CN101696478A - Lead-free copper-based alloy powder material and preparation method thereof - Google Patents
Lead-free copper-based alloy powder material and preparation method thereof Download PDFInfo
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- CN101696478A CN101696478A CN200910154060A CN200910154060A CN101696478A CN 101696478 A CN101696478 A CN 101696478A CN 200910154060 A CN200910154060 A CN 200910154060A CN 200910154060 A CN200910154060 A CN 200910154060A CN 101696478 A CN101696478 A CN 101696478A
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- 239000010949 copper Substances 0.000 title claims abstract description 76
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 67
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000000843 powder Substances 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 43
- 239000000956 alloy Substances 0.000 title claims abstract description 38
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011135 tin Substances 0.000 claims abstract description 31
- 239000011701 zinc Substances 0.000 claims abstract description 29
- 229910052718 tin Inorganic materials 0.000 claims abstract description 27
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims description 27
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- RIRXDDRGHVUXNJ-UHFFFAOYSA-N [Cu].[P] Chemical compound [Cu].[P] RIRXDDRGHVUXNJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000889 atomisation Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 4
- 229910000906 Bronze Inorganic materials 0.000 claims description 3
- 238000003723 Smelting Methods 0.000 claims description 3
- 230000003064 anti-oxidating effect Effects 0.000 claims description 3
- 239000010974 bronze Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012634 fragment Substances 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 238000005272 metallurgy Methods 0.000 claims 4
- 239000011133 lead Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005245 sintering Methods 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 238000005452 bending Methods 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000012254 powdered material Substances 0.000 description 3
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 210000002345 respiratory system Anatomy 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000001079 digestive effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000035987 intoxication Effects 0.000 description 1
- 231100000566 intoxication Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 210000001539 phagocyte Anatomy 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012372 quality testing Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to copper-based alloy powder, in particular to lead-free copper-based alloy powder used for manufacturing mechanical parts, automobile bearings and the like, and a preparation method thereof. A lead-free copper-based alloy powder material consists of the following components in percentage by weight: 87 to 89 percent of Cu, 5 to 7 percent of Sn, and 5 to 7 percent of Zn; and the total weight of the Cu, the Sn and the Zn is 100 percent. The preparation method realizes no lead by blending the content of copper, tin and zinc, and saves cost; and the wear resistance and bonding strength of a bearing material produced by sintering the alloy powder can be equal to or even superior to those of a sintered copper-lead bimetallic material. The lead-free copper-based alloy powder material is a novel material capable of replacing the copper-lead bimetallic material, is mainly used in aspects such as the mechanical parts, automobile bearings and the like, improves the influence of a lead-containing metal material on the environment in the sintering process, and avoids lead-containing rejected materials causing negative effect on the environment.
Description
Technical field
The present invention relates to a kind of copper-base alloy powder, relate in particular to lead-free copper-based alloy powder that is used for manufacturing mechanical components, automobile bearing etc. and preparation method thereof.
Background technology
The copper-base alloy powder of traditional manufacturing bearing bush material is made up of copper, lead, tin, zinc (or phosphorus), owing to contain lead, toxic to human body, environment there is pollution, plumbous and its compound is respectively organized all toxic to human body, route of intoxication can suck its steam or dust by respiratory tract, and phagocytic cell brings to blood rapidly with it in the respiratory tract then; Or absorb through digestive tube, enter circulation of blood and poison.Regulation in European Union's " some objectionable impurities is used in restriction in electric, the electronics ", from July 1st, 2006, the new electronics and the electric installation that devote market must not contain objectionable impuritiess such as lead.Simultaneously; along with people to improving day by day of environmental protection consciousness and self health requirements and popularizing of mechanize traffic, production and daily life instrument; people recognize the pollution to people and environment of refuse that various tool in use produced; people wish that the various parts of institute's tool using all are environmentally friendly machines; therefore, seeking lead in the copper-base alloy powder that a kind of nontoxic constituent element replaces traditional manufacturing bush material, to become development inevitable.
Chinese invention patent application (application number 200810072435.1, applying date 2008.12.23) a kind of novel copper-base alloy powder is disclosed, its prescription is formed: bismuth 1%～15%, tin 0.5%～10%, zinc 0.3%～15%, surplus are copper.Its manufacture method is: earlier copper is put into high-frequency melting furnace, after the fusing, put into tin, bismuth, zinc more successively, after all melting and mixing, be poured in the filter bag, through the ejection of V-arrangement nozzle, and be ground into powder by High-Pressure Water, drying gets final product.This patent is because this copper-base alloy powder replaces lead with bismuth, and not leaded, to the human body toxicological harmless, environmentally safe is a kind of environment-friendly type copper-base alloy powder.But bismuth is a rare metal, has increased a large amount of costs undoubtedly.
Summary of the invention
In order to solve the technological deficiency that existing leaded copper base alloy exists, an object of the present invention is to provide a kind of lead-free copper-based alloy powder material,, realized that product is unleaded by the content of allotment copper, tin, phosphorus, provide cost savings simultaneously, have good wear resistance and bonding strength.Another object of the present invention provides the preparation method of above-mentioned lead-free copper-based alloy powder material.
In order to realize first above-mentioned purpose, the present invention has adopted following technical scheme:
A kind of lead-free copper-based alloy powder material, this alloy powder material is made of following composition by weight percentage: Cu 87～89%, Sn 5～7%, Zn 5～7%; The gross weight of above-mentioned Cu, Sn, Zn is 100%.
As preferably, this alloy powder material is made of following composition by weight percentage: Cu 87～89%, Sn 5～6%, Zn 5～6%; The gross weight of above-mentioned Cu, Sn, Zn is 100%.
Preferred as other, this alloy powder material is made of following composition by weight percentage: Cu 87～89%, Sn 6～7%, Zn 5～7%; The gross weight of above-mentioned Cu, Sn, Zn is 100%.
In order to realize second above-mentioned purpose, the present invention has adopted following technical scheme:
The preparation method of lead-free copper-based alloy powder body material, this method adopt intermediate frequency (IF) smelting equipment to carry out melting, produce high pressure gas by air compressor machine metal liquid stream is atomized, and specifically comprise the steps:
(1) batching: prepare copper, tin and zinc according to formula ratio;
(2) reinforced melting:
1. baker slowly transfers to 40kw with intermediate frequency power, transfers to 60kw after 20 minutes, transfers to 100kw baker when furnace bottom is rubescent after 20 minutes and just finishes;
2. order of addition(of ingredients): intermediate frequency power is transferred to 200kw, add copper earlier, to fusing fully, add tin, zinc then successively;
3. after treating that all raw materials all melt, intermediate frequency power is transferred to 100kw, IF-FRE is transferred to 800HZ, overheated 5 minutes, temperature of superheat is 100-250 ℃;
4. add little charcoal lump, the part copper liquid that contacts with air was carried out antioxidation treatment after 2 minutes, charcoal is pulled out;
5. add the glass fragment copper liquid is dragged for the slag processing, intermediate frequency power should be transferred to 20～30kw when adding glass, frequency transfers to 700-750HZ;
6. slag is dragged for clean after, repeating step 3. with step 4.;
(3) atomizing operation:
Leaking the footpath in the middle of the atomizing operation is 3.0-5.0mm, and temperature control is as follows in the atomization process:
A, intermediate frequency power can be transferred to 140kw when initially atomizing;
When remaining 2/3 bronze medal liquid in b, the flue, power is transferred to 100kw;
Copper liquid remains and power was transferred to below the 40kw in 1/2 o'clock in c, the stove;
Copper liquid remains and power was transferred to below the 10kw in 1/3 o'clock in d, the stove;
(4) cool off, sieve after atomizing finishes and promptly can obtain described copper base alloy powder body material.
As preferred version, when the atomizing operation, the copper liquid of pouring out for the first time needs to catch with the iron wooden dipper as cleaning converter nose usefulness, adds when treating down the stove melting.
As preferred version, in the atomization process, copper liquid height is not less than 15cm in the maintenance tundish.
As preferred version, the 2. middle phosphor-copper that adds of step, phosphor-copper content is less than 0.05%.
The present invention is owing to adopted above technical scheme, by the content of allotment copper, tin, zinc, realized that product is unleaded, provide cost savings simultaneously, use this product agglomerating bearing materials, its wear resistance and bonding strength can reach even be better than sintering copper-lead bimetallic material.The present invention is mainly used in aspects such as component of machine, automobile bearing for can replace the bimetallic type material of copper-lead, improves the influence to environment in sintering process of leaded metallic substance, avoids leaded waste products that environment is caused adverse consequences.
Embodiment
Below in conjunction with embodiment specific embodiments of the present invention is made a detailed explanation.
Embodiment 1
One, formula for a product
1, raw material
Copper: the copper billet of 99.90% above purity or copper powder (requiring lead tolerance) less than 0.01%; Tin: tin slab or the glass putty (require lead tolerance less than 0.01%) of purity more than 99.90%; Zinc: the zinc ingot metal (require foreign matter content be less than 0.03%) of purity more than 99.95%.
2, prescription (pressing 200kg/ calculates)
The weight percent of copper: 88%, the weight percent of tin: 6%, the weight percent of zinc: 6%;
Copper: 200 * 0.88=176 (kg)
Tin: 200 * 0.60=12 (kg)
Zinc: 200 * 0.60=12 (kg)
Phosphor-copper: 200 * 0.0003 ÷ 0.14=0.43 (kg)
Annotate: for increasing copper liquid flowing property, the special a certain amount of phosphor-copper (content is less than 0.05%, and the content of phosphorus can be ignored) that adds.
3, production unit and technology
Equipment: this product adopts intermediate frequency (IF) smelting equipment to carry out melting, produces high pressure gas by air compressor machine metal liquid stream is smashed.
Technology: its detailed process flow is as follows:
(1) batching
Raw material weight carries out every raw material and weighs on the adhere rigidly to charger sheet, after material has been joined, surplus stock is examined heavily, and the remaining weight of each raw material and answer surplus stock weight to compare is confirmed to feed intake after errorless.
(2) reinforced melting
1. baker slowly transfers to 40kw with intermediate frequency power, transfers to 60kw after 20 minutes, transfers to 100kw baker when furnace bottom is rubescent after 20 minutes and just finishes.
2. order of addition(of ingredients): intermediate frequency power is transferred to 200kw, add copper billet or copper powder earlier, to fusing fully, add tin, zinc, phosphor-copper successively.
3. after treating that all raw materials all melt, intermediate frequency power is transferred to 100kw, IF-FRE is transferred to 800HZ, overheated 5 minutes, temperature of superheat is 100-250 ℃.
4. add 2cm
3About the size charcoal lump, the part copper liquid that contacts with air was carried out antioxidation treatment after 2 minutes, charcoal is pulled out.
5. add the glass fragment copper liquid is dragged for the slag processing, intermediate frequency power should be transferred to 20-30kw when noting adding glass, frequency transfers to 700-750HZ.
6. slag is dragged for clean after, repeating step 3., content 4..
(3) atomizing operation
1. main technique, technical parameter
Middle leakage footpath is 3.0-5.0mm; Form of nozzle: adopt annular distance formula nozzle
Injection diameter: 2.0-4.0mm; Nozzle hole number: 4-10
Nozzle angle: 10-24 degree; Air compressor machine air pressure: 0.68-1.10MP.
When 2. atomizing operation, the copper liquid of pouring out for the first time needs to catch with the iron wooden dipper as cleaning converter nose usefulness, adds when treating down the stove melting;
3. in the atomization process, keep that copper liquid height is not less than 15cm in the tundish constantly;
4. temperature method of controlling in the atomization process:
A, intermediate frequency power can be transferred to 140kw when initially atomizing;
Residue transfers to 100kw with power during 2/3 bronze medal liquid in b, the flue, and notes observing copper liquid color, if copper liquid has and emits white cigarette phenomenon to produce in the stove, needs power is transferred to more low value;
Copper liquid remains and power was transferred to below the 40kw in 1/2 o'clock in c, the stove;
Copper liquid remains and power was transferred to below the 10kw in 1/3 o'clock in d, the stove;
Annotate: above temperature-controlled process specifically is foundation with the law of conservation of energy, formulates in conjunction with actual production equipment and production technique, and this method is fit to the general atomization process of 6-6-0 powder, and the diameter of leting slip a remark (3.0-5.0mm) air pressure is (0.55-1.10MP).
(4) screening, packing, warehouse-in
1. with powder on request the order number sieve;
2. close batch good powder and keep sample and send quality testing department, pack, put in storage after showing verification of conformity after testing.
Embodiment 1 described product agglomerating bearing materials use properties examining report
| The powdered material performance | Loose density: 〉=4.95g/cm 3Mobile :≤15s/50g |
| Bending strength | ??200～250Mpa |
| Compressibility | ??6.5～7.8g/cm 3 |
| Wear resistance | Frictional coefficient: 0.09 (lubricant is arranged)～0.16 (unlubricated dose) |
| Corrosion resistance nature | Corrosion speed in the seawater: 0.03mm/ |
Embodiment 2
The lead-free copper-based alloy powder body material, its prescription is as follows:
Cu?87.5％、Sn?6.5％、Zn?6.0％
Embodiment 2 described product agglomerating bearing materials use properties examining reports
| The powdered material performance | Loose density: 〉=4.95g/cm 3Mobile :≤15s/50g |
| Bending strength | ??200～300Mpa |
| Compressibility | ??6.0～7.8g/cm 3 |
| Wear resistance | Frictional coefficient: 0.09 (lubricant is arranged)～0.16 (unlubricated dose) |
| Corrosion resistance nature | Corrosion speed in the seawater: 0.03mm/ |
The preparation method of embodiment 2 such as embodiment 1.
Embodiment 3
The lead-free copper-based alloy powder body material, its prescription is as follows:
Cu?88.5％、Sn?6.0％、Zn?5.5％。
Embodiment 3 described product agglomerating bearing materials use properties examining reports
| The powdered material performance | Loose density: 〉=4.95g/cm 3Mobile :≤15s/50g |
| Bending strength | ??250～300Mpa |
| Compressibility | ??6.5～7.8g/cm 3 |
| Wear resistance | Frictional coefficient: 0.09 (lubricant is arranged)～0.16 (unlubricated dose) |
| Corrosion resistance nature | Corrosion speed in the seawater: 0.03mm/ |
The preparation method of embodiment 3 such as embodiment 1.
Comparative Examples 1
Copper-lead bimetallic alloy powder body material, its prescription is as follows:
Comparative Examples 1 described product agglomerating bearing materials use properties examining report
| Bending strength | ??470～565Mpa |
| Tensile property | ??5～18％ |
| Wear resistance | ??0.08～0.14 |
| Corrosion resistance nature | Sea-water corrosion speed 0.08mm/ |
By above more as can be seen, wear resistance of the present invention and bonding strength can reach even be better than sintering copper-lead bimetallic material.
Claims (8)
1. lead-free copper-based alloy powder material is characterized in that this alloy powder material is made of following composition by weight percentage:
Cu??????87～89％
Sn??????5～7％
Zn??????5～7％；
The gross weight of above-mentioned Cu, Sn, Zn is 100%.
2. a kind of lead-free copper-based alloy powder material according to claim 1 is characterized in that this alloy powder material is made of following composition by weight percentage:
Cu??????87～89％
Sn??????5～6％
Zn??????5～6％；
The gross weight of above-mentioned Cu, Sn, Zn is 100%.
3. a kind of lead-free copper-based alloy powder material according to claim 1 is characterized in that this alloy powder material is made of following composition by weight percentage:
Cu??????87～89％
Sn??????6～7％
Zn??????5～7％；
The gross weight of above-mentioned Cu, Sn, Zn is 100%.
4. according to the preparation method of claim 1 or 2 or 3 described lead-free copper-based alloy powder materials, it is characterized in that this method adopts intermediate frequency (IF) smelting equipment to carry out melting, produce high pressure gas by air compressor machine metal liquid stream is atomized, specifically comprise the steps:
(1) batching: prepare copper, tin and zinc according to formula ratio;
(2) reinforced melting:
1. baker slowly transfers to 40kw with intermediate frequency power, transfers to 60kw after 20 minutes, transfers to 100kw baker when furnace bottom is rubescent after 20 minutes and just finishes;
2. order of addition(of ingredients): intermediate frequency power is transferred to 200kw, add copper earlier, to fusing fully, add tin, zinc then successively;
3. after treating that all raw materials all melt, intermediate frequency power is transferred to 100kw, IF-FRE is transferred to 800HZ, overheated 5 minutes, temperature of superheat is 100-250 ℃;
4. add little charcoal lump, the part copper liquid that contacts with air was carried out antioxidation treatment after 2 minutes, charcoal is pulled out;
5. add the glass fragment copper liquid is dragged for the slag processing, intermediate frequency power should be transferred to 20～30kw when adding glass, frequency transfers to 700-750HZ;
6. slag is dragged for clean after, repeating step 3. with step 4.;
(3) atomizing operation:
Leaking the footpath in the middle of the atomizing operation is 3.0-5.0mm, and temperature control is as follows in the atomization process:
A, intermediate frequency power can be transferred to 140kw when initially atomizing;
When remaining 2/3 bronze medal liquid in b, the flue, power is transferred to 100kw;
Copper liquid remains and power was transferred to below the 40kw in 1/2 o'clock in c, the stove;
Copper liquid remains and power was transferred to below the 10kw in 1/3 o'clock in d, the stove;
(4) cool off, sieve after atomizing finishes and promptly can obtain described copper base alloy powder body material.
5. the preparation method of powder used in metallurgy lead-free copper-based alloy powder body material according to claim 4, when it is characterized in that atomizing operation, the copper liquid of pouring out for the first time needs to catch with the iron wooden dipper as cleaning converter nose usefulness, adds when treating down the stove melting.
6. the preparation method of powder used in metallurgy lead-free copper-based alloy powder body material according to claim 4 is characterized in that in the atomization process, and copper liquid height is not less than 15cm in the maintenance tundish.
7. the preparation method of powder used in metallurgy lead-free copper-based alloy powder body material according to claim 4 is characterized in that the technology, the technical parameter that atomize are as follows:
Form of nozzle: adopt annular distance formula nozzle
Injection diameter: 2.0-4.0mm
Nozzle hole number: 4-10
Nozzle angle: 10-24 degree
Air compressor machine air pressure: 0.68-1.10MP.
8. the preparation method of powder used in metallurgy lead-free copper-based alloy powder body material according to claim 4 is characterized in that adding phosphor-copper during step 2., and phosphor-copper content is less than 0.05%.
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| CN2009101540608A CN101696478B (en) | 2009-10-23 | 2009-10-23 | Lead-free copper-based alloy powder material and preparation method thereof |
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| CN2009101540608A CN101696478B (en) | 2009-10-23 | 2009-10-23 | Lead-free copper-based alloy powder material and preparation method thereof |
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| CN112746196A (en) * | 2020-12-30 | 2021-05-04 | 河北大洲智造科技有限公司 | Lead-free multi-component bronze alloy spherical powder material and preparation method and application thereof |
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| CN112746196A (en) * | 2020-12-30 | 2021-05-04 | 河北大洲智造科技有限公司 | Lead-free multi-component bronze alloy spherical powder material and preparation method and application thereof |
| CN114351508A (en) * | 2022-01-24 | 2022-04-15 | 沈勇 | Pulp molding die and pulp molding device |
| CN114351508B (en) * | 2022-01-24 | 2024-01-30 | 沈勇 | Pulp molding die and pulp molding device |
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