CN114250049B - Ultralow-viscosity adhesive for metal 3DP printing process and preparation method thereof - Google Patents
Ultralow-viscosity adhesive for metal 3DP printing process and preparation method thereof Download PDFInfo
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- CN114250049B CN114250049B CN202110669293.2A CN202110669293A CN114250049B CN 114250049 B CN114250049 B CN 114250049B CN 202110669293 A CN202110669293 A CN 202110669293A CN 114250049 B CN114250049 B CN 114250049B
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- 239000000853 adhesive Substances 0.000 title claims abstract description 97
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 97
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 88
- 239000002184 metal Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000007639 printing Methods 0.000 title claims abstract description 31
- 230000008569 process Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 48
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 33
- 239000003085 diluting agent Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000003906 humectant Substances 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 229920003987 resole Polymers 0.000 claims description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 82
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 235000015895 biscuits Nutrition 0.000 description 46
- 238000010438 heat treatment Methods 0.000 description 44
- 239000007921 spray Substances 0.000 description 36
- 238000005245 sintering Methods 0.000 description 23
- 238000005507 spraying Methods 0.000 description 17
- 229910000984 420 stainless steel Inorganic materials 0.000 description 14
- 238000001816 cooling Methods 0.000 description 14
- 238000001723 curing Methods 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 13
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 229920001568 phenolic resin Polymers 0.000 description 11
- 239000005011 phenolic resin Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000005452 bending Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000005238 degreasing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000003860 storage Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 238000010408 sweeping Methods 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000012835 hanging drop method Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
An ultralow-viscosity adhesive for a metal 3DP printing process and a preparation method thereof belong to the field of additive manufacturing. The adhesive comprises the following components in percentage by mass: 3 to 20 percent of binder base stock, 75 to 92.5 percent of diluent, 0.5 to 3.0 percent of amphiphilic adhesion promoter, 3 to 12 percent of humectant and 1 to 5 percent of glidant; the amphiphilic adhesion promoter is a molecule with an amphiphilic structure, one end of the amphiphilic adhesion promoter contains a polar group, the other end of the amphiphilic adhesion promoter is an organic chain segment containing a reactive functional group, the polar group and the surface group of the metal powder generate intermolecular forces or chemical bonding, the other end of the amphiphilic adhesion promoter generates stronger intermolecular forces or generates physical entanglement or chemical reaction between the organic chain segment containing the reactive functional group and the binder base material, the function of a bridge is achieved between the binder base material and the metal powder, the separation of the binder base material and the metal powder can be avoided, and the coating effect of the binder on the metal powder is improved.
Description
Technical Field
The invention belongs to the field of additive manufacturing, and particularly relates to a metal 3DP process ultralow-viscosity adhesive and a preparation method thereof.
Background
Three-dimensional printing (Three-Dimension Printing,3 DP) is also called binder spraying (Binder Jetting Printing, BJP), which is based on the principle of droplet spraying, and is used for selectively spraying and binding loose powder according to a path designed by a computer, stacking and forming the loose powder layer by layer, and finally obtaining a required product through post-treatment. The process requires that the metal powder is spherical or nearly spherical, is prepared by an air atomization process, has uniform particle size, excellent fluidity and particle size distribution range of 15-60 mu m. The binder requirements for the printer head are: stable performance, long-term storage, low viscosity (< 50 mPa.s), surface tension of 30-60mN/m, low corrosiveness to spray nozzle, difficult blockage of spray nozzle, difficult drying, and long-term use. The adhesive is required to meet the requirements, and auxiliaries such as a humectant, a glidant, a surfactant, a pH regulator and the like are added into the system to improve the performance of the adhesive.
At present, few manufacturers for preparing metal products by using a 3DP printing technology are available in the market, and the market of the 3DP metal printer mainly adopts foreign manufacturers. In 1997, exOne introduced the first metal binder jet 3D printer prometals RTS-300 in the world, pulling open the development prologue of metal 3DP printers. The company adopts a heat curing mode, spreads a layer of powder, sprays a layer of water-based adhesive, and then carries out heat treatment at 180-200 ℃ for curing and forming to obtain the biscuit. However, the device requires insulation of the entire chamber to maintain the powder at 40-80 ℃, increasing the manufacturing cost of the 3DP device. In 2012, a single-channel injection technology Metal 3D printer DM P2500 is developed by a Digital Metal company of Swedish manufacturer, powder spreading and binder injection are completed at one time, the printing rate is improved, epoxy resin is used as an adhesive, the device does not need to be heated and cured in a later period, the steps are simplified, and the efficiency is improved. However, the equipment still needs to perform heat preservation operation on the whole cavity, so that the manufacturing cost of the equipment is increased, the viscosity of the epoxy resin adhesive is higher, and strict requirements are imposed on the spray head. Hewlett-Packard company is one of the important manufacturers who produce the shower nozzle, relies on self advantage, promotes Metal 3DP printer-HP Metal Jet in 2018, spreads the powder first, then sprays water-based adhesive through the thermal foaming 3D print head on the Metal powder, evaporates the moisture in the binder, leaves the polymer and will Metal adhesive, so this equipment needs the powder bed to heat, keep warm continually, can increase energy consumption and improve equipment cost. At present, the metal 3DP printer is still blank in the domestic market, and only the metal 3DP printer which is promoted by the Wuhan Yi company is realized in the market. The equipment uses phenolic resin as a binder, a layer of powder is paved and a layer of binder is sprayed, and finally the whole cavity is cured at 150-200 ℃ to obtain a metal biscuit, so that the equipment cavity does not need to be insulated, the running cost of the equipment can be reduced, but the viscosity of the binder is 10-15 cP, the viscosity is higher, only an industrial spray head can be used for spray printing, the equipment cost is increased, the spray head is a consumable product, the periodic replacement is needed, and the running cost of the equipment in the use process is further increased. Therefore, the metal 3DP printer has great development space and research potential in equipment, adhesives and process flows.
At present, the 3DP technology is adopted to prepare metal parts, which has the following disadvantages: 1. because of the limitation of the 3DP technology, loose powder is solidified and molded by using an adhesive, and then degreased and sintered to finally obtain the required finished product. The porosity of the cured biscuit is higher, and the dimensional shrinkage of the degreased and sintered product is larger; and if the degreasing is not complete, the adhesive residue can affect the performance of the final product. 2. The influence of the spray heads on the market has high requirements on the surface tension and viscosity of the adhesive, and the selection of the adhesive type is limited, so that only a small part of the adhesive is suitable for the process. The above disadvantages make the requirement on the adhesive higher and higher, so people are required to further develop or improve the adhesive to obtain the metal 3DP adhesive formula with excellent performance. The adhesives commonly used in the metal 3DP technology at present are epoxies, UV glues, aqueous adhesives, phenolics, etc. The epoxy adhesive has high viscosity and is not easy to dilute, and most of epoxy in the market is bi-component, and expensive industrial double spray heads are needed for printing, so that the manufacturing cost is increased; the UV adhesive has higher requirements on a spray head and a metal 3DP machine, a light curing assembly needs to be added, the machine structure is complex, and the equipment cost is increased; the water-based adhesive contains a large amount of water, the cavity is required to be maintained at a certain temperature, the volatilization speed of the water is increased, the water is further required to be heated, removed and solidified and formed in the later period, the energy consumption is increased, the equipment cost is high, the bonding strength of the water-based adhesive is weak, and the defects that cracks are easy to generate in the manufacture of large-size metal parts are overcome; the phenolic adhesive has adjustable viscosity and high bonding strength, and can be cured in a later stage, so that the equipment does not need to be provided with a cavity heat preservation device or a UV curing device, the equipment is simple, and the equipment manufacturing difficulty and the manufacturing cost are reduced. However, the viscosity of the phenolic resin adhesive used in the market at present is at least 10cP, and the common commercial spray heads can not spray, and all the spray heads are industrial spray heads, so that the equipment cost is increased. If the diluent is forcibly added to reduce the viscosity, the effect of the bonding is not achieved because the concentration of the bonding material contained therein is low.
The invention aims to prepare the phenolic resin with ultralow viscosity, the viscosity of the adhesive is between 2 and 6cP, the ultralow viscosity adhesive can reduce the requirement on a spray head, and the common commercial spray head can be selected for metal printing, so that the manufacturing cost of equipment is greatly reduced, and the phenolic resin with ultralow viscosity makes a contribution to promoting the popularization and popularization of metal 3 DP.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides an ultralow-viscosity adhesive for a metal 3DP process and a preparation method thereof.
The adhesive has extremely low viscosity and no insoluble matters. The invention has low requirement on metal 3DP machine, lower requirement on spray head, wider adaptability of glue, and low price commercial spray head.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides an ultralow-viscosity adhesive for a metal 3DP printing process and a preparation method thereof, and is characterized in that the adhesive comprises the following components in percentage by mass: 3 to 20 percent of binder base stock, 75 to 92.5 percent of diluent, 0.5 to 3.0 percent of amphiphilic adhesion promoter, 3 to 12 percent of humectant and 1 to 5 percent of glidant; the amphiphilic adhesion promoter is a molecule with an amphiphilic structure, one end of the amphiphilic adhesion promoter contains a polar group, the other end of the amphiphilic adhesion promoter is an organic chain segment containing a reactive functional group, the polar group and the surface group of the metal powder generate intermolecular forces or chemical bonding, the other end of the amphiphilic adhesion promoter generates stronger intermolecular forces or generates physical entanglement or chemical reaction between the organic chain segment containing the reactive functional group and the binder base material, the function of a bridge is achieved between the binder base material and the metal powder, the separation of the binder base material and the metal powder can be avoided, and the coating effect of the binder on the metal powder is improved.
Preferably, the binder is selected to be a resole.
Preferably, the selected diluent is at least one of ethanol, isopropanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, and ethylene glycol butyl ether.
Preferably, the amphiphilic adhesion agent selected is at least one of 3-aminopropyl trimethoxysilane, aminopropyl triethoxysilane, N- β - (aminoethyl) - γ -aminopropyl methyldimethoxysilane.
Preferably, the humectant is at least one of ethylene glycol, propylene glycol, glycerol, polypropylene glycol, diethylene glycol.
Preferably, the glidant is selected from at least one of ethylene glycol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600, sodium polyacrylate.
The invention also provides a preparation method of the ultralow-viscosity adhesive for the metal 3DP printing process, which comprises the following steps:
step one: mechanically stirring the binder base material, the diluent and the humectant uniformly, and carrying out ultrasonic treatment;
step two: and (3) adding the amphiphilic adhesion promoter and the glidant into the mixture uniformly mixed in the step one, uniformly stirring, performing ultrasonic treatment and filtering treatment to obtain the adhesive.
The amphiphilic adhesion promoter is a molecule with an amphiphilic structure, one end of the amphiphilic adhesion promoter contains a polar group, the other end of the amphiphilic adhesion promoter is an organic chain segment containing a reactive functional group, groups such as siloxane and the like are hydrolyzed in a solvent (water in the solvent is self-contained water), hydroxyl is generated, the hydroxyl further generates hydrogen bonds with the hydroxyl on the metal surface, and the hydrogen bonds are dehydrated and condensed to generate Si-O-M chemical bonds with the metal surface at high temperature; the amino group in the organic chain segment with the amino functional group at the other end is a polar group, can generate a hydrogen bond with the hydroxyl group in the phenolic resin, can also generate a chemical bond with the phenolic resin, and meanwhile, the organic chain segment in the amphiphilic adhesion promoter can be physically entangled with the phenolic polymer. The amphiphilic adhesion promoter reacts with or bonds with the metal and the binder, so that the bonding effect of the binder is greatly improved, and the required biscuit strength can be still achieved by reducing the concentration of the binder.
The invention has the advantages that: the adhesive has wide adaptability and lower requirements on the spray heads, can be used without selecting expensive industrial spray heads and can be used by adopting low-cost commercial spray heads by optimizing the formula of the adhesive; meanwhile, the adhesive is a single component, and is heated in the later period to be automatically solidified, so that the metal powder is not required to be treated, the requirement on the metal powder is low, and the process flow can be reduced; in addition, the adhesive has lower requirements on metal 3DP machines, does not need devices such as ultraviolet lamps, infrared lamps, cavity heat preservation and the like, and reduces the cost and the manufacturing difficulty of the machines.
Detailed Description
The following describes the present invention in detail. The following description of technical features is based on the representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, "%" means mass% unless otherwise specified.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In the present specification, the piezoelectric nozzle ink-jet printing technology is adopted for the metal powder 3DP process in the embodiment of the present invention. The printing process is similar to the printing process, is linear motion, can be used by combining two or more spray heads according to the requirement, further improves the printing efficiency, selects proper binder and piezoelectric spray heads to be matched, is used on metal powder, is beneficial to shortening the 3D printing time, and achieves the purpose of rapid prototyping.
Examples
The present invention is specifically illustrated by the following examples, but the present invention is not limited to the examples.
< evaluation method >
The adhesive viscosity and surface tension are mainly focused on the metal 3DP adhesive, the bending strength of a biscuit is focused on the cured product, and the compactness of the product is focused on the sintered product, so that the following test is carried out.
Viscosity test: the viscosity of the adhesive is tested by adopting a rotary method in GB/T10247-2008 standard, using a Brookfield DV3T rotary viscosity tester, selecting a model SC4-18 rotor, and testing the viscosity of the adhesive at 25 ℃.
Surface tension test: the adhesive surface tension was measured using the hanging drop method using a KRUSS DSA25S instrument using ISO 19403-3-2017 standard.
Biscuit strength: the cured biscuit is printed out to be 31.75 multiplied by 12.70 multiplied by 6.35mm by adopting the ASTM B312-2009 standard 3 The bending strength of the metal greensheet is obtained by using an electronic universal tester.
Density: and measuring the density of the sintered metal part by using an Archimedes drainage method by adopting GB/T3850-2015 standard on the sintered part, and further calculating the density of the part.
Example 1
Table 1 example 1 formulation table
| Composition of the components | Name of the name | Mass fraction/% |
| Base material | Resol phenolic resin | 3 |
| Diluent agent | Ethanol | 91 |
| Humectant type | Glycerol | 3 |
| Glidant | Polyethylene glycol 200 | 1 |
| Amphiphilic adhesion promoter | 3-aminopropyl trimethoxysilane | 2 |
Step one: mechanically stirring the base material, the diluent and the humectant for 30min according to the formula of the table, performing ultrasonic treatment for 10min, and uniformly mixing.
Step two: adding the amphiphilic adhesion promoter and the glidant in the formula into the mixture uniformly mixed in the step one, stirring uniformly, and performing suction filtration to prepare the adhesive using the metal 3DP technology.
The adhesive prepared above was subjected to viscosity and surface tension test at room temperature (25 ℃ C.) to give an adhesive having a viscosity of 2.14 mPas and a surface Zhang Liwei 24.31.31 mN.m -1 。
The using method of the adhesive comprises the following steps: a) Importing a required printing model on metal 3DP equipment; b) Adding the prepared binder into an ink storage tank, and placing metal powder with the particle size of 15-60 mu m into a powder supply cylinder; c) Performing printing operation, spraying an adhesive according to a path designed by a computer by a spray head every time one layer of powder is paved, then descending one layer of powder supply cylinder by one layer of powder supply cylinder, paving the powder on the forming cylinder by using a powder paving roller, spraying an adhesive again, and overlapping layer by layer to finally obtain an uncured biscuit; d) Placing the forming cylinder containing the biscuit in a baking oven at 150 ℃ for 2 hours for heating and curing, and sweeping off superfluous powder to obtain the required biscuit; e) Placing the biscuit in a vacuum furnace, heating from 25 ℃ to 450 ℃ at a heating rate of 1 ℃/min, preserving heat for 2 hours for degreasing, heating to a metal sintering temperature at a heating rate of 3 ℃/min (420 stainless steel is taken as an example, the sintering temperature is set at 1350 ℃) for 2 hours, cooling to 250 ℃ at a heating rate of 5 ℃/min, and cooling to normal temperature along with the furnace, thus finally obtaining the required metal workpiece.
Taking 420 stainless steel powder as an example, the bending strength of the cured obtained biscuit is 4.2MPa, and the density of the degreased and sintered finished product is 87.73 percent.
When the content of the base material is lower than 3%, the strength of the biscuit is weaker, and the printed part is difficult to take out; when the content of the base material is 3%, the biscuit has certain strength, small-size parts can be printed, and large-size parts (the sizes of the parts exceed 5 cm) are easy to break when taken out. When the content of the base material is low, the distance between particles is larger, the porosity after sintering is higher, and the compactness of the part is lower. The binder content should be increased appropriately for parts of larger size and more complex shape.
Example 2
Table 2 example 2 formulation table
| Composition of the components | Name of the name | Mass fraction/% |
| Base material | Resol phenolic resin | 20 |
| Diluent agent | Ethanol | 74 |
| Humectant type | Glycerol | 3 |
| Glidant | Polyethylene glycol 200 | 1 |
| Amphiphilic adhesion promoter | 3-aminopropyl trimethoxysilane | 2 |
Step one: mechanically stirring the base material, the diluent and the humectant for 30min according to the formula of the table, performing ultrasonic treatment for 10min, and uniformly mixing.
Step two: adding the amphiphilic adhesion promoter and the glidant in the formula into the mixture uniformly mixed in the step one, stirring uniformly, and performing suction filtration to prepare the adhesive using the metal 3DP technology.
The adhesive prepared above was subjected to viscosity and surface tension test at room temperature (25 ℃ C.) to give an adhesive having a viscosity of 3.55 mPas and a surface Zhang Liwei 32.78.32.78 mN.m -1 . When example 2 is compared with example 1, it can be seen that increasing the binder content significantly increases the binder viscosity and surface tension, but the binder viscosity and surface tension remain relatively low due to the lower overall binder content.
The using method of the adhesive comprises the following steps: a) Importing a required printing model on metal 3DP equipment; b) Adding the prepared binder into an ink storage tank, and placing metal powder with the particle size of 15-60 mu m into a powder supply cylinder; c) And (3) performing printing operation, spraying an adhesive according to a path designed by a computer by a spray head every time one layer of powder is paved, then descending one layer of forming cylinder, lifting one layer of powder supply cylinder, paving the powder on the forming cylinder by using a powder paving roller, spraying an adhesive again, and stacking layer by layer to finally obtain an uncured biscuit. d) And (3) placing the forming cylinder containing the biscuit in an oven at 150 ℃ for 2 hours for heating and curing, and sweeping off the redundant powder to obtain the required biscuit. e) Placing the biscuit in a vacuum furnace, heating from 25 ℃ to 450 ℃ at a heating rate of 1 ℃/min, preserving heat for 2 hours for degreasing, heating to a metal sintering temperature at a heating rate of 3 ℃/min (420 stainless steel is taken as an example, the sintering temperature is set at 1350 ℃) for 2 hours, cooling to 250 ℃ at a heating rate of 5 ℃/min, and cooling to normal temperature along with the furnace, thus finally obtaining the required metal workpiece.
Taking 420 stainless steel powder as an example, the bending strength of the cured biscuit is 9.3MPa, and the sintering density is 93.79%. The increase of the binder base stock content obviously improves the strength and the density of the biscuit after sintering, but the binder base stock content is too high (more than 20 percent), the binder viscosity is more than 6 mPa.s, the binder is not easy to spray from a common spray head, the industrial spray head needs to be replaced, and the equipment cost is increased; the permeability of the printed product is strong, and the boundary precision and the surface roughness are reduced; the base material with too high content is not easy to be discharged in the later degreasing and sintering process, so that the metal components are influenced, and the final strength of the metal part is further influenced.
Example 3
Table 3 example 3 formulation table
| Composition of the components | Name of the name | Mass fraction/% |
| Base material | Resol phenolic resin | 12 |
| Diluent agent | Ethanol | 10 |
| Diluent agent | Ethylene glycol monomethyl ether | 62 |
| Humectant type | Glycerol | 8 |
| Glidant | Ethylene glycol | 5 |
| Amphiphilic adhesion promoter | Aminopropyl triethoxysilane | 3 |
Step one: mechanically stirring the base material, the diluent and the humectant for 30min according to the formula of the table, performing ultrasonic treatment for 10min, and uniformly mixing.
Step two: adding the amphiphilic adhesion promoter and the glidant in the formula into the mixture uniformly mixed in the step one, stirring uniformly, and performing suction filtration to prepare the adhesive using the metal 3DP technology.
The adhesive thus obtained was subjected to viscosity and surface tension tests at ordinary temperature (25 ℃ C.) to give an adhesive having a viscosity of 4.29 mPas and a surface Zhang Liwei 34.93.93 mN.m -1 . In example 3, compared with example 2, it can be seen that the change of the diluent has a larger influence on the viscosity and the surface tension of the system, the diluent is changed from the ethanol solvent to the mixed solvent of ethanol and ethylene glycol monomethyl ether, and even if the content of the base material is reduced, the viscosity of the binder is still increased from 3.55 mPas to 4.29 mPas, because the viscosity and the surface tension of the ethanol solvent are lower, when the system is the ethanol solvent, the viscosity and the surface tension of the system can be greatly reduced, but the strong volatility of the ethanol can cause fine cracks to be generated in the heating and curing process, so that the crack can be avoided by adding the solvent with higher boiling point into the system.
The using method of the adhesive comprises the following steps: a) Importing a required printing model on metal 3DP equipment; b) Adding the prepared binder into an ink storage tank, and placing metal powder with the particle size of 15-60 mu m into a powder supply cylinder; c) And (3) performing printing operation, spraying an adhesive according to a path designed by a computer by a spray head every time one layer of powder is paved, then descending one layer of forming cylinder, lifting one layer of powder supply cylinder, paving the powder on the forming cylinder by using a powder paving roller, spraying an adhesive again, and stacking layer by layer to finally obtain an uncured biscuit. d) And (3) placing the forming cylinder containing the biscuit in a 180 ℃ oven for 2 hours for heating and curing, and sweeping off the redundant powder to obtain the required biscuit. e) Placing the biscuit in a vacuum furnace, heating from 25 ℃ to 450 ℃ at a heating rate of 1 ℃/min, preserving heat for 2 hours for degreasing, heating to a metal sintering temperature at a heating rate of 3 ℃/min (420 stainless steel is taken as an example, the sintering temperature is set at 1350 ℃) for 2 hours, cooling to 250 ℃ at a heating rate of 5 ℃/min, and cooling to normal temperature along with the furnace, thus finally obtaining the required metal workpiece.
Taking 420 stainless steel powder as an example, the bending strength of the cured biscuit is 7.6MPa, and the sintering density is 96.28%.
Example 4
Table 4 example 4 formulation table
Step one: mechanically stirring the base material, the diluent and the humectant for 30min according to the formula of the table, performing ultrasonic treatment for 10min, and uniformly mixing.
Step two: adding the amphiphilic adhesion promoter and the glidant in the formula into the mixture uniformly mixed in the step one, stirring uniformly, and performing suction filtration to prepare the adhesive using the metal 3DP technology.
The adhesive prepared above was subjected to viscosity and surface tension test at room temperature (25 ℃ C.) to give an adhesive having a viscosity of 4.46 mPas and a surface Zhang Liwei 38.04 mN.m -1 . In comparison with example 4 and example 3, the diluent is replaced with a solvent having a higher viscosity, a higher boiling point and a poorer volatility, which has a larger influence on the viscosity and the surface tension of the system, so that cracking of the product caused by too high volatilization rate of the diluent in the curing process can be avoided, but the curing temperature can be slightly increased, and the curing time can be prolonged.
The using method of the adhesive comprises the following steps: a) Importing a required printing model on metal 3DP equipment; b) Adding the prepared binder into an ink storage tank, and placing metal powder with the particle size of 15-60 mu m into a powder supply cylinder; c) And (3) performing printing operation, spraying an adhesive according to a path designed by a computer by a spray head every time one layer of powder is paved, then descending one layer of forming cylinder, lifting one layer of powder supply cylinder, paving the powder on the forming cylinder by using a powder paving roller, spraying an adhesive again, and stacking layer by layer to finally obtain an uncured biscuit. d) And (3) placing the forming cylinder containing the biscuit in a baking oven at 200 ℃ for 3 hours for heating and curing, and sweeping off the redundant powder to obtain the required biscuit. e) Placing the biscuit in a vacuum furnace, heating from 25 ℃ to 450 ℃ at a heating rate of 1 ℃/min, preserving heat for 2 hours for degreasing, heating to a metal sintering temperature at a heating rate of 3 ℃/min (420 stainless steel is taken as an example, the sintering temperature is set at 1350 ℃) for 2 hours, cooling to 250 ℃ at a heating rate of 5 ℃/min, and cooling to normal temperature along with the furnace, thus finally obtaining the required metal workpiece.
Taking 420 stainless steel powder as an example, the bending strength of the cured biscuit is 7.4MPa, and the sintering density is 98.01%.
Example 5
Table 5 example 5 formulation table
| Composition of the components | Name of the name | Mass fraction/% |
| Base material | Resol phenolic resin | 12 |
| Diluent agent | Ethanol | 10 |
| Diluent agent | Ethylene glycol monomethyl ether | 62 |
| Humectant type | Diethylene glycol | 3 |
| Humectant type | Propylene glycol | 5 |
| Glidant | Ethylene glycol | 5 |
| Amphiphilic adhesion promoter | Aminopropyl triethoxysilane | 3 |
Step one: mechanically stirring the base material, the diluent and the humectant for 30min according to the formula of the table, performing ultrasonic treatment for 10min, and uniformly mixing.
Step two: adding the amphiphilic adhesion promoter and the glidant in the formula into the mixture uniformly mixed in the step one, stirring uniformly, and performing suction filtration to prepare the adhesive using the metal 3DP technology.
The adhesive thus obtained was subjected to viscosity and surface tension tests at ordinary temperature (25 ℃ C.) to give an adhesive having a viscosity of 4.22 mPa.s and a surface Zhang Liwei 33.17.17 mN.m -1 . In comparison with example 5 and example 3, the viscosity of the humectant is higher, the viscosity of the binder is greatly affected, and if the content of the humectant in the system needs to be increased, the viscosity of the binder is kept to be relatively low, and ethylene glycol and propylene glycol with relatively low viscosity can be used as the humectant.
The using method of the adhesive comprises the following steps: a) Importing a required printing model on metal 3DP equipment; b) Adding the prepared binder into an ink storage tank, and placing metal powder with the particle size of 15-60 mu m into a powder supply cylinder; c) And (3) performing printing operation, spraying an adhesive according to a path designed by a computer by a spray head every time one layer of powder is paved, then descending one layer of forming cylinder, lifting one layer of powder supply cylinder, paving the powder on the forming cylinder by using a powder paving roller, spraying an adhesive again, and stacking layer by layer to finally obtain an uncured biscuit. d) And (3) placing the forming cylinder containing the biscuit in a 180 ℃ oven for 2 hours for heating and curing, and sweeping off the redundant powder to obtain the required biscuit. e) Placing the biscuit in a vacuum furnace, heating from 25 ℃ to 450 ℃ at a heating rate of 1 ℃/min, preserving heat for 2 hours for degreasing, heating to a metal sintering temperature at a heating rate of 3 ℃/min (420 stainless steel is taken as an example, the sintering temperature is set at 1350 ℃) for 2 hours, cooling to 250 ℃ at a heating rate of 5 ℃/min, and cooling to normal temperature along with the furnace, thus finally obtaining the required metal workpiece.
Taking 420 stainless steel powder as an example, the bending strength of the cured biscuit is 6.9MPa, and the sintering density is 97.21%. The humectant can reduce the volatilization rate of the adhesive, avoid the blockage of a spray head in the printing process, and reduce cracks caused by too fast volatilization of the adhesive in the curing process.
Example 6
Table 6 example 6 formulation table
| Composition of the components | Name of the name | Mass fraction/% |
| Base material | Resol phenolic resin | 12 |
| Diluent agent | Ethanol | 10 |
| Diluent agent | Ethylene glycol monomethyl ether | 62 |
| Humectant type | Diethylene glycol | 3 |
| Humectant type | Propylene glycol | 5 |
| Glidant | Sodium polyacrylate | 2 |
| Glidant | Polyethylene glycol 400 | 3 |
| Amphiphilic adhesion promoter | Aminopropyl triethoxysilane | 3 |
Step one: mechanically stirring the base material, the diluent and the humectant for 30min according to the formula of the table, performing ultrasonic treatment for 10min, and uniformly mixing.
Step two: adding the amphiphilic adhesion promoter and the glidant in the formula into the mixture uniformly mixed in the step one, stirring uniformly, and performing suction filtration to prepare the adhesive using the metal 3DP technology.
The adhesive prepared above was subjected to viscosity and surface tension test at room temperature (25 ℃ C.) to give an adhesive having a viscosity of 4.30 mPas and a surface Zhang Liwei 33.86 mN.m -1 . In comparison of example 6 with example 5, the glidant reduces the frictional resistance between the spray head and the adhesive, increases the fluidity of the adhesive in the metal powder, and properly increases the penetration thickness.
The using method of the adhesive comprises the following steps: a) Importing a required printing model on metal 3DP equipment; b) Adding the prepared binder into an ink storage tank, and placing metal powder with the particle size of 15-60 mu m into a powder supply cylinder; c) And (3) performing printing operation, spraying an adhesive according to a path designed by a computer by a spray head every time one layer of powder is paved, then descending one layer of forming cylinder, lifting one layer of powder supply cylinder, paving the powder on the forming cylinder by using a powder paving roller, spraying an adhesive again, and stacking layer by layer to finally obtain an uncured biscuit. d) And (3) placing the forming cylinder containing the biscuit in a 180 ℃ oven for 2 hours for heating and curing, and sweeping off the redundant powder to obtain the required biscuit. e) Placing the biscuit in a vacuum furnace, heating from 25 ℃ to 450 ℃ at a heating rate of 1 ℃/min, preserving heat for 2 hours for degreasing, heating to a metal sintering temperature at a heating rate of 3 ℃/min (420 stainless steel is taken as an example, the sintering temperature is set at 1350 ℃) for 2 hours, cooling to 250 ℃ at a heating rate of 5 ℃/min, and cooling to normal temperature along with the furnace, thus finally obtaining the required metal workpiece.
Taking 420 stainless steel powder as an example, the bending strength of the cured biscuit is 6.9MPa, and the sintering density is 98.13%.
Example 7
Table 7 example 7 recipe table
Step one: mechanically stirring the base material, the diluent and the humectant for 30min according to the formula of the table, performing ultrasonic treatment for 10min, and uniformly mixing.
Step two: adding the amphiphilic adhesion promoter and the glidant in the formula into the mixture uniformly mixed in the step one, stirring uniformly, and performing suction filtration to prepare the adhesive using the metal 3DP technology.
The adhesive thus obtained was subjected to viscosity and surface tension tests at ordinary temperature (25 ℃ C.) to give an adhesive having a viscosity of 3.84 mPas and a surface Zhang Liwei 31.58.58 mN.m -1 . Example 7 is compared to example 5, the amphipathic adhesion promoter increases the wettability of the adhesive with the metal powder while increasing the penetration thickness of the adhesive to some extent.
The using method of the adhesive comprises the following steps: a) Importing a required printing model on metal 3DP equipment; b) Adding the prepared binder into an ink storage tank, and placing metal powder with the particle size of 15-60 mu m into a powder supply cylinder; c) And (3) performing printing operation, spraying an adhesive according to a path designed by a computer by a spray head every time one layer of powder is paved, then descending one layer of forming cylinder, lifting one layer of powder supply cylinder, paving the powder on the forming cylinder by using a powder paving roller, spraying an adhesive again, and stacking layer by layer to finally obtain an uncured biscuit. d) And (3) placing the forming cylinder containing the biscuit in a 180 ℃ oven for 2 hours for heating and curing, and sweeping off the redundant powder to obtain the required biscuit. e) Placing the biscuit in a vacuum furnace, heating from 25 ℃ to 450 ℃ at a heating rate of 1 ℃/min, preserving heat for 2 hours for degreasing, heating to a metal sintering temperature at a heating rate of 3 ℃/min (420 stainless steel is taken as an example, the sintering temperature is set at 1350 ℃) for 2 hours, cooling to 250 ℃ at a heating rate of 5 ℃/min, and cooling to normal temperature along with the furnace, thus finally obtaining the required metal workpiece.
Taking 420 stainless steel powder as an example, the bending strength of the cured biscuit is 7.9MPa, and the sintering density is 97.97%. The amphiphilic adhesion promoter can increase the penetration thickness of the adhesive, enhance the filling of the adhesive in metal particles, increase the number of bonding necks among the particles, and further enhance the strength of the biscuit.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it is to be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications may be made.
Claims (1)
1. The ultra-low viscosity adhesive for the metal 3DP printing process is characterized by comprising the following components in percentage by mass: 3-20% of binder base stock, 72-92.5% of diluent, 0.5-3.0% of amphiphilic adhesion promoter, 3-12% of humectant and 1-5% of glidant;
the selected amphiphilic adhesion promoter is at least one of 3-aminopropyl trimethoxy silane, aminopropyl triethoxy silane and N-beta- (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane;
the binder base material is selected to be resole;
the selected diluent is at least one of ethanol, isopropanol, ethylene glycol methyl ether, ethylene glycol ethyl ether and ethylene glycol butyl ether; the humectant is at least one of propylene glycol, glycerol, polypropylene glycol and diethylene glycol; the glidant is at least one of glycol, polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 600 and sodium polyacrylate;
the preparation method comprises the following steps:
step one: mechanically stirring the binder base material, the diluent and the humectant uniformly, and carrying out ultrasonic treatment;
step two: adding an amphiphilic adhesion promoter and a glidant into the mixture uniformly mixed in the first step, uniformly stirring, performing ultrasonic treatment and filtering treatment to obtain the binder;
the viscosity of the adhesive is 2-6 cP.
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| CN107745068A (en) * | 2017-11-05 | 2018-03-02 | 中北大学 | A kind of laser 3D printing precoated sand and preparation method thereof |
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| CN107745068A (en) * | 2017-11-05 | 2018-03-02 | 中北大学 | A kind of laser 3D printing precoated sand and preparation method thereof |
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