US20220062985A1 - Porous silver powders and method for preparing the same - Google Patents
Porous silver powders and method for preparing the same Download PDFInfo
- Publication number
- US20220062985A1 US20220062985A1 US17/398,012 US202117398012A US2022062985A1 US 20220062985 A1 US20220062985 A1 US 20220062985A1 US 202117398012 A US202117398012 A US 202117398012A US 2022062985 A1 US2022062985 A1 US 2022062985A1
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- United States
- Prior art keywords
- silver powder
- powder
- porous silver
- alloy
- alloying element
- 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.)
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 54
- 239000004332 silver Substances 0.000 title claims abstract description 54
- 239000000843 powder Substances 0.000 title claims description 56
- 238000000034 method Methods 0.000 title description 11
- 239000002245 particle Substances 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims description 96
- 239000000956 alloy Substances 0.000 claims description 96
- 238000005275 alloying Methods 0.000 claims description 63
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000005530 etching Methods 0.000 claims description 26
- 238000005266 casting Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- 238000002074 melt spinning Methods 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000003637 basic solution Substances 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 13
- 230000001954 sterilising effect Effects 0.000 abstract description 13
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 13
- 239000002904 solvent Substances 0.000 description 12
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
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- 230000007423 decrease Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000007712 rapid solidification Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
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- 238000007906 compression Methods 0.000 description 3
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- 238000011156 evaluation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
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- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- -1 and preferably Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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- 230000008901 benefit Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
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- 230000002070 germicidal effect Effects 0.000 description 1
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- 238000005058 metal casting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000037368 penetrate the skin Effects 0.000 description 1
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- 230000002688 persistence Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 230000000241 respiratory effect Effects 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 210000004927 skin cell Anatomy 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- B22F1/0018—
-
- B22F1/0081—
-
- 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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
-
- 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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
-
- 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
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
-
- 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
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- 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
- C22C1/0466—Alloys based on noble metals
-
- 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
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/08—Metallic powder characterised by particles having an amorphous microstructure
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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
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
-
- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
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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
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
- B22F2304/056—Particle size above 100 nm up to 300 nm
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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
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
- B22F2304/058—Particle size above 300 nm up to 1 micrometer
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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
- B22F2304/00—Physical aspects of the powder
- B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
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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
- B22F2304/00—Physical aspects of the powder
- B22F2304/15—Millimeter size particles, i.e. above 500 micrometer
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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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Definitions
- the present invention relates to porous silver powder and a preparation method thereof. More specifically, the present invention relates to porous silver powder that is easy to prepare, improves a sterilization effect because an specific surface area and a porosity are easily adjustable, improves electrical conductivity when molded as sintered body, contributes to reducing use of expensive silver when applied in various industrial fields, thus achieving price competitiveness, and is harmless to the human body because a particle size is adjustable to prevent the porous silver powder from being absorbed into the body; and a preparation method thereof.
- Silver (Ag) powder has drawn much attention, for example, as a material of a solar cell, an adhesive material of a semiconductor chip package, a material of a touch panel pattern, a filler material of a vehicle product, medical and biomaterials, etc. in various industrial fields.
- Nano ink has been applied for various purposes in the field of solar cells, sensors, touch screens, flexible display, etc., and is used in the form of conductive ink, dielectric ink, or the like.
- ink containing silver (Ag) is still expensive and is limited in exhibiting desired performance. Accordingly, research has been conducted on using inexpensive copper instead of silver but an additional process is needed to maintain an inert gas environment so as to prevent oxidation of copper in a sintering process, thereby increasing manufacturing costs.
- a silver (Ag)-tin (Sn)-based alloy including low-melting-point metals is applied to conductive paste or ink but electrical conductivity decreases significantly due to generation of an intermetallic compound of silver (Ag) and tin (Sn).
- nano powder is formed to a very small size of less than 100 nm and thus may penetrate the skin, thus causing adverse health effects, and is not likely to be discharged from the body when absorbed into the body due to the very small size.
- silver nano powder when silver nano powder is applied in a medical or bio field, the silver nano powder may be harmful to the human body.
- porous silver powder which is easy to prepare, improves a sterilization effect because an specific surface area and porosity are easy to adjust, increases electrical conductivity when molded as sintered body, contributes to reducing use of expensive silver when applied in various industrial fields, thus achieving price competitiveness, and is harmless to the human body because a particle size is adjustable to prevent the porous silver powder from being absorbed into the body, and a preparation method thereof are required.
- the present invention is directed to providing porous silver powder that is easy to prepare, improves a sterilization effect because an specific surface area and a porosity are easily adjustable, improves electrical conductivity when molded as sintered body, contributes to reducing use of expensive silver when applied to various industrial fields, thereby securing price competitiveness, and is harmless to the human body because a particle size is adjustable to prevent the porous silver powder from being absorbed into the body; and a preparation method thereof.
- the present invention provides a porous silver powder, wherein pores are formed by etching alloy powder containing silver (Ag) and an alloying element other than silver (Ag) with an acid solution or a basic solution to remove at least part of the alloying element.
- the present invention provides the porous silver powder, wherein residual content of the alloying element is 0.5 to 3% by weight based on the total weight of the porous silver powder.
- the present invention provides the porous silver powder, wherein the alloying element comprises at least one material selected from the group consisting of silicon (Si), bismuth (Bi), germanium (Ge), copper (Cu), iron (Fe), nickel (Ni), chromium (CR), and cobalt (Co).
- the alloying element comprises at least one material selected from the group consisting of silicon (Si), bismuth (Bi), germanium (Ge), copper (Cu), iron (Fe), nickel (Ni), chromium (CR), and cobalt (Co).
- the present invention provides the porous silver powder, wherein the alloying element further comprises at least one transition metal element.
- the present invention provides the porous silver powder, wherein the basic solution comprises at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, an ammonia solution, zinc chloride, tetramethyl ammonium hydroxide (TMAH), and ethyltrimethyl ammonium hydroxide (ETMAH).
- the basic solution comprises at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, an ammonia solution, zinc chloride, tetramethyl ammonium hydroxide (TMAH), and ethyltrimethyl ammonium hydroxide (ETMAH).
- the present invention provides the porous silver powder, wherein an average particle size D 50 of the porous silver powder is in a range of 100 to 20,000 nm.
- the present invention provides the porous silver powder, wherein a porosity is in a range of 5 to 50% and a specific surface area (BET) is in a range of 4.0 to 8.0 m 2 /g.
- the present invention provides the porous silver powder, wherein an atomic ratio between silver (Ag) and the alloying element contained in the alloy powder is 1:9 or 8:2.
- the present invention provides a preparation method of the porous silver powder, comprising: preparing a master alloy containing silver (Ag) and an alloying element other than silver (Ag); manufacturing an alloy casting by dissolving and rapidly solidifying the master alloy; grinding the alloy casting into alloy powder; and removing at least part of the alloying element by etching the alloy powder with an acid solution or a basic solution.
- the present invention provides the preparation method of claim 9 , wherein the rapidly solidifying of the master alloy is carried out by melt spinning, wherein, in the melt spinning, an average cooling rate is 10 6 to 10 8 ° C./sec.
- FIG. 1 is a flowchart of a preparation method of porous silver powder according to the present invention
- FIG. 2 illustrates a device for rapidly solidifying porous silver powder by melt spinning, according to the present invention
- FIGS. 3A and 3B show surfaces of porous silver powder of Example 1 of the present invention before and after etching, observed using a field emission scanning electron microscope (FE-SEM);
- FIGS. 4A and 4B show surfaces of porous silver powder of Example 2 of the present invention before and after etching, observed using the FE-SEM;
- FIGS. 5A and 5B show surfaces of porous silver powder of Example 3 of the present invention before and after etching, observed using the FE-SEM;
- FIGS. 6A and 6B show cross sections of the porous silver powder of Example 1 of the present invention before and after etching, observed using the FE-SEM;
- FIG. 7 schematically illustrates a process of compressing porous silver powder using a mold, according to an embodiment of the present invention.
- Porous silver powder according to the present invention may be formed in a porous structure by a chemical method. That is, the porous silver powder may be formed of alloy powder of a binary or higher system including silver (Ag) and an alloying element other than silver (Ag), and specifically, multiple pores may be formed on a surface or the inside of the alloy powder by removing at least part of the alloying element by etching the alloy powder with an acid solvent or a basic solvent, and preferably, a polar solvent such as the basic solvent.
- the etching of the alloy powder performed to form pores in the porous silver powder refers to forming pores in the alloy powder by dissolving the alloying element from the alloy powder with an acid solution or a basic solution and extracting the dissolved alloying element with a solvent.
- a porosity i.e., a ratio of total volume of pores to total volume of the porous silver powder, may be easily adjusted by adjusting the content of the alloying element in the alloy powder excluding silver (Ag) during the preparation of the alloy powder or adjusting a cooling rate when a molten alloy is cooled to prepare the alloy powder.
- the porosity increases as the content of the alloying element contained in the alloy powder excluding silver (Ag), i.e., the content of the alloying element in the pores in the alloy powder from which the alloying element is extracted and removed using the solvent during the etching of the alloy powder, increases or increases as a cooling rate of the molten alloy decreases during the cooling of the molten alloy because the alloying element is removed during the etching of the alloy powder due to the growth of crystal grains due to the alloying element other than silver (Ag).
- the porous silver powder according to the present invention may have a porosity of 5 to 50% and thus particularly have a specific surface area (BET) of 4.0 to 8.0 m 2 /g and preferably 5.0 to 6.0 m 2 /g.
- BET specific surface area
- a surface area of the porous silver powder is insufficient and thus a sterilization effect, an antibacterial effect, an antifungal effect, an antiviral effect or the like may decrease, and a melting point of a metal may increase due to a reduction of the amount of surface energy due to the insufficient surface area of the porous silver powder and thus a sintering process should be performed under relatively high pressure and at relatively high temperature, e.g., a temperature higher than 300° C., when sintered body is formed of the porous silver powder, thus increasing manufacturing time and costs.
- Part of the alloying element may remain when the porous silver powder according to the present invention is etched, thus improving some physical properties of the porous silver powder, and the residual content of the alloying element may be 0.5 to 3% by weight based on the total weight of the porous silver powder.
- the remaining alloying element improves dislocation density of the porous silver powder and thus overall mechanical properties, such as strength and durability, of the porous silver powder may increase, thereby maintaining the shape of the porous silver powder for a long time.
- overall mechanical properties, such as strength and durability, of the porous silver powder may increase, thereby maintaining the shape of the porous silver powder for a long time.
- the content of the remaining alloying element is less than 0.5% by weight, it is difficult to expect an improvement in additional mechanical properties due to the alloying element, and when the content of the remaining alloying element is greater than 3% by weight, electrical conductivity of the porous silver powder decreases and a melting point increases, thus increasing costs of a sintering process.
- An atomic ratio (at %) between silver (Ag) and the alloying element contained in the alloy powder may be 1:9 or 8:2, and preferably, 2:8 or 6:4.
- a total atomic weight of the alloy powder is 10
- an atomic weight of silver (Ag) is less than 1
- the content of the alloy element is greater than that of silver (Ag) and thus the content of the alloying element to be removed by etching increases, thereby making it difficult to maintain the shape of the powder after etching
- an atomic weight of silver (Ag) is greater than 8
- the content of the alloying element to be removed by etching decreases and a porosity of pores formed in the porous silver powder decreases, thereby decreasing a sterilization effect of the porous silver powder and decreasing electrical conductivity of sintered body and the like formed of the porous silver powder.
- the alloying element contained in the alloy powder may be an element that does not form an intermetallic compound when combined and reacted with silver (Ag).
- the alloying element may include at least one material selected from the group consisting of silicon (Si), bismuth (Bi), germanium (Ge), copper (Cu), iron (Fe), nickel (Ni), chromium (Cr) and cobalt (Co), and preferably, silicon (Si), bismuth (Bi), germanium (Ge) or the like having high brittleness may be selectively used for ease of grinding.
- the alloying element may further include at least one transition metal element, and the transition metal element may be selected from among elements of period 4 to 7 and elements of Group 3 to 12 listed in the periodic table of elements, and preferably, scandium (Sc), titanium (Ti), chromium (Cr) or the like may be used.
- the transition metal element may additionally improve the sterilization effect, electrical conductivity, etc. of silver (Ag).
- the acid solvent serving as the polar solvent may include at least one among a phosphoric acid (H 3 PO 4 ) solution, a sulfuric acid (H 2 SO 4 ) solution, an acetic acid (CH 3 COOH) solution, and a hydrofluoric acid (HF) solution.
- a phosphoric acid (H 3 PO 4 ) solution may include at least one among a phosphoric acid (H 3 PO 4 ) solution, a sulfuric acid (H 2 SO 4 ) solution, an acetic acid (CH 3 COOH) solution, and a hydrofluoric acid (HF) solution.
- H 3 PO 4 phosphoric acid
- SO 4 sulfuric acid
- CH 3 COOH acetic acid
- HF hydrofluoric acid
- the basic solvent serving as the polar solvent may include at least one among a sodium hydroxide (NaOH) solution, a potassium hydroxide (KOH) solution, a lithium hydroxide (LiOH) solution, a sodium cyanide (NaCN) solution, an ammonium hydroxide (NH 4 OH) solution, a tetra methyl ammonium hydroxide (TMAH)solution, an ethyltrimetyl ammonium hydroxide (ETMAH) solution, an ammonia (NH 3 ) aqueous solution, and a zinc chloride (ZNCL) solution, and preferably, sodium hydroxide or potassium hydroxide with low toxicity and low persistence may be selected and used.
- the acid solvent or the basic solvent may be diluted with distilled water for efficient solvent extraction.
- An average particle size D50 of the porous silver powder according to the present invention may be set to 100 to 20,000 nm, and preferably, 300 to 3,000 nm, so that the porous silver powder may be applicable to an electronic ink material.
- the average particle size D 50 refers to a particle size defined with respect to 50% of a distribution of particle sizes (diameters) of powder, based on the volume of the porous silver powder, and may be measured by, for example, a laser diffraction method.
- silver powder is formed to a particle size of less than 100 nm and thus is difficult to be discharged and promotes platelet aggregation and causes cardiovascular disease due to the small particle size when absorbed into skin cells, thereby causing a bad effect on the human body. Therefore, it is difficult to apply the silver powder to the bio industry and the medical field.
- an average particle size of the porous silver powder according to the present invention is adjustable to 100 nm or more, and preferably, 1,000 nm or more, and thus, the porous silver powder may be prevented from being absorbed into the skin and may be easily discharged out of the body even when absorbed into the body through the respiratory organ, thereby securing safety to the body.
- An average pore size of the porous silver powder according to the present invention may be 10 to 1,000 nm, and preferably, 1 to 500 nm, and it was confirmed that an average particle size of pores of the porous silver powder formed when etched was 100 nm or less.
- the average particle size of the pores of the porous silver powder may be the same or substantially the same as an average particle size of the alloying element removed by etching.
- FIG. 1 is a flowchart of a preparation method of porous silver powder according to the present invention.
- the preparation method of porous silver powder according to the present invention includes preparing a master alloy silver (Ag) and an alloying element other than silver (Ag) (S 110 ), manufacturing an alloy casting by dissolving and rapidly solidifying the master alloy (S 120 ), grinding the alloy casting into alloy powder (S 130 ), and removing at least part of the alloying element by etching the alloy powder with an acid solvent or a basic solvent (S 140 ).
- a master alloy may be prepared by mixing and dissolving silver (Ag) and the alloying element.
- silver (Ag) and the alloying element may be weighed using an electronic scale such that an atomic ratio therebetween is 1:9 or 8:2 and thereafter may be dissolved to prepare a master alloy with a uniform composition.
- Silicon (Si) may be selected as the alloying element to be mixed with silver (Ag) in the preparing of the master alloy (S 110 ).
- a melting point of silver (Ag) is about 961° C. and a melting point of silicon (Si) is about 1,414° C., and thus, the difference between the melting points thereof is about 450° C.
- silver (Ag) and silicon (Si) are put and dissolved together in the same container, silver (Ag) with a relatively low melting point is easily dissolved but much energy is needed to completely dissolve silicon (Si) with a relatively high melting point. Therefore, as silver (Ag) that is first dissolved is volatilized or sublimated, an atomic ratio between silver (Ag) and silicon (Si) that constitute the alloying elements changes, thus making it difficult to prepare a master alloy with a uniform composition.
- the master alloy may be cast using casting equipment such as a vacuum arc furnace or a vacuum induction melting (VIM) furnace, after an inert atmosphere is formed by injecting an inert gas such as argon (Ar) in a vacuum state to evenly dissolve the alloying element without being oxidized.
- an inert gas such as argon (Ar)
- a molten alloy may be applied to subsequent operation (S 120 ) without being solidified in the form of a master alloy.
- the master alloy prepared in the preparing of the master alloy (S 110 ) is dissolved and rapid solidified to manufacture an alloy casting.
- the rapid solidification an average cooling rate is high and thus crystal growth of a certain alloying element may be suppressed as much as possible due to rapid cooling of the molten metal, and thus, the rapid solidification is effective for preparation of porous silver powder of a nano composite structure.
- the rapid solidification may be performed by melting spinning at an average cooling rate of 10 6 to 10 8 ° C./sec, and pores of porous silver powder prepared by rapid solidification may be formed in nano sizes, thereby improving a specific surface area may be improved and easily controlling a particle size of resultant powder.
- FIG. 2 illustrates a device for rapidly solidifying porous silver powder by melt spinning, according to the present invention.
- a rate of cooling from a liquid state to a solid state is very high, i.e., 10 6 to 10 8 ° C./sec, and in this case, production of a solid nucleus is promoted during the melt spinning, thereby quickly completing a phase change to the solid state.
- the alloy casting manufactured by melt spinning may be in the form of a ribbon having an ultra-thin thickness and a certain width, and a microstructure thereof may be a nanostructure or an amorphous structure.
- the alloy casting rapidly solidified by melt spinning in the manufacturing of the alloy casting (S 120 ) is mechanically ground into alloy powder.
- the alloy casting is first ground using a paint shaker, a pin crush or the like to prepare alloy powder having an average particle size of 1 to 50 ⁇ m.
- the alloy powder prepared by first grinding the alloy casting may be second ground into more fine powder by a dry or wet method.
- the alloy powder is ground using an air classifier mill or the like by feeding the alloy powder to a high-speed gas flow to be collided against a blade or the like
- the alloy powder is ground using a bead mill or the like by putting water or an organic solvent and 0.1 to 0.5 ⁇ ceramic balls into a container and grinding the alloy powder using a shear force generated by starting a rotating part.
- the alloying element is partially removed by etching the alloy powder, which is finally ground in the grinding of the alloy casting into alloy powder (S 130 ), with an acid or basic solvent.
- the etching of the alloy powder may be performed for about thirty minutes to five hours but embodiments are not limited thereto.
- pores may be formed in a region of the alloy powder from which the alloying element is removed, thereby obtaining the porous silver powder of the present invention, and as described above, an average particle size D 50 of the finally obtained porous silver powder may be in a range of 100 to 20,000 nm and be adjustable according to a field to which the porous silver powder is applied, a porosity thereof may be in a range of 5 to 50%, and a specific surface area (BET) thereof may be in a range of 4.0 to 8.0 m 2 /g.
- BET specific surface area
- porous silver powder and the preparation method thereof will be described with respect to examples below.
- silver (Ag) and silicon (Si) were mixed at an atomic ratio of 0.67:1 and dissolved at about 1500° C. to prepare a master alloy.
- the master alloy was dissolved by melt spinning and rapidly solidified to manufacture an alloy casting.
- the alloy casting was mechanically ground using a paint shaker to prepare alloy powder with an average particle size D 50 of 10 ⁇ m.
- Porous silver powder was prepared under the same condition as in Example 1 except that silver (Ag) and silicon (Si) were mixed at an atomic ratio of 0.43:1.
- Porous silver powder was prepared under the same condition as in Example 1 except that silver (Ag) and silicon (Si) were mixed at an atomic ratio of 0.25:1.
- FIGS. 3A and 3B show surfaces of powder of Example 1 observed using a field emission scanning electron microscope (FE-SEM) before and after etching.
- FIGS. 4A and 4B show surfaces of powder of Example 2 observed before and after etching.
- FIGS. 5A and 5 B show surfaces of powder of Example 3 observed before and after etching.
- FIGS. 6A and 6B show cross sections of the powder of Example 1 observed after etching.
- alloy powder was etched and cleaned using a sodium hydroxide solution and thus silicon (Si) was almost removed and only silver (Ag) remained in porous silver powder.
- FIGS. 5A and 5B are photographs showing a surface of porous silver powder of Example 3 of the present invention, observed using the FE-SEM.
- Example 3 powder was etched and cleaned using a potassium hydroxide solution and thus silicon (Si) was partially removed and only silver (Ag) remained in porous silver powder.
- FIGS. 6A and 6B are photographs showing a cross section of the porous silver powder of Example 1 of the present invention.
- the porous silver powder was etched and cleaned using a sodium hydroxide solution and thus silicon (Si) was almost removed and only silver (Ag) remained in porous silver powder.
- porous silver powder prepared by rapid solidification and etching has a relatively large specific surface area and a relatively high porosity and thus excellent sterilization effect may be achieved only with a small amount thereof and high electrical conductivity may be exhibited when provided in the form of sintered body or the like.
- silver nano powder is contained in a conductive paste, an adhesive or an ink to achieve electromagnetic wave shielding performance, whereas it is expected that high electromagnetic wave shielding performance of 60 db can be achieved with only 35% of porous silver powder according to Examples 1 to 3 of the present invention, thereby reducing manufacturing costs.
- the residual content of alloying elements in porous silver powder was measured by wet spectroscopy (ICP), and as shown in FIG. 7 , a mold was filled with porous silver powder containing residual content of different alloying elements, a constant force was applied to compress the porous silver powder (temperature: 300° C., time: sixty minutes), and a reduction of the volume thereof before/after the compression was measured to evaluate mechanical properties of the porous silver powder, and evaluation results are as shown in Table 1 below.
- porous silver powder in porous silver powder according to the present invention, an alloy can be easily prepared using certain alloying elements, a specific surface area and a porosity can be easily adjusted to improve a sterilization effect, electrical conductivity can be improved when molded as sintered body at a low temperature and under low pressure, use of silver can be reduced when the porous silver powder is applied in various industrial fields, thus securing prices competitiveness, and the porous silver powder can be prevented from being absorbed into the body by adjusting a particle size and thus is harmless to the human body.
Abstract
Provided is a porous silver powder and a preparation method thereof. More specifically, the present invention relates to porous silver powder that is easy to prepare, improves a sterilization effect because an specific surface area and a porosity are easily adjustable, improves electrical conductivity when molded as sintered body, contributes to reducing use of expensive silver when applied in various industrial fields, thus achieving price competitiveness, and is harmless to the human body because a particle size is adjustable to prevent the porous silver powder from being absorbed into the body; and a preparation method thereof.
Description
- This application claims the benefit of Korean Patent Application No. 10-2020-0110160, filed with the Korean Intellectual Property Office on Aug. 31, 2020, the disclosure of which is incorporated herein by reference in its entirety.
- The present invention relates to porous silver powder and a preparation method thereof. More specifically, the present invention relates to porous silver powder that is easy to prepare, improves a sterilization effect because an specific surface area and a porosity are easily adjustable, improves electrical conductivity when molded as sintered body, contributes to reducing use of expensive silver when applied in various industrial fields, thus achieving price competitiveness, and is harmless to the human body because a particle size is adjustable to prevent the porous silver powder from being absorbed into the body; and a preparation method thereof.
- Silver (Ag) powder has drawn much attention, for example, as a material of a solar cell, an adhesive material of a semiconductor chip package, a material of a touch panel pattern, a filler material of a vehicle product, medical and biomaterials, etc. in various industrial fields.
- Particularly, there is a growing need for nano ink to which silver nano powder is applied to print a micro-electronic circuit. Nano ink has been applied for various purposes in the field of solar cells, sensors, touch screens, flexible display, etc., and is used in the form of conductive ink, dielectric ink, or the like.
- However, ink containing silver (Ag) is still expensive and is limited in exhibiting desired performance. Accordingly, research has been conducted on using inexpensive copper instead of silver but an additional process is needed to maintain an inert gas environment so as to prevent oxidation of copper in a sintering process, thereby increasing manufacturing costs.
- A silver (Ag)-tin (Sn)-based alloy including low-melting-point metals is applied to conductive paste or ink but electrical conductivity decreases significantly due to generation of an intermetallic compound of silver (Ag) and tin (Sn).
- When a surface of silver nano powder combines with oxygen atoms in the air and bacterial cell membrane, the bacterial cell membrane is oxidized, thus achieving a sterilization effect. However, when the content of expensive silver is increased, manufacturing costs increase and thus research is being conducted to increase a surface area of silver powder per unit mass so as to effectively increase a sterilization effect but there are technical limits in a manufacturing process.
- Generally, nano powder is formed to a very small size of less than 100 nm and thus may penetrate the skin, thus causing adverse health effects, and is not likely to be discharged from the body when absorbed into the body due to the very small size. In particular, when silver nano powder is applied in a medical or bio field, the silver nano powder may be harmful to the human body.
- Therefore, porous silver powder, which is easy to prepare, improves a sterilization effect because an specific surface area and porosity are easy to adjust, increases electrical conductivity when molded as sintered body, contributes to reducing use of expensive silver when applied in various industrial fields, thus achieving price competitiveness, and is harmless to the human body because a particle size is adjustable to prevent the porous silver powder from being absorbed into the body, and a preparation method thereof are required.
- The present invention is directed to providing porous silver powder that is easy to prepare, improves a sterilization effect because an specific surface area and a porosity are easily adjustable, improves electrical conductivity when molded as sintered body, contributes to reducing use of expensive silver when applied to various industrial fields, thereby securing price competitiveness, and is harmless to the human body because a particle size is adjustable to prevent the porous silver powder from being absorbed into the body; and a preparation method thereof.
- To achieve the object, the present invention provides a porous silver powder, wherein pores are formed by etching alloy powder containing silver (Ag) and an alloying element other than silver (Ag) with an acid solution or a basic solution to remove at least part of the alloying element.
- Also, the present invention provides the porous silver powder, wherein residual content of the alloying element is 0.5 to 3% by weight based on the total weight of the porous silver powder.
- And, the present invention provides the porous silver powder, wherein the alloying element comprises at least one material selected from the group consisting of silicon (Si), bismuth (Bi), germanium (Ge), copper (Cu), iron (Fe), nickel (Ni), chromium (CR), and cobalt (Co).
- Further, the present invention provides the porous silver powder, wherein the alloying element further comprises at least one transition metal element.
- And, the present invention provides the porous silver powder, wherein the basic solution comprises at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, an ammonia solution, zinc chloride, tetramethyl ammonium hydroxide (TMAH), and ethyltrimethyl ammonium hydroxide (ETMAH).
- Also, the present invention provides the porous silver powder, wherein an average particle size D50 of the porous silver powder is in a range of 100 to 20,000 nm.
- Further, the present invention provides the porous silver powder, wherein a porosity is in a range of 5 to 50% and a specific surface area (BET) is in a range of 4.0 to 8.0 m2/g.
- And, the present invention provides the porous silver powder, wherein an atomic ratio between silver (Ag) and the alloying element contained in the alloy powder is 1:9 or 8:2.
- Also, the present invention provides a preparation method of the porous silver powder, comprising: preparing a master alloy containing silver (Ag) and an alloying element other than silver (Ag); manufacturing an alloy casting by dissolving and rapidly solidifying the master alloy; grinding the alloy casting into alloy powder; and removing at least part of the alloying element by etching the alloy powder with an acid solution or a basic solution.
- Further, the present invention provides the preparation method of claim 9, wherein the rapidly solidifying of the master alloy is carried out by melt spinning, wherein, in the melt spinning, an average cooling rate is 106 to 108° C./sec.
-
FIG. 1 is a flowchart of a preparation method of porous silver powder according to the present invention; -
FIG. 2 illustrates a device for rapidly solidifying porous silver powder by melt spinning, according to the present invention; -
FIGS. 3A and 3B show surfaces of porous silver powder of Example 1 of the present invention before and after etching, observed using a field emission scanning electron microscope (FE-SEM); -
FIGS. 4A and 4B show surfaces of porous silver powder of Example 2 of the present invention before and after etching, observed using the FE-SEM; -
FIGS. 5A and 5B show surfaces of porous silver powder of Example 3 of the present invention before and after etching, observed using the FE-SEM; -
FIGS. 6A and 6B show cross sections of the porous silver powder of Example 1 of the present invention before and after etching, observed using the FE-SEM; and -
FIG. 7 schematically illustrates a process of compressing porous silver powder using a mold, according to an embodiment of the present invention. - Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention is, however, not limited thereto and may be embodied in many different forms. Rather, the embodiments set forth herein are provided so that this disclosure will be thorough and complete, and fully convey the scope of the invention to those of ordinary skill in the art.
- Porous silver powder according to the present invention may be formed in a porous structure by a chemical method. That is, the porous silver powder may be formed of alloy powder of a binary or higher system including silver (Ag) and an alloying element other than silver (Ag), and specifically, multiple pores may be formed on a surface or the inside of the alloy powder by removing at least part of the alloying element by etching the alloy powder with an acid solvent or a basic solvent, and preferably, a polar solvent such as the basic solvent.
- Here, the etching of the alloy powder performed to form pores in the porous silver powder refers to forming pores in the alloy powder by dissolving the alloying element from the alloy powder with an acid solution or a basic solution and extracting the dissolved alloying element with a solvent.
- Accordingly, in the porous silver powder according to the present invention, a porosity, i.e., a ratio of total volume of pores to total volume of the porous silver powder, may be easily adjusted by adjusting the content of the alloying element in the alloy powder excluding silver (Ag) during the preparation of the alloy powder or adjusting a cooling rate when a molten alloy is cooled to prepare the alloy powder.
- That is, the porosity increases as the content of the alloying element contained in the alloy powder excluding silver (Ag), i.e., the content of the alloying element in the pores in the alloy powder from which the alloying element is extracted and removed using the solvent during the etching of the alloy powder, increases or increases as a cooling rate of the molten alloy decreases during the cooling of the molten alloy because the alloying element is removed during the etching of the alloy powder due to the growth of crystal grains due to the alloying element other than silver (Ag).
- Specifically, the porous silver powder according to the present invention may have a porosity of 5 to 50% and thus particularly have a specific surface area (BET) of 4.0 to 8.0 m2/g and preferably 5.0 to 6.0 m2/g. Here, when the porosity is less than 5%, a surface area of the porous silver powder is insufficient and thus a sterilization effect, an antibacterial effect, an antifungal effect, an antiviral effect or the like may decrease, and a melting point of a metal may increase due to a reduction of the amount of surface energy due to the insufficient surface area of the porous silver powder and thus a sintering process should be performed under relatively high pressure and at relatively high temperature, e.g., a temperature higher than 300° C., when sintered body is formed of the porous silver powder, thus increasing manufacturing time and costs.
- [34] When the porosity is greater than 50%, the shape of the porous silver powder is difficult to maintain and the sterilization effect, electrical conductivity, etc. may decrease due to a reduction of the content of silver (Ag).
- Part of the alloying element may remain when the porous silver powder according to the present invention is etched, thus improving some physical properties of the porous silver powder, and the residual content of the alloying element may be 0.5 to 3% by weight based on the total weight of the porous silver powder.
- Specifically, the remaining alloying element improves dislocation density of the porous silver powder and thus overall mechanical properties, such as strength and durability, of the porous silver powder may increase, thereby maintaining the shape of the porous silver powder for a long time. When the content of the remaining alloying element is less than 0.5% by weight, it is difficult to expect an improvement in additional mechanical properties due to the alloying element, and when the content of the remaining alloying element is greater than 3% by weight, electrical conductivity of the porous silver powder decreases and a melting point increases, thus increasing costs of a sintering process.
- An atomic ratio (at %) between silver (Ag) and the alloying element contained in the alloy powder may be 1:9 or 8:2, and preferably, 2:8 or 6:4.
- If it is assumed that a total atomic weight of the alloy powder is 10, when an atomic weight of silver (Ag) is less than 1, the content of the alloy element is greater than that of silver (Ag) and thus the content of the alloying element to be removed by etching increases, thereby making it difficult to maintain the shape of the powder after etching, and when an atomic weight of silver (Ag) is greater than 8, the content of the alloying element to be removed by etching decreases and a porosity of pores formed in the porous silver powder decreases, thereby decreasing a sterilization effect of the porous silver powder and decreasing electrical conductivity of sintered body and the like formed of the porous silver powder.
- The alloying element contained in the alloy powder may be an element that does not form an intermetallic compound when combined and reacted with silver (Ag). Specifically, the alloying element may include at least one material selected from the group consisting of silicon (Si), bismuth (Bi), germanium (Ge), copper (Cu), iron (Fe), nickel (Ni), chromium (Cr) and cobalt (Co), and preferably, silicon (Si), bismuth (Bi), germanium (Ge) or the like having high brittleness may be selectively used for ease of grinding.
- The alloying element may further include at least one transition metal element, and the transition metal element may be selected from among elements of period 4 to 7 and elements of Group 3 to 12 listed in the periodic table of elements, and preferably, scandium (Sc), titanium (Ti), chromium (Cr) or the like may be used. The transition metal element may additionally improve the sterilization effect, electrical conductivity, etc. of silver (Ag).
- The acid solvent serving as the polar solvent may include at least one among a phosphoric acid (H3PO4) solution, a sulfuric acid (H2SO4) solution, an acetic acid (CH3COOH) solution, and a hydrofluoric acid (HF) solution. The basic solvent serving as the polar solvent may include at least one among a sodium hydroxide (NaOH) solution, a potassium hydroxide (KOH) solution, a lithium hydroxide (LiOH) solution, a sodium cyanide (NaCN) solution, an ammonium hydroxide (NH4OH) solution, a tetra methyl ammonium hydroxide (TMAH)solution, an ethyltrimetyl ammonium hydroxide (ETMAH) solution, an ammonia (NH3) aqueous solution, and a zinc chloride (ZNCL) solution, and preferably, sodium hydroxide or potassium hydroxide with low toxicity and low persistence may be selected and used. The acid solvent or the basic solvent may be diluted with distilled water for efficient solvent extraction.
- An average particle size D50 of the porous silver powder according to the present invention may be set to 100 to 20,000 nm, and preferably, 300 to 3,000 nm, so that the porous silver powder may be applicable to an electronic ink material.
- Here, the average particle size D50 refers to a particle size defined with respect to 50% of a distribution of particle sizes (diameters) of powder, based on the volume of the porous silver powder, and may be measured by, for example, a laser diffraction method.
- Generally, silver powder is formed to a particle size of less than 100 nm and thus is difficult to be discharged and promotes platelet aggregation and causes cardiovascular disease due to the small particle size when absorbed into skin cells, thereby causing a bad effect on the human body. Therefore, it is difficult to apply the silver powder to the bio industry and the medical field.
- However, an average particle size of the porous silver powder according to the present invention is adjustable to 100 nm or more, and preferably, 1,000 nm or more, and thus, the porous silver powder may be prevented from being absorbed into the skin and may be easily discharged out of the body even when absorbed into the body through the respiratory organ, thereby securing safety to the body.
- An average pore size of the porous silver powder according to the present invention may be 10 to 1,000 nm, and preferably, 1 to 500 nm, and it was confirmed that an average particle size of pores of the porous silver powder formed when etched was 100 nm or less. Here, the average particle size of the pores of the porous silver powder may be the same or substantially the same as an average particle size of the alloying element removed by etching.
-
FIG. 1 is a flowchart of a preparation method of porous silver powder according to the present invention. - The preparation method of porous silver powder according to the present invention includes preparing a master alloy silver (Ag) and an alloying element other than silver (Ag) (S110), manufacturing an alloy casting by dissolving and rapidly solidifying the master alloy (S120), grinding the alloy casting into alloy powder (S130), and removing at least part of the alloying element by etching the alloy powder with an acid solvent or a basic solvent (S140).
- In the preparing of the master alloy (S110), a master alloy may be prepared by mixing and dissolving silver (Ag) and the alloying element. In the mixing of silver (Ag) and the alloying element, silver (Ag) and the alloying element may be weighed using an electronic scale such that an atomic ratio therebetween is 1:9 or 8:2 and thereafter may be dissolved to prepare a master alloy with a uniform composition.
- Silicon (Si) may be selected as the alloying element to be mixed with silver (Ag) in the preparing of the master alloy (S110). A melting point of silver (Ag) is about 961° C. and a melting point of silicon (Si) is about 1,414° C., and thus, the difference between the melting points thereof is about 450° C.
- Accordingly, when silver (Ag) and silicon (Si) are put and dissolved together in the same container, silver (Ag) with a relatively low melting point is easily dissolved but much energy is needed to completely dissolve silicon (Si) with a relatively high melting point. Therefore, as silver (Ag) that is first dissolved is volatilized or sublimated, an atomic ratio between silver (Ag) and silicon (Si) that constitute the alloying elements changes, thus making it difficult to prepare a master alloy with a uniform composition.
- Therefore, in the preparing of the master alloy (S110), the master alloy may be cast using casting equipment such as a vacuum arc furnace or a vacuum induction melting (VIM) furnace, after an inert atmosphere is formed by injecting an inert gas such as argon (Ar) in a vacuum state to evenly dissolve the alloying element without being oxidized. Alternatively, in order to save energy, a molten alloy may be applied to subsequent operation (S120) without being solidified in the form of a master alloy.
- Thereafter, in the manufacturing of the alloy casting (S120), the master alloy prepared in the preparing of the master alloy (S110) is dissolved and rapid solidified to manufacture an alloy casting. Here, in the rapid solidification, an average cooling rate is high and thus crystal growth of a certain alloying element may be suppressed as much as possible due to rapid cooling of the molten metal, and thus, the rapid solidification is effective for preparation of porous silver powder of a nano composite structure.
- In the manufacturing of the alloy casting (S120), the rapid solidification may be performed by melting spinning at an average cooling rate of 106 to 108° C./sec, and pores of porous silver powder prepared by rapid solidification may be formed in nano sizes, thereby improving a specific surface area may be improved and easily controlling a particle size of resultant powder.
-
FIG. 2 illustrates a device for rapidly solidifying porous silver powder by melt spinning, according to the present invention. - Unlike general metal casting methods, in the melt spinning, a rate of cooling from a liquid state to a solid state is very high, i.e., 106 to 108° C./sec, and in this case, production of a solid nucleus is promoted during the melt spinning, thereby quickly completing a phase change to the solid state.
- The alloy casting manufactured by melt spinning may be in the form of a ribbon having an ultra-thin thickness and a certain width, and a microstructure thereof may be a nanostructure or an amorphous structure.
- In the grinding of the alloy casting into alloy powder (S130), the alloy casting rapidly solidified by melt spinning in the manufacturing of the alloy casting (S120) is mechanically ground into alloy powder.
- In the grinding of the alloy casting into alloy powder (S130), the alloy casting is first ground using a paint shaker, a pin crush or the like to prepare alloy powder having an average particle size of 1 to 50 μm.
- The alloy powder prepared by first grinding the alloy casting may be second ground into more fine powder by a dry or wet method. Here, in the dry method, the alloy powder is ground using an air classifier mill or the like by feeding the alloy powder to a high-speed gas flow to be collided against a blade or the like, and in the wet method, the alloy powder is ground using a bead mill or the like by putting water or an organic solvent and 0.1 to 0.5φ ceramic balls into a container and grinding the alloy powder using a shear force generated by starting a rotating part.
- Next, in the removing of the alloying element (S140), the alloying element is partially removed by etching the alloy powder, which is finally ground in the grinding of the alloy casting into alloy powder (S130), with an acid or basic solvent. The etching of the alloy powder may be performed for about thirty minutes to five hours but embodiments are not limited thereto.
- In the removing of the alloying element (S140), pores may be formed in a region of the alloy powder from which the alloying element is removed, thereby obtaining the porous silver powder of the present invention, and as described above, an average particle size D50 of the finally obtained porous silver powder may be in a range of 100 to 20,000 nm and be adjustable according to a field to which the porous silver powder is applied, a porosity thereof may be in a range of 5 to 50%, and a specific surface area (BET) thereof may be in a range of 4.0 to 8.0 m2/g.
- The porous silver powder and the preparation method thereof will be described with respect to examples below.
- 1. Preparation Example of Porous Silver Powder
- silver (Ag) and silicon (Si) were mixed at an atomic ratio of 0.67:1 and dissolved at about 1500° C. to prepare a master alloy. The master alloy was dissolved by melt spinning and rapidly solidified to manufacture an alloy casting. Next, the alloy casting was mechanically ground using a paint shaker to prepare alloy powder with an average particle size D50 of 10 μm.
- 100 ml of distilled water and 25 g of NaOH were mixed and then heated at 60° C. The alloy powder was added to the heated basic solution and silicon (Si) was removed to prepare porous silver powder.
- Porous silver powder was prepared under the same condition as in Example 1 except that silver (Ag) and silicon (Si) were mixed at an atomic ratio of 0.43:1.
- Porous silver powder was prepared under the same condition as in Example 1 except that silver (Ag) and silicon (Si) were mixed at an atomic ratio of 0.25:1.
- 2. Evaluation of Etching Results
-
FIGS. 3A and 3B show surfaces of powder of Example 1 observed using a field emission scanning electron microscope (FE-SEM) before and after etching.FIGS. 4A and 4B show surfaces of powder of Example 2 observed before and after etching.FIGS. 5A and 5B show surfaces of powder of Example 3 observed before and after etching.FIGS. 6A and 6B show cross sections of the powder of Example 1 observed after etching. - Referring to
FIGS. 3A to 4B , in Examples 1 and 2, alloy powder was etched and cleaned using a sodium hydroxide solution and thus silicon (Si) was almost removed and only silver (Ag) remained in porous silver powder. -
FIGS. 5A and 5B are photographs showing a surface of porous silver powder of Example 3 of the present invention, observed using the FE-SEM. Referring toFIGS. 5A and 5B , in Example 3, powder was etched and cleaned using a potassium hydroxide solution and thus silicon (Si) was partially removed and only silver (Ag) remained in porous silver powder. -
FIGS. 6A and 6B are photographs showing a cross section of the porous silver powder of Example 1 of the present invention. Referring toFIGS. 6A and 6B , in Example 1, the porous silver powder was etched and cleaned using a sodium hydroxide solution and thus silicon (Si) was almost removed and only silver (Ag) remained in porous silver powder. - It is expected from the results of
FIGS. 3A to 6B that according to a preparation method of a porous silver powder of the present invention, porous silver powder prepared by rapid solidification and etching has a relatively large specific surface area and a relatively high porosity and thus excellent sterilization effect may be achieved only with a small amount thereof and high electrical conductivity may be exhibited when provided in the form of sintered body or the like. - Specifically, generally, 60% or more of silver nano powder is contained in a conductive paste, an adhesive or an ink to achieve electromagnetic wave shielding performance, whereas it is expected that high electromagnetic wave shielding performance of 60 db can be achieved with only 35% of porous silver powder according to Examples 1 to 3 of the present invention, thereby reducing manufacturing costs.
- In addition, when a sterilization test was conducted using the porous silver powder according to Examples 1 to 3 of the present invention for about one hour, 99.9% or more of both colon bacillus and staphylococcus aureus were removed and thus germicidal, antibacterial, antifungal, and antiviral effects of the porous silver powder were verified.
- 3. Evaluation of Mechanical Characteristics of Porous Silver Powder
- The residual content of alloying elements in porous silver powder was measured by wet spectroscopy (ICP), and as shown in
FIG. 7 , a mold was filled with porous silver powder containing residual content of different alloying elements, a constant force was applied to compress the porous silver powder (temperature: 300° C., time: sixty minutes), and a reduction of the volume thereof before/after the compression was measured to evaluate mechanical properties of the porous silver powder, and evaluation results are as shown in Table 1 below. -
TABLE 1 residual quantity (wt %) of compressive force of compressive force of compressive force of alloying 0.4 MPa 0.6 MPa 0.8 MPa element volume #1 #2 #3 #1 #2 #3 #1 #2 #3 0.1 before 12 12 12 12 12 12 12 12 12 compressed (ml) after 10.1 10.3 10.1 8.6 8.7 8.4 7.6 7.7 7.6 compressed (ml) reduction rate 15.8 14.2 15.8 28.3 27.5 30.0 36.7 35.8 37.6 (%) 0.2 before 12 12 12 12 12 12 12 12 12 compressed (ml) after 10.3 10.3 10.0 8.7 8.5 8.5 8.0 8.1 7.2 compressed (ml) reduction rate 14.2 14.2 17.6 27.5 29.2 29.2 34.3 32.5 40 (%) 0.4 before 12 12 12 12 12 12 12 12 12 compressed (ml) after 10.3 10.0 10.1 8.5 8.4 8.8 8.0 7.9 7.9 compressed (ml) reduction rate 14.2 17.6 15.8 29.2 30.0 27.6 34.3 34.2 34.2 (%) 0.5 before 12 12 12 12 12 12 12 12 12 compressed (ml) after 10.7 11.0 11.1 9.7 9.4 9.5 9.1 8.4 9.0 compressed (ml) reduction rate 10.8 8.3 7.5 19.2 21.7 20.8 24.2 30.0 25.0 (%) 1.0 before 12 12 12 12 12 12 12 12 12 compressed (ml) after 10.9 11.3 11.2 9.7 9.5 9.8 9 8.9 9.2 compressed (ml) reduction rate 9.2 5.8 6.7 19.2 20.8 18.3 25.0 25.8 23.3 (%) 3.0 before 12 12 12 12 12 12 12 12 12 compressed (ml) after 11.1 11.5 11.3 10.3 10.2 10.5 10.1 9.8 10.0 compressed (ml) reduction rate 7.5 4.2 5.8 14.2 15.0 12.5 15.8 18.3 17.6 (%) - As shown in Table 1 above, a change of the volume of the porous silver powder before/after the compression decreased significantly when the residual content of the alloying elements was 0.5 wt % or more and thus the mechanical properties of the porous silver powder were improved, whereas a change of the volume of the porous silver powder before/after the compression increased when the residual content of the alloying elements was 0.4 wt % or less and thus the porous silver powder clumped and an average particle size, porosity, a specific surface area, etc. were not maintained when compressed.
- While the present invention has been described above with respect to exemplary embodiments thereof, it would be understood by those of ordinary skilled in the art that various changes and modifications may be made without departing from the technical conception and scope of the present invention defined in the following claims. Thus, it is clear that all modifications are included in the technical scope of the present invention as long as they include the components as claimed in the claims of the present invention.
- In porous silver powder according to the present invention, an alloy can be easily prepared using certain alloying elements, a specific surface area and a porosity can be easily adjusted to improve a sterilization effect, electrical conductivity can be improved when molded as sintered body at a low temperature and under low pressure, use of silver can be reduced when the porous silver powder is applied in various industrial fields, thus securing prices competitiveness, and the porous silver powder can be prevented from being absorbed into the body by adjusting a particle size and thus is harmless to the human body.
Claims (18)
1. Porous silver powder, wherein pores are formed by etching alloy powder containing silver (Ag) and an alloying element other than silver (Ag) with an acid solution or a basic solution to remove at least part of the alloying element.
2. The porous silver powder of claim 1 , wherein residual content of the alloying element is 0.5 to 3% by weight based on the total weight of the porous silver powder.
3. The porous silver powder of claim 1 , wherein the alloying element comprises at least one material selected from the group consisting of silicon (Si), bismuth (Bi), germanium (Ge), copper (Cu), iron (Fe), nickel (Ni), chromium (CR), and cobalt (Co).
4. The porous silver powder of claim 3 , wherein the alloying element further comprises at least one transition metal element.
5. The porous silver powder of claim 1 , wherein the basic solution comprises at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, an ammonia solution, zinc chloride, tetramethyl ammonium hydroxide (TMAH), and ethyltrimethyl ammonium hydroxide (ETMAH).
6. The porous silver powder of claim 1 , wherein an average particle size D50 of the porous silver powder is in a range of 100 to 20,000 nm.
7. The porous silver powder of claim 1 , wherein a porosity is in a range of 5 to 50% and a specific surface area (BET) is in a range of 4.0 to 8.0 m2/g.
8. The porous silver powder of claim 1 , wherein an atomic ratio between silver (Ag) and the alloying element contained in the alloy powder is 1:9 or 8:2.
9. A preparation method of the porous silver powder of claim 1 , comprising:
preparing a master alloy containing silver (Ag) and an alloying element other than silver (Ag);
manufacturing an alloy casting by dissolving and rapidly solidifying the master alloy;
grinding the alloy casting into alloy powder; and
removing at least part of the alloying element by etching the alloy powder with an acid solution or a basic solution.
10. The preparation method of claim 9 , wherein the rapidly solidifying of the master alloy is carried out by melt spinning, wherein, in the melt spinning, an average cooling rate is 106 to 108° C./sec.
11. The porous silver powder of claim 2 , wherein the alloying element comprises at least one material selected from the group consisting of silicon (Si), bismuth (Bi), germanium (Ge), copper (Cu), iron (Fe), nickel (Ni), chromium (CR), and cobalt (Co).
12. The porous silver powder of claim 11 , wherein the alloying element further comprises at least one transition metal element.
13. The porous silver powder of claim 2 , wherein the basic solution comprises at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, an ammonia solution, zinc chloride, tetramethyl ammonium hydroxide (TMAH), and ethyltrimethyl ammonium hydroxide (ETMAH).
14. The porous silver powder of claim 2 , wherein an average particle size D50 of the porous silver powder is in a range of 100 to 20,000 nm.
15. The porous silver powder of claim 2 , wherein a porosity is in a range of 5 to 50% and a specific surface area (BET) is in a range of 4.0 to 8.0 m2/g.
16. The porous silver powder of claim 2 , wherein an atomic ratio between silver (Ag) and the alloying element contained in the alloy powder is 1:9 or 8:2.
17. A preparation method of the porous silver powder of claim 2 , comprising:
preparing a master alloy containing silver (Ag) and an alloying element other than silver (Ag);
manufacturing an alloy casting by dissolving and rapidly solidifying the master alloy;
grinding the alloy casting into alloy powder; and
removing at least part of the alloying element by etching the alloy powder with an acid solution or a basic solution.
18. The preparation method of claim 17 , wherein the rapidly solidifying of the master alloy is carried out by melt spinning, wherein, in the melt spinning, an average cooling rate is 106 to 108° C./sec.
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