CN105734387A - TiB2 based metal ceramic and manufacturing method thereof - Google Patents
TiB2 based metal ceramic and manufacturing method thereof Download PDFInfo
- Publication number
- CN105734387A CN105734387A CN201610152927.6A CN201610152927A CN105734387A CN 105734387 A CN105734387 A CN 105734387A CN 201610152927 A CN201610152927 A CN 201610152927A CN 105734387 A CN105734387 A CN 105734387A
- Authority
- CN
- China
- Prior art keywords
- tib
- powder
- incubated
- pressed compact
- ceramic metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/14—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on borides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2201/00—Treatment under specific atmosphere
- B22F2201/01—Reducing atmosphere
- B22F2201/013—Hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2201/00—Treatment under specific atmosphere
- B22F2201/20—Use of vacuum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Abstract
The invention relates to TiB2 based metal ceramic. The TiB2 based metal ceramic comprises, by volume percent, 65%-90% of TiB2 and 10%-35% of Fe and Ni; and in the Fe and Ni, the mass ratio of the Fe to the Ni is 3:7 to 8:2. The TiB2 based metal ceramic has the high bending strength and high breaking tenacity, the bending strength ranges from 600 MPa to 1100 MPa, and the breaking tenacity ranges from 15 MPa.m<1/2> to 21 MPa.m<1/2>.
Description
Technical field
The present invention relates to a kind of high-compactness high-strength and high ductility TiB2 based ceramic metal and preparation method thereof.
Background technology
Titanium diboride (TiB2) there is excellent combination property, fusing point and hardness are high, heat stability, non-oxidizability, corrosion resistance and anti-wear performance are good, are acknowledged as the new and high technology material of great popularization and application prospect in the field of new such as composite, ceramic metal as excellent hard phase.In recent years, vast researcher is by adding TiB prepared by metal sintering additive2The research of based ceramic metal shows, TiB2Based ceramic metal has high red hardness, good fracture toughness, thermal fatigue resistance, thermal shock resistance, and the combination of hardness fracture toughness is better than general hard alloy, and has the hollow ability with antisticking of anti-crescent moon.Compared with other ceramic materials, when processing ferroalloy, there is good heat conductivity, do not react with ferroalloy, it is suitable for high speed processing, in polish medium carbon steel, spheroidal graphite cast-iron, alusil alloy and processing ferroalloy etc., has a good application prospect.Additionally, TiB2Based ceramic metal has outstanding corrosion resistance and anti-wear performance, its be more widely applied still have to be developed with exploration.
The TiB of current preparation2Based ceramic metal, the content of the metallic addition owing to adding is usually no more than the 10% of gross mass so that TiB2Although based ceramic metal has high rigidity, but bending strength and fracture toughness are relatively low.Therefore, a kind of sinter additives is sought, by increasing its content so that the TiB of preparation2While based ceramic metal has higher hardness, its bending strength and fracture toughness are also greatly improved, and just become particularly important.Fe and Ni is to TiB2Granule has good wettability, with Fe, Ni for single sinter additives or the TiB for preparing with the polynary sinter additives containing Fe or Ni2Based ceramic metal is studied more and more, but using Fe-Ni as binary sinter additives, especially using the Fe-Ni of the high volume content TiB prepared as sinter additives2The research of Base Metal pottery be not also seen in bibliographical information.Therefore, the present invention prepares TiB using the Fe-Ni of high volume content as sinter additives2Base Metal is made pottery, and probes into its performance and application, has highly important scientific research and practice significance.
Summary of the invention
It is contemplated that overcome the deficiencies in the prior art, it is provided that a kind of TiB2Base Metal pottery its preparation method.
In order to achieve the above object, technical scheme provided by the invention is:
Described TiB2Based ceramic metal includes the component of following percent by volume:
TiB265%～90%；
Fe and Ni10%～35%；
In described Fe and Ni, the mass ratio of Fe, Ni is 3:7 to 8:2.
Wherein, described TiB2Particle mean size be 1 μm～6 μm..Described TiB2Based ceramic metal has high-compactness, high-flexural strength, high-fracture toughness, and its consistency is 92.48%～99.50%, and bending strength is 600MPa～1100Mpa, and fracture toughness is 15MPam1/2～21MPam1/2。
Above-mentioned TiB2The preparation method of based ceramic metal comprises the steps:
(1) TiB is prepared in the ratio described in claim 12Powder, Fe powder, Ni powder；By TiB2Powder is mixed homogeneously with forming agent, adds the Fe powder as sinter additives and Ni powder, then through planetary ball mill batch mixing, obtains mixed-powder；Every 100g mixed-powder adds 0.5～3g forming agent；
(2) mixed-powder adopt steel mold pressing molding obtain cuboid pressed compact, then with cold isostatic press pressurize 1～5min；
(3) in atmosphere of hydrogen, cuboid pressed compact it is warming up to 500 DEG C～600 DEG C and is incubated 1.5～2h to carry out ungrease treatment, removing forming agent, then proceed to be warming up to 800 DEG C and be incubated 0.5～1h to carry out reduction treatment, obtaining the pressed compact after defat reduction；
(4) pressed compact after defat being reduced carries out vacuum-sintering, obtains TiB2Based ceramic metal.
Wherein, step (1) described forming agent is hard paraffin.During the described planetary ball mill batch mixing of step (1), ratio of grinding media to material is (0.5～3): 1.The sheath material that the described cold isostatic press of step (2) uses is rubber finger sleeve, and cold isostatic press dwell pressure is 150～200MPa.Step (3) is described to be warming up to cuboid pressed compact 500 DEG C～600 DEG C and is incubated 1.5～2h, preferred 2h is to carry out ungrease treatment, then proceed to be warming up to 800 DEG C and be incubated 0.5～1h, when preferred 1h is to carry out reduction treatment, it is that cuboid pressed compact is incubated 1.5～2h with the ramp of 2 DEG C/min～5 DEG C/min to 500 DEG C～600 DEG C, then proceedes to the ramp with 4 DEG C/min～6 DEG C/min and to 800 DEG C and be incubated 0.5～1h.
9, method as claimed in claim 5, it is characterised in that step (4) described vacuum-sintering is 10-2～10-1Under the vacuum of Pa, the pressed compact after defat being reduced to 600 DEG C～800 DEG C, is incubated 0.5h～1h with the ramp of 4 DEG C/min～6 DEG C/min；Then 10-3～10-2Under the vacuum of Pa, with the ramp of 5 DEG C/min～7 DEG C/min to 1400 DEG C～1500 DEG C, it is incubated 0h～0.5h；Then 10-2～10-1Under the vacuum of Pa, with the ramp of 4 DEG C/min～7 DEG C/min to 1600 DEG C～1800 DEG C, it is incubated 0.5h～1h；It is cooled to 1300 DEG C～1400 DEG C, is incubated 0h～0.5h；It is finally cooled to 800 DEG C～900 DEG C, after insulation 0h～0.5h, continues cool to room temperature.
The invention will be further described below:
The present invention, using Fe-Ni as sinter additives, is prepared for a kind of having higher hardness bending strength simultaneously and the also higher TiB of fracture toughness2Base Metal is made pottery.
Below to preparation TiB2Four steps of based ceramic metal are described in detail:
Step (1): often the 100g titanium diboride of forming agent, ferrum, the specifically comprising the following steps that of nickel mixed-powder are added in preparation
A () measures 50ml gasoline and and is placed in heating in water bath pot by beaker and heats, be dissolved in gasoline by the forming agent of 0.5～3g in 500ml beaker；
B () is by 49.80～68.93g titanium diboride (TiB2) powder pours in beaker, and with magnetic stirrer 10～15min, then put in air dry oven by beaker and be dried, baking temperature is set to 80 DEG C；
C titanium diboride (TiB that () will dry2) powder crosses 80 mesh sieves, it is subsequently poured in ball grinder, then 12.75～34.48g ferrum (Fe) powder and 9.32～30.12g nickel (Ni) powder are added in ball grinder, add the stainless steel ball of 50～80g；
D () carries out ball mill mixing by being put on planetary ball mill after ball grinder applying argon gas, rotate clockwise 15～30min and rotate counterclockwise 15～30min alternate rotation 4～6h；
E mixed powder is crossed 80 mesh sieve by (), finally give the mixed-powder of mix homogeneously.
Preferably, the described forming agent of step (a) is hard paraffin.
Step (2): mixed-powder adopts steel mold pressing molding obtain cuboid pressed compact, then uses cold isostatic press pressurize, makes what green density improved further to specifically comprise the following steps that
A () loads in mould with electronic balance weighing 3～5g mixed-powder, adopt Bidirectional pressure to prepare the cuboid pressed compact of long 24～25mm, wide 6～7mm, high 5～7mm；
B cuboid pressed compact is loaded (a corresponding fingerstall of pressed compact) in rubber finger sleeve and seals by (), then compressing further by isostatic cool pressing；
C () removes the pressed compact after rubber finger sleeve obtains isostatic cool pressing.
Preferably, the pressure of the described two-way compacting of step (a) is 3～5MPa, and the dwell time is 10～60 seconds.
Preferably, the pressure of the pressurize of the described cold isostatic press of step (b) is 150～200MPa, and the dwell time is 1～5min.
Step (3): in atmosphere of hydrogen, is warming up to pressed compact 500 DEG C～600 DEG C insulation 2h and carries out ungrease treatment, after be continuously heating to 800 DEG C of insulation 1h and reduce, obtain the specifically comprising the following steps that of pressed compact after defat reduction
A () be layer overlay Al in rustless steel sintering boat2O3Powder, puts into the pressed compact after isostatic pressed in sintering boat, then uses Al2O3Pressed compact is all covered by powder；
B sintering boat is put in the heating furnace of atmosphere of hydrogen protection by (); first pass into the hydrogen 1～2min air to drive away in stove; then it is incubated 2h with the ramp of 2 DEG C/min～5 DEG C/min to 500 DEG C～600 DEG C; rear continuation to 800 DEG C with the ramp of 4 DEG C/min～6 DEG C/min, is closed power supply after insulation 1h and is cooled to room temperature；
C () is by the Al on pressed compact surface2O3Powder is cleaned out, and obtains the pressed compact after defat reduction.
Preferably, in the described cooling procedure of step (b), until sample cooling stops logical hydrogen again after terminating.Hydrogen is reducibility gas, sample can be prevented in temperature-rise period by the dioxygen oxidation in air, simultaneously at 800 DEG C of temperature, can ferrum oxidized in sample be reduced.
Wherein, defat refers to and makes paraffin remove from sample, and paraffin can be decomposed into gas between 500～600 degree and run away with hydrogen stream.Insulation 1～2h is removed to make paraffin be completely decomposed into gas, makes defat more complete.Al2O3Powder covers sample has two to act on greatly, and one acts as the medium of heat transfer, makes sample be heated evenly, and thus ensure that all samples is in the middle of same temperature as far as possible；Two is when hydrogen flows through sample surfaces also raw sample time, plays the effect regulating hydrogen stream, so makes sample reduction more abundant.Reduction is by utilizing the thermal reduction of hydrogen to realize.Owing to being added with the Fe of high level in this ceramic metal as sinter additives, ferrum is easily oxidized to ferrum oxide in atmosphere, ferrum oxide will could by hydrogen reducing under 800 DEG C of high temperature, insulation is to make the reduction of ferrum oxide more thorough.
Step (4): the pressed compact after defat being reduced carries out vacuum-sintering, obtains TiB2Specifically comprising the following steps that of based ceramic metal
(a) defat is reduced after pressed compact put in tungsten crucible, and with thin Zirconium oxide powder by sample landfill, after sample put in vacuum sintering furnace be sintered；
B the vacuum of vacuum drying oven is first extracted into 10 by ()-2～10-1Pa, then with the ramp of 4 DEG C/min～6 DEG C/min to 600 DEG C～800 DEG C, is incubated 0.5h～1h；10-3～10-2Under the vacuum of Pa, continue the ramp with 5 DEG C/min～7 DEG C/min to 1400 DEG C～1500 DEG C, be incubated 0h～0.5h；101～10-1Under the vacuum of Pa, then with the ramp of 4 DEG C/min～7 DEG C/min to 1600 DEG C～1800 DEG C, it is incubated 0.5h～1h；It is cooled to 1300 DEG C～1400 DEG C with the speed of 5 DEG C/min～8 DEG C/min again, is incubated 0h～0.5h；Finally it is cooled to 800 DEG C～900 DEG C with the speed of 7 DEG C/min～10 DEG C/min, after insulation 0h～0.5h, continues cool to room temperature.
C sample after sintering is taken out by (), clean out the Zirconium oxide powder being bonded at sintered sample surface, the TiB after being sintered2Based ceramic metal.
Preferably, the described vacuum-sintering process of step (b), is 10 in vacuum-2～10-1Pa is incubated 0.5h～1h with the ramp of 4 DEG C/min～6 DEG C/min to 600 DEG C～800 DEG C, is conducive to removing totally the forming agent remained in sample further.
Preferably, the described vacuum-sintering process of step (b), in being warming up to 1600 DEG C～1800 DEG C insulation 0.5h～1h processes, vacuum is adjusted to 101～10-1Pa, is in order to avoid the ferrum Ni binder of at high temperature liquid vapors away too much.
In vacuum-sintering process, sintering temperature-rise period adopts multistage heating rate more slowly, the impurity such as carbon, oxygen in sample can be made to get rid of comparatively thorough, makes sample sintering more abundant simultaneously.In cooling procedure, adopt interim rate of temperature fall comparatively slowly, can avoid sintered sample because of temperature shock gross distortion.
The present invention is with the TiB of 1 μm～6 μm2For hard phase, prepare TiB with Fe, Ni for binding agent2Based ceramic metal, wherein hard phase TiB2Volume content be 65vol.%～90vol.%, the volume content of Binder Phase Fe-Ni is 10vol.%～35vol.%, and according to ferrum nickel binary alloy phase diagram, the ratio of ferrum nickel is preferably Fe:Ni=8:2～3:7.Compared with prior art, the TiB that prepared by the present invention2Based ceramic metal has the advantage that
(1) at this TiB2In based ceramic metal, Fe-Ni is at hard phase TiB2Distribute very evenly between granule, and Fe-Ni forms the network structure of connection in whole material, enhances adhesion between Binder Phase and hard phase, substantially increases the mechanical performance of material.
(2) this TiB2Based ceramic metal, while keeping higher hardness, bending strength has reached 600MPa～1100Mpa, and fracture toughness has reached 15MPam1/2～21MPam1/2, this is the TiB than other systems2Based ceramic metal wants much higher.
(3) TiB that the present invention produces2It is simple that based ceramic metal has technological process, and equipment is simple, low cost and other advantages.
In a word, the TiB that prepared by the present invention2TiB prepared by based ceramic metal and additive method2Based ceramic metal is compared, maximum is particular in that: the present invention uses the ferrum nickel of high volume content as binding agent first, its percent by volume reaches between 10vol.%～35vol.%, and according to ferrum nickel binary alloy phase diagram, the ferrum nickel weight ratio that the additive of each group of volumn concentration is arranged is that Fe:Ni=8:2～3:7 totally 6 kinds of ratios are to seek its impact on material structure and performance.TiB prepared by the present invention2Based ceramic metal has high-compactness, high intensity and high-fracture toughness, and its preparation technology and equipment are simply, and cost is low, has a good application prospect.
Accompanying drawing explanation
Fig. 1 is TiB prepared by this invention2-(Fe-Ni) ceramic-metallic XRD thing phase spectral line；
Fig. 2 is TiB prepared by this invention2The ceramic-metallic surface finish pattern photo of-(Fe-Ni)；
Fig. 3 is TiB prepared by this invention2The ceramic-metallic fractograph pattern photo of-(Fe-Ni).
Detailed description of the invention
Embodiment 1
TiB2-35vol.% (Fe-Ni) ceramic metal (in Binder Phase, ferrum nickel weight ratio is Fe:Ni=6:4)
1. weigh 1g hard paraffin, put in the beaker equipped with 50ml gasoline, beaker is put in water bath heating in water bath and stirs acceleration paraffin and dissolve.Weigh 50.43gTiB2Powder is poured in beaker, and makes TiB with magnetic stirrer 10min2The gasoline solution of powder and paraffin fully mixes.After by mixed TiB2Powder slurries is put in air dry oven and is dried, and baking temperature is set as 80 DEG C, and dry 1.5h is dried completely to powder.The powder of drying is crossed 80 order mesh screens, obtains TiB2Mixed-powder with paraffin.
2. by TiB2Pour in stainless steel jar mill with the mixed-powder of paraffin, and weigh 29.74g iron powder, 19.83g nikel powder adds in ball grinder together, with spoon stir 1min make TiB2, iron powder, nikel powder tentatively mix.Weigh 50g stainless steel ball to add in ball grinder, tightly build ball grinder, be then put on planetary ball mill and carry out ball mill mixing.Drum's speed of rotation is set to 350r/min, rotating alternate run, often rotates 15min and changes rotation direction, altogether a ball mill mixing 3h.Mixed-powder is crossed 80 order mesh screens after terminating by batch mixing, obtains TiB2, ferrum, nickel mixed-powder.
3. in selecting, stamping length and width are of a size of the punching block mould of 25mm × 7mm, weigh 4.97g mixed-powder die-filling, after on press, carry out Bidirectional pressure system, dwell time 5s with the pressure of 4MPa, obtain little cuboid pressed compact after the demoulding.Little cuboid loaded in latex finger cot and seal fingerstall with tenacity viscose, after allowing, carrying out cold etc. pressing.Selecting isostatic cool pressing pressure is 200MPa, dwell time 3min, and latex finger cot is removed after terminating by isostatic cool pressing, obtains the pressed compact that consistency is greatly improved.
4. toward layer overlay Al in rustless steel sintering boat2O3Powder, puts into sintering boat week by the pressed compact after isostatic cool pressing, and uses Al2O3Powder is by pressed compact all standing.Then sintering boat is put into ungrease treatment in the heating furnace of nitrogen atmosphere protection, before putting into sintering boat, first leads to hydrogen 1min by complete for the air of stove emptying.By the temperature in stove from the room temperature ramp to 500 DEG C with 4 DEG C/min, insulation 1h carries out defat.Continuing the ramp with 7 DEG C/min to 800 DEG C after insulation terminates, insulation 1h reduces, and closes power supply and is cooled to room temperature, be then shut off hydrogen after insulation terminates.Pressed compact is taken out the Al cleaning out surface2O3Powder, obtains the pressed compact after defat reduction.
5. the pressed compact after defat being reduced is put in tungsten crucible, fills Zirconium oxide powder and makes each pressed compact keep apart, and with Zirconium oxide powder by pressed compact all standing, is then put in vacuum sintering furnace by the tungsten crucible filling sample and is sintered.Vacuum is extracted into 10-2Pa, then by the temperature in vacuum drying oven from room temperature with the ramp of 5 DEG C/min to 700 DEG C, be incubated 0.5h；Again vacuum is brought up to 10-3Pa, with the ramp of 7 DEG C/min to 1450 DEG C, is incubated 0.5h；Finally vacuum is adjusted to 10-1Pa, with the ramp of 6 DEG C/min to 1700 DEG C, is incubated 1h.Insulation is cooled to 1300 DEG C with the speed of 8 DEG C/min after terminating, and is incubated 0h～0.5h；Finally it is cooled to 800 DEG C with the speed of 10 DEG C/min, after insulation 0h～0.5h, continues cool to room temperature.6. take out the sample after sintering, clean out the Zirconium oxide powder of surface adhesion, the TiB after being sintered2-35vol.% (Fe-Ni) ceramic metal.
Adopt TiB prepared by said method2-35vol.% (Fe-Ni) ceramic metal, Binder Phase is evenly distributed on hard phase TiB2Between granule, having excellent comprehensive mechanical performance, this ceramic-metallic relative density is 99.03%, and Vickers hardness is 8.56GPa, and bending strength is 1050.92MPa, and fracture toughness is 17.75MPam1/2。
Embodiment 2
TiB2-30vol.% (Fe-Ni) ceramic metal (in Binder Phase, ferrum nickel weight ratio is Fe:Ni=7:3)
1. weigh 1.5g hard paraffin, put in the beaker equipped with 50ml gasoline, beaker is put in water bath heating in water bath and stirs acceleration paraffin and dissolve.Weigh 56.40gTiB2Powder is poured in beaker, and makes TiB with magnetic stirrer 15min2The gasoline solution of powder and paraffin fully mixes.After by mixed TiB2Powder slurries is put in air dry oven and is dried, and baking temperature is set as 90 DEG C, and dry 2h is dried completely to powder.The powder of drying is crossed 80 order mesh screens, obtains TiB2Mixed-powder with paraffin.
2. by TiB2Pour in stainless steel jar mill with the mixed-powder of paraffin, and weigh 30.52g iron powder, 13.08g nikel powder adds in ball grinder together, with spoon stir 2min make TiB2、Iron powder, nikel powder tentatively mix.Weigh 40g stainless steel ball to add in ball grinder, tightly build ball grinder, be then put on planetary ball mill and carry out ball mill mixing.Drum's speed of rotation is set to 400r/min, rotating alternate run, often rotates 20min and changes rotation direction, altogether a ball mill mixing 4h.Mixed-powder is crossed 80 order mesh screens after terminating by batch mixing, obtains TiB2, ferrum, nickel mixed-powder.
3. in selecting, stamping length and width are of a size of the punching block mould of 25mm × 7mm, weigh 5.07g mixed-powder die-filling, after on press, carry out Bidirectional pressure system, dwell time 4s with the pressure of 5MPa, obtain little cuboid pressed compact after the demoulding.Little cuboid loaded in latex finger cot and seal fingerstall with tenacity viscose, after allowing, carrying out cold etc. pressing.Selecting isostatic cool pressing pressure is 190MPa, dwell time 4min, and latex finger cot is removed after terminating by isostatic cool pressing, obtains the pressed compact that consistency is greatly improved.
4. toward layer overlay Al in rustless steel sintering boat2O3Powder, puts into sintering boat week by the pressed compact after isostatic cool pressing, and uses Al2O3Powder is by pressed compact all standing.Then sintering boat is put into ungrease treatment in the heating furnace of nitrogen atmosphere protection, before putting into sintering boat, first leads to hydrogen 2min by complete for the air of stove emptying.By the temperature in stove from the room temperature ramp to 550 DEG C with 5 DEG C/min, insulation 1h carries out defat.Continuing the ramp with 6 DEG C/min to 800 DEG C after insulation terminates, insulation 1h reduces, and closes power supply and is cooled to room temperature, be then shut off hydrogen after insulation terminates.Pressed compact is taken out the Al cleaning out surface2O3Powder, obtains the pressed compact after defat reduction.
5. the pressed compact after defat being reduced is put in tungsten crucible, fills Zirconium oxide powder and makes each pressed compact keep apart, and with Zirconium oxide powder by pressed compact all standing, is then put in vacuum sintering furnace by the tungsten crucible filling sample and is sintered.Vacuum is extracted into 10-1Pa, then by the temperature in vacuum drying oven from room temperature with the ramp of 6 DEG C/min to 800 DEG C, be incubated 0.5h；Again vacuum is brought up to 10-3Pa, with the ramp of 6 DEG C/min to 1500 DEG C, is incubated 0.5h；Finally vacuum is adjusted to 10-1Pa, with the ramp of 7 DEG C/min to 1800 DEG C, is incubated 1h.Insulation is cooled to 1400 DEG C with the speed of 8 DEG C/min after terminating, and is incubated 0.25h；Finally it is cooled to 900 DEG C with the speed of 10 DEG C/min, after insulation 0.2h, continues cool to room temperature.
6. take out the sample after sintering, clean out the Zirconium oxide powder of surface adhesion, the TiB after being sintered2-30vol.% (Fe-Ni) ceramic metal.
Adopt TiB prepared by said method2-30vol.% (Fe-Ni) ceramic metal, Fe-Ni is at hard phase TiB2Being evenly distributed between granule, have good comprehensive mechanical performance, this ceramic-metallic relative density is 96.56%, and Vickers hardness is 9.96GPa, and bending strength is 829.34MPa, and fracture toughness is 18.04MPam1/2。
Embodiment 3
TiB2-25vol.% (Fe-Ni) ceramic metal (in Binder Phase, ferrum nickel weight ratio is Fe:Ni=5:5).
1. weigh 2g hard paraffin, put in the beaker equipped with 50ml gasoline, beaker is put in water bath heating in water bath and stirs acceleration paraffin and dissolve.Weigh 61.88gTiB2Powder is poured in beaker, and makes TiB with magnetic stirrer 5min2The gasoline solution of powder and paraffin fully mixes.After by mixed TiB2Powder slurries is put in air dry oven and is dried, and baking temperature is set as 95 DEG C, and dry 1.5h is dried completely to powder.The powder of drying is crossed 80 order mesh screens, obtains TiB2Mixed-powder with paraffin.
2. by TiB2Pour in stainless steel jar mill with the mixed-powder of paraffin, and weigh 19.06g iron powder, 19.06g nikel powder adds in ball grinder together, with spoon stir 3min make TiB2、Iron powder, nikel powder tentatively mix.Weigh 45g stainless steel ball to add in ball grinder, tightly build ball grinder, be then put on planetary ball mill and carry out ball mill mixing.Drum's speed of rotation is set to 300r/min, rotating alternate run, often rotates 10min and changes rotation direction, altogether a ball mill mixing 4.5h.Mixed-powder is crossed 80 order mesh screens after terminating by batch mixing, obtains TiB2, ferrum, nickel mixed-powder.
3. in selecting, stamping length and width are of a size of the punching block mould of 25mm × 7mm, weigh 5.0g mixed-powder die-filling, after on press, carry out Bidirectional pressure system, dwell time 6s with the pressure of 3MPa, obtain little cuboid pressed compact after the demoulding.Little cuboid loaded in latex finger cot and seal fingerstall with tenacity viscose, after allowing, carrying out cold etc. pressing.Selecting isostatic cool pressing pressure is 180MPa, dwell time 3min, and latex finger cot is removed after terminating by isostatic cool pressing, obtains the pressed compact that consistency is greatly improved.
4. toward layer overlay Al in rustless steel sintering boat2O3Powder, puts into sintering boat week by the pressed compact after isostatic cool pressing, and uses Al2O3Powder is by pressed compact all standing.Then sintering boat is put into ungrease treatment in the heating furnace of nitrogen atmosphere protection, before putting into sintering boat, first leads to hydrogen 1.5min by complete for the air of stove emptying.By the temperature in stove from the room temperature ramp to 600 DEG C with 4 DEG C/min, insulation 1h carries out defat.Continuing the ramp with 5 DEG C/min to 800 DEG C after insulation terminates, insulation 1h reduces, and closes power supply and is cooled to room temperature, be then shut off hydrogen after insulation terminates.Pressed compact is taken out the Al cleaning out surface2O3Powder, obtains the pressed compact after defat reduction.
5. the pressed compact after defat being reduced is put in tungsten crucible, fills Zirconium oxide powder and makes each pressed compact keep apart, and with Zirconium oxide powder by pressed compact all standing, is then put in vacuum sintering furnace by the tungsten crucible filling sample and is sintered.Vacuum is extracted into 10-2Pa, then by the temperature in vacuum drying oven from room temperature with the ramp of 5 DEG C/min to 600 DEG C, be incubated 1h；Again vacuum is brought up to 10-3Pa, with the ramp of 7 DEG C/min to 1400 DEG C, is incubated 0.5h；Finally vacuum is adjusted to 10-2Pa, with the ramp of 7 DEG C/min to 1600 DEG C, is incubated 1h.Insulation is cooled to 1350 DEG C with the speed of 6 DEG C/min after terminating, and is incubated 0h～0.5h；Finally it is cooled to 850 DEG C with the speed of 9 DEG C/min, after insulation 0.5h, continues cool to room temperature.
6. take out the sample after sintering, clean out the Zirconium oxide powder of surface adhesion, the TiB after being sintered2-25vol.% (Fe-Ni) ceramic metal.
Adopt TiB prepared by said method2-25vol.% (Fe-Ni) ceramic metal, Fe-Ni is at hard phase TiB2Being evenly distributed between granule, have good comprehensive mechanical performance, this ceramic-metallic relative density is 94.43%, and Vickers hardness is 10.42GPa, and bending strength is 724.30MPa, and fracture toughness is 16.14MPam1/2。
Embodiment 4
TiB2-20vol.% (Fe-Ni) ceramic metal (in Binder Phase, ferrum nickel weight ratio is Fe:Ni=4:6).
1. weigh 2.5g hard paraffin, put in the beaker equipped with 50ml gasoline, beaker is put in water bath heating in water bath and stirs acceleration paraffin and dissolve.Weigh 68.41gTiB2Powder is poured in beaker, and makes TiB with magnetic stirrer 7min2The gasoline solution of powder and paraffin fully mixes.After by mixed TiB2Powder slurries is put in air dry oven and is dried, and baking temperature is set as 100 DEG C, and dry 1h is dried completely to powder.The powder of drying is crossed 80 order mesh screens, obtains TiB2Mixed-powder with paraffin.
2. by TiB2Pour in stainless steel jar mill with the mixed-powder of paraffin, and weigh 12.75g iron powder, 19.13g nikel powder adds in ball grinder together, with spoon stir 4min make TiB2、Iron powder, nikel powder tentatively mix.Weigh 50g stainless steel ball to add in ball grinder, tightly build ball grinder, be then put on planetary ball mill and carry out ball mill mixing.Drum's speed of rotation is set to 400r/min, rotating alternate run, often rotates 30min and changes rotation direction, altogether a ball mill mixing 5h.Mixed-powder is crossed 80 order mesh screens after terminating by batch mixing, obtains TiB2, ferrum, nickel mixed-powder.
3. in selecting, stamping length and width are of a size of the punching block mould of 25mm × 7mm, weigh 4.59g mixed-powder die-filling, after on press, carry out Bidirectional pressure system, dwell time 3s with the pressure of 6MPa, obtain little cuboid pressed compact after the demoulding.Little cuboid loaded in latex finger cot and seal fingerstall with tenacity viscose, after allowing, carrying out cold etc. pressing.Selecting isostatic cool pressing pressure is 170MPa, dwell time 5min, and latex finger cot is removed after terminating by isostatic cool pressing, obtains the pressed compact that consistency is greatly improved.
4. toward layer overlay Al in rustless steel sintering boat2O3Powder, puts into sintering boat week by the pressed compact after isostatic cool pressing, and uses Al2O3Powder is by pressed compact all standing.Then sintering boat is put into ungrease treatment in the heating furnace of nitrogen atmosphere protection, before putting into sintering boat, first leads to hydrogen 2min by complete for the air of stove emptying.By the temperature in stove from the room temperature ramp to 500 DEG C with 5 DEG C/min, insulation 1h carries out defat.Continuing the ramp with 6 DEG C/min to 800 DEG C after insulation terminates, insulation 1h reduces, and closes power supply and is cooled to room temperature, be then shut off hydrogen after insulation terminates.Pressed compact is taken out the Al cleaning out surface2O3Powder, obtains the pressed compact after defat reduction.
5. the pressed compact after defat being reduced is put in tungsten crucible, fills Zirconium oxide powder and makes each pressed compact keep apart, and with Zirconium oxide powder by pressed compact all standing, is then put in vacuum sintering furnace by the tungsten crucible filling sample and is sintered.Vacuum is extracted into 10-1Pa, then by the temperature in vacuum drying oven from room temperature with the ramp of 5 DEG C/min to 700 DEG C, be incubated 1h；Again vacuum is brought up to 10-3Pa, with the ramp of 6 DEG C/min to 1450 DEG C, is incubated 0.5h；Finally vacuum is adjusted to 10-1Pa, with the ramp of 5 DEG C/min to 1700 DEG C, is incubated 1h.Insulation is cooled to 1300 DEG C with the speed of 8 DEG C/min after terminating, and is incubated 0.3h；Finally it is cooled to 800 DEG C with the speed of 10 DEG C/min, after insulation 0.5h, continues cool to room temperature.
6. take out the sample after sintering, clean out the Zirconium oxide powder of surface adhesion, the TiB after being sintered2-20vol.% (Fe-Ni) ceramic metal.
Adopt TiB prepared by said method2-20vol.% (Fe-Ni) ceramic metal, Fe-Ni is at hard phase TiB2Being evenly distributed between granule, have good comprehensive mechanical performance, this ceramic-metallic relative density is 92.86%, and Vickers hardness is 11.21GPa, and bending strength is 643.71MPa, and fracture toughness is 15.19MPam1/2。
Claims (9)
1. a TiB2Based ceramic metal, it is characterised in that described TiB2Based ceramic metal includes the component of following percent by volume:
TiB265%～90%；
Fe and Ni10%～35%；
In described Fe and Ni, the mass ratio of Fe, Ni is 3:7 to 8:2.
2. TiB as claimed in claim 12Based ceramic metal, it is characterised in that described TiB2Particle mean size be 1 μm～6 μm.
3. TiB as claimed in claim 1 or 22Based ceramic metal, it is characterised in that described TiB2Based ceramic metal consistency is 92.48%～99.50%；Bending strength is 600MPa～1100Mpa；Fracture toughness is 15MPam1/2～21MPam1/2。
4. TiB as claimed in claim 32The preparation method of based ceramic metal, it is characterised in that described method comprises the steps:
(1) TiB is prepared in the ratio described in claim 12Powder, Fe powder, Ni powder；By TiB2Powder is mixed homogeneously with forming agent, adds Fe powder and Ni powder, then through planetary ball mill batch mixing, obtains mixed-powder；Every 100g mixed-powder adds 0.5～3g forming agent；
(2) mixed-powder adopt steel mold pressing molding obtain cuboid pressed compact, then with cold isostatic press pressurize 1～5min；
(3) in atmosphere of hydrogen, cuboid pressed compact it is warming up to 500 DEG C～600 DEG C and is incubated 1.5～2h to carry out ungrease treatment, removing forming agent, then proceed to be warming up to 800 DEG C and be incubated 0.5～1h to carry out reduction treatment, obtaining the pressed compact after defat reduction；
(4) pressed compact after defat being reduced carries out vacuum-sintering, obtains TiB2Based ceramic metal.
5. method as claimed in claim 4, it is characterised in that step (1) described forming agent is hard paraffin.
6. method as claimed in claim 4, it is characterised in that during the described planetary ball mill batch mixing of step (1), ratio of grinding media to material is (0.5～3): 1.
7. method as claimed in claim 4, it is characterised in that the described cold isostatic press dwell pressure of step (2) is 150～200MPa.
8. method as claimed in claim 4, it is characterized in that, step (3) is described to be warming up to cuboid pressed compact 500 DEG C～600 DEG C and is incubated 1.5～2h to carry out ungrease treatment, when then proceeding to be warming up to 800 DEG C and be incubated 0.5～1h to carry out reduction treatment, it is that cuboid pressed compact is incubated 1.5～2h with the ramp of 2 DEG C/min～5 DEG C/min to 500 DEG C～600 DEG C, then proceedes to the ramp with 4 DEG C/min～6 DEG C/min and to 800 DEG C and be incubated 0.5～1h.
9. method as claimed in claim 4, it is characterised in that step (4) described vacuum-sintering is 10-2～10-1Under the vacuum of Pa, the pressed compact after defat being reduced to 600 DEG C～800 DEG C, is incubated 0.5h～1h with the ramp of 4 DEG C/min～6 DEG C/min；Then 10-3～10-2Under the vacuum of Pa, with the ramp of 5 DEG C/min～7 DEG C/min to 1400 DEG C～1500 DEG C, it is incubated 0h～0.5h；Then 10-2～10-1Under the vacuum of Pa, with the ramp of 4 DEG C/min～7 DEG C/min to 1600 DEG C～1800 DEG C, it is incubated 0.5h～1h；It is cooled to 1300 DEG C～1400 DEG C, is incubated 0h～0.5h；It is finally cooled to 800 DEG C～900 DEG C, after insulation 0h～0.5h, continues cool to room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610152927.6A CN105734387B (en) | 2016-03-17 | 2016-03-17 | A kind of TiB2Based ceramic metal and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610152927.6A CN105734387B (en) | 2016-03-17 | 2016-03-17 | A kind of TiB2Based ceramic metal and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105734387A true CN105734387A (en) | 2016-07-06 |
| CN105734387B CN105734387B (en) | 2018-02-23 |
Family
ID=56251208
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610152927.6A Expired - Fee Related CN105734387B (en) | 2016-03-17 | 2016-03-17 | A kind of TiB2Based ceramic metal and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105734387B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107020372A (en) * | 2017-04-26 | 2017-08-08 | 武汉理工大学 | A kind of water-based spray prilling process of titanium diboride/nickel molybdenum composite granule |
| CN107058844A (en) * | 2017-05-22 | 2017-08-18 | 华北电力大学（保定） | A kind of micropore metal ceramics and preparation method as wet electrical dust precipitator pole plate |
| CN107188566A (en) * | 2017-06-28 | 2017-09-22 | 常州麒通国际贸易有限公司 | A kind of preparation method of titanium diboride cermet |
| CN108080815A (en) * | 2017-06-12 | 2018-05-29 | 吉林大学 | A kind of novel nano pottery aluminium Al-alloy welding wire and preparation method |
| CN109355521A (en) * | 2018-09-12 | 2019-02-19 | 张家港市山牧新材料技术开发有限公司 | A kind of preparation method of titanium diboride Base Metal composite material |
| CN114101680A (en) * | 2021-11-17 | 2022-03-01 | 北京理工大学 | Preparation method of hard layer on surface of titanium alloy |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405347A (en) * | 2001-08-16 | 2003-03-26 | 郭庆虎 | High-strength, high-anti-friction hard alloy, and manufacture method and application thereof |
| CN1995427A (en) * | 2003-01-13 | 2007-07-11 | 杰出金属实业公司 | Hard alloy composition |
| CN104844219A (en) * | 2015-05-09 | 2015-08-19 | 浙江阿波罗工具有限公司 | Composite ceramic saw web material and preparation method thereof |
-
2016
- 2016-03-17 CN CN201610152927.6A patent/CN105734387B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405347A (en) * | 2001-08-16 | 2003-03-26 | 郭庆虎 | High-strength, high-anti-friction hard alloy, and manufacture method and application thereof |
| CN1995427A (en) * | 2003-01-13 | 2007-07-11 | 杰出金属实业公司 | Hard alloy composition |
| CN104844219A (en) * | 2015-05-09 | 2015-08-19 | 浙江阿波罗工具有限公司 | Composite ceramic saw web material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| J.M.SANCHEZ ET AL: "Consolidation，Microstructure and Mechanical Properties of Newly Developed TiB2-Based Materials", 《SCRIPTA METALLURGICA ET MATERIALIA》 * |
| 邹建平 等: "TiB2基陶瓷复合材料研究进展", 《陶瓷科学与艺术》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107020372A (en) * | 2017-04-26 | 2017-08-08 | 武汉理工大学 | A kind of water-based spray prilling process of titanium diboride/nickel molybdenum composite granule |
| CN107020372B (en) * | 2017-04-26 | 2019-04-26 | 武汉理工大学 | A kind of water-based spray prilling process of titanium diboride/nickel molybdenum composite granule |
| CN107058844A (en) * | 2017-05-22 | 2017-08-18 | 华北电力大学（保定） | A kind of micropore metal ceramics and preparation method as wet electrical dust precipitator pole plate |
| CN107058844B (en) * | 2017-05-22 | 2019-04-30 | 华北电力大学（保定） | A kind of micropore metal ceramics and preparation method as wet electrical dust precipitator pole plate |
| CN108080815A (en) * | 2017-06-12 | 2018-05-29 | 吉林大学 | A kind of novel nano pottery aluminium Al-alloy welding wire and preparation method |
| CN107188566A (en) * | 2017-06-28 | 2017-09-22 | 常州麒通国际贸易有限公司 | A kind of preparation method of titanium diboride cermet |
| CN109355521A (en) * | 2018-09-12 | 2019-02-19 | 张家港市山牧新材料技术开发有限公司 | A kind of preparation method of titanium diboride Base Metal composite material |
| CN114101680A (en) * | 2021-11-17 | 2022-03-01 | 北京理工大学 | Preparation method of hard layer on surface of titanium alloy |
| CN114101680B (en) * | 2021-11-17 | 2022-08-19 | 北京理工大学 | Preparation method of hard layer on surface of titanium alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105734387B (en) | 2018-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105734387B (en) | A kind of TiB2Based ceramic metal and preparation method thereof | |
| CN108103381B (en) | High-strength FeCoNiCrMn high-entropy alloy and preparation method thereof | |
| CN104120291B (en) | A kind of TiC, TiB2The preparation method of particle enhanced nickel base composite material | |
| CN109439940B (en) | Method for preparing particle reinforced aluminum matrix composite material by hot-pressing sintering under atmospheric atmosphere | |
| CN107119207B (en) | It is a kind of non-metering than TiC enhancing Cu-base composites and preparation method thereof | |
| CN109852830A (en) | A kind of superfine carbide particles reiforced metal-base composition and preparation method thereof | |
| CN106834878A (en) | A kind of method that microwave sintering prepares endogenous high-entropy alloy-base composite material | |
| CN110655407A (en) | Preparation method of silicon carbide ceramic with controllable resistance | |
| CN105441815A (en) | Preparation method for modified superfine low-oxygen water-atomized alloy powder used for diamond tool | |
| CN108220642A (en) | A kind of preparation method of CoCrCuFeMoNi high-entropy alloys granule reinforced copper base composite material | |
| CN108421985A (en) | A method of preparing entropy alloy in oxide dispersion intensifying | |
| CN103194629B (en) | Method for preparing tungsten molybdenum copper composite material | |
| CN104004942B (en) | TiC particle-reinforced nickel-based composite material and preparation method thereof | |
| CN114525424B (en) | Titanium-based composite material and preparation method thereof | |
| CN109487141A (en) | A kind of preparation method of plate carbide solid solution toughening mixed crystal Ti (C, N) based ceramic metal | |
| CN114525438B (en) | Tungsten copper composite material and preparation method thereof | |
| CN107267845A (en) | Nano particle TiC strengthens the microwave synthesis method of high-entropy alloy-base composite material | |
| CN109576546A (en) | A kind of preparation method of the high-strength tenacity without magnetic Ti (C, N) based ceramic metal | |
| CN104232995A (en) | High-toughness ultrafine-grain composite titanium alloy and application and preparation method thereof | |
| CN114799155A (en) | Preparation method of ceramic particle reinforced refractory high-entropy alloy | |
| CN105543535B (en) | Al4SiC4With Cr cooperative reinforcings net/spherical copper product and preparation method | |
| CN104593657A (en) | Boron carbide-based composite material and preparation method thereof | |
| CN108441668A (en) | A kind of silver tungsten contact material and preparation method thereof | |
| CN110791693B (en) | High-entropy alloy with low Al content, high strength and toughness and acid corrosion resistance and preparation method thereof | |
| CN106086493B (en) | A kind of method that fast low temperature sintering prepares CuCr alloy materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180223 Termination date: 20200317 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |