CN100445407C - Multi-scale cermets for high temperature erosion-corrosion service - Google Patents

Multi-scale cermets for high temperature erosion-corrosion service Download PDF

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CN100445407C
CN100445407C CNB2004800136701A CN200480013670A CN100445407C CN 100445407 C CN100445407 C CN 100445407C CN B2004800136701 A CNB2004800136701 A CN B2004800136701A CN 200480013670 A CN200480013670 A CN 200480013670A CN 100445407 C CN100445407 C CN 100445407C
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volume
cermet
phase
material piece
group
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CN1791691A (en
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N-R·V·班加鲁
具滋荣
全昌旻
陈炫佑
J·R·彼得森
R·L·安特拉姆
C·J·福勒
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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Abstract

A cermet composition represented by the formula (PQ)(RS)X comprising: a ceramic phase (PQ), a binder phase (RS) and X wherein X is at least one member selected from the group consisting of an oxide dispersoid E, an intermetallic compound F and a derivative compound G wherein said ceramic phase (PQ) is dispersed in the binder phase (RS) as particles of diameter in the range of about 0.5 to 3000 microns, and said X is dispersed in the binder phase (RS) as particles in the size range of about 1 nm to 400 nm.

Description

The multistage sintering metal of high temperature resistance erosion-corrosion service
Technical field
The present invention is broadly directed to sintering metal, particularly multistage (multi-scale) cermet compositions and preparation method thereof.These sintering metals are applicable to the high-temperature applications of the material that need have excellent anti-erosion and erosion resistance.
Background technology
Erosion resistant material can be used for suffer erosion many Application Areass of power of surface.For example, refinery process vessel walls and the internals that are exposed in various chemistry and petroleum environments in the aggressive fluids that contains hard solids (for example catalyst particle) can suffer erosion and corrode.The material degradation (especially at high temperature) of protecting these containers and internals against erosion and corrosion to cause is a technological challenge.For needing protection in order to avoid be subjected to the most serious erosion and corrosive assembly; for example be used for solids and fluid are flowed the isolating inner cyclonic separator inwall of (for example being used for the inside cyclonic separator with catalyst particle and the isolating fluidized bed catalytic cracker of process fluid (FCCU)), what use at present is refractory liner.The prior art of erosion resistant material is the chemically combined alumina refractory of casting.These can be cast alumina refractory and are applied on the surface that needs protection, and harden when thermofixation, and adhere to from the teeth outwards by metal crab-bolt (anchor) or metal reinforcement.It also is adhered on other refractory surfaces easily.A kind of typical chemical constitution of commercially available refractory materials is 80.0 weight %Al 2O 3, 7.2 weight %SiO 2, 1.0 weight %Fe 2O 3, 4.8 weight %MgO/CaO, 4.5 weight %P 2O 5Be subjected to the very big restriction of the excessive mechanical wear of lining that causes by high-velocity particles bump, mechanical disruptionization and spallation (spallation) work-ing life of the refractory liner under the prior art situation.Therefore, for high-temperature applications, need have the excellent anti-erosion and the material of corrosion resistance properties.Cermet compositions of the present invention has just satisfied these needs.
Ceramic-metal composite material is known as sintering metal.For high rigidity and fracture toughness property suitably the sintering metal with enough chemical stabilities of design the resistance to fouling more much higher than refractory materials well known in the prior art can be provided.Sintering metal contains ceramic phase and tackiness agent mutually usually, and generally uses powder metallurgy technology to make, and wherein metal and ceramic powder is mixed, compacting and high temperature sintering to be to form closely knit briquetting.
What the present invention relates to be applicable to high-temperature applications contains ceramic phase and dispersion strengthened binder multistage cermet compositions mutually.Except the erosion resistance of excellence, the intensity of dispersion strengthened binder phase and toughness are to make sintering metal have some material parameters of the resistance to fouling of raising in chemistry and refining of petroleum are operated or in other needs the operation of the resistance to fouling under the elevated temperature.
The present invention includes novel and improved cermet compositions.
The present invention also comprises the suitable cermet compositions of at high temperature using.
In addition, the present invention includes a kind of improved protective money metal surface avoids corroding and corroding method under hot conditions.
According to following detailed description, can be well understood to these purposes and other purpose.
Brief summary of the invention
The present invention includes (RS) cermet compositions shown in the X of a kind of formula (PQ), it comprises: ceramic phase (PQ), tackiness agent phase (RS) and X, wherein X is selected from least a in the group of being made up of oxide dispersion E, intermetallic compound F and derivative compound G, wherein said ceramic phase (PQ) is dispersed in the tackiness agent phase (RS) as about 0.5 to the 3000 micron particle of diameter, and described X is that the particle of about 1 nanometer to 400 nanometer is dispersed in the tackiness agent phase (RS) as size.
Brief description of drawings
Fig. 1 is to use γ ' Ni 3(AlTi) strengthened binder phase (Ni (surplus): 15Cr: 3Al: multistage sintering metal synoptic diagram of 1Ti) making and demonstration cube γ ' Ni 3(AlTi) reppd tackiness agent phase transmission type microscope (TEM) image.
Fig. 2 shows that β NiAl is reppd, use β NiAl strengthened binder phase (Fe (surplus): 18Cr: 8Ni: the multistage sintering metal synoptic diagram of 5Al) making.
Fig. 3 a demonstrates the TiB Y/Al oxide dispersion, that use 20 volume %FeCrAlY alloy binder to make 2Ceramic-metallic SEM image, Fig. 3 b are the TEM images of selected adhesive area identical shown in Fig. 3 a.
Detailed Description Of The Invention
The combination of mechanically deform and degradation has produced corrosion function. For ductile metals and alloy, The adhesive phase in the cermet for example, the spillage of material on surface mostly with carry out in regular turn extrude, forge Make with rupture relevant. Following formula can illustrate the spillage of material by aggressivity (E) expression analytically.
E ∝ ρ p · v 2 p P t · f ( α )
V wherein pBe the speed of the eater (erodant) of z bump target compound, r pBe the density of the eater of bump target compound, P tBe the plastic flow stress of target compound, α is an angle of attack.
The applicant believes, at first by the sintering metal skeleton, can control ceramic-metallic erosion action by the intensity and the toughness of metal-to-metal adhesive then.Therefore, in the present invention, the applicant finds out a kind of by the basic simultaneously method that keeps fracture toughness property to improve ceramic-metallic erosion-resisting characteristics of the flow strength that improves the metal-to-metal adhesive phase.A kind of method that improves the material stress of fluidity be make strengthen the phase fine dispersion metal-to-metal adhesive mutually in.This is a multistage ceramic-metallic principle of the present invention.
Formula (PQ) (RS) component of the multistage cermet compositions shown in the X is that mark is made the ceramic phase of (PQ).In ceramic phase (PQ), P is the metal that is selected from the group of being made up of the IV of family, the V of family, the VI of family element and composition thereof in Al, Si, Mg, the long formula periodic table of elements (LongForm of The Periodic Table of Elements).Q is selected from the group of being made up of carbide, nitride, boride, carbonitride, oxide compound and composition thereof.Therefore, the ceramic phase (PQ) in the multistage cermet compositions is metallic carbide, metal nitride, metal boride, carbonitride or metal oxide.(PQ) mol ratio of P: Q is not wait in 0.5: 1 to 30: 1 in.As illustrative example, as P=Cr, when Q is carbide, (PQ) can be Cr so 23C 6, wherein P: Q is about 4: 1.As P=Cr, when Q is carbide, (PQ) can be Cr so 7C 3, wherein P: Q is about 2: 1.The multistage sintering metal of the pottery mutual-assistance has hardness, and has resistance to fouling under up to about 1500 ℃.In multistage cermet compositions, (PQ) account for about 30 to 95 volume % of multistage sintering metal volume, preferred 50 to 95 volume %, more preferably 70 to 90 volume %.
Formula (PQ) (RS) another component of the multistage cermet compositions shown in the X is that mark is made the tackiness agent phase of (RS).In this tackiness agent phase (RS), R is the base metal that is selected from the group of being made up of Fe, Ni, Co, Mn and composition thereof.S is the fusion composition that is selected from Si, Cr, Ti, Al, Nb, Mo and composition thereof.In addition, this tackiness agent is the external phase of multistage composite thing mutually, and ceramic phase (PQ) is that about 0.5 to 3000 micron particle distribution is in tackiness agent phase (RS) as size.Preferably, size is about 1 to 2000 micron.More preferably, size is about 1 to 1000 micron.The dispersive ceramic particle can have Any shape.Some non-limitative examples comprise sphere, ellipse, polyhedron, distorted spherical, distorted ellipsoidal and distortion polyhedron.Particle size diameter is meant the measuring result to the major axis of particle of 3-D shape.Can use microscopy, for example optical microscopy (OM), scanning electron microscopy (SEM) and electronic transmission microscopy (TEM) are measured granularity.In multistage cermet compositions, (RS) account for 4.5 to 70 volume % of multistage sintering metal volume.The mass ratio of base metal R and fused metal S is 50/50 to 90/10.In a preferred specific embodiments, the chromium content in the tackiness agent phase (RS) is at least 12 weight % of tackiness agent phase (RS) gross weight.
Formula (PQ) is the another component of the multistage cermet compositions shown in the X (RS), and wherein X is the oxide dispersion phase that mark is made E.Oxide dispersion comprises the oxide compound of the group that oxide compound of being selected from by Al, Ti, Nb, Zr, Hf, V, Ta, Cr, Mo, W, Fe, Mn, Ni, Si, Y and composition thereof forms mutually.One of oxide dispersion be characterised in that this oxide dispersion E as about 1 nanometer of diameter to about 400 nanometers, preferably approximately 1 nanometer to about 200 nanometers, more preferably about 1 nanometer to the particle of about 100 nanometers is dispersed in the basic successive tackiness agent phase (RS).In a preferred specific embodiments, oxide dispersion can be added tackiness agent mutually in.In another embodiment, they can on-the-spot formation in preparation process.In another embodiment, they can in use form.When oxide compound is on-the-spot formation, with the element that forms oxide compound before sintering process, be added to tackiness agent mutually in.The element that forms oxide compound is Al, Ti, Nb, Zr, Hf, V, Ta, Cr, Mo, W, Fe, Mn, Ni, Si, Y and composition thereof.In multistage cermet compositions, E accounts for about 0.1 to 10 volume % of multistage sintering metal volume.
Formula (PQ) (RS) the another component of the multistage cermet compositions shown in the X (wherein X is intermetallic compound F) is selected from by γ ' (gamma ') and β (beta)--Ni for example 3Al, Ni 3Ti, Ni 3Nb, NiAl, Ni 2AlTi, NiTi, Ni 2AlSi, FeAl, Fe 3Al, CoAl, Co 3Al, Ti 3Al, Al 3Ti, TiAl, Ti 2AlNb, TiAl 2Mn, TaAl 3, NbAl 3And composition thereof--the group of composition.Intermetallic compound F can be formed in the sintering metal sintering process by tackiness agent phase (RS), is perhaps formed by special processing, and for example the medium temperature that is cooled to the process of envrionment temperature from sintering temperature keeps.In addition, intermetallic compound particles can add in the binder powders and mixing with powder type, as making ceramic-metallic initial powder.Intermetallic compound particles also can in use on-the-spotly form, and perhaps handles forming by suitable sintering post-heating.One of intermetallic compound F be characterised in that they as about 1 nanometer of diameter to about 400 nanometers, preferably approximately 1 nanometer to about 200 nanometers, more preferably about 1 nanometer to the particle of about 100 nanometers is dispersed in the successive tackiness agent phase (RS).Intermetallic compound F accounts for about 0.1 to 10 volume % of multistage sintering metal volume.
Fig. 1 is to use γ ' Ni 3(AlTi) strengthened binder phase (Ni (surplus): 15Cr: 3Al: multistage sintering metal synoptic diagram of 1Ti) making and demonstration cube γ ' Ni 3(AlTi) reppd tackiness agent phase transmission type microscope (TEM) image.Fig. 2 shows that β NiAl is reppd, use β NiAl strengthened binder phase (Fe (surplus): 18Cr: 8Ni: the multistage sintering metal synoptic diagram of 5Al) making.
Formula (PQ) is the another component of the multistage cermet compositions shown in the X (RS), and wherein X is the derivative compound G that is derived by ceramic phase (PQ) under the situation that is with or without tackiness agent facies unit (RS) fellowship.For example, G can be expressed as P aR bS cQ d, wherein P, Q, R, S as mentioned above, and a, b, c, d are 0 to 30 integer or mark.As the non-restrictive illustrative example, when P is that VI family element Cr, Q are carbide, b and c when being 0, G can be Cr 23C 6, Cr 7C 3, Cr 3C 2One of derivative compound G be characterised in that they as about 1 nanometer of diameter to about 400 nanometers, preferably approximately 1 nanometer to about 200 nanometers, more preferably about 1 nanometer to the particle of about 100 nanometers is dispersed in the successive tackiness agent phase (RS).In multistage cermet compositions, G accounts for about 0.01 to 10 volume % of multistage sintering metal volume.X (PQ) (RS) the total volume percent among the X be about 0.01 to 10 volume % of sintering metal volume.
Therefore, in multistage cermet compositions, there are continuous adhesive phase (RS) and at least two disperse phase: pottery (PQ); At least a with among oxide dispersion E, intermetallic compound F and the derivative compound G makes that disperseing the diameter of ceramic phase (PQ) is about 0.5 to 3000 micron, and disperseing the diameter of E, F and G component is about 1 nanometer to 400 nanometer.Multistage sintering metal of the present invention has been represented in this dispersed particle distribution (wherein a group (E, F, G) comprises thin other particle range of level, and another group (PQ) comprises slightly other particle range of level).Disperse phase (PQ), E, F and G in the tackiness agent phase (RS) can exist with the accumulative form.The non-limitative example of aggregated forms comprises the concatermer of diad, triplet, tetrad and Geng Gao quantity.
The volume percent of sintering metal phase (and cermet components) does not comprise the pore volume that is caused by porous.Sintering metal can characterize by the porous of 0.1 to 15 volume %.Preferably, the porous volume be the sintering metal volume 0.1 to being lower than 10%.Comprise these holes of porous preferred do not link to each other but as discrete pore distribution in cermet body.Mean pore size preferably is equal to or less than the mean particle size of ceramic phase (PQ).
In sintering metal of the present invention, tackiness agent is designed to not only have the crack blunting ability mutually, and provides step-out erosion-resistant sintering metal independently mutually as anti-erosion.A method that improves the resistance to fouling of tackiness agent phase be by E, F, the G component is independent or the stress of fluidity of the dispersion-strengthened raising of bonded under use temperature.
Cermet compositions of the present invention has the anti-erosion and the corrosive nature of raising.Measure erosion rate by heat erosion and the wear test (HEAT) described in the embodiment part of the present disclosure.Multistage ceramic-metallic erosion rate of the present invention is lower than every gram SiC eater 1.0 * 10 -6Cubic centimetre.Measure erosion rate by the thermo-gravimetric analysis of describing in the embodiment part of the present disclosure (TGA).When exposing at least 65 hours under 800 ℃ in the air of 100 cc/min, multistage ceramic-metallic erosion rate of the present invention is lower than 1 * 10 -10Gram 2/ centimetre 4Second, or the average oxide layer thickness is lower than 150 microns, preferably is lower than 30 microns.
Preferably, this sintering metal has greater than about 3MPam 1/2, be preferably greater than about 5MPam 1/2, most preferably greater than about 10MPam 1/2Fracture toughness property.Fracture toughness property is the ability of resisting crack propagation in the material under dull loading condition.Fracture toughness property is meant the critical stress intensity factor when crackle begins to spread in an unstable manner in material.The loading (wherein on the tension side of crooked sample precrack being arranged) of preferred use three-point bending geometric format is measured fracture toughness property with Theory of Fracture Mechanics.Mainly be described the present invention of earlier paragraphs ceramic-metallic (RS) mutual-assistance its have this specific character.
, by general powder metallurgy technology, for example mix, grinding, compacting, sintering and cooling than using suitable ceramic powder and binder powders to make raw material with volume required, make cermet compositions.These powder are ground in ball milling in the presence of organic liquid (for example ethanol), to being enough to make the mutually abundant dispersive time of these powder.Remove liquid and, place punch die and be pressed into green compact the ground powder for drying.Then with the gained green compact be higher than about 1200 ℃ to being up to about 1750 ℃ sintering temperature about 10 minutes to about 4 hours.This sintering operation is preferably at inert atmosphere or reducing atmosphere or carry out under vacuum.For example, inert atmosphere can be an argon gas, and reducing atmosphere can be a hydrogen.After this, make the sintered compact cooling, be cooled to envrionment conditions usually.Sintering metal according to method preparation of the present invention can be made the cermet material piece that thickness surpasses 5 millimeters.
A ceramic-metallic feature of the present invention is their microstructural stability, even also be so at elevated temperatures, this makes them be particularly suitable for the protective money metal surface to avoid corroding to about 850 ℃ temperature at about 300 ℃.This stability makes them can use above 2 years for example about 2 years to about 10 years.On the contrary, many known sintering metals can produce under elevated temperature and change, and this can form the phase that ceramic-metallic character is had disadvantageous effect.
The ceramic-metallic high-temperature stability of the present invention makes them be suitable for using at present the Application Areas of refractory materials.Suitable purposes non-limiting enumerated and comprises the lining that is used for process vessel, transfer line, cyclonic separator the fluid-solid cyclonic separator of the cyclonic separator of the used fluidized bed catalytic cracker of rendering industry (for example), grid inserts, thermowell, valve body, guiding valve valve and conduit, catalyst regenerator etc.Like this, by provide one deck ceramic composite article layer of the present invention to protect for this surface to be exposed to corrode or corrosive environment under, metallic surface under especially about 300 ℃ to about 850 ℃.Can sintering metal of the present invention be fixed on the metallic surface by mechanical means or welding.
Embodiment
The mensuration of volume percent:
Measure the volume percent of each phase, component and pore volume (or porosity) by 2 dimension area fractions by scanning electron microscopy.At the enterprising line scanning electron microscopic of agglomerating cermet specimens (SEM) to obtain preferred secondary electron image of amplifying 1000 times.For the zone of SEM scanning, use energy distributing x-ray spectrometry (EDXS) to obtain the X ray point image.Five adjacent areas at sample carry out SEM and EDXS analysis.Use image analysis software then: (EDAX Inc.Mahwah, New Jersey 07430 USA) tie up area fractions to 2 of each each phase of area test to EDXImaging/Mapping version 3 .2.Determine the arithmetical av of area fraction by five measuring results.Determine volume percent (volume %) by the average area mark being multiply by 100 then.Volume % shown in the embodiment has for recording the phasor that is lower than 2 volume %+/-50% precision, have for recording the phasor that equals greater than 2 volume %+/-20% precision.
The mensuration of weight percent:
By standard EDXS assay sintering metal mutually in the weight percent of each element.
Add following non-limiting examples with further elaboration the present invention.
Embodiment 1:TiB 2Sintering metal
With 80 volume % mean diameters 14.0 microns TiB 2Powder (99.5% purity, from AlfaAesar, 99% sifts out now-325) and Fe-26Cr powdered alloy (99.5% purity of 20 volume %, 74 weight %Fe:26 weight %Cr, from Alfa Aesar, sift out between+325 orders at-150 orders) be the sintering metal that feedstock production does not contain the Y/Al oxide dispersion.In the HDPE grinding pot, disperse TiB with ethanol 2Powder and Fe-26Cr powdered alloy.Zirconium white (YTZ) ball of strengthening with yttrium oxide in ball milling (10 millimeters of diameters are from Tosoh Ceramics) mixed powder 24 hours with 100rpm in ethanol.By in vacuum drying oven, from mixed powder, removing ethanol in 24 hours with 130 ℃ of heating.With 5,000psi is with the exsiccant powder pressing in the punch die of 40 mm dias in uniaxial hydraulic press (SPEX 3630 Automated X-press).In argon gas, the disc green compact made are warming up to 400 ℃ with 25 ℃/minute speed, and keep 30 minutes to remove residual solvent.Speed with 15 ℃/minute is heated to disc in 1700 ℃ in argon gas then, and keeps 30 minutes at 1700 ℃.Cool the temperature to-15 ℃/minute speed then and be lower than 100 ℃.
The gained sintering metal contains:
I) 79 volume % mean particle sizes are 7 microns TiB 2
Ii) 7 volume % mean particle sizes are 2 microns M 2B, wherein M=56Cr: 41Fe: 3Ti (weight %)
The iii) poor Cr alloy binder of 14 volume % (82 weight %Fe: 16 weight %Cr: 2 weight %Ti).
Embodiment 2:TiB 2Multistage sintering metal
With 80 volume % mean diameters 14.0 microns TiB 2Powder (99.5% purity, from AlfaAesar, 99% sifts out below-325 orders) and 20 volume % mean diameters be 6.7 microns FeCrAlY powdered alloy (Osprey Metals, Fe (surplus): 19.9Cr: 5.3Al: 0.64Y, 95.1% sifts out below-16 orders) contain the sintering metal of Y/Al oxide dispersion for feedstock production.Last according to embodiment 1 described processing powder, cermet disc is heated to 1500 ℃ and kept 2 hours at 1500 ℃ with 15 ℃/minute speed in argon gas.Cool the temperature to below 100 ℃ with-15 ℃/minute speed then.
The gained sintering metal contains:
I) 79 volume % mean particle sizes are 7 microns TiB 2
Ii) 4 volume % mean particle sizes are 2 microns M 2B, wherein M=53Cr: 45Fe: 2Ti (weight %)
Iii) 1 volume % granularity is the Y/Al oxide dispersion of 5-80 nanometer
The iv) poor Cr alloy binder of 16 volume % (78Fe: 17Cr: 3Al: 2Ti, weight %).
Fig. 3 a is the TiB according to embodiment 2 processing 2Ceramic-metallic SEM image, wherein scale bar is represented 5 microns.In the figure, TiB 2Present dark color mutually, tackiness agent presents light color mutually.The M of rich Cr 2The Type B boride mutually with the Y/Al oxide compound be also shown in mutually tackiness agent mutually in.Fig. 3 b is the TEM image of the selected adhesive area identical with Fig. 3 a, and just wherein scale bar is represented 0.1 micron.In this image, observe size and be the trickle Y/Al oxide dispersion of 5-80 nanometer.These trickle Y/Al oxide dispersions present dark color, and tackiness agent presents light color mutually.
Embodiment 3: erosion test
Each sintering metal to embodiment 1 and 2 carries out heat erosion and wear test (HEAT).Program thereby is as follows:
1) diameter is about 35 millimeters, thickness and is about 5 millimeters cermet disc samples weighing.
2) make the center of disc one side stand SiC particle (200 granularities, #1 level black silicon carbide, UK abrasive material then by 1200 gram/minute of entrainment of warm air, Northbrook, IL) it is 0.5 inch pipe that diameter is come from processing, this warm air, and its end is with 1 inch of 45 distance objective.The speed of SiC is 45.7 meter per seconds.
3) under 732 ℃, step (2) was carried out 7 hours.
4) after 7 hours, make sample be cooled to envrionment temperature and weighing measurement weight loss.
5) measure the erosion of commercially available castable refractory sample and as reference standard.The erosion of reference standard is decided to be value 1, and in table 1, the result and the reference standard of cermet specimens is compared.In table 1, any value greater than 1 is all represented to compare with reference standard and is improved to some extent.The erosion of the sample that contains the Y/Al oxide dispersion of embodiment 2 is compared with the sample that does not contain the Y/Al oxide dispersion of embodiment 1, demonstrates better HEAT result.
Figure C20048001367000161
Embodiment 4: corrosion test
Each sintering metal to embodiment 1 and 2 carries out corrosion test.Program thereby is as follows:
1) cermet specimens with about 10 mm square and about 1 mm thick is polished to 600 granularity diamond precision machined surfaces, and cleans in acetone.
2) in thermogravimetric analyzer (TGA), down this sample is exposed in the air of 100 cc/min then in 800 ℃.
3) under 800 ℃, step (2) was carried out 65 hours.
4) after 65 hours, make sample be cooled to envrionment temperature.
5) measure the thickness of oxide skin by the cross section microscopy of corrosion surface.
6) in table 2, any be lower than 150 microns, preferably be lower than 30 microns value and all represent acceptable erosion resistance.
Table 2
Figure C20048001367000171

Claims (32)

1. (RS) cermet compositions shown in the X of a formula (PQ), it comprises: ceramic phase (PQ), tackiness agent phase (RS) and X, wherein tackiness agent phase (RS) contains and is selected from by Fe, Ni, Co, the base metal R of the group that Mn and composition thereof forms and being selected from by Si, Cr, Ti, Al, Nb, the fused metal S of the group that Mo and composition thereof forms, X is selected from by oxide dispersion E, at least a in the group that intermetallic compound F and derivative compound G form, wherein said ceramic phase (PQ) is dispersed in the tackiness agent phase (RS) as the particle of 0.5 to 3000 micron of diameter, and described X is that the particle of 1 nanometer to 400 nanometer is dispersed in the tackiness agent phase (RS) as size.
2. the cermet compositions of claim 1, wherein ceramic phase (PQ) contains the metal P that is selected from the group of being made up of Al, Si, Mg, IV family, V family, VI family element and composition thereof and is selected from Q by the group of forming of carbide, nitride, boride, carbonitride, oxide compound and composition thereof, and wherein ceramic phase (PQ) accounts for 30 to 95 volume % of cermet compositions volume.
3. the cermet compositions of claim 2, wherein the mol ratio of P and Q is not wait in 0.5: 1 to 30: 1 in the ceramic phase (PQ).
4. the cermet compositions of claim 2, wherein ceramic phase (PQ) accounts for 55 to 95 volume % of sintering metal volume.
5. the cermet compositions of claim 1, wherein tackiness agent phase (RS) accounts for 4.5 to 70 volume % of sintering metal volume, and the mass ratio of base metal R and fused metal S is 50/50 to 90/10.
6. the cermet compositions of claim 1, wherein oxide dispersion E is selected from the group that oxide compound by Al, Ti, Nb, Zr, Hf, V, Ta, Cr, Mo, W, Fe, Mn, Ni, Si, Y and composition thereof is formed, and accounts for 0.1 to 10 volume % of sintering metal volume.
7. the cermet compositions of claim 1, wherein intermetallic compound F is selected from the group of being made up of γ ' and β and composition thereof, and accounts for 0.1 to 10 volume % of sintering metal volume.
8. the cermet compositions of claim 7, wherein intermetallic compound F is selected from by Ni 3Al, Ni 3Ti, Ni 3Nb, NiAl, Ni 2AlTi, NiTi, Ni 2AlSi, FeAl, Fe 3Al, CoAl, Co 3Al, Ti 3Al, Al 3Ti, TiAl, Ti 2AlNb, TiAl 2Mn, TaAl 3, NbAl 3And composition thereof the group formed.
9. the cermet compositions of claim 1, wherein derivative compound G is derived from ceramic phase (PQ) or ceramic phase (PQ) and tackiness agent (RS) mutually, and accounts for 0.01 to 10 volume % of sintering metal volume.
10. the cermet compositions of claim 1, it has greater than 3 MPam 1/2Fracture toughness property.
11. the cermet compositions of claim 1, it has and is lower than every gram SiC eater 1 * 10 -6The erosion rate of cubic centimetre.
12. the cermet compositions of claim 1, when when exposing at least 65 hours under 800 ℃ in the air of 100 cc/min, it has and is lower than 1 * 10 -10Gram 2/ centimetre 4Erosion rate or the mean thickness of second are lower than 150 microns oxide skin.
13. the cermet compositions of claim 1, it has and is lower than every gram SiC eater 1 * 10 -6The erosion rate of cubic centimetre, and when in exposure at least 65 hours time the in the air of 100 cc/min under 800 ℃ has and is lower than 1 * 10 -10Gram 2/ centimetre 4Erosion rate or the mean thickness of second are lower than 150 microns oxide skin.
14. a protection is in the method that is up to the metallic surface that suffers erosion under 850 ℃ the temperature, this method is included as this metallic surface cermet compositions according to claim 1-13 is provided.
15. the method for the metallic surface that a protection suffers erosion under 300 ℃ to 850 ℃ temperature, this method are included as this metallic surface cermet compositions according to claim 1-13 are provided.
16. the method for claim 14, wherein said surface comprises the internal surface of liquid-solid cyclonic separator.
17. a formula (PQ) is the cermet material piece shown in the X (RS), it comprises: ceramic phase (PQ), tackiness agent phase (RS) and X, wherein tackiness agent phase (RS) contains and is selected from by Fe, Ni, Co, the base metal R of the group that Mn and composition thereof forms and being selected from by Si, Cr, Ti, Al, Nb, the fused metal S of the group that Mo and composition thereof forms, X is selected from by oxide dispersion E, at least a in the group that intermetallic compound F and derivative compound G form, wherein said ceramic phase (PQ) is dispersed in the tackiness agent phase (RS) as the particle of 0.5 to 3000 micron of diameter, described X is that the particle of 1 nanometer to 400 nanometer is dispersed in the tackiness agent phase (RS) as size, and wherein the total thickness of cermet material piece greater than 5 millimeters.
18. the cermet material piece of claim 17, wherein ceramic phase (PQ) contains the metal P that is selected from the group of being made up of Al, Si, Mg, IV family, V family, VI family element and composition thereof and is selected from Q by the group of forming of carbide, nitride, boride, carbonitride, oxide compound and composition thereof, and wherein ceramic phase (PQ) accounts for 30 to 95 volume % of cermet compositions volume.
19. the cermet material piece of claim 18, wherein the mol ratio of P and Q is not wait in 0.5: 1 to 30: 1 in the ceramic phase (PQ).
20. the cermet material piece of claim 18, wherein ceramic phase (PQ) accounts for 55 to 95 volume % of sintering metal volume.
21. the cermet material piece of claim 17, wherein tackiness agent phase (RS) accounts for 4.5 to 70 volume % of sintering metal volume, and the mass ratio of base metal R and fused metal S is 50/50 to 90/10.
22. the cermet material piece of claim 17, wherein oxide dispersion E accounts for 0.1 to 10 volume % of sintering metal volume.
23. the cermet material piece of claim 17, wherein intermetallic compound F is by being selected from the group that γ ' and β and composition thereof form, and accounts for 0.1 to 10 volume % of sintering metal volume.
24. the cermet material piece of claim 23, wherein intermetallic compound F is selected from by Ni 3Al, Ni 3Ti, Ni 3Nb, NiAl, Ni 2AlTi, NiTi, Ni 2AlSi, FeAl, Fe 3Al, CoAl, Co 3Al, Ti 3Al, Al 3Ti, TiAl, Ti 2AlNb, TiAl 2Mn, TaAl 3, NbAl 3And composition thereof the group formed.
25. the cermet material piece of claim 17, wherein derivative compound G is derived from ceramic phase (PQ) or ceramic phase (PQ) and tackiness agent (RS) mutually, and accounts for 0.01 to 10 volume % of sintering metal volume.
26. the cermet material piece of claim 17, it has greater than 3MPam 1/2Fracture toughness property.
27. the cermet material piece of claim 17, it has and is lower than every gram SiC eater 1 * 10 -6The erosion rate of cubic centimetre.
28. the cermet material piece of claim 17, when when exposing at least 65 hours under 800 ℃ in the air of 100 cc/min, it has and is lower than 1 * 10 -10Gram 2/ centimetre 4Erosion rate or the mean thickness of second are lower than 150 microns oxide skin.
29. the cermet material piece of claim 17, it has and is lower than every gram SiC eater 1 * 10 -6The erosion rate of cubic centimetre, and when in exposure at least 65 hours time the in the air of 100 cc/min under 800 ℃ has and is lower than 1 * 10 -10Gram 2/ centimetre 4Erosion rate or the mean thickness of second are lower than 150 microns oxide skin.
30. a protection is in the method that is up to the metallic surface that suffers erosion under 850 ℃ the temperature, this method is included as this metallic surface and provides and surpass 5 millimeters cermet material piece according to the total thickness of claim 17-29.
31. the method for the metallic surface that a protection suffers erosion under 300 ℃ to 850 ℃ temperature, this method are included as this metallic surface and provide according to the total thickness of the claim 17-29 cermet material piece greater than 5 millimeters.
32. the method for claim 30, wherein said surface comprises the internal surface of liquid-solid cyclonic separator.
CNB2004800136701A 2003-05-20 2004-05-18 Multi-scale cermets for high temperature erosion-corrosion service Expired - Fee Related CN100445407C (en)

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US7842139B2 (en) * 2006-06-30 2010-11-30 Exxonmobil Research And Engineering Company Erosion resistant cermet linings for oil and gas exploration, refining and petrochemical processing applications
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CN102134663B (en) * 2011-03-04 2012-07-25 株洲硬质合金集团有限公司 Hard alloy with iron-aluminum intermetallic compound as main binding phase and preparation method of hard alloy
CN102978499B (en) * 2012-12-24 2015-08-12 株洲硬质合金集团有限公司 Wimet of a kind of High-temperature-resandant andant wear-resistant and preparation method thereof
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