3D printing method and combination of supporting bath and 3D printing material

Abstract

The invention provides a 3D printing method and a combination of a supporting bath and a 3D printing material.The 3D printing method comprises the following steps that a preset mass of component B of bi-component addition type RTV silica gel is weighed and placed in a mixing container, a preset mass of hydrophobic treatment fumed silica is weighed and added into the mixing container, and the component B and the hydrophobic treatment fumed silica are mixed; fully and uniformly mixing the component B and fumed silica by using a homogenizer; pouring out the uniformly mixed mixture, putting the mixture into a vacuum defoaming machine, and vacuumizing until bubbles are removed, so as to obtain a supporting bath material; the bath supporting material provided by the invention is formed by compounding the component B of the bi-component addition type RTV silica gel and the hydrophobic fumed silica, has high yield stress and good shear thinning characteristics, can effectively support low-viscosity printing ink, and improves the stability and precision of the printing process; meanwhile, the support bath has good flowability, self-repairability and structure recovery capability, and the problems of insufficient support force, printing deformation and the like in the prior art are effectively solved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of 3D printing of silicone, in particular to a 3D printing method and the combination of support bath and 3D printing material. BACKGROUND

[0002] As a new manufacturing process, suspension 3D printing has the potential of manufacturing. It replaces the 2D platform with a 3D support bath, which provides support to the printed structure through the support bath material, reduces the requirement of self-supporting strength of the ink itself, and improves the performance of the material. The support bath material has a certain yield stress. When the print head passes, the shear stress applied by the print head exceeds the yield stress, causing local shear thinning and liquefaction of the support bath material, so that the ink can flow out of the print head. After the print head leaves, the support bath material exhibits self-healing properties, restores the yield stress, and wraps the extruded material to form a stable structure. In the support bath, ink of any shape can be printed in any path. After printing is completed, the ink is solidified by using a cross-linking agent or light irradiation, and the support bath is removed, obtaining a structure that meets the requirements of feature topography. Currently, this has been used to manufacture hollow structures and structures with overhanging features.

[0003] Known support baths and inks have their own defects. For example, mineral oil as a support bath, the non-reactive nature of the ink and the support bath causes the support bath material to hinder the fusion bonding between the printing inks; carbomer solution as a support bath, the insufficient yield stress of the support bath causes low-viscosity ink to be difficult to form; two-component addition type RTV silicone mixed as a printing ink, the short operable time of the ink increases the risk of needle blockage. This results in the existing support bath being specifically suitable for certain specific materials and applications. The current defects cause the existing support bath material to be unable to meet the needs of low-hardness silicone 3D printing. SUMMARY

[0004] The summary section of the present application is used to introduce the concepts in a brief form, which will be described in detail in the specific embodiments section. The summary section of the present application is not intended to identify key or essential features of the claimed technical solutions, nor is it intended to limit the scope of the claimed technical solutions.

[0005] In order to overcome the deficiencies of the prior art, the application combines the characteristics of hydrophobic treatment of fumed silica that can change the rheological properties of silica gel and the characteristics of two-component addition type RTV silicone rubber that does not produce by-products, has extremely low shrinkage, requires small amount of catalyst, and the crosslinking density and vulcanization speed are easy to control, to form an adjustable printing window through the reaction of the two components of the two-component addition type RTV silicone rubber. The application proposes a suspension printing method of super-soft silicone rubber based on the support bath and the 3D printing material. The suspension printing method of super-soft silicone rubber realizes the suspension printing by using the low interfacial tension between the two components of the addition type RTV silicone rubber.

[0006] In order to achieve the above-mentioned purpose, the application adopts the following technical solutions:

[0007] A 3D printing method is provided, comprising the following steps:

[0008] A component of a two-component addition type RTV silicone rubber with a preset mass is placed in a mixing container, and fumed silica with a preset mass is added to the mixing container, and a homogenizer is used to mix the B component and the fumed silica uniformly;

[0009] The uniformly mixed mixture is poured out and placed in a vacuum defoaming machine, vacuum is extracted until the bubbles are removed, and a support bath material is obtained;

[0010] A component of a two-component addition type RTV silicone rubber with a preset mass is placed in a mixing container, and fumed silica with a preset mass is added to the mixing container, and a homogenizer is used to mix the B component and the fumed silica uniformly;

[0011] The uniformly mixed mixture is poured out and placed in a vacuum defoaming machine, vacuum is extracted until the bubbles are removed, and a support bath material is obtained;

[0012] The 3D printing material is used to perform 3D printing in the support bath material.

[0013] Further, the hydrophobic treatment comprises: using HMDS to react with the silicon hydroxyl on the surface of the fumed silica, and replacing the hydrophilic hydroxyl with the hydrophobic trimethylsilyl group.

[0014] Further, the B component of the two-component addition type RTV silicone rubber comprises one or more of the B components of the two-component addition type RTV silicone rubber with hardness of 0A, 5A, 10A, 15A, 20A, and 25A.

[0015] Further, the A component of the two-component addition type RTV silicone rubber comprises one or more of the A components of the two-component addition type RTV silicone rubber with hardness of 0A, 5A, 10A, 15A, 20A, and 25A.

[0016] Further, the support bath material comprises, by weight parts:

[0017] 2 to 15 parts of fumed silica;

[0018] The B component of the two-component addition-curing RTV silicone is 85 to 98 parts.

[0019] Furthermore, the mass percentage of component B of the two-component addition-curing RTV silicone in the support bath material ranges from 85% to 98%.

[0020] Furthermore, the mass percentage of fumed silica in the support bath material ranges from 2% to 15%.

[0021] Furthermore, the 3D printing material comprises, by weight parts:

[0022] 2 to 15 parts of fumed silica;

[0023] The A component of the two-component addition-curing RTV silicone is 85 to 98 parts.

[0024] Furthermore, the mass percentage of component A in the two-component addition-curing RTV silicone in the 3D printing material ranges from 85% to 98%.

[0025] Furthermore, the mass percentage of fumed silica in the 3D printing material ranges from 2% to 15%.

[0026] Furthermore, the structural formula of the hydrophobically treated fumed silica is:

[0027] .

[0028] Furthermore, the equation for the reaction between the printing material and the support bath material is as follows:

[0029]

[0030] This application also provides a combination of a support bath and its 3D printing material, wherein the support bath material comprises, by weight parts:

[0031] 2 to 15 parts of fumed silica;

[0032] 85 to 98 parts of component B of the two-component addition-curing RTV silicone;

[0033] The 3D printing material comprises, by weight parts:

[0034] 2 to 15 parts of fumed silica;

[0035] The A component of the two-component addition-curing RTV silicone is 85 to 98 parts.

[0036] The advantages of this application are: it provides a 3D printing method using a support bath material with good stability and rheological properties, as well as a combination of the support bath and the 3D printing material. The provided support bath material is composed of the B component of a two-component addition-curing RTV silicone and hydrophobic fumed silica, which has high yield stress and good shear thinning properties, effectively supporting low-viscosity printing ink and improving the stability and accuracy of the printing process. At the same time, the support bath has good fluidity, self-healing and structural recovery capabilities, effectively solving the problems of insufficient support force and printing deformation in the prior art.

[0037] The printing material of this invention is based on RTV silicone A component and the same hydrophobic fumed silica. It can undergo an addition reaction with component B in the support bath during the printing process, achieving in-situ curing along the printing path and avoiding material diffusion and deformation problems. Attached Figure Description

[0038] The accompanying drawings, which form part of this application, are used to provide a further understanding of the application and to make other features, objects, and advantages of the application more apparent. The illustrative embodiments and descriptions of this application are used to explain the application and do not constitute an undue limitation of the application.

[0039] Furthermore, throughout the accompanying drawings, the same or similar reference numerals denote the same or similar elements. It should be understood that the drawings are schematic, and the elements are not necessarily drawn to scale.

[0040] In the attached diagram:

[0041] Figure 1 This is a schematic diagram illustrating the principle of the 3D printing material of this invention reacting with the support bath to solidify.

[0042] Figure 2 The diagrams shown are (A) shear stress-shear rate and (B) viscosity-time of the support bath prepared in Example 1 of the present invention.

[0043] Figure 3 The diagrams shown are (A) shear stress-shear rate and (B) viscosity-time of the support bath prepared in Example 2 of the present invention.

[0044] Figure 4 The diagrams shown are (A) shear stress-shear rate and (B) viscosity-time of the support bath prepared in Example 3 of the present invention.

[0045] Figure 5 The diagrams shown are (A) shear stress-shear rate and (B) viscosity-time of the support bath prepared in Example 4 of the present invention.

[0046] Figure 6The diagrams shown are (A) shear stress-shear rate and (B) viscosity-time of the support bath prepared in Example 5 of the present invention.

[0047] Figure 7 This is a diagram illustrating the printing effect of the support bath in Example 6 of the present invention, which uses the support bath and 3D printing material. Detailed Implementation

[0048] Embodiments of this disclosure will now be described in more detail with reference to the accompanying drawings. While some embodiments of this disclosure are shown in the drawings, it should be understood that this disclosure can be implemented in various forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of this disclosure. It should be understood that the accompanying drawings and embodiments of this disclosure are for illustrative purposes only and are not intended to limit the scope of protection of this disclosure.

[0049] It should also be noted that, for ease of description, only the parts relevant to the invention are shown in the accompanying drawings. Unless otherwise specified, the embodiments and features described in this disclosure can be combined with each other.

[0050] It should be noted that the concepts of "first" and "second" mentioned in this disclosure are used only to distinguish different devices, modules or units, and are not used to limit the order of functions performed by these devices, modules or units or their interdependencies.

[0051] It should be noted that the terms "a" and "a plurality of" used in this disclosure are illustrative rather than restrictive, and those skilled in the art should understand that, unless otherwise expressly indicated in the context, they should be understood as "one or more".

[0052] The names of messages or information exchanged between multiple devices in the embodiments of this disclosure are for illustrative purposes only and are not intended to limit the scope of such messages or information.

[0053] This disclosure will now be described in detail with reference to the accompanying drawings and embodiments.

[0054] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0055] A support bath material, wherein the mass percentage of component B of the two-component addition-cured RTV silicone in the support bath material ranges from 85% to 98%.

[0056] The mass percentage of fumed silica in the support bath material ranges from 2% to 15%.

[0057] A 3D printing material, wherein the mass percentage of component A of the two-component addition-curing RTV silicone in the 3D printing material ranges from 85% to 98%.

[0058] The mass percentage of fumed silica in the 3D printing material ranges from 2% to 15%.

[0059] The hydrophobically treated fumed silica was purchased from Evonik Degussa GmbH, Germany, and the two-component addition-cure RTV silicone was purchased from Hongyejie Technology Co., Ltd., China.

[0060] Example 1

[0061] In this embodiment, the proportions of each component are as follows: 4% hydrophobically treated fumed silica and 96% component B of a two-component addition-type RTV silicone with a curing hardness of 5A. The preparation of the support bath material using this proportion is detailed below:

[0062] S1: Weigh 96g of component B of a two-component addition-type RTV silicone with a curing hardness of 5A into a beaker, weigh 4g of hydrophobic treated fumed silica and add it to the beaker, and use a homogenizer to mix component B and fumed silica thoroughly and evenly.

[0063] S2: Pour out the well-mixed mixture and place it in a vacuum defoamer. Vacuum the mixture until the air bubbles are removed to obtain the support bath material.

[0064] Shear stress-shear rate characteristics (26℃) and viscosity-time characteristics (26℃, 0-30 seconds, 0.01s) were tested using an Anton Paar MCR102 rotational rheometer. -1 30-40 seconds (10 s) -1 40-120 seconds 0.01s -1 ).

[0065] Example 2

[0066] In this embodiment, the proportions of each component are 6% hydrophobically treated fumed silica and 94% component B of a two-component addition-type RTV silicone with a curing hardness of 5A. The preparation of the support bath material using this mass proportion is as follows:

[0067] S1: Weigh 94g of component B of a two-component addition-type RTV silicone with a curing hardness of 5A into a beaker, weigh 6g of hydrophobic treated fumed silica and add it to the beaker, and use a homogenizer to thoroughly mix component B and fumed silica.

[0068] S2: Pour out the well-mixed mixture and place it in a vacuum defoamer. Vacuum the mixture until the air bubbles are removed to obtain the support bath material.

[0069] Shear stress-shear rate characteristics (26℃) and viscosity-time characteristics (26℃, 0-30 seconds, 0.01s) were tested using an Anton Paar MCR102 rotational rheometer. -1 30-40 seconds (10 s) -1 40-120 seconds 0.01s -1 ).

[0070] Example 3

[0071] In this embodiment, the proportions of each component are as follows: 8% hydrophobically treated fumed silica and 92% component B of a two-component addition-type RTV silicone with a curing hardness of 5A. The preparation of the support bath material using this mass proportion is carried out through the following steps:

[0072] S1: Weigh 92g of component B of a two-component addition-type RTV silicone with a curing hardness of 5A into a beaker, weigh 8g of hydrophobic treated fumed silica and add it to the beaker, and use a homogenizer to thoroughly mix component B and fumed silica.

[0073] S2: Pour out the well-mixed mixture and place it in a vacuum defoamer. Vacuum the mixture until the air bubbles are removed to obtain the support bath material.

[0074] Shear stress-shear rate characteristics (26℃) and viscosity-time characteristics (26℃, 0-30 seconds, 0.01s) were tested using an Anton Paar MCR102 rotational rheometer. -1 30-40 seconds (10 s) -1 40-120 seconds 0.01s -1 ).

[0075] Example 4

[0076] In this embodiment, the proportions of each component are as follows: 10% hydrophobically treated fumed silica and 90% component B of a two-component addition-type RTV silicone with a curing hardness of 5A. The preparation of the support bath material using this proportion is detailed below:

[0077] S1: Weigh 90g of component B of a two-component addition-type RTV silicone with a curing hardness of 5A into a beaker, weigh 10g of hydrophobic treated fumed silica and add it to the beaker, and use a homogenizer to mix component B and fumed silica thoroughly and evenly.

[0078] S2: Pour out the well-mixed mixture and place it in a vacuum defoamer. Vacuum the mixture until the air bubbles are removed to obtain the support bath material.

[0079] Shear stress-shear rate characteristics (26℃) and viscosity-time characteristics (26℃, 0-30 seconds, 0.01s) were tested using an Anton Paar MCR102 rotational rheometer. -1 30-40 seconds (10 s) -1 40-120 seconds 0.01s -1 ).

[0080] Example 5

[0081] In this embodiment, the proportions of each component are as follows: 12% hydrophobically treated fumed silica and 88% component B of a two-component addition-type RTV silicone with a curing hardness of 5A. The preparation of the support bath material using this mass proportion is carried out through the following steps:

[0082] S1: Weigh 88g of component B of a two-component addition-type RTV silicone with a curing hardness of 5A into a beaker, weigh 12g of hydrophobic treated fumed silica and add it to the beaker, and use a homogenizer to mix component B and fumed silica thoroughly and evenly.

[0083] S2: Pour out the well-mixed mixture and place it in a vacuum defoamer. Vacuum the mixture until the air bubbles are removed to obtain the support bath material.

[0084] Shear stress-shear rate characteristics (26℃) and viscosity-time characteristics (26℃, 0-30 seconds, 0.01s) were tested using an Anton Paar MCR102 rotational rheometer. -1 30-40 seconds (10 s) -1 40-120 seconds 0.01s -1 ).

[0085] Example 6

[0086] In this embodiment, the proportions of each component are as follows: 8% hydrophobic treated fumed silica and 92% component B of a two-component addition-cure RTV silicone with a curing hardness of 5A; the ink consists of 7% hydrophobic treated fumed silica and 93% component A of a two-component addition-cure RTV silicone with a curing hardness of 5A. The preparation of the support bath material using these proportions is detailed below:

[0087] S1: Weigh 92g of component B of a two-component addition-type RTV silicone with a curing hardness of 5A into a beaker, weigh 8g of hydrophobic treated fumed silica and add it to the beaker, and use a homogenizer to thoroughly mix component B and fumed silica.

[0088] S2: Pour out the well-mixed mixture and place it in a vacuum defoamer. Vacuum the mixture until the air bubbles are removed to obtain the support bath material.

[0089] S1: Weigh 93g of component A of the two-component addition-type RTV silicone with a curing hardness of 5A into a beaker, weigh 7g of hydrophobic treated fumed silica and add it to the beaker, and use a homogenizer to thoroughly mix component B with the fumed silica.

[0090] S2: Pour out the well-mixed mixture and place it in a vacuum defoamer. Vacuum the mixture until the air bubbles are removed to obtain the ink material.

[0091] S3. Print the ink material into the support bath, place it at 70°C for 2 hours to cure, and then remove it.

[0092] The above description is merely a selection of preferred embodiments of this disclosure and an explanation of the technical principles employed. Those skilled in the art should understand that the scope of the invention involved in the embodiments of this disclosure is not limited to technical solutions formed by specific combinations of the above-described technical features, but should also cover other technical solutions formed by arbitrary combinations of the above-described technical features or their equivalents without departing from the above-described inventive concept. For example, technical solutions formed by substituting the above-described features with (but not limited to) technical features with similar functions disclosed in the embodiments of this disclosure.

Claims

1. A 3D printing method, characterized in that: The 3D printing method includes the following steps: Weigh a predetermined amount of component B of the two-component addition-type RTV silicone and place it in a mixing container. Weigh a predetermined amount of hydrophobic treated fumed silica and add it to the mixing container. Use a homogenizer to thoroughly mix component B and fumed silica. Pour out the well-mixed mixture and place it in a vacuum defoamer. Vacuum the mixture until the air bubbles are removed to obtain the support bath material. Weigh a predetermined amount of component A of the two-component addition-type RTV silicone and place it in a mixing container. Weigh a predetermined amount of hydrophobic treated fumed silica and add it to the mixing container. Use a homogenizer to thoroughly mix component A and fumed silica. Pour out the well-mixed mixture and place it in a vacuum defoamer. Evacuate the mixture until the air bubbles are removed to obtain 3D printing material. 3D printing is performed on the support bath material using 3D printing materials.

2. The 3D printing method according to claim 1, characterized in that: The hydrophobic treatment includes: HMDS reacts with the silanol groups on the surface of fumed silica, replacing the hydrophilic hydroxyl groups with hydrophobic trimethylsilyl groups.

3. The 3D printing method according to claim 1, characterized in that: The B component of the two-component addition-curing RTV silicone includes one or more of the B components of two-component addition-curing RTV silicone with hardness of 0A, 5A, 10A, 15A, 20A, and 25A.

4. The 3D printing method according to claim 1, characterized in that: The A component of the two-component addition-curing RTV silicone includes one or more of the A components of two-component addition-curing RTV silicone with a hardness of 0 to 25A.

5. The 3D printing method according to claim 1, characterized in that: The supporting bath material comprises, by weight parts: 2 to 15 parts of fumed silica; The B component of the two-component addition-curing RTV silicone is 85 to 98 parts.

6. The 3D printing method according to claim 5, characterized in that: The mass percentage of component B in the two-component addition-cured RTV silicone in the support bath material ranges from 85% to 98%.

7. The 3D printing method according to claim 5, characterized in that: The mass percentage of fumed silica in the support bath material ranges from 2% to 15%.

8. The 3D printing method according to claim 1, characterized in that: The 3D printing material comprises, by weight parts: 2 to 15 parts of fumed silica; The A component of the two-component addition-curing RTV silicone is 85 to 98 parts.

9. The 3D printing method according to claim 8, characterized in that: The mass percentage of component A in the two-component addition-curing RTV silicone of the 3D printing material ranges from 85% to 98%.

10. The 3D printing method according to claim 8, characterized in that: The mass percentage of fumed silica in the 3D printing material ranges from 2% to 15%.

11. The 3D printing method according to claim 1, characterized in that: The structural formula of the hydrophobically treated fumed silica is: 。 12. The 3D printing method according to claim 1, characterized in that: The equation for the reaction between the printing material and the support bath material is: 。 13. A support bath and a combination of the support bath and its 3D printing material, characterized in that: Including the mass fractions of support bath material and 3D printing material in the 3D printing method as described in any one of claims 1-12, wherein, The supporting bath material comprises, by weight parts: 2 to 15 parts of fumed silica; 85 to 98 parts of component B of the two-component addition-curing RTV silicone; The 3D printing material comprises, by weight parts: 2 to 15 parts of fumed silica; The A component of the two-component addition-curing RTV silicone is 85 to 98 parts.

Images