CN107513642A - Co-based alloy powder and its preparation method and application - Google Patents
Co-based alloy powder and its preparation method and application Download PDFInfo
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- CN107513642A CN107513642A CN201710967273.7A CN201710967273A CN107513642A CN 107513642 A CN107513642 A CN 107513642A CN 201710967273 A CN201710967273 A CN 201710967273A CN 107513642 A CN107513642 A CN 107513642A
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- 239000000956 alloy Substances 0.000 title claims abstract description 131
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 98
- 239000000843 powder Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 55
- 239000010941 cobalt Substances 0.000 claims abstract description 55
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 44
- 235000016768 molybdenum Nutrition 0.000 claims abstract description 42
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 41
- 239000010937 tungsten Substances 0.000 claims abstract description 41
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 38
- 239000011651 chromium Substances 0.000 claims abstract description 38
- 239000000126 substance Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 57
- 150000004706 metal oxides Chemical class 0.000 claims description 57
- 238000000889 atomisation Methods 0.000 claims description 49
- 238000010438 heat treatment Methods 0.000 claims description 38
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 37
- 229910052750 molybdenum Inorganic materials 0.000 claims description 37
- 239000011733 molybdenum Substances 0.000 claims description 37
- 238000010146 3D printing Methods 0.000 claims description 29
- 238000002844 melting Methods 0.000 claims description 23
- 230000008018 melting Effects 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 18
- 239000011159 matrix material Substances 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 230000000149 penetrating effect Effects 0.000 claims description 7
- 229910000531 Co alloy Inorganic materials 0.000 claims description 5
- -1 wherein Chemical compound 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 25
- 229910052573 porcelain Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- QBACCBHDCANWCQ-UHFFFAOYSA-N chromium cobalt molybdenum tungsten Chemical compound [Co][Cr][Mo][W] QBACCBHDCANWCQ-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000470 constituent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 125000003636 chemical group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910002064 alloy oxide Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003564 dental alloy Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000002320 enamel (paints) Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 208000037805 labour Diseases 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/60—Treatment of workpieces or articles after build-up
- B22F10/64—Treatment of workpieces or articles after build-up by thermal means
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
-
- B22F1/0003—
-
- 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
- B22F1/14—Treatment of metallic powder
- B22F1/142—Thermal or thermo-mechanical treatment
-
- 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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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- 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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/36—Process control of energy beam parameters
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- 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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/36—Process control of energy beam parameters
- B22F10/366—Scanning parameters, e.g. hatch distance or scanning strategy
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- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- 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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
- B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Organic Chemistry (AREA)
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Abstract
The present invention relates to a kind of Co-based alloy powder and its preparation method and application, and by weight percentage, the Co-based alloy powder is made up of following chemical composition：22 32% chromium, 4 10% molybdenums, 4 10% tungsten, 0 1% silicon, 0 0.75% iron, 0 0.35% carbon, 0.05 0.2% nitrogen, surplus is cobalt.Good fluidity, the particle diameter of Co-based alloy powder of the present invention be small and centralized particle diameter, Co-base alloy material mechanical performance made from the Co-based alloy powder can reach 5 types/type5 of the requirements of GB17168/ISO 22674, and tensile strength reaches 1326MPa, nonproportional cyclic straining reaches 948MPa；Modulus of elasticity reaches 206GPa, fracture elongation up to 13.8%.
Description
Technical field
The present invention relates to medical material tech field, more particularly to a kind of Co-based alloy powder and its prepare and method and
Using.
Background technology
Displayed with the extensive use of ceramometal restoration, the problem of more and more repairing failures.Substantial amounts of research knot
Fruit shows that ceramometal restoration collapses incidence highest of the porcelain in golden porcelain repairing failure, is primarily due to the oral environment in complexity
In, ceramometal restoration can be by the masticatory force of all directions, and good Metal-ceramic combining strength, alloy high strength are to prevent from repairing
Body collapses the basis of porcelain and the deformation of thin-walled tooth.At present, the dental alloy such as preparation material ASTM F75 of dental prosthesis, stainless steel
Intensity is only capable of reaching 4 types/type4 of the requirements of GB17168/ISO 22674, when causing to be embedded in tooth body dental prosthesis deformation or
Dental prosthesis crackled glaze during person's use.
In addition, using precinct laser fusion technology, i.e. metal three-dimensional printing technology, in Aero-Space, mould, personalized justice
Tooth and medical domain etc. have huge applications space.Particularly in terms of personalized dental prosthesis is manufactured, precinct laser melting
Technology can meet the manufacture characteristics such as the personalization of dental prosthesis, high accuracy, labyrinth；However, precinct laser melts skill
The research of art raw material is always the bottleneck that is promoted of the technology, precinct laser melting original material mainly based on dusty material,
It is required that dusty material has good mobility, chemical purity height etc..
Medical Cobalt-Based Alloys are using cobalt and chromium as the solid solution of basis, mainly contain the alloying elements such as cobalt, chromium, molybdenum；
The tissue of cobalt-base alloys is mainly made up of austenitic matrix and carbide reinforced matrix.Medical Cobalt-Based Alloys are due to good
Corrosion resistance and golden porcelain associativity, it is widely used in artificial tooth in gear division reparation, support, various casting crowns, inlay and solid
Determine the manufacture of bridge.But to still suffer from alloy strength not high enough so as to causing repairing failure for Co-base alloy material of the prior art
The problem of.
The content of the invention
Based on this, it is necessary to it is not high enough so as to causing to repair to still suffer from alloy strength for cobalt-base alloys of the prior art
A kind of the problem of failure, there is provided Co-based alloy powder.The Co-based alloy powder alloy strength is high.
To achieve the above object, concrete technical scheme is as follows：
A kind of Co-based alloy powder, by weight percentage, the Co-based alloy powder are made up of following chemical composition：
22-32% chromium, 4-10% molybdenums, 4-10% tungsten, 0-1% silicon, 0-0.75% iron, 0-0.35% carbon, 0.05-0.2%
Nitrogen, surplus are cobalt, wherein, molybdenum is identical with the percentage by weight of tungsten in the Co-based alloy powder.
In wherein some embodiments, by weight percentage, the Co-based alloy powder is made up of following chemical composition：
22-28% chromium, 4.8-7.5% molybdenums, 4.8-7.5% tungsten, 0-1% silicon, 0-0.75% iron, 0-0.35% carbon, 0.05-
0.1% nitrogen, surplus are cobalt, wherein, molybdenum is identical with the percentage by weight of tungsten in the Co-based alloy powder.
In wherein some embodiments, the particle diameter of the Co-based alloy powder is 10-63 μm.Co-based alloy powder particle diameter is
During 10-63 microns, the Co-based alloy powder can be suitable for SLM (selective laser melting) technology 3D printing.
It is a further object of the present invention to provide the preparation method of above-mentioned Co-based alloy powder.
A kind of preparation method of above-mentioned Co-based alloy powder, comprises the following steps：
(1) raw metal of the Co-based alloy powder is taken, the raw metal is chromium, molybdenum, tungsten and cobalt, described in removal
The metal oxide layer on raw metal surface, the chromium that metal oxide layer must be removed, the molybdenum for removing metal oxide layer, remove metal oxidation
The tungsten of layer and the cobalt for removing metal oxide layer；
(2) 30-70wt% of the cobalt of the removal metal oxide layer is added into smelting furnace as matrix, adds described go
Except the chromium of metal oxide layer, after heating melting, the molybdenum and tungsten of the removal metal oxide layer are added, after complete melting, is added
Enter the cobalt of remaining removal metal oxide layer, completely after melting, heating, obtain liquation；
(3) using high pressure nitrogen as atomization gas, step (2) liquation is sprayed into atomisation tower and is atomized, obtains mist
Droplet after change；Keep being full of nitrogen in atomisation tower in atomization process and keep the pressure in atomisation tower to be less than 1 air
Pressure；
(4) droplet after atomization is cooled down, collects the powder after cooling and carry out the pre-heat treatment, produce the cobalt-base alloys
Powder.
In wherein some embodiments, the step (4) the pre-heat treatment includes：Powder after the cooling is existed
1-12h is incubated under conditions of 300-500 DEG C.When being atomized due to liquation by high pressure nitrogen, the droplet after atomization can absorb nitrogen,
Droplet after the part nitrogen of absorption and atomization chemically reacts, and unreacted nitrogen still wraps up after atomization small
In drop, after cooling, still there is unreacted nitrogen in Co-based alloy powder, by the pre-heat treatment, make unreacted nitrogen
Gas further chemically reacts with chromium, so the method for warming up is most important for Co-based alloy powder fixed nitrogen,
Directly affect Co-based alloy powder machine-shaping (such as：3D printing technique) after ductility and hardness.
It is 0.1- that the pressure in atomisation tower is kept in wherein some embodiments, in step (3) described atomization process
0.9MPa。
In wherein some embodiments, the penetrating pressure of high pressure nitrogen described in step (3) is 1-5MPa, in step (2)
The temperature of the liquation is 1650-1700 DEG C.
It is yet another object of the invention to provide application of the above-mentioned Co-based alloy powder in dental prosthesis is prepared.
It is yet another object of the invention to provide a kind of dental prosthesis.
A kind of dental prosthesis, its preparing raw material include above-mentioned Co-based alloy powder.
It is yet another object of the invention to provide the preparation method of above-mentioned dental prosthesis.
A kind of preparation method of above-mentioned dental prosthesis, comprises the following steps：
(1) 3D printing：3D printing is carried out by raw material of above-mentioned cobalt billon powder, the condition of the 3D printing includes：Swash
Luminous power is 50-180W, sweep speed 80-400mm/s, sweep span 0.06-0.12mm, obtains 3D printing dummy；
(2) it is heat-treated：Step (1) the 3D printing dummy is placed in nitrogen atmosphere, in 800-1150 DEG C of condition
Lower insulation 1-2h, then room temperature is air-cooled to, obtain the dental prosthesis.
In wherein some embodiments, the heat treatment is：Step (1) the 3D printing dummy is placed in nitrogen atmosphere
In, 1.5h is incubated under the conditions of 1100 DEG C, then room temperature is air-cooled to, obtain dental prosthesis.
In the preparation process of above-mentioned dental prosthesis, 3D printing dummy is placed in nitrogen atmosphere, in 800-1150
1-2h is incubated under the conditions of DEG C, then is air-cooled to room temperature, is that dental prosthesis is heat-treated, its mechanics for dental prosthesis
Performance is particularly significant, and aging temp is too low or too high, can all cause different phases (cobalt has two kinds of allotropes, Fcc and hcp)
Transformation, dental prosthesis is caused to occur splitting porcelain during porcelain on follow-up, collapse phenomena such as porcelain, excessive high hardness, ductility are deteriorated, from
And cause function that the alloy formula of this dental prosthesis designs can not be effectively played；Secondly, the heat treatment method enters one
It can guarantee that to step that nitrogen fully acts on chromium in dental prosthesis, prevents crisp phase constitution (the hcp phases or intermetallic of matrix cobalt
The σ brittlement phases of thing) generation, and stable dental prosthesis ductility；In addition, the heat treatment method can make equivalent molybdenum and tungsten with
Cobalt is dissolved to form hardening constituent, so as to play a part of the thermal coefficient of expansion of stable dental prosthesis；In addition, the heat treatment method can
Further separate out the molybdenum tungsten hardening constituent to be formed a small amount of, make the intensity enhancing of dental prosthesis again will not hardness it is too high.
In the present invention, the effect for the chemical constituent that the Co-based alloy powder contains is as follows：
The chemical composition cobalt contained in Co-based alloy powder of the present invention is basic metallic element, and playing solid solution, other are closed
The effect of gold.
The chemical composition chromium contained in Co-based alloy powder of the present invention, effect mainly strengthen the corrosion resistance of alloy
And intensity, but excessive chromium can make alloy become fragile, ductility reduction.
The chemical composition molybdenum contained in Co-based alloy powder of the present invention strengthens the strong of alloy by being acted synergistically with tungsten
Degree, hardness.
When the chemical composition W content contained in Co-based alloy powder of the present invention is 4-10wt%, alloy oxidation is hindered
Film generates, and makes alloy oxide film thinning, fine and close, enhancing cobalt-base alloys matrix and enamel coating gold porcelain adhesion；Secondly, the weight hundred of tungsten
When point content is more than 4wt%, itself and wait the molybdenum of percentage by weight to act synergistically to contribute to the linear expansion coefficient of stable alloy；By
After heat treatment, the tungsten and molybdenum that wait percentage by weight form second-phase strength phase, strengthen the intensity of cobalt-base alloys matrix.
The chemical composition nitrogen contained in Co-based alloy powder of the present invention, which can consume, easily makes matrix cobalt from the (modeling of Fcc phases
Property phase) the excessive chemical composition chromium that changes to σ phases (brittlement phase), Co-based alloy powder of the present invention is closed after processing
Golden material plasticity enhancing, hardness are unlikely to raise.
Compared with prior art, the invention has the advantages that：
Good fluidity, the particle diameter of Co-based alloy powder of the present invention be small and centralized particle diameter.Cobalt-based of the present invention
Co-base alloy material mechanical performance made from alloy powder can reach 5 types/type5 of the requirements of GB17168/ISO 22674, stretching
Intensity can reach 1326MPa, nonproportional cyclic straining can reach 948MPa；Modulus of elasticity reaches 206GPa, fracture elongation can
Reach 13.8%.Inventor is further improved to the preparation method of Co-based alloy powder, by a large amount of performing creative labours
It was found that during raw metal melts, added at twice using cobalt as matrix, relative to the preparation method of conventional method
(once adding cobalt), cobalt can be reduced during melt-processed due to being lost in caused by gasification by adding cobalt at twice, further
Improve the mechanical performance of Co-base alloy material prepared by Co-based alloy powder of the present invention in ground.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment, but protection scope of the present invention is unlimited
In specific embodiment.
Embodiment 1
The dosage of the raw metal of the embodiment 1 of table 1
| Raw material | Cobalt | Chromium | Molybdenum | Tungsten |
| Dosage (wt%) | 62 | 28 | 5 | 5 |
The preparation method of the present embodiment Co-based alloy powder, comprises the following steps：
(1) according to the dosage of table 1, chromium, molybdenum, tungsten and cobalt are taken, removes chromium, molybdenum, tungsten and the metal oxide layer on cobalt surface,
The chromium that metal oxide layer must be removed, the molybdenum, the tungsten and removal metal oxide layer of removal metal oxide layer that remove metal oxide layer
Cobalt；
(2) 35wt% of the cobalt of the removal metal oxide layer is added into smelting furnace as matrix, adds the removal
The chromium of metal oxide layer, after heating melting, the molybdenum and tungsten of the removal metal oxide layer are added, after complete melting, is added
After the remaining cobalt for removing metal oxide layer, completely melting, heating, the liquation that temperature is 1695 DEG C is obtained；
(3) using high pressure nitrogen as atomization gas, step (2) liquation and high pressure nitrogen are sprayed into atomisation tower, high pressure
The penetrating pressure of nitrogen is 3.4MPa, and the liquation is atomized in the presence of high pressure nitrogen, it is atomized after droplet；
It is 0.85MPa to keep being full of nitrogen in atomisation tower and keeping the pressure in atomisation tower in atomization process；
(4) droplet after atomization is cooled down, particle diameter carries out the pre-heat treatment for 10-63 μm of powder after collecting cooling, i.e.,
Obtain Co-based alloy powder.Wherein, the pre-heat treatment condition is：Through 320 DEG C of insulation 8h.
Co-based alloy powder described in the present embodiment is processed using 3D printing technique, comprised the following steps:
(1) 3D printing：Co-based alloy powder described in embodiment 1 is put into selective laser printer, laser work(is set
Rate 120W, 30 μm of powdering thickness, sweep speed 250mm/s, sweep span 0.06mm, obtains 3D printing sample；
(2) it is heat-treated：Step (1) the 3D printing sample is heat-treated together with substrate, the heat treatment includes
1.5h is incubated under the conditions of 1100 DEG C in nitrogen atmosphere, then is air-cooled to room temperature, obtains the Co-base alloy material of the present embodiment, gained cobalt
The chemical composition of base alloy material is as shown in table 2.
The chemical composition of the Co-base alloy material of 2 embodiment of table 1
Embodiment 2
The dosage of the raw metal of the embodiment 2 of table 3
| Raw material | Cobalt | Chromium | Molybdenum | Tungsten |
| Dosage (wt%) | 57 | 27 | 8 | 8 |
Co-based alloy powder described in the present embodiment is processed using 3D printing technique, comprised the following steps:
(1) according to the dosage of table 3, chromium, molybdenum, tungsten and cobalt are taken, removes chromium, molybdenum, tungsten and the metal oxide layer on cobalt surface,
The chromium that metal oxide layer must be removed, the molybdenum, the tungsten and removal metal oxide layer of removal metal oxide layer that remove metal oxide layer
Cobalt；
(2) 68wt% of the cobalt of the removal metal oxide layer is added into smelting furnace as matrix, adds the removal
The chromium of metal oxide layer, after heating melting, the molybdenum and tungsten of the removal metal oxide layer are added, after complete melting, is added
After the remaining cobalt for removing metal oxide layer, completely melting, heating, the liquation that temperature is 1660 DEG C is obtained；
(3) using high pressure nitrogen as atomization gas, step (2) liquation and high pressure nitrogen are sprayed into atomisation tower, high pressure
The penetrating pressure of nitrogen is 4.5MPa, and the liquation is atomized in the presence of high pressure nitrogen, it is atomized after droplet；
It is 0.55MPa to keep being full of nitrogen in atomisation tower and keeping the pressure in atomisation tower in atomization process；
(4) droplet after atomization is cooled down, particle diameter carries out the pre-heat treatment for 10-63 μm of powder after collecting cooling, i.e.,
Obtain Co-based alloy powder.Wherein, the pre-heat treatment is through 480 DEG C of insulation 1.5h.
Co-based alloy powder described in the present embodiment is processed using 3D printing technique, comprised the following steps:
(1) 3D printing：Co-based alloy powder described in the present embodiment is put into selective laser printer, laser work(is set
Rate 120W, 30 μm of powdering thickness, sweep speed 250mm/s, sweep span 0.06mm, obtains 3D printing sample；
(2) it is heat-treated：Step (1) the 3D printing sample is heat-treated with substrate, the heat treatment is included in nitrogen
Atmosphere is incubated 2h under the conditions of 850 DEG C in enclosing, then is air-cooled to room temperature, obtains the Co-base alloy material of the present embodiment, gained cobalt-base alloys
The chemical composition of material is as shown in table 4.
The chemical composition of the Co-base alloy material of 4 embodiment of table 2
Embodiment 3
The dosage of the raw metal of the embodiment 3 of table 5
| Raw material | Cobalt | Chromium | Molybdenum | Tungsten |
| Dosage (wt%) | 58.2 | 23 | 9.4 | 9.4 |
Co-based alloy powder described in the present embodiment is processed using 3D printing technique, comprised the following steps:
(1) according to the dosage of table 5, chromium, molybdenum, tungsten and cobalt are taken, removes chromium, molybdenum, tungsten and the metal oxide layer on cobalt surface,
The chromium that metal oxide layer must be removed, the molybdenum, the tungsten and removal metal oxide layer of removal metal oxide layer that remove metal oxide layer
Cobalt；
(2) 55wt% of the cobalt of the removal metal oxide layer is added into smelting furnace as matrix, adds the removal
The chromium of metal oxide layer, after heating melting, the molybdenum and tungsten of the removal metal oxide layer are added, after complete melting, is added
After the remaining cobalt for removing metal oxide layer, completely melting, heating, the liquation that temperature is 1680 DEG C is obtained；
(3) using high pressure nitrogen as atomization gas, step (2) liquation and high pressure nitrogen are sprayed into atomisation tower, high pressure
The penetrating pressure of nitrogen is 1.5MPa, and the liquation is atomized in the presence of high pressure nitrogen, it is atomized after droplet；
It is 0.3MPa to keep being full of nitrogen in atomisation tower and keeping the pressure in atomisation tower in atomization process；
(4) droplet after atomization is cooled down, particle diameter carries out the pre-heat treatment for 10-63 μm of powder after collecting cooling, i.e.,
Obtain Co-based alloy powder.Wherein, the pre-heat treatment is through 450 DEG C of insulation 1.5h.
Co-based alloy powder described in the present embodiment is processed using 3D printing technique, comprised the following steps:
(1) 3D printing：Co-based alloy powder described in the present embodiment is put into selective laser printer, laser work(is set
Rate 120W, 30 μm of powdering thickness, sweep speed 250mm/s, sweep span 0.06mm, obtains 3D printing sample；
(2) it is heat-treated：Step (1) the 3D printing sample is heat-treated with substrate, the heat treatment is included in nitrogen
Atmosphere is incubated 1h under the conditions of 850 DEG C in enclosing, then is air-cooled to room temperature, obtains the Co-base alloy material of the present embodiment, gained cobalt-base alloys
The chemical composition of material is as shown in table 6.
The chemical composition of the Co-base alloy material of 6 embodiment of table 3
Embodiment 4
The dosage of the raw metal of the embodiment 4 of table 7
| Raw material | Cobalt | Chromium | Molybdenum | Tungsten |
| Dosage (wt%) | 61 | 31.0 | 4.0 | 4.0 |
The preparation method of the present embodiment Co-based alloy powder, comprises the following steps：
(1) according to the dosage of table 7, chromium, molybdenum, tungsten and cobalt are taken, removes chromium, molybdenum, tungsten and the metal oxide layer on cobalt surface,
The chromium that metal oxide layer must be removed, the molybdenum, the tungsten and removal metal oxide layer of removal metal oxide layer that remove metal oxide layer
Cobalt；
(2) 35wt% of the cobalt of the removal metal oxide layer is added into smelting furnace as matrix, adds the removal
The chromium of metal oxide layer, after heating melting, the molybdenum and tungsten of the removal metal oxide layer are added, after complete melting, is added
After the remaining cobalt for removing metal oxide layer, completely melting, heating, the liquation that temperature is 1695 DEG C is obtained；
(3) using high pressure nitrogen as atomization gas, step (2) liquation and high pressure nitrogen are sprayed into atomisation tower, high pressure
The penetrating pressure of nitrogen is 3.4MPa, and the liquation is atomized in the presence of high pressure nitrogen, it is atomized after droplet；
It is 0.85MPa to keep being full of nitrogen in atomisation tower and keeping the pressure in atomisation tower in atomization process；
(4) droplet after atomization is cooled down, particle diameter carries out the pre-heat treatment for 10-63 μm of powder after collecting cooling, i.e.,
Obtain Co-based alloy powder.Wherein, the pre-heat treatment is through 250 DEG C of insulation 8h.
The preparation method of the Co-base alloy material of the present embodiment is the same as embodiment 1, the chemical group of obtained Co-base alloy material
Cheng Rubiao 8.
The chemical composition of the Co-base alloy material of 8 embodiment of table 4
Comparative example 1
The dosage of the raw metal of the comparative example 1 of table 9
| Raw material | Cobalt | Chromium | Molybdenum | Tungsten |
| Dosage (wt%) | 62 | 28 | 4 | 6 |
The preparation method of the Co-based alloy powder of this comparative example is the same as embodiment 1.
The preparation method of the Co-base alloy material of this comparative example is the same as embodiment 1, the chemical group of obtained Co-base alloy material
Cheng Rubiao 10.
The chemical composition of the Co-base alloy material of 10 comparative example of table 1
Comparative example 2
The dosage of the raw metal of the comparative example 2 of table 11
| Raw material | Cobalt | Chromium | Molybdenum | Tungsten |
| Dosage (wt%) | 62 | 28 | 5 | 5 |
The preparation method of this comparative example Co-based alloy powder, comprises the following steps：
(1) according to the dosage of table 11, chromium, molybdenum, tungsten and cobalt are taken, removes chromium, molybdenum, tungsten and the oxidation of the metal on cobalt surface
Layer, the chromium that metal oxide layer must be removed, the molybdenum for removing metal oxide layer, remove the tungsten of metal oxide layer and remove metal oxidation
The cobalt of layer；
(2) cobalt of the removal metal oxide layer is added into smelting furnace as matrix, adds the removal metal oxidation
The chromium of layer, after heating melting, the molybdenum and tungsten of the removal metal oxide layer are added, after complete melting, heating, obtaining temperature is
1695 DEG C of liquation；
(3) using high pressure nitrogen as atomization gas, step (2) liquation and high pressure nitrogen are sprayed into atomisation tower, high pressure
The penetrating pressure of nitrogen is 3.4MPa, and the liquation is atomized in the presence of high pressure nitrogen, it is atomized after droplet；
It is 0.85MPa to keep being full of nitrogen in atomisation tower and keeping the pressure in atomisation tower in atomization process；
(4) droplet after atomization is cooled down, particle diameter carries out the pre-heat treatment for 10-63 μm of powder after collecting cooling, i.e.,
Obtain Co-based alloy powder.Wherein, the pre-heat treatment is through 320 DEG C of insulation 8h.
The preparation method of the Co-base alloy material of this comparative example is the same as embodiment 1, the chemical group of obtained Co-base alloy material
Cheng Rubiao 12.
The chemical composition of the Co-base alloy material of 12 comparative example of table 2
The Co-based alloy powder performance test of embodiment 5
Test purpose：
Embodiment 1-4 and the Co-based alloy powder of comparative example 1 performance are tested.
Test result：
Co-based alloy powder performance test is as shown in table 13.
The performance test results of the Co-based alloy powder of table 13
Interpretation of result：As shown in Table 1, embodiment 1-4 Co-based alloy powder Hall flow velocity is in 17.5s/50g-28.6s/
In the range of 50g, therefore embodiment 1-4 Co-based alloy powder good fluidity, in the Co-based alloy powder of comparative example 1 due to molybdenum and
The content of tungsten differs and differs larger, and Hall flow velocity is 31.3s/50g, and the Co-based alloy powder mobility of comparative example 1 is relative
It is poor in embodiment 1-4 cobalt-base alloys；The D50 numerical value being distributed from powder size, embodiment 1-4 Co-based alloy powders
D50s of the D50 somewhat than the Co-based alloy powder of comparative example 1 is small, therefore embodiment 1-4 Co-based alloy powder integral particle particle diameter is relative
It is smaller in the overall particle diameter of the Co-based alloy powder of comparative example 1；In addition, from (D90-D10)/D50 result, embodiment 1-4
Co-based alloy powder particle diameter it is more narrower than the particle diameter distribution of the Co-based alloy powder of comparative example 1.It is it follows that of the present invention
The good fluidity of cobalt-base alloys, particle diameter is small and centralized particle diameter.
The Co-base alloy material performance test of embodiment 6
Test purpose：
Embodiment 1-4 and comparative example 1-2 Co-base alloy material performance are tested.
Test result：
Co-base alloy material performance test is as shown in table 14.
The Co-base alloy material the performance test results of table 14
Interpretation of result：As seen from the above table, the tensile strength of embodiment 1-4 Co-base alloy material, nonproportional cyclic straining
Can respectively be up to 1173MPa, more than 506MPa, the particularly tensile strength of the Co-base alloy material of embodiment 1 be 1326MPa,
206MPa；And the tensile strength and nonproportional cyclic straining of the Co-base alloy material of comparative example 1 respectively be only 887MPa,
468MPa, main cause are that the molybdenum that the Co-base alloy material of comparative example 1 contains and tungsten difference are larger, cause the cobalt-based of comparative example 1
The more difficult formation hardening constituent of alloy material；The fracture elongation 9.5-13.8% of embodiment 1-4 Co-base alloy material, hence it is evident that be more than
The fracture elongation of comparative example 1 and comparative example 2, showing embodiment 1-4 Co-base alloy material has good ductility；Implement
Example 1-4 modulus of elasticity is up to more than 190Gpa, bigger than comparative example 1-2 modulus of elasticity；The Co-base alloy material of comparative example 2 by
It is disposable addition cobalt in preparation process, causes the loss of cobalt in process to increase, so as to cause in comparative example 2
The overall mechanical properties of Co-base alloy material are deteriorated.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously
Can not therefore it be construed as limiting the scope of the patent.It should be pointed out that come for one of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
- A kind of 1. Co-based alloy powder, it is characterised in that by weight percentage, the Co-based alloy powder by following chemistry into It is grouped into：22-32% chromium, 4-10% molybdenums, 4-10% tungsten, 0-1% silicon, 0-0.75% iron, 0-0.35% carbon, 0.05-0.2% nitrogen, it is remaining Measure as cobalt, wherein, molybdenum is identical with the percentage by weight of tungsten in the Co-based alloy powder.
- 2. Co-based alloy powder according to claim 1, it is characterised in that by weight percentage, the cobalt-based alloy powder End is made up of following chemical composition：22-28% chromium, 4.8-7.5% molybdenums, 4.8-7.5% tungsten, 0-1% silicon, 0-0.75% iron, 0-0.35% carbon, 0.05- 0.1% nitrogen, surplus are cobalt, wherein, molybdenum is identical with the percentage by weight of tungsten in the Co-based alloy powder.
- 3. according to any one of the claim 1-2 Co-based alloy powders, it is characterised in that the particle diameter of the Co-based alloy powder For 10-63 μm.
- 4. a kind of preparation method of the Co-based alloy powder as described in claim any one of 1-3, it is characterised in that including following step Suddenly：(1) raw metal of the Co-based alloy powder is taken, the raw metal is chromium, molybdenum, tungsten and cobalt, removes the metal The metal oxide layer on raw material surface, the chromium that metal oxide layer must be removed, the molybdenum for removing metal oxide layer, remove metal oxide layer Tungsten and the cobalt for removing metal oxide layer；(2) 30-70wt% of the cobalt of the removal metal oxide layer is added into smelting furnace as matrix, adds the removal gold Belong to the chromium of oxide layer, after heating melting, add the molybdenum and tungsten of the removal metal oxide layer, after complete melting, add surplus The cobalt of remaining removal metal oxide layer, completely after melting, heating, obtains liquation；(3) using high pressure nitrogen as atomization gas, step (2) liquation is sprayed into atomisation tower and is atomized, after atomized Droplet；Keep being full of nitrogen in atomisation tower in atomization process and keep the pressure in atomisation tower to be less than 1 atmospheric pressure；(4) droplet after atomization is cooled down, collects the powder after cooling and carry out the pre-heat treatment, produce the cobalt-based alloy powder End.
- 5. the preparation method of Co-based alloy powder according to claim 4, it is characterised in that step (4) described the pre-heat treatment Including：Powder after the cooling is incubated 1-12h under conditions of 300-500 DEG C.
- 6. according to the preparation method of any one of the claim 4-5 Co-based alloy powders, it is characterised in that step (3) is described It is 0.1-0.9MPa that the pressure in atomisation tower is kept in atomization process.
- 7. according to the preparation method of any one of the claim 4-5 Co-based alloy powders, it is characterised in that institute in step (3) The penetrating pressure for stating high pressure nitrogen is 1-5MPa, and the temperature of liquation described in step (2) is 1650-1700 DEG C.
- 8. a kind of dental prosthesis, it is characterised in that its preparing raw material includes any one of the claim 1-3 cobalt-based alloy powder End.
- 9. a kind of preparation method of dental prosthesis as claimed in claim 8, it is characterised in that comprise the following steps：(1) 3D printing：3D printing is carried out by raw material of the cobalt billon powder described in claim any one of 1-3, the 3D is beaten The condition of print includes：Laser power is 50-180W, sweep speed 80-400mm/s, sweep span 0.06-0.12mm, is obtained 3D printing dummy；(2) it is heat-treated：Step (1) the 3D printing dummy is placed in nitrogen atmosphere, protected under conditions of 800-1150 DEG C Warm 1-2h, then room temperature is air-cooled to, obtain the dental prosthesis.
- 10. the preparation method of dental prosthesis according to claim 9, it is characterised in that the heat treatment is：By step (1) the 3D printing dummy is placed in nitrogen atmosphere, and 1.5h is incubated under the conditions of 1100 DEG C, then is air-cooled to room temperature, obtains dentistry Dummy.
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| CN111054915A (en) * | 2019-12-17 | 2020-04-24 | 南通金源智能技术有限公司 | 3D printing metal powder for dental fixed and movable restoration and preparation method thereof |
| CN111172432A (en) * | 2020-01-10 | 2020-05-19 | 四川大学 | High-strength high-toughness cobalt-chromium-molybdenum-tungsten alloy manufactured based on laser additive and preparation method thereof |
| CN111996415B (en) * | 2020-07-02 | 2021-04-27 | 中怡(深圳)医疗科技集团有限公司 | Cobalt-chromium alloy biological material and preparation method thereof |
| CN111996415A (en) * | 2020-07-02 | 2020-11-27 | 俞光锋 | Cobalt-chromium alloy biological material and preparation method thereof |
| CN112795815B (en) * | 2020-12-31 | 2021-12-14 | 广州湘龙高新材料科技股份有限公司 | Cobalt-chromium-molybdenum-tungsten-silicon alloy powder |
| CN112809011A (en) * | 2020-12-31 | 2021-05-18 | 广州湘龙高新材料科技股份有限公司 | Preparation method of cobalt-chromium-molybdenum-tungsten-silicon alloy |
| CN112795815A (en) * | 2020-12-31 | 2021-05-14 | 广州湘龙高新材料科技股份有限公司 | Cobalt-chromium-molybdenum-tungsten-silicon alloy powder |
| CN116411205A (en) * | 2023-03-10 | 2023-07-11 | 上海中洲特种合金材料股份有限公司 | Cobalt-base alloy powder for build-up welding of chain saw guide plate |
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