O-N material and hybrid-type (alpha+beta) type Si-Al-O-N material.Why they have good cutting character, it is believed that it is because Si
3N
4The little high viscosity glassy phase that has the toughness produce excellence simultaneously of thermal expansivity.This fact adds the microstructure that causes hot strength and hardness, has formed the important many character in utmost point pass in the cutting application.
Also know, add the key element of titanium nitride or titanium carbide and so on resistant to elevated temperatures hard, can improve the wear resisting property and the thermal conductivity of Si-Al-O-N material, type Si-Al-O-N and a kind of intergranular be mutually mutually or β+α) to contain β type Si-Al-O-N and a kind of intergranular in the sintering structure of this material.In addition, add ZrO
2And Hfo
2One type oxide, expection can be played active influence to some character of material toughness for example.
According to us the various materials of extensive selection are carried out the result of process test, when β type Si-Al-O-N material is used neutralization as some thermostability alloy of cutting at some cast iron, demonstrate good cutting character.When adopting hybrid (alpha+beta) type Si-Al-O-N material, then can carry out machining and obtain good result wider class cast iron and thermostability material.
We have found that, nitrogen and (or) in the higher Si-Al-O-N material of aluminium content, can improve under its room temperature comparatively high temps particularly down hardness and do not bring disadvantageous effect to its toughness.So just obtained to help the good influence of anti-plastic deformation.For example, cutting edge is being exposed under the high temperature, promptly in high rate of cutting and big following time of feed rate, viscous deformation can take place.This viscous deformation causes forming in the cutting edge crackle, and when this crack growth, just can make breaks down.For a kind of β type Si-Al-O-N material, the formation of this kind crackle had been described, referring to " smithcraft (Metals Tech), nineteen eighty-three; 10 phases, the 482-489 page or leaf (Bhattacharyya etc.: the abrasion mechanism during sialon cutter machining nickel-base material ").
The result who obtains according to the present invention has been found that, surprising fully is, if the Si-Al-O-N material that adopts following composition and prepare as follows, the character of above-mentioned cutting tool can also further be improved, contain in the structure of this material the α type with (or) β type Si-Al-O-N and a kind of finely divided many types of mixture mutually.The volume ratio of this many types of phase should be greater than 0.5%, more preferably greater than 1%.Remove this, another kind of advantage seemingly, some character of cutting tool is toughness for example, when there being other rich yttriums β phase time for example mutually, can not be subjected to significant weakening.
The result with the Si-Al-O-N material of many types of phase that check makes according to the present invention shows said magnesium one dvielement that is enriched with mutually.A spot of this element just might have influence on the formation of many types of phase, and magnesium collect suddenly many types of mutually in, the Mg content in the glassy phase just reduces, this is the high temperature properties that helps cutter material.Can expect, even other are unfavorable for the metal of glassy phase, calcium one metalloid for example, also may be melted in this many types of mutually in, and make the tough property improvement of high temperature.
As previously mentioned, have found that the content of correctly regulating glassy phase is to counting for much of using.A large amount of glassy phases can make material too soft, and reduces the mach performance of cutting.The total amount of intergranular phase should be less than the 20%(volume), if the amount of glassy phase is very big, then most preferably less than the 15%(volume).On the other hand, if the amount of glassy phase when sintering temperature very little, just be difficult under barometric point, make the material densified sintering product.In order to form needed α type, β type and many types of filamentary structure, there is a certain amount of glassy phase also still important.Exist bar-shaped type or fibrous crystal can improve the intensity and the toughness of material.Glassy phase quantity during sintering should be greater than the 2%(volume), a part wherein can recrystallize into other rich metallographic phase in mutually at intergranular.When growing α type or many types of material in sintering process, can also reduce a part of original glassy phase, at this moment, in the agglomerated material that makes according to the present invention, the total amount of intergranular phase can drop to the minimum 0.5%(of reaching volume).If improve used pressure in sintering, then the quantity of intergranular phase can be reduced to Schwellenwert 0.1%(volume).
The composition of glassy phase have influence on Si-Al-O-N in mutually aluminium and the dissolving of oxygen.Be difficult to make the composition of dense sintering to possess very low Z value (under barometric point).On the other hand, the material with very high Z value adds for example Y of assisted sintering agent than easy-sintering and can reduce
2O
3And so on content.But, we have found that, for contain β mutually and the Z value approximately greater than the material of 1.5-2, can make toughness be subjected to a certain degree destruction, and this adds and has material impact man-hour for this kind material being used for cutting machine.Its reason perhaps is that β has enlarged when the dissolving of a large amount of aluminium and oxygen is arranged, thereby chemical bond is weakened.In addition, we also are also noted that and consumed by the sex this dissolving of chemically stable, owing to the aluminium displacement that higher amount is arranged has reduced.
Like this, in some metal cuttings is used, people can not get rid of, preferably may be still will be with the material of high Z value.
We find already, and importantly, the Si-Al-O-N material that makes according to the present invention, its total composition drop in the appropriate part in the M-Si-Al-O-N phasor, and top M is a kind of like this metal of for example yttrium of referring to previously.Compare with the composition of commercially available Si-Al-O-N cutter material, in the material that makes according to the present invention, nitrogen and (or) content of magnesium is all higher.The selection of elements Si, Al, O and N amount preferably will make total composition fall into the rich nitrogen and the rich aluminium district of phasor under equilibrium conditions, and this phasor is by defining with lower line segment: line segment Si
6-ZAl
ZO
ZN
8-Z, i.e. β type Si-Al-O-N phase, and binary phase diagram AlN-Al
3O
3And AlN-Si
3N
4Line segment.But, β type Si-Al-O-N phase region when other metallic compounds of being added with as sintering adjuvant, will move with the quantity of adding metal.According to a kind of so total composition and suitable manufacture method, obtained desirable microstructure and mutually composition, comprise many types of phase.When the Si-Al-O-N material being used for a kind of material that is difficult to cut of mechanical cutting for example during heat-staple alloy, we find that many types of percentage by volume should be greater than 1%, preferably greater than 2%.Adopt a kind of comprehensive composition outside the above-mentioned phasor, can make unbalanced or composite ceramics, this pottery contains many types of phase and Al
2O
3Or many types of phase and Al
2O
3With β type Si-Al-O-N mutually.And in this situation, the percentage by volume of many types of phase should be greater than 1%, more preferably greater than 2%.In any case but the quantity of many types of phase must not surpass the 99%(volume).
In the Si-Al-O-N material of a kind of hybrid-type (alpha+beta) type, improve the ratio of α type to the β type, can improve stability to viscous deformation.When hybrid-type (alpha+beta) type Si-Al-O-N material was used as cutter material, the percentage by volume that we have observed the phase of α type should surpass 20%, and the corresponding of β type is lower than 80%; But preferably the α type accounts for 30% of volume mutually at least, and the β type accounts for 70% of volume mutually at the most.This helps the cutting character of this kind material in some applications, but in order to obtain observed excellent in machinability energy in the material that makes in foundation the present invention, just must have the many types of phase of some amount in its microstructure.Many types of percentage by volume should be 0.5% at least, preferably is at least 1%.When many types of percentage by volume is too big, can damage the cutting ability of this material, particularly abrasion resistance properties.During as cutter material, the quantity of many types of phase should be less than 70%, preferably less than 50%.The quantity that is α type phase or β type phase should not surpass the 99%(volume).
In the Si-Al-O-N material that foundation the present invention makes, add one or more resistant to elevated temperatures hard key elements, when particularly adding nitride or nitrogen oxidation and for example closing TiN, ZrN or cube AlON, can obtain the stupalith that a kind of wear resisting property has improved.In addition, the metal nitride of TiN and ZrN and so on also can improve its sinterability.Add other resistant to elevated temperatures hard key elements and also can obtain similar advantage aspect wear resistance: they are the transition element in periodictable IV-VI family; Aluminium, silicon, boron one dvielement and with carbon, nitrogen and (or) compound of oxygen; Or their mixture, wherein preferably titanium carbide, titanium nitride, silicon carbide, norbide and (or) cuboidal AlON.Add the hard key element percentage by volume be necessary for 2% at least, but more preferably greater than the 5%(volume) and be no more than 60% volume.
Al in phasor
2O
3The composition of preparation can contain many types of phase, AlN and Al in the neighborhood of-AlN juncture when low temperature
2O
3, and under higher temperature, will form cubical AlON phase.But, have volume more than 1%() many types of phase time can improve these character.Under very high temperature or when adding oxide compound, nitride or oxynitride, for Al as sintering adjuvant
2O
3The composition of one junction point also can be found the formation of many types of phase.
Add fibre-like or hard refractory material that must shape, the toughness of ceramic composite is also had very active influence.
The material of this fibre-like preferably with chat in the leading portion and high temperature resistant hard key element or its mixture, particularly SiC, TiN, B
4Fibrous material such as C and TiC.Remove this, Al
2O
3Fiber and Si
2N
2The O fiber also can be used for this kind purpose.The diameter of above fiber or whiskers should be less than 2 microns, preferably less than 1 micron.For the fiber of diameter less than 1 micron, its aspect ratio (ratio of length over diameter) should or preferably surpass 20 above 10.Just because of the very thin class whisker crystal that has Materials with High Strength, could obtain best effect.In order to produce active influence, the percentage by volume of this kind fiber material should be above 1% but less than 50%.
Optimal results is normally at interval 5-30%(volume) in try to achieve, but this scope is according to the selection of filamentary material, about diameter and aspect ratio, changes and can have slightly.
In a word, we find, selected starting material quantity should make the many types of phase that contains in the sintering structure of cutter material, by volume, account for the 0.5-70% of Si-Al-O-N fertile material, a kind of α type Si-Al-O-N that this fertile material contains the 20-99% volume with (or) a kind of β type Si-Al-O-N of 5-80% volume with (or) constitute the 0.1-20% volume a kind of partially crystallizable intergranular mutually, and (perhaps) aluminum oxide.Generally speaking, if the major portion of above-mentioned intergranular phase is a glassy phase, and be under not adding high pressure, to carry out sintering, the contained intergranular of the fertile material of this moment should be 0.5% and be at most 10% mutually by volume usually at least.The structure that sinters into contains at least 1% and maximum 50% the many types of phase of Si-Al-O-N by volume.In addition, hybrid-type (alpha+beta) type preferably by volume contains at least 30% α type Si-Al-O-N and maximum 70% β type Si-Al-O-N mutually.
If the percentage by volume of many types of phase surpasses a certain quantity, when as cutter material, can reduce its wear resistance.In this kind application, this may not be a restriction.Coat very thin wearing layer, just might be used for cutting tool to this class material of the many types of phase of richness.
Can use the PVD(physical vapor deposition) method and CVD(chemical vapor deposition) method, give wearing layer thin on the stupalith coated.On the Si-Al-O-N material that makes according to the present invention, the transition element in IV, V and the IV family and (or) nitride, oxynitride or the oxide film of element aluminum, can both make between rete and the substrate and produce good binding.Particularly when adopting multilayer film, when having the boride, carbide, carbonitride of above-mentioned element or oxidation carbide the most suitable (referring to English Patent 1464022).In addition, it might also be mentioned European patent 83850211-0(Sandvik), this Patent publish: the yttrium thing intermediate coat of the hard borides intermediate coat of III-group or hard, favourable to the Si-Al-O-N material.Said this class film has found that the material that helps making according to the present invention.
The wearing layer that an above-mentioned class is thin helps the material that makes according to the present invention is used for cutting tool, or is used for can making further improved place by means of wear-resistant coating, for example is used for the wear parts material.
It is many types of that to influence mechanism with respect to this kind material character favourable current also not fully aware of, but we know, many multiple phases with wurtzite-type crystal structure, superstructure as AlN or this compound, for example many types of phase, it is little all to have low thermal expansivity, and the thermal conductivity of these phases is then greater than with Si
3N
4The type structure is the phase on basis.In addition, precipitation goes out finely divided many types of material and can strengthen said material from glass.Separating out of many types of phase reduced amount of glass, changed the composition of surplus glassy phase, and also changed viscosity thus.Many types of grain growing causes a kind of significant state or filamentous form.All these states can both have great effect for the following character of this kind material, proneness of react with or the like when these character comprise resistance to sudden heating, toughness, hardness and are reduced in high temperature.
The material that makes according to the present invention is the Si-Al-O-N type that contains many types of phase, and has the superstructure of wurtzite-type, because it has the excellent high temperature properties and the stability of thermal shocking, thereby has a lot of important properties in multiple application.The category of using for example can comprise engine parts, wear parts, and owing to the thermal conductive resin of this material is used as heat exchanger.
Other character of this kind material that makes according to the present invention, for example high resistance add low thermal expansivity and big thermal conductivity etc., also are very important for the substrate material as electronic industry.Require the novel material that comprehensively has above-mentioned each performance when making intensive integrated circuits more.
Knew to have the agglomerated material of β type Si-Al-O-N phase already, its thermal conductivity is in the acceptable scope.For hybrid (alpha+beta) type Si-Al-O-N material, also be like this.But, if the percentage height of α type Si-Al-O-N phase, then thermal conductivity will reduce.Have many types of phase in this class agglomerated material, because the excellent heat conductivity rate of this many types of phase makes material have extremely good properties in this respect more than 30%.For this reason, in as substrate material or the application of heat exchanger one class, the percentage by volume of many types of phase should surpass 30%, preferably be at least 40%.The percentage by volume of α type or β type Si-Al-O-N should be 70% at most, and preferably is at most 60%.If material contains these two kinds of Si-Al-O-N of α type and β type mutually, then their total percentages by volume should be 70% at the most, preferably are at most 60%.The structure that has sintered into also can contain a kind of crystallization phases of partially crystallizable, and it by volume occupies 0.1-20%, if the percentage by volume of glassy phase is big, then it preferably is less than the 15%(volume).This structure can also contain crystalline AlN, and its percentage by volume should be less than 30%, preferably less than 20%.In a kind of like this stupalith near place, phasor AlN angle, the percentage by volume of α type and β type Si-Al-O-N is lower than 10%, and most preferably less than 90%, and the percentage by volume of many types of phase will be higher than 5%, preferably more than 10%.If glassy phase is very big, then the percentage by volume of intergranular phase should be 0.1-20%, and preferably less than 15%.When requiring high resistivity, the percentage by volume of intergranular phase is at most 10% usually under the bigger condition of glassy phase part.If the percentage by volume of crystalline A lN is less than 80%, and the percentage by volume of many types of phase then can obtain to be easier to the agglomerating material greater than 20% o'clock.The percentage by volume of oxide compound, nitride or the oxynitride of the aluminium that exists as crystallization phases is in any case be to surpass 99%.The ceramic composite that Si-Al-O-N is many types of to combine with SiC and form, but owing to very big structural similarity and matching are arranged in that this two class is alternate, and have the character of many excellences.
SiC and the many types of matrix material mutually of Si-Al-O-N depend on comprehensive composition and sintering adjuvant, can high temperature and (or) high pressure prepares down.The feature of these mixtures is that high thermal conductivity adds physical strength and chemical inertia.Thereby, obviously can be used as heat exchanger or some engine parts.But, resistance is very low, thereby the electric substrate of important requirement can not be arranged resistance with work.On the other hand, because electric conductivity is arranged, so can carry out electric spark machine to this kind pottery with a lot of easy and economic means.Why this just will add TiN, TaN etc. and so on resistant to elevated temperatures key element, improves the reason of this class stupalith electric conductivity.
SiC and many types of stupalith or the matrix material mutually of Si-Al-O-N, when the percentage by volume of many types of phase wherein greater than 1% preferably greater than 2% the time, promptly have desirable character.The percentage by volume of SiC must surpass 5%, preferably greater than 10%.The percentage by volume of other intergranular phases, when major portion be crystallization phases and be preferably lower than 15% and the part of glassy phase when accounting for significant proportion just must remain on below 5%.Exist than these two kinds on the α type and β type of low heat conductivity mutually, its total percentage by volume should be less than 15%, preferably less than 10%.And exist percentage by volume up to 95% preferably be no more than 90% crystalline A lN, to the character of this type of synthetic materials and have no adverse effect.
In order to obtain Si
3N
4-SiO
2-Al
2O
3Near the composition in AlN district, or, form certain multi-structure or many types of mixture in-the AlN phasor, preferably AlN is used as a kind of raw material in order to help in the agglomerated material that foundation the present invention makes.The heterogeneous material of having described a kind of special production in the relevant document is 21R for example, can be used as required raw material, might as well be referring to United States Patent (USP) 4113503(Lucas industrial) with English Patent 2118927(Kennametal company).Composition in the present patent application authority in some scope can be made by the starting material of 21R and so on, but because aforesaid reason will recommend to adopt AlN especially specially.But, use AlN must take anhydrous grinding system, this requirement to lubricant and breaking method just occurred.For all compositions in the scope of the invention are all meeted the requirements, yet require above-mentioned dry powder with respect to (for example) aluminum oxide that adds this system to (the alumina lap body has been adopted in supposition in shredder), have consistent composition, silicon-dioxide then places on the surface of silicon nitride.Adopt the AlN Ginding process that many advantages are obviously arranged.Add Si
3N
4Behind the used starting material of AlN and so on, necessary oxide compound just can be consistent with the oxide impurity in the above nitride in the stupalith.
According to top described, the material that can understand fully various Si-Al-O-N types is to produce required character in which way haply.Listed some in the table 1 and formed example to illustrate aforesaid various character.The method of making is that different raw materials is ground with lubricant.If the employing ball mill then needs the milling time of 1-3 day.Afterwards, with ground raw material drying, be crushed to the powder shape with good fluidity, this is very important for the operation that is pressed into desired shape later on.Sintering is finished by a kind of like this mode in rich nitrogen atmosphere, the trend that promptly stops silicon nitride to decompose as much as possible.Temperature is 1700-1860 ℃, partly depends on the pressure that adopts in the stove.
Heterogeneous starting material in the table 1 are respectively the AlO to consist of about 20%
3, 58% AlN and 20% SiN
4Synthetic.Remaining component impurity for example has Fe, C or the like.
Its feature of the stupalith that makes is explained in the mode in the table 2, each quantity mutually that occurs in comprising hardness (HV1), Z value and making material.
More than all contain 0-20% in each number material can not use the detected glassy phase of X-ray diffraction method.
In order to make this type of material can be used as good cutting material, importantly to make it to maintain the hardness under the comparatively high temps.For some material of testing, show its temperature variant situation of hardness (HVO.1) with Fig. 1.As a comparison, marked with A with A among the figure
2O
3Traditional machining ceramic for the basis.
Examples more given below are about machining heat stable material (example 1 is to example 10) and cast iron (example 11 is to example 18), and wherein material that will make according to the present invention and known alloy material are contrasted.
The machining of thermally-stabilised alloy
Example 1
Adopt the inserts machining (Xite) " Inceley 901 " of SNGN 120412E type, the cutting data are as follows:
Cutting speed: 150 and 310 meters/minute
The depth of cut: 0.15 millimeter/change
Depth of cut: 2.0 millimeters
The result:
The relative notch wear rate of the relative cutter life of stupalith opposite flank wear rate
3 125% 80% 105%
4 100% 100% 155%
5 100% 100% 100%
6 75% 100% 100%
Example 2
In the test of another machining " Inceley 901 ", used cutting data are as follows:
Cutting speed: 310 meters/minute
The depth of cut: 0.14 millimeter/change
Depth of cut: 2.0 millimeters
The result:
Stupalith flank wear rate notch wear rate
(millimeter/minute) (millimeter/minute)
3 0.32 0.32
4 0.35 0.44
Example 3
With CNGN 120812E type inserts " Inceley 713C " (low-carbon (LC)) carried out the turning machine machining experiment, used cutting data are as follows:
Cutting speed: 183 meters/minute
The depth of cut: 0.15 millimeter/change
After 96 second machining time, the wearing and tearing that record flange are 1 millimeter.
The result:
Stupalith flank wear rate
(millimeter)
3 1.0
4 1.4
A large amount of flakes after 1 short period of time
Example 4
To having adopted following data with the example identical materials, adding break is 78 seconds in the test:
Cutting speed: 213 meters/minute
The depth of cut: 0.12 millimeter/change
The result:
Stupalith flank wear (millimeter)
3 1.0
4 1.4
Example 5
In the bore operation to material " Rene ", adopted the inserts and the following cutting data of RNGN 120800E type:
Cutting speed: 259 meters/minute
The depth of cut: 0.2 millimeter/change
The wear-out life of stupalith was determined as 47 seconds, stupalith 4 be 36 seconds.
Example 6
In the bore operation to material " Waspaley ", adopted the inserts and the following data of RNGN 120800E type:
Cutting speed: 225-260 rice/minute
The depth of cut: 0.15 millimeter/change
After 33 seconds total machining times, all observed flake on the stupalith 3 and 4.In stupalith 1, catastrophic destruction was only just taken place through several seconds.
Example 7
During with hastelloy " Hastealley X " (heat treated) material machining one annular element, adopted the inserts and following column data of RNGN 120800E type:
Cutting speed: 282 meters/minute
The depth of cut: 0.175 millimeter/change
Depth of cut: 2.5 millimeters
The wear-out life of stupalith 3 is higher by 10% than material 4 approximately, and this is because lateral wearing and tearing are lower.1 of stupalith provides very short cutter life, only is the several seconds.
Example 8
Adopt the inserts machining " Incenel 718 " (solution is heat treated) of SNGN 120416T type, find that the wearing and tearing of notch play a decisive role to wear-out life.
Cutting speed: 70-130-180-220 rice/minute
The depth of cut: 0.20 millimeter/change
Depth of cut: 2.0 millimeters
The result:
Stupalith notch wear rate (millimeter/minute)
70 meters/minute 130 meters/minute 180 meters/minute 220 meters/minute of cutting speeds
1 0.4 0.5 0.7 0.8
3 0.3 0.4 0.6 0.6
4 0.3 0.5 0.7 0.8
Example 9
Inserts (circular groove: 0.20 * 20 °) machining " Incenel 718 " stick-like with SNGN 120416T type, adopt following data:
Cutting speed: 180 meters/minute
The depth of cut: 0.25 millimeter/change
Cutting speed: 2.0 millimeters
Adopt liquid coolant.
The result:
Stupalith blade life (%) flank wear rate (%) notch wear rate (%)
1 93 122 86
3 100 100 100
29 117 103 74
Example 10
Stick-like with SNGN 120416T type inserts (circular groove: 0.20 * 20 °) processing " Inceley 901 ", adopt following data:
Cutting speed: 310 meters/minute
The depth of cut: 0.15 millimeter/change
Depth of cut: 2.0 millimeters
Use 45 ° advancing angle and liquid coolant.
The result:
Stupalith blade life (%) flank wear rate (%) notch wear rate (%)
1 6 - -
3 100 100 100
29 89 125 106
Material 1 shows very big scarp and comes off
Pig-casting machine processing
Example 11
In graphitic cast iron, test SNGN 120416E type inserts, adopted following cutting data:
Cutting speed: 300 meters/minute
The depth of cut: 0.15 millimeter/change
Depth of cut: 2.0 millimeters
The result:
(%) note of relative average abrasion life-span of stupalith
3 113
4 102
6 77
1 100 reference points
Example 12
Be below on the result that obtains in the similar operation of example, the cutting data are as follows:
Cutting speed: 300 meters/minute
The depth of cut: 0.50 millimeter/change
Depth of cut: 3.0 millimeters
The result:
(%) note of relative average abrasion life-span of stupalith
9 49
2 113
1 100 reference points
Example 13
In graphitic cast iron continuous length turning test, the flank wear rate that under different rate of cutting, records:
Cutting speed: 400-600-800 rice/minute
The depth of cut: 0.3 millimeter/change
Depth of cut: 2.0 millimeters
The result:
The flank wear rate (meter/minute) of stupalith under certain cutting speed (meter/minute)
Cutting speed: 400 600 800
3 0.011 0.012 0.10
4 0.013 0.014 0.12
1 0.013 0.015 0.13
Example 14
In the test of another rough turn brake wheel in graphitic cast iron, adopt following cutting data:
Cutting speed: 750 meters/minute
The depth of cut: 0.3 millimeter/change
Depth of cut: 2-3 millimeter
The result:
Stupalith wear-out life (Schwellenwert)
1 3.3
3 10
Example 15
Adopt SNGN 120416T type inserts (circular groove: 0.20 * 20 °), cast iron done a test of intermittent type machining surface planing operation:
Cutting speed: 300 meters/minute
The depth of cut: 0.5 millimeter/change
Cutting speed: 3.0 millimeters
Stupalith 1 and 4 has obtained identical wear-out life, and material 3 has obtained being approximately higher than 20% wear-out life.Judge that wear-out life is as the criterion with inserts destruction.
Example 16
The inserts of following cutting data and SNGN 120416T type is adopted in a test of machining spheroidal graphite cast iron (SS0737).
Cutting speed: 400-600-800 rice/minute
The depth of cut: 0.3 millimeter/change
Depth of cut: 2.0 millimeters
The result:
Wear-out life (the feed number of times before inserts breaks)
400 meters/minute 600 meters/minute 800 meters/minute of stupaliths
1 15 15 15
3 15 15 15
4 14 15 15
Note: this test is interrupted after 15 feeds, is equivalent to have extremely good toughness.Conventional Al
2O
3The base pottery can only have feed several times.
Example 17
Adopt SNGN 120416T type inserts (circular groove: 0.20 * 20 °) that graphitic cast iron has been carried out intermittent type machining planing operation, the cutting data are as follows:
Cutting speed: 300 meters/minute
The depth of cut: 0.20 millimeter/change
Depth of cut: 2.0 millimeters
The result:
The relative blade of the average blade life of the stupalith stability of breaking
(%)
(flank wear＜0.5 millimeter)
14 minutes 100
22 35 minutes 7
23 25 minutes 7
26 - 70
=in the intermittent type cutting operation
Example 18
Adopt stupalith 1 machining graphitic cast iron, this material relates to not two kinds of situations of coating and coating, afterwards scribbles 1.5 microns Al in a kind of situation
2O
3Layer (lA) or 1.5 microns TiN+1.5 micron Al
2O
3Layer (1B), adopt following cutting data:
Cutting speed: 200-300-400 rice/minute
The depth of cut: 0.30 millimeter/change
Depth of cut: 2.0 millimeters
The result:
Stupalith flank wear rate (under certain rate of cutting) (millimeter/minute)
(not coating and cated) rate of cutting (rice/minute) 200 300 400
1 0.03 0.05 0.14
1A 0.01 0.03 0.04
1B 0.01 0.03 0.06
From above each example as can be known, the Si-Al-O-N material that contains many types of phase is not compared with containing many types of this stupalith mutually, and the former feature is to have improved abrasion resistance.For example, stupalith 3 and 29 has shown excellent test-results when machining thermostability alloy.Observe in addition, add hard element or coated high temperature material and can both improve wearability.
The definition of various phases
In described in front content and the following claims that will speak of, occurred various be the integral part of the material that makes according to the present invention mutually.
1. β type Si-Al-O-N sexangle phase, crystalline structure and β type Si
3N
4Identical.Can state and be general expression: Si
6-ZAl
ZO
ZN
8-Z, 0＜Z＜4.2 wherein.Appear at discuss in the material mutually for crystallized form, can measure mutually according to its characteristic X-ray diffractogram.
2. α type Si-Al-O-N sexangle phase, crystalline structure and α type Si
3N
4Identical.Can be described as general expression: M
X(Si, Al)
12(O, N)
160＜X＜2 wherein.Metal M can be the mixture of Y, Li, Ca, Mg and lanthanon or these metals.Other metals with suitable ionic radius also can be stablized this α type phase.These can spread out according to X ray mutually and measure.
3. α type Si
3N
4With β type Si
3N
4Be Si
3N
4Two kinds do not replace form.In addition, crystalline A lN also is unsubstituted, has the structure of wurtzite-type.
4. permitted the heterogenetic collective noun in many types of Si-Al-O-N system or the M-Si-Al-O-N system, the wurtzite structure feature of their crystalline structure and AIN is closely related, but much bigger structure cell is arranged.Metal M can be the mixture of Y, Li, Ca, Mg, Be, Sc and lanthanon or these metals.But, other have other elements of similar size and analog structure behavior, also can enter in the many types of wurtzite structure of this M-Si-Al-O-N more or less, the many types of phase of all these can be at the quadrant of high alumina and high nitrogen-containing sign, promptly in zone, from the Si-Al-O-N system, find near the AIN angle.This also is so in M-Si-Al-O-N system, wherein can find the form of replacement.All these are many types of all have extension the solubility zone, and can have the Al/Si that changes with sintering temperature than and the O/N ratio.Under very high temperature, these many types of will being formed in Al-O-N system and the M-Al-O-N system.Under advantageous conditions, can form and arrange good structure, but because all many types of crystalline structure are all closely related with the structure of wurtzite, so have the randomness of some structure.Therefore, it only is a certain multi-structure that this class usually can not in so many words be characterized by with X-ray diffraction method mutually, even also be like this can measure the existing of many types of phase the time.
5.YAG(a kind of cube phase yttrium aluminium garnet), molecular formula is Y
3Al
5O
12Certain can occur and replacement and the while of Al be replaced O with N with Si.Therefore, this structure can distort to and make its X-ray diffractogram correspond to symmetry to be lower than cuboidal a kind of phase, for example b phase.Also can constitute similarly metallic aluminium oriental garnet with other sintering metals.
6.YAM(a kind of branch crystalline phase yttrium aluminium melilith), molecular formula is Y
4Al
2O
9, can with N-YAM(Y
4Si
2O
7N
2) form the continuous series of solid solution.
7. in the system of M-Si-Al-O-N type, crystalline structure and phosphatic rock ore deposit or the identical phase of wollastonite mine can appear.An example when M is Y is that a kind of to have molecular formula be YSiO
2The monocline crystalline phase of the wollastonite type of N.In addition, depend on metal used in the sintering adjuvant, also other crystallization phasess can occur, as the X phase in the Si-Al-O-N system or the crystalline structure of other types.
8. the mixture of intergranular phase or phase is formed at the process that sinters the M-Si-Al-O-N system into, and have a kind of special sintering adjuvant this moment, as Al
2O
3, SiO
2(or) oxide compound, nitride or the oxynitride of M, M represents Y, Ca, Sc, Mg, Be or lanthanon, or their mixture.Other similar compounds that form the metal of glass also can be used as sintering adjuvant.Intergranular is liquid in sintering process.It the time is cured as glassy phase in cooling, but also is cured as some other phase, and as the YAG that narrated in the top the 5th to the 7th section etc., by thermal treatment, the major portion of this kind liquid phase can change such crystalline phase into when sintering, and wherein the ratio of glassy phase is very low.These crystalline phases can be measured by X-ray diffraction method.
Claims (7)
1,, it is characterized in that this kind stupalith includes many types of Si-Al-O-N based on the stupalith of silicon nitride, aluminium nitride and aluminum oxide; α type Si-Al-O-N mutually and the Si-Al-O-N of β type one of mutually or both; With the part be crystalloid intergranular mutually.
2, stupalith according to claim 1, wherein the agglomerating structure by volume the per-cent meter contain: 0.5～70% many types of phase; 20～99% α type phase or 5～80% β type phase; And 0.1～20% intergranular phase.
3, stupalith according to claim 1, wherein sintering structure by volume the per-cent meter contain: 0.5～70% many types of phase; At least 30% α type phase and maximum 70% β types mixed phase mutually; With 0.1～20% intergranular mutually.
4, stupalith according to claim 3 is characterized in that in the agglomerating structure that by volume the per-cent meter contains 70% mixed phase altogether at the most.
5, stupalith according to claim 3, it is characterized in that the agglomerating structure by volume the per-cent meter contain: 30～99% many types of Si-Al-O-N, maximum 70% α type Si-Al-O-N phase; Maximum 70% β type Si-Al-O-N; Maximum 30% crystalline A lN; With 0.1～20% intergranular mutually.
6,, it is characterized in that in the agglomerating structure that by volume the per-cent meter contains at least 1% or maximum 50% many types of phase according to the described stupalith of any one claim in above-mentioned 2 to 4.
7,, it is characterized in that in the agglomerating structure that by volume the per-cent meter contains maximum 15% intergranular phase according to the described stupalith of any one claim in above-mentioned 2 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85101384 CN1017422B (en) | 1984-04-06 | 1985-04-01 | Nitride-based ceramic material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE8401921A SE451581B (en) | 1984-04-06 | 1984-04-06 | CERAMIC MATERIAL MAINLY BASED ON SILICON NITRIDE, ALUMINUM NITRIDE AND ALUMINUM OXIDE |
| CN 85101384 CN1017422B (en) | 1984-04-06 | 1985-04-01 | Nitride-based ceramic material |
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| CN1017422B true CN1017422B (en) | 1992-07-15 |
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| CN1317229C (en) * | 2005-08-11 | 2007-05-23 | 武汉理工大学 | Semitransparent nitride multiple phase ceramic and its preparation method |
| DE102005045666A1 (en) | 2005-09-14 | 2007-03-15 | Itn Nanovation Gmbh | Layer or coating and composition for its production |
| SE530251C8 (en) * | 2006-12-27 | 2008-05-06 | Sandvik Intellectual Property | Ceramic material and inserts for chip-forming metalwork made from the material |
| EP2407442B1 (en) | 2009-03-13 | 2017-05-03 | NGK Spark Plug Co., Ltd. | Sialon sintered body and cutting insert |
| CN102765942A (en) * | 2012-07-23 | 2012-11-07 | 天津大学 | Method for preparing O'/beta-Sialon two-phase ceramic by sol-gel method |
| CN108840687A (en) * | 2018-07-26 | 2018-11-20 | 深圳市东川技术研究有限公司 | A kind of high-intensitive sintering process for matching grand new material |
| CN113135746B (en) * | 2020-01-17 | 2022-01-04 | 中国科学院上海硅酸盐研究所 | High-insulation low-heat-conduction high-compressive-strength ceramic material and preparation method thereof |
-
1985
- 1985-04-01 CN CN 85101384 patent/CN1017422B/en not_active Expired
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|---|---|
| CN85101384A (en) | 1987-05-20 |
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