CN114231774A - Manufacturing process of silver-germanium infrared health-care ornament - Google Patents
Manufacturing process of silver-germanium infrared health-care ornament Download PDFInfo
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- CN114231774A CN114231774A CN202111334032.1A CN202111334032A CN114231774A CN 114231774 A CN114231774 A CN 114231774A CN 202111334032 A CN202111334032 A CN 202111334032A CN 114231774 A CN114231774 A CN 114231774A
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- BPYMJIZUWGOKJS-UHFFFAOYSA-N [Ge].[Ag] Chemical compound [Ge].[Ag] BPYMJIZUWGOKJS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 95
- 238000000034 method Methods 0.000 claims abstract description 43
- 230000008569 process Effects 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 35
- 229910001316 Ag alloy Inorganic materials 0.000 claims abstract description 31
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- 238000010146 3D printing Methods 0.000 claims abstract description 21
- 238000005238 degreasing Methods 0.000 claims abstract description 16
- 230000036541 health Effects 0.000 claims abstract description 10
- 238000012545 processing Methods 0.000 claims abstract description 10
- 238000007639 printing Methods 0.000 claims description 25
- 239000011812 mixed powder Substances 0.000 claims description 24
- 229910052732 germanium Inorganic materials 0.000 claims description 23
- 239000000853 adhesive Substances 0.000 claims description 20
- 230000001070 adhesive effect Effects 0.000 claims description 20
- 238000001723 curing Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000007667 floating Methods 0.000 claims description 6
- 238000007641 inkjet printing Methods 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 238000000889 atomisation Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 238000000016 photochemical curing Methods 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 3
- 230000007480 spreading Effects 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- 238000013461 design Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 210000003127 knee Anatomy 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 23
- 210000001161 mammalian embryo Anatomy 0.000 description 13
- 230000006872 improvement Effects 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000007664 blowing Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 210000002257 embryonic structure Anatomy 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 241001391944 Commicarpus scandens Species 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910017942 Ag—Ge Inorganic materials 0.000 description 2
- 229910000927 Ge alloy Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000009692 water atomization Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 208000027499 body ache Diseases 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/10—Formation of a green body
- B22F10/14—Formation of a green body by jetting of binder onto a bed of metal powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention belongs to the technical field of metal material additive manufacturing, and particularly relates to a manufacturing process of a silver-germanium infrared health-care ornament, which comprises the following steps: uniformly mixing Ag alloy powder and Ge powder, then adopting a binder to spray a 3D printing metal forming technology to obtain a blank with a shape completely conforming to a pre-designed 3D pattern, degreasing and sintering to obtain a silver-germanium sintered piece, and finally performing die holding post-treatment processing to finally obtain the finished product of the silver-germanium ornament. The invention not only avoids the defects of large brittleness, high hardness, poor flexibility and poor ductility of the material, easy brittle fracture and scrapping and difficult processing into exquisite and fine products in the processing process of the germanium-silver alloy; and the 3D printing technology is applied to the design and manufacture of the germanium-silver ornaments, so that the one-step forming of the complex three-dimensional design product is realized, and the design feasibility of the germanium-silver ornaments is greatly widened, such as: the product is used in health care products such as ornaments, waistbands, neck bands, hand rings, knee pads, pillows and the like, and has great application value.
Description
Technical Field
The invention belongs to the technical field of metal material additive manufacturing, and particularly relates to a manufacturing process for producing a silver-germanium ornament with an infrared health care function based on a binder spraying 3D printing metal forming technology.
Background
Research shows that germanium is a metal applicable to human body medical care, the semiconductor property of germanium can generate fluctuation by means of heat energy of human body temperature when the germanium contacts with a human body, negative ions are released by utilizing the fluctuation, the current balance function of the negative ions can promote the expansion of blood capillaries, promote the blood circulation of the human body, adjust the ion balance of the human body, relieve fatigue, relieve body ache and promote the human body to recover the positive and negative charge balance state. However, in order to make germanium have its health-care function, metal germanium must be in contact with human skin, so that germanium alloy is often made into ornaments to be worn next to the skin. However, metal germanium is a crystal with atomic arrangement similar to that of diamond, is very brittle and is easy to break, and cannot be independently processed into ornaments. In the jewelry industry, health care germanium products are usually made by grinding metal germanium into round particles with the diameter of 1-5mm, and the round particles are embedded in metal necklaces and bracelets to be worn next to the skin. The disadvantages of this process: firstly, the effective contact area of the germanium particles and the human body is too small, the waste is serious for expensive germanium materials with rare storage capacity, and the inlaid germanium particles are easy to fall off; secondly, the flexibility and the artistry of the silver-germanium ornament design are severely limited by the simple embedding process mode, the product is rough, clumsy and not exquisite enough, and the aesthetic experience of the silver-germanium ornament as a fashion ornament is influenced.
The inventor of the invention finds that after the germanium and the silver are smelted into the alloy, the effect of the germanium is not influenced, and the killing and inhibiting effects of silver ions on bacteria and viruses are increased, so that the processing of the metal germanium into the germanium-silver ornament is an ideal scheme for manufacturing the health-care products. However, the smelting and processing of germanium and silver are quite difficult, and the silver-germanium alloy has high hardness, large brittleness and poor flexibility, so that the alloy is difficult to be plastically processed into a delicate ornament like common silver, especially the alloy with high germanium content.
In view of the above, the present invention provides a method for producing a silver-germanium ornament based on a binder-jetting 3D printing and forming technology, in which powdered silver alloy powder and germanium powder are mixed and then printed and formed at a time, and then sintered to form a finished silver-germanium product. The method avoids the defects that the material is large in brittleness, high in hardness, poor in flexibility and ductility, easy to break and scrap and difficult to process into a delicate and exquisite product in the processing process of the Ag-Ge alloy; and the 3D printing technology is applied to the design and manufacture of the silver-germanium ornament, so that the one-step forming of a complex three-dimensional design product is realized, and the design feasibility of the silver-germanium product is greatly widened, such as: the product is used in health care products such as ornaments, waistbands, neck bands, hand rings, knee pads, pillows and the like, and has great application value.
Disclosure of Invention
The invention aims to: aiming at the defects of the existing silver-germanium process technology, the manufacturing process of the silver-germanium infrared health care ornament comprises the following steps:
a manufacturing process of a silver germanium infrared health care ornament at least comprises the following steps:
the method comprises the following steps: weighing Ag alloy powder and Ge powder according to mass percent, and fully and uniformly stirring in a mixer to obtain mixed powder;
step two: putting the mixed powder obtained in the step one into a powder feeding cylinder of a binder spraying 3D printing device, firstly spreading a layer of mixed powder on a powder bed and leveling the mixed powder by using a scraper, then selectively spraying a light-cured binder on the powder bed by using an ink-jet printing head, and irradiating the powder bed by using infrared rays to cure and bond the part sprayed with the light-cured binder; each time one layer is created, the printing surface moves downwards by a layer thickness distance, the next layer of mixed powder is spread, the adhesive and the light-cured adhesive are sprayed in the selected area, and then light curing is carried out; repeating the process until printing is finished, and thus, superposing layer by layer to manufacture a three-dimensional structure until a green blank (green blank) with the shape completely conforming to the pre-designed 3D graph is obtained; the print thickness of each layer is usually 40-100 μm; the relative density of the green embryo obtained by printing is 65-75%.
Step three: taking out the complete 3D printing green body obtained in the step two, and removing floating powder on the surface of the green body; placing the green body piece in a degreasing furnace, and heating to decompose the phenolic resin binder in the green body to obtain a degreased green body (brown body);
step four: putting the degreased green blank obtained in the third step into an atmosphere sintering furnace, and sintering under the protection of protective gas to obtain a compact sintered part; in the sintering process, the Ag and the Ge are alloyed, and the relative density of a sintered part is more than 98%.
Step five: and D, performing conventional die holding post-treatment processing on the sintered piece obtained in the step four to finally obtain the finished product of the silver-germanium ornament.
As an improvement of the manufacturing process of the silver-germanium infrared health-care ornament, the silver alloy powder in the first step is spherical powder prepared by an air atomization method or a water atomization method, and the particle size range of the silver alloy powder is 1-45 mu m.
As an improvement of the manufacturing process of the silver-germanium infrared health-care ornament, the silver alloy powder in the step one comprises at least one of Ag, Au, Cu, Si, Ni, Al, Zn and Ge, and the Ag alloy powder comprises the following components: ag (90-98 wt%); cu (0-8 wt%); si (0-3 wt%); ni (0-3 wt%); al (0-3 wt%); zn (0-3 wt%).
As an improvement of the manufacturing process of the silver-germanium infrared health-care ornament, the Ge powder in the first step is pure Ge powder, is brittle powder obtained by a mechanical crushing or airflow crushing method, and has the particle size distribution of 0.1-25 mu m.
As an improvement of the manufacturing process of the silver-germanium infrared health-care ornament, in the mixed powder in the first step, the mass ratio of Ge powder is 0.5-10 wt%.
As an improvement of the manufacturing process of the silver-germanium infrared health-care ornament, the photo-curing adhesive in the step two is water-soluble phenolic resin glue.
As an improvement of the manufacturing process of the silver-germanium infrared health-care ornament, the heating temperature range in the third step is 200-.
As an improvement of the manufacturing process of the silver-germanium infrared health-care ornament, the protective gas in the fourth step is nitrogen or argon, and the sintering process conditions are as follows: the maximum sintering temperature range is 900-930 ℃, and the sintering period is 19-24 hr.
Compared with the prior art, the invention creatively adopts the Binder Jetting 3D printing (Binder Jetting jet 3D printing) metal forming technology to realize the production and the manufacture of the silver-germanium ornament. Specifically, Ag alloy powder and Ge powder are uniformly mixed, a binder is adopted to spray a 3D printing metal forming technology to obtain a blank with a shape completely conforming to a pre-designed 3D graph, degreasing and sintering are carried out to obtain a silver-germanium sintered piece, and finally conventional die holding post-treatment processing is carried out to obtain the finished product of the silver-germanium ornament.
The invention mixes the silver alloy powder and germanium powder in powder state, prints and forms in one step, and then becomes silver germanium finished product after sintering. The method avoids the defects that the material is large in brittleness, high in hardness, poor in flexibility and ductility, easy to break and scrap and difficult to process into a delicate and exquisite product in the processing process of the Ag-Ge alloy; and the 3D printing technology is applied to the design and manufacture of the silver-germanium ornament, so that the one-step forming of a complex three-dimensional design product is realized, and the design feasibility of the silver-germanium product is greatly widened, such as: the product is used in health care products such as ornaments, waistbands, neck bands, hand rings, knee pads, pillows and the like, and has great application value.
Detailed Description
The present invention and its advantageous effects are described in further detail below with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
smelting Ag alloy according to the following weight percentage: ag (94.5%) -Cu (2.1%) -Si (1.2%) -Zn (2.2%). The Ag alloy is melted and then made into spherical powder by using an air atomization method, and micro powder below 500 meshes is screened out. The Ge powder is 5N grade pure germanium powder sold in market, is brittle powder obtained by mechanical crushing, and is screened to obtain fine powder below 500 meshes. Mixing the Ag alloy powder with Ge powder and silver alloy powder: the weight percentages of the germanium powder =97:3 are respectively weighed and then mixed for more than 6hr by a Y-shaped mixer until the two are uniformly mixed.
Putting the mixed powder into a powder feeding cylinder of a binder-sprayed metal 3D printing device, inputting a pre-drawn 3D image, and starting a printing process flow: a layer of the mixed powder is spread on a powder bed and scraped off by a doctor blade, and then a light-curing adhesive is selectively sprayed onto the powder bed by an ink-jet printing head, and the powder bed is irradiated with infrared rays to cure and bond the part on which the light-curing adhesive is sprayed. Each time one layer is created, the printing surface moves downwards by a layer thickness distance, the next layer of mixed powder is spread, the adhesive and the light-cured adhesive are sprayed in the selected area, and then light curing is carried out; the process is repeated until printing is completed, and a green blank with a shape completely conforming to the pre-designed 3D graph is obtained. The printing thickness of each layer was set to 50 μm; the light-cured binder adopts water-soluble phenolic resin glue. The green embryos obtained were printed with a relative density of 70%.
After printing is finished, taking out the obtained complete 3D printing green blank, and blowing off floating powder on the surface of the green blank by using compressed air; and (3) placing the green embryo piece in a degreasing furnace, and heating according to a set process curve to decompose the organic binder in the green embryo to obtain a brown embryo. The degreasing temperature is 400 deg.C, maintaining for 6hr, and protecting with nitrogen gas in the degreasing furnace.
And (3) putting the degreased brown blank into an atmosphere sintering furnace, sintering according to a preset process curve, and alloying Ag and Ge in the sintering process to obtain a compact sintered part. The sintering process conditions are as follows: setting the maximum sintering temperature range at 925 deg.C, and the sintering period totally consuming 24 hr; the linear shrinkage of the sintered article was found to be 16.8% and the relative density of the sintered article was found to be 98.5%.
And grinding and polishing the sintered part to finally obtain the finished product of the silver-germanium ornament, wherein the product contains Ag91.7% and Ge 3%.
Example 2:
smelting Ag alloy according to the following weight percentage: ag (95.4%) -Cu (1.1%) -Se (0.8%) -
Zn (2.0%) -Al (0.7%). The Ag alloy is put into a graphite crucible, melted by a medium-frequency melting furnace, spherical powder is prepared by adopting an air atomization method, and micro powder below 500 meshes is screened out. The Ge powder is 5N grade pure germanium powder sold in market, is brittle powder obtained by mechanical crushing, and is screened to obtain fine powder below 500 meshes. Mixing the silver alloy powder with Ge powder and silver alloy powder: the weight percentages of Ge powder =97:3 are respectively weighed and then mixed for more than 6hr by a Y-type mixer until the two are uniformly mixed.
Putting the mixed powder into a powder feeding cylinder of a binder-sprayed metal 3D printing device, inputting a pre-drawn 3D image, and starting a printing process flow: a layer of the mixed powder is spread on a powder bed and scraped off by a doctor blade, and then a light-curing adhesive is selectively sprayed onto the powder bed by an ink-jet printing head, and the powder bed is irradiated with infrared rays to cure and bond the part on which the light-curing adhesive is sprayed. Each time a layer is created, the print surface is moved down a layer thickness distance, the next layer of mixed powder is spread, the adhesive and light-curable binder are sprayed in selected areas, and then light-cured. The process is repeated until printing is completed, and a green blank with a shape completely conforming to the pre-designed 3D graph is obtained. The printing thickness of each layer was set to 80 μm; the light-cured binder adopts water-soluble phenolic resin glue. The green embryos obtained were printed with a relative density of 67%.
After printing is finished, taking out the obtained complete 3D printing green blank, and blowing off floating powder on the surface of the green blank by using compressed air; and (3) placing the green embryo piece in a degreasing furnace, and heating according to a set process curve to decompose the organic binder in the green embryo to obtain a brown embryo. The degreasing temperature is 400 deg.C, maintaining for 8hr, and protecting with nitrogen gas in the degreasing furnace.
And (4) putting the degreased brown blank into an atmosphere sintering furnace, and sintering according to a preset process curve to obtain a compact sintered part. The sintering process conditions are as follows: setting the maximum sintering temperature range at 915 deg.C, and the sintering period for 20 hr; the linear shrinkage of the sintered article was found to be 16.1% and the relative density of the sintered article was found to be 98.2%.
And grinding and polishing the sintered part to finally obtain the finished product of the silver-germanium ornament, wherein the product contains Ag92.5% and Ge 3%.
Example 3:
smelting Ag alloy according to the following weight percentage: ag (95.4%) -Cu (1.1%) -Se (0.8%) -Zn (2.0%) -Al (0.7%). The Ag alloy is melted and then made into spherical powder by using an air atomization method, and micro powder below 500 meshes is screened out. The Ge powder is 5N grade pure germanium powder sold in market, is brittle powder obtained by mechanical crushing, and is screened to obtain fine powder below 500 meshes. Mixing the silver alloy powder with Ge powder and silver alloy powder: the weight percentages of Ge powder =95:5 are respectively weighed, and then mixed for more than 6hr by a Y-type mixer until the two are uniformly mixed.
Putting the mixed powder into a powder feeding cylinder of a binder-sprayed metal 3D printing device, inputting a pre-drawn 3D image, and starting a printing process flow: spreading a layer of mixed powder on a powder bed and leveling the powder by a scraper, then selectively spraying light-cured phenolic resin glue on the powder bed by an ink-jet printing head, and irradiating the powder bed by infrared rays to cure and bond the parts sprayed with the light-cured adhesive. Each time one layer is created, the printing surface moves downwards by a layer thickness distance, the next layer of mixed powder is spread, the adhesive and the light-cured adhesive are sprayed in the selected area, and then light curing is carried out; the process is repeated until printing is completed, and a green blank with a shape completely conforming to the pre-designed 3D graph is obtained. The printing thickness of each layer was set to 50 μm; the light-cured binder adopts water-soluble phenolic resin glue. The relative density of the green embryos obtained by printing was 68%.
After printing is finished, taking out the obtained complete 3D printing green blank, and blowing off floating powder on the surface of the green blank by using compressed air; and (3) placing the green embryo piece in a degreasing furnace, and heating according to a set process curve to decompose the organic binder in the green embryo to obtain a brown embryo. The degreasing temperature is 400 deg.C, maintaining for 8hr, and protecting with nitrogen gas in the degreasing furnace.
And (4) putting the degreased brown blank into an atmosphere sintering furnace, and sintering according to a preset process curve to obtain a compact sintered part. The sintering process conditions are as follows: setting the maximum sintering temperature at 920 deg.C, and the sintering period takes 26 hr; the linear shrinkage of the sintered article was found to be 17.1% and the relative density of the sintered article was found to be 96.8%.
And carrying out Hot Isostatic Pressing (HIP) process treatment on the sintered part, wherein the pressure transmission medium is argon, the heating temperature is 750-.
And grinding and polishing the sintered part to finally obtain a finished product of the silver-germanium product, wherein the product contains Ag90.6% and Ge 5%.
Example 4:
smelting Ag alloy according to the following weight percentage: ag (96.5%) -Cu (2.5%) -Zn (1.0%). Melting the Ag alloy, preparing powder by a water atomization method, and screening micro powder below 500 meshes. The Ge powder is 5N grade pure germanium powder sold in market, is brittle powder obtained by mechanical crushing, and is screened to obtain fine powder below 500 meshes. Mixing the silver alloy powder with Ge powder and silver alloy powder: the weight percentages of Ge powder =97:3 are respectively weighed and then mixed for more than 6hr by a Y-type mixer until the two are uniformly mixed.
Putting the mixed powder into a powder feeding cylinder of a binder-sprayed metal 3D printing device, inputting a pre-drawn 3D image, and starting a printing process flow: a layer of the mixed powder is spread on a powder bed and scraped off by a doctor blade, and then a light-curing adhesive is selectively sprayed onto the powder bed by an ink-jet printing head, and the powder bed is irradiated with infrared rays to cure and bond the part on which the light-curing adhesive is sprayed. Each time one layer is created, the printing surface moves downwards by a layer thickness distance, the next layer of mixed powder is spread, the adhesive and the light-cured adhesive are sprayed in the selected area, and then light curing is carried out; the process is repeated until printing is completed, and a green blank with a shape completely conforming to the pre-designed 3D graph is obtained. The printing thickness of each layer was set to 50 μm; the light-cured binder adopts water-soluble phenolic resin glue. The green embryos obtained were printed with a relative density of 66%.
After printing is finished, taking out the obtained complete 3D printing green blank, and blowing off floating powder on the surface of the green blank by using compressed air; and (3) placing the green embryo piece in a degreasing furnace, and heating according to a set process curve to decompose the organic binder in the green embryo to obtain a brown embryo. The degreasing temperature is 300 deg.C, maintaining for 8hr, and protecting with nitrogen gas in the degreasing furnace.
And (4) putting the degreased brown blank into an atmosphere sintering furnace, and sintering according to a preset process curve to obtain a compact sintered part. The sintering process conditions are as follows: setting the maximum sintering temperature range at 930 deg.C, and the sintering period takes 28 hr; the linear shrinkage of the sintered article was found to be 18.1% and the relative density of the sintered article was found to be 98.8%.
And grinding and polishing the sintered part to finally obtain the finished product of the silver-germanium ornament, wherein the product contains Ag93.6% and Ge 3%.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and the related alloy element ratio changes within the formula scope of the present invention should also fall within the protection scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (8)
1. A manufacturing process of silver germanium infrared health care ornaments is characterized by at least comprising the following steps:
the method comprises the following steps: weighing Ag alloy powder and Ge powder according to mass percent, and fully and uniformly stirring in a mixer to obtain mixed powder;
step two: putting the mixed powder obtained in the step one into a powder feeding cylinder of a binder spraying 3D printing device, firstly spreading a layer of mixed powder on a powder bed and leveling the mixed powder by using a scraper, then selectively spraying a light-cured binder on the powder bed by using an ink-jet printing head, and irradiating the powder bed by using infrared rays to cure and bond the part sprayed with the light-cured binder; each time one layer is created, the printing surface moves downwards by a layer thickness distance, the next layer of mixed powder is spread, the adhesive and the light-cured adhesive are sprayed in the selected area, and then light curing is carried out; repeating the process until printing is finished, and manufacturing a three-dimensional structure by overlapping layer by layer until a green body with a shape completely conforming to a pre-designed 3D graph is obtained;
step three: taking out the complete 3D printing green body obtained in the step two, and removing floating powder on the surface of the green body; placing the green body piece in a degreasing furnace, and heating to decompose the photo-curing binder in the green body to obtain a degreased green body;
step four: putting the degreased green blank obtained in the third step into an atmosphere sintering furnace, and sintering under the protection of protective gas to obtain a compact sintered part;
step five: and D, performing die holding post-treatment processing on the sintered piece obtained in the step four to finally obtain the finished product of the silver-germanium ornament.
2. The manufacturing process of the silver-germanium infrared health-care ornament according to claim 1, wherein the silver alloy powder in the first step is spherical powder prepared by an air atomization method, and the particle size range of the silver alloy powder is 1-45 mu m.
3. The manufacturing process of the silver-germanium infrared health-care ornament as claimed in claim 1, wherein the constituent elements of the silver alloy powder in the first step include at least one of Ag, Au, Cu, Si, Ni, Al, Zn and Ge, and the Ag alloy powder comprises the following components: ag (90-98 wt%); cu (0-8 wt%); si (0-3 wt%); ni (0-3 wt%); al (0-3 wt%); zn (0-3 wt%).
4. The manufacturing process of the silver germanium infrared health-care ornament according to claim 1, wherein the Ge powder in the first step is pure Ge powder, is brittle powder obtained by a mechanical crushing or airflow crushing method, and has the particle size distribution of 0.1-25 mu m.
5. The manufacturing process of the silver germanium infrared health-care ornament as claimed in claim 1, wherein in the mixed powder of the first step, the mass ratio of Ge powder is 0.5-10 wt%.
6. The manufacturing process of the silver germanium infrared health care ornament according to claim 1, wherein the photo-curing adhesive in the second step is water-soluble phenolic resin glue.
7. The process for preparing silver germanium infrared health-care ornament according to claim 1, wherein the heating temperature in the third step is 200-.
8. The manufacturing process of the silver germanium infrared health care ornament according to claim 1, wherein the protective gas in the fourth step is nitrogen or argon, and the sintering process conditions are as follows: the maximum sintering temperature range is 900-930 ℃, and the sintering period is 19-24 hr.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117358926A (en) * | 2023-12-05 | 2024-01-09 | 天津大学 | Preparation method of germanium diaphragm array and light field imaging system |
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