CN115926635A - Ultraviolet-thermal dual-curing adhesive, preparation method and application in 3D printing - Google Patents
Ultraviolet-thermal dual-curing adhesive, preparation method and application in 3D printing Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention discloses an ultraviolet-thermal dual-curing adhesive and a preparation method thereof, wherein the ultraviolet-thermal dual-curing adhesive comprises 30-40 parts by weight of ultraviolet photosensitive resin, 10-20 parts by weight of thermosetting resin, 45-55 parts by weight of organic solvent and 1-8 wt% of photoinitiator of the ultraviolet photosensitive resin. The invention also discloses a 3D printing method using the binder, wherein ultraviolet light curing is carried out for 1-10s after each layer of the binder is sprayed to the powder material layer, then the next layer is manufactured, and heat curing is carried out after green body printing is finished. The invention combines the advantages of rapid photocuring and high strength of thermocuring, improves the printing precision of the green body and simultaneously improves the strength of the green body.
Description
Technical Field
The invention belongs to the field of additive manufacturing, and particularly relates to an ultraviolet-thermal dual-curing binder, a preparation method and application thereof in 3D printing.
Background
Additive manufacturing technology (also known as 3D printing technology) is one of the most representative rapid prototyping technologies. According to the method, the digital model is sliced, and computer-aided control equipment is used for accurately depositing the molding materials layer by layer according to the digital model slice, so that the 3D printing technology can quickly and efficiently manufacture the complex structure which cannot be manufactured by the traditional processing technology due to the layer-by-layer overlapped manufacturing mode. At present, the 3D printing technology has been widely applied in the fields of automobile manufacturing, tool preparation, aerospace, and the like.
Binder jetting 3D printing technology (3 DP), which is a powder bed based 3D printing technology, is one of the existing additive manufacturing technologies. The method comprises the steps of selectively spraying adhesive components to a designated area of a powder bed through a piezoelectric printing spray head according to a slice pattern of a model, enabling the adhesive to adhere powder particles in the area, then enabling the powder bed to descend by one layer thickness, enabling new powder to be spread to the printing area again through a scraper or a powder spreading roller, enabling the spray head to continuously print and spray on the new powder bed, enabling the powder between layers to be adhered together through the adhesive, and repeating the process to achieve layer-by-layer stacking of the model. The formed part is referred to as a green part, which is typically subjected to a series of post-treatments such as degreasing, sintering, infiltration, etc., to form the final finished part.
Compared with other existing 3D printing technologies based on powder beds, the 3DP technology is relatively low in energy consumption, does not need an inert gas protection environment, can produce parts in large batches, and is unlimited in forming size, so that the 3DP printing technology is easy to popularize commercially. The binder, a key component in the 3DP technology, not only takes on the task of binding the powder particles together, but also directly determines the quality of the final product. At present, most of adhesives select high molecular polymers as main components of the adhesives, such as polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyacrylamide (PAM) and the like, are diluted by using a large amount of solvents, such as water, alcohol, ethers and the like, and the polymer components are left in a powder bed to play a role in adhesion after the solvents are volatilized. This has led to several problems in the prior art of adhesives:
1. after long-time printing, a small amount of polymer is remained on the surface of the piezoelectric type spray nozzle, so that spray nozzle spray holes are easily blocked, the quality of a subsequent printing layer is reduced, and meanwhile, the maintenance of the spray nozzle is not facilitated.
2. The viscosity of the polymer is usually much higher than the viscosity working range (4-20mPa.s) of the commercially available piezoelectric printing nozzle, so that a large amount of solvent is needed to dilute the polymer component to meet the working requirement of the piezoelectric printing nozzle, the content of effective components playing a binding role in the binder is low, the strength of a green body is low, and a subsequent series of post-treatment processes cannot be supported.
3. In order to solve the problem of low green strength, the spraying amount of the binder is usually increased during the printing process to compensate the defect of insufficient effective binding components in the binder. Since the binder solution does not solidify immediately when sprayed onto the powder layer, the binder solution continues to penetrate into the powder layer under the influence of capillary forces and gravity, resulting in deformation and distortion of the green body.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an ultraviolet-thermal dual-curing adhesive, a preparation method and application thereof in 3D printing. The invention overcomes the problem of insufficient effective binding components in the traditional binder, and improves the green strength; and solves the problem of green body deformation caused by excessive penetration of a large amount of binder spray, and improves the surface quality of the green body.
The solvents that can be used include, but are not limited to, the above-mentioned ones, as long as the solvents that can completely dissolve the above-mentioned photosensitive resin and thermosetting resin can be applied to the present invention.
The invention provides an ultraviolet-heat dual-curing adhesive which comprises 30-40 parts by weight of ultraviolet photosensitive resin, 10-20 parts by weight of thermosetting resin, 45-55 parts by weight of organic solvent and 1-8 wt% of photoinitiator of the ultraviolet photosensitive resin.
Optionally, the ultraviolet photosensitive resin is selected from bifunctional acrylate, or a combination of bifunctional acrylate and at least one of monofunctional acrylate and trifunctional acrylate crosslinking agent; the difunctional acrylate is at least one selected from difunctional reactive diluent monomer 1, 6-hexanediol diacrylate, triethylene glycol dimethacrylate and tripropylene glycol diacrylate.
Optionally, the photoinitiator is selected from at least one of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, 1-hydroxycyclohexylphenyl ketone, and phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
Optionally, the thermosetting resin is phenolic resin or epoxy resin.
Optionally, the organic solvent is at least one selected from ethanol, n-propanol, isopropanol, ethylene glycol monomethyl ether, and diethylene glycol diethyl ether.
The invention also provides a preparation method of the ultraviolet-thermal dual-curing adhesive, which comprises the following steps:
mixing ultraviolet photosensitive resin and a photoinitiator to form a first heavy ultraviolet curing system;
step two, mixing the thermosetting resin with an organic solvent to form a second thermosetting system;
and step three, uniformly mixing the first double ultraviolet curing system and the second double ultraviolet curing system, and filtering to obtain the ultraviolet-heat double curing adhesive.
Optionally, the viscosity of the ultraviolet-thermal dual-curing adhesive is 5-15mpa.s, and the surface tension is 25-35mN/m.
The invention also provides an ultraviolet-thermal dual-curing 3D printing method, which adopts a 3D printer, wherein the 3D printer comprises a spraying system, a powder spreading mechanism, a powder bed and an ultraviolet generator mechanism, and the 3D printing method comprises the following steps:
a first step of spraying the ultraviolet-thermal dual curing adhesive according to any one of claims 1 to 5 onto a powder bed on which a powder material is spread, using a spraying system;
moving the ultraviolet generator mechanism to the upper part of the powder bed and emitting ultraviolet light, staying for 1-10s and then leaving the powder bed, and descending the printing platform by one layer thickness;
step three, the powder paving mechanism is used for flatly paving and covering the new powder material on the last solidified printing layer;
step four, repeating the step one to the step three until printing of the green body is completed;
and fifthly, transferring the loose powder material which is not bonded and the green body into a heating furnace together, heating the green body and the green body until the loose powder material is completely solidified, taking out the green body, naturally cooling the green body to room temperature, and removing the loose powder which surrounds the green body.
Optionally, the injection system uses a piezoelectric printing head.
Optionally, in the fifth step, the temperature for heating and curing is 150 ℃ to 200 ℃. Wherein:
in the first heavy ultraviolet curing system, a monomer with low viscosity is used, the printing requirement of the piezoelectric type printing nozzle is met, the monomer does not need to be diluted additionally, the polymerization reaction is carried out only when the monomer is exposed to ultraviolet light, and the nozzle hole cannot be blocked due to residue. The adhesive can be used as a diluent of an adhesive solution to reduce the content of Volatile Organic Compounds (VOC) in the adhesive solution, can exert an adhesive effect, and is beneficial to improving the strength of green compacts.
In the first heavy ultraviolet curing system, the high-efficiency photoinitiator is added, so that the ultraviolet curing speed is improved, the binder is irradiated and cured by an ultraviolet light source of a printer immediately after being sprayed to a powder bed in the printing process, the whole viscosity of the binder is rapidly increased due to the partially cured photosensitive resin, the permeation resistance of the binder in the powder bed is increased, the diffusion of the binder at the edge of a model is reduced, the problem of excessive permeation caused by large spraying amount of the binder is solved, and the surface quality of a green body is improved.
In the second thermosetting system, a thermosetting resin is used, which has a stronger adhesive strength than a photosensitive resin, and can further improve the green strength.
The invention has the following beneficial effects:
1. the ultraviolet-thermal dual-curing adhesive disclosed by the invention is low in viscosity, is suitable for spraying of a piezoelectric type spray head, and reduces the risk of blocking the spray head and the equipment failure rate compared with the traditional polymer adhesive;
2. the method is different from the mode of singly using photocuring or thermocuring by the traditional 3DP technology, combines the advantages of quick photocuring and high thermocuring strength, and can improve the printing precision of the green body and the strength of the green body; by separating the two steps of controlling precision and increasing strength in the 3DP technology printing process, firstly, the diffusion of the binder in a powder bed is limited in the printing process by using an ultraviolet curing mode, so that the binder is cured in situ, and the precision of a green body is improved; thermal energy is then used to activate the thermosetting components in the binder after printing is complete, further improving green strength.
Drawings
Fig. 1 is a flowchart of the uv-thermal dual-curing 3D printing method of example 5;
FIG. 2 is a schematic diagram showing the printing effect of the powder bed on the cross section when the binder injection amount is normal in example 5;
FIG. 3 is a schematic diagram showing the cross-sectional printing effect of the powder bed in case of excessive binder ejection in example 6;
FIG. 4 is a schematic diagram showing the printing effect of the powder bed section when the binder of the comparative example is sprayed excessively.
Detailed Description
The invention is further explained below with reference to the figures and the specific embodiments.
Example 1
Taking 30% by mass of triethylene glycol dimethacrylate as a photosensitive resin matrix material, adding 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide serving as a photoinitiator and accounting for 6% of the mass of the photosensitive resin, uniformly stirring and mixing the mixture in a stirrer until the photoinitiator is completely dissolved in the photosensitive resin, and preparing the first heavy ultraviolet curing component.
Taking 17% of thermosetting phenolic resin by mass fraction to dissolve in 53% of ethanol solvent by mass fraction, and uniformly mixing the mixture in a stirrer until the phenolic resin is completely dissolved in the ethanol solvent to prepare a second thermosetting component.
And (2) putting all the components into a stirrer, uniformly mixing and stirring for more than 1 hour until the two components are not obviously layered, filtering large-particle solid impurities in the binder by using a filter to obtain a mixed solution, and obtaining a filtrate, namely the ultraviolet-thermal dual-curing binder.
The viscosity of the adhesive is 5-15mPa.s, and the surface tension is 25-35mN/m so as to meet the spraying requirement of a sprayer.
Example 2
Taking 30% by mass of triethylene glycol dimethacrylate as a photosensitive resin matrix material, adding 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide serving as a photoinitiator accounting for 8% of the mass of the photosensitive resin, uniformly stirring and mixing the mixture in a stirrer until the photoinitiator is completely dissolved in the photosensitive resin, and preparing the first heavy ultraviolet curing component.
And (3) dissolving 20% of thermosetting phenolic resin in 50% of ethanol solvent by mass, and uniformly mixing the mixture in a stirrer until the phenolic resin is completely dissolved in the ethanol solvent to prepare a second thermosetting component.
And (3) putting all the components into a stirrer, uniformly mixing and stirring for more than 1 hour until the two components are not obviously layered, filtering large-particle solid impurities in the binder by using a filter to obtain a mixed solution, and obtaining a filtrate, namely the ultraviolet-thermal dual-curing binder.
The viscosity of the adhesive is 5-15mPa.s, and the surface tension is 25-35mN/m so as to meet the spraying requirement of a sprayer.
Example 3
Taking 15% by mass of triethylene glycol dimethacrylate and 15% by mass of 1, 6-hexanediol diacrylate as base materials of photosensitive resin, adding 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide serving as a photoinitiator accounting for 6% of the mass of the photosensitive resin and 1-hydroxycyclohexyl phenyl ketone serving as a photoinitiator accounting for 1% of the mass of the photosensitive resin, placing the mixture in a stirrer, uniformly stirring and mixing until the photoinitiator is completely dissolved in the photosensitive resin, and preparing the first heavy ultraviolet curing component.
Dissolving 20% of thermosetting phenolic resin by mass in a mixed solvent of 35% of ethanol by mass and 15% of ethylene glycol methyl ether by mass, and uniformly mixing the mixture in a stirrer until the phenolic resin is completely dissolved in the mixed solvent to prepare a second thermosetting component.
And (2) putting all the components into a stirrer, uniformly mixing and stirring for more than 1 hour until the two components are not obviously layered, filtering large-particle solid impurities in the binder by using a filter to obtain a mixed solution, and obtaining a filtrate, namely the ultraviolet-thermal dual-curing binder.
The viscosity of the adhesive is 5-15mPa.s, and the surface tension is 25-35mN/m so as to meet the spraying requirement of a sprayer.
Example 4
Taking 35% of photosensitive resin mixture by mass fraction, adding 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide serving as a photoinitiator and accounting for 6% of the photosensitive resin by mass fraction, placing the mixture in a stirrer, uniformly stirring and mixing until the photoinitiator is completely dissolved in the photosensitive resin, and preparing the first heavy ultraviolet curing component. Wherein the photosensitive resin mixture comprises 10-20 parts of monofunctional acrylate, 30-40 parts of difunctional acrylate and 20-30 parts of trifunctional acrylate crosslinking agent according to parts by weight.
Dissolving 15% of thermosetting epoxy resin in 50% of ethanol solvent by mass, and uniformly mixing the mixture in a stirrer until the phenolic resin is completely dissolved in the ethanol solvent to prepare a second thermosetting component.
And (3) putting all the components into a stirrer, uniformly mixing and stirring for more than 1 hour until the two components are not obviously layered, filtering large-particle solid impurities in the binder by using a filter to obtain a mixed solution, and obtaining a filtrate, namely the ultraviolet-thermal dual-curing binder.
The viscosity of the adhesive is 5-15mPa.s, and the surface tension is 25-35mN/m so as to meet the spraying requirement of a sprayer.
Example 5
An ultraviolet-thermal dual curing 3D printing method using a 3D printer and the ultraviolet-thermal dual curing adhesive prepared in examples 1 to 4. Conventionally, a 3D printer includes a jetting system, a powder spreading mechanism, a powder bed, and an ultraviolet light generator mechanism. The ultraviolet light generator can emit ultraviolet light with the wavelength of 365nm-405nm, and the specific wavelength needs to be matched with the absorption wavelength of the photoinitiator in the ultraviolet-thermal dual curing adhesive so as to achieve efficient photocuring reaction. The jet system uses a piezoelectric print head. Referring to fig. 1, the specific process steps are as follows:
step 1: and (3) accurately spraying the ultraviolet-thermal dual-curing adhesive to a powder bed flatly paved with the powder material according to digital model slice data by using a spray head.
Step 2: the uv generator mechanism moves over the powder bed and emits uv light for a 1-10s, e.g., 5s, until the binder is photo-cured and the uv generator mechanism leaves the powder bed. The photosensitive component in the uv-thermal dual cure adhesive cures, and the viscosity of the adhesive increases dramatically and the diffusion resistance increases dramatically, so that the adhesive is fixed in place, which can also be referred to as in-situ curing. The printing platform is then lowered by one layer thickness.
And step 3: and the powder spreading mechanism lays and covers the new powder material to the last solidified printing layer.
And 4, step 4: and (4) repeating the steps 1, 2 and 3 until the printing of the green body is completed.
And 5: and after printing of the green body is finished, transferring the green body together with the loose powder material which is not bonded and the green body into a heating furnace for heating until the thermosetting binder is completely cured, taking out the green body, naturally cooling the green body to room temperature, and removing the loose powder surrounding the green body to obtain the complete green body. The heating temperature and time should be determined according to the characteristics of the thermosetting resin in the uv-thermal dual curing binder to achieve high green strength. For example, for thermosetting phenolic resins, the heating temperature is from 150 ℃ to 200 ℃.
Wherein the jetting amount of each layer of binder is expressed by binder saturation = volume of binder jetted to the powder bed/volume of pores of the powder bed in the jetted region. In this embodiment, the saturation of the binder is about 50%, and the obtained pattern is as shown in fig. 2, taking printing a geometric model as an example, and the actual printing forming area coincides with the digital model setting area when viewed from the powder bed cross section, so that the printing effect meets the requirement.
Example 6
The difference between example 6 and example 5 is that the adhesive saturation of each layer of adhesive is greater than 100%, which is the case of excessive adhesive spray. Because each printing layer is cured by ultraviolet light in advance in the printing process, the binder can not continuously permeate, the curing of the binder is not complete, after the whole printing process is finished, the green body is transferred to a heating furnace, the thermosetting resin is completely cured, and the green body strength is further improved. The printing effect is shown in fig. 3, because the binder is sprayed excessively, the green body boundary will inevitably exceed the digital model boundary, but the exceeding range is controlled in a small range, and the green body shape will not be deformed obviously and can still be used normally.
Comparative example
The 3D printing method of the comparative example was:
step 1: and (3) accurately spraying the adhesive to the powder bed paved with the powder material flatly according to the digital model slice data by using a spray head. The binder is composed of thermosetting phenolic resin with a mass fraction of 20% and ethanol solution with a mass fraction of 80%.
Step 2: the printing platform descends by one layer thickness, and the powder spreading mechanism spreads the new powder material flatly and covers the last solidified printing layer.
And step 3: and (3) repeating the steps 1 and 2 until the printing of the green body is finished.
And 4, step 4: after the green body printing is completed, the green body together with the loose powder material which is not bonded is transferred to a heating furnace and is also heated at 150-200 ℃ until the curing is completed.
The binder saturation of the binder of each layer of the comparative example is greater than 100%, also in the case of excess binder spray. Referring to fig. 4, when the binder is excessively sprayed and printed by the printing method of the comparative example, the binder in the powder bed cannot be cured in time, so that the binder excessively permeates in the powder bed and exceeds the region set by the digital model, the green compact is distorted and deformed, and the boundary of the green compact far exceeds the set boundary of the digital model and is seriously deformed.
In addition, the uv-thermal dual-curing binder of example 5 includes a photosensitive resin and a thermosetting resin, both of which provide strength to the green body, resulting in a higher green body strength using this printing method than the printing method of comparative example. Helps maintain the integrity of the green body during post-processing and helps in the manufacture of thin-walled parts.
The above examples are only intended to further illustrate the uv-thermal dual curing binder of the present invention and the preparation method and application thereof in 3D printing, but the present invention is not limited to the examples, and any simple modification, equivalent change and modification made to the above examples according to the technical spirit of the present invention fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. An ultraviolet-thermal dual curing adhesive, characterized in that: the ultraviolet-thermal dual-curing adhesive comprises 30-40 parts by weight of ultraviolet photosensitive resin, 10-20 parts by weight of thermosetting resin, 45-55 parts by weight of organic solvent and 1-8 wt% of photoinitiator.
2. The ultraviolet-thermal dual curing adhesive according to claim 1, characterized in that: the ultraviolet photosensitive resin is selected from bifunctional acrylate, or a combination of bifunctional acrylate and at least one of monofunctional acrylate and trifunctional acrylate crosslinking agent; the difunctional acrylate is at least one selected from difunctional reactive diluent monomer 1, 6-hexanediol diacrylate, triethylene glycol dimethacrylate and tripropylene glycol diacrylate.
3. The ultraviolet-thermal dual curing adhesive according to claim 1, characterized in that: the photoinitiator is at least one selected from 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 1-hydroxycyclohexyl phenyl ketone and phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide.
4. The ultraviolet-thermal dual curing adhesive according to claim 1, characterized in that: the thermosetting resin is phenolic resin or epoxy resin.
5. The ultraviolet-thermal dual curing adhesive according to claim 1, characterized in that: the organic solvent is at least one of ethanol, n-propanol, isopropanol, ethylene glycol monomethyl ether and diethylene glycol ethyl ether.
6. The method for preparing the ultraviolet-thermal dual curing adhesive according to any one of claims 1 to 5, comprising:
step one, mixing ultraviolet photosensitive resin and a photoinitiator to form a first heavy ultraviolet curing system;
step two, mixing the thermosetting resin with an organic solvent to form a second thermosetting system;
and step three, uniformly mixing the first double ultraviolet curing system and the second double ultraviolet curing system, and filtering to obtain the ultraviolet-heat double curing adhesive.
7. The method of manufacturing according to claim 6, characterized in that: the viscosity of the ultraviolet-thermal dual-curing adhesive is 5-15mPa.s, and the surface tension is 25-35mN/m.
8. The ultraviolet-thermal dual-curing 3D printing method is characterized in that a 3D printer is adopted, the 3D printer comprises a spraying system, a powder spreading mechanism, a powder bed and an ultraviolet generator mechanism, and the 3D printing method comprises the following steps:
a first step of spraying the ultraviolet-thermal dual curing adhesive according to any one of claims 1 to 5 onto a powder bed on which a powder material is spread, using a spraying system;
moving the ultraviolet generator mechanism to the position above the powder bed and emitting ultraviolet light, staying for 1-10s and then leaving the powder bed, and descending the printing platform by one layer thickness;
step three, the powder paving mechanism is used for flatly paving and covering the new powder material on the last solidified printing layer;
step four, repeating the step one to the step three until printing of the green body is completed;
and fifthly, transferring the loose powder material which is not bonded and the green body into a heating furnace together, heating the green body and the green body until the loose powder material is completely solidified, taking out the green body, naturally cooling the green body to room temperature, and removing the loose powder which surrounds the green body.
9. The ultraviolet-thermal dual-cure 3D printing method according to claim 8, wherein: the injection system adopts a piezoelectric type printing nozzle.
10. The ultraviolet-thermal dual-cure 3D printing method according to claim 8, wherein: in the fifth step, the temperature for heating and curing is 150-200 ℃.
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