CN109762116A - A kind of ultraviolet light auxiliary solidification is straight to write silicon rubber increasing material manufacturing method - Google Patents
A kind of ultraviolet light auxiliary solidification is straight to write silicon rubber increasing material manufacturing method Download PDFInfo
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- CN109762116A CN109762116A CN201910080164.2A CN201910080164A CN109762116A CN 109762116 A CN109762116 A CN 109762116A CN 201910080164 A CN201910080164 A CN 201910080164A CN 109762116 A CN109762116 A CN 109762116A
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Abstract
The present invention provides a kind of straight writing silicon rubber increasing material manufacturing methods of ultraviolet light auxiliary solidification, are related to material increasing field.Silicon rubber presoma is carried out the straight writing of ultraviolet light auxiliary solidification by the present invention, obtains silicon rubber preformed member；The silicon rubber presoma is made of liquid silastic and photosensitive component；The silicon rubber preformed member is subjected to vulcanizing treatment again, obtains silicone elastomer.The present invention introduces photosensitive component into liquid silastic, assigns quick-setting ability under its ultraviolet light, efficiently solves the bottleneck problem that liquid silastic is difficult to rapid shaping, to realize traditional silicon rubber complex structural member increasing material manufacturing molding；Method provided by the invention is without being specially synthesized silicon rubber presoma, and method is simple, and applicable silicon rubber type is extensive, it is compatible with traditional silicon rubber curing techniques, without expensive molding equipment, it is easy to implement the molding of various high performance silicon rubber complex three-dimensional structures, is had a extensive future.
Description
Technical field
The present invention relates to increases material manufacturing technology field, in particular to a kind of straight silicon rubber of writing of ultraviolet light auxiliary solidification increases material
Manufacturing method.
Background technique
Organosilicon material have lower glass transition temperature, high-low temperature resistant, surface tension, excellent electric property,
Gas permeability and bio-compatibility, be other high-molecular organic materials it is incomparable and substitution.More and more people will at this stage
Some monomers are introduced into polymeric siloxane systems, are prepared for the elastomer silicone with property, the organosilicon bullet of photoresponse
Property body also receives more and more attention.This is because illumination is not only easy at manipulation or in-situ chemical as environmental stimuli
The desired external of reason manipulates condition, and has the characteristics that neat and tidy.In addition, the radiation wavelength and intensity of illumination are accurately may be used
Control, and there is high-caliber resolution ratio, the quick response in confined space may be implemented.
The technology for being presently used in forming elastomer silicone includes soft lithographic and its deriving technology, such as molding, dipping casting,
Spin coating etc..Most of in these technologies are only limitted to generate geometrically simple structure, are difficult the complicated three-dimensional structure of preparation.Separately
Outside, these technologies of preparing need to deaerate, and bubble formation is usually had in degasification process, coarse so as to cause surface of shaped parts, machine
Tool performance is poor.
In recent years, silicon rubber increases material manufacturing technology (also known as 3D printing) receives more and more attention.Femmer et al.
The 3D printing of dimethyl silicone polymer (PDMS) is demonstrated using digital light processing (DLP) method for the first time, resolution ratio is up to 100
(the Printyour own membrane:direct rapidprototyping of micron
ofpolydimethylsiloxane.Lab on a Chip,2014,14(15):2610.).Qin et al. is with translucent non-current
PDMS elastomer using direct write squeeze out method realize the labyrinths such as artificial cobweb real free form production knot
Structure (Structural optimization of 3D-printed synthetic spider webs for high
strength.Nature Communications,2015,6:7038.).But these technologies still have significant limitation, former
Material silicon rubber presoma needs to be specially synthesized, or need property such as high viscosity or noncurrent PDMS etc., in the market
Most of silicon rubber systems are liquid silastic, it is difficult to rapid shaping, thus it is not suitable for increases material manufacturing technology.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of straight writing silicon rubber increasing material manufacturing sides of ultraviolet light auxiliary solidification
Method.Method provided by the invention is wide suitable for range, solves the bottleneck problem that liquid silastic is difficult to rapid shaping, realizes
Traditional silicon rubber complex structural member increasing material manufacturing molding.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of ultraviolet light auxiliary solidification is straight to write silicon rubber increasing material manufacturing method, comprising the following steps:
(1) silicon rubber presoma is subjected to the straight writing of ultraviolet light auxiliary solidification, obtains silicon rubber preformed member；The silicon rubber
Glue presoma is made of liquid silastic and photosensitive component；
(2) the silicon rubber preformed member is subjected to after cure processing, obtains silicone elastomer.
Preferably, the mass ratio of the liquid silastic and photosensitive component is 50~90:10~50.
Preferably, the liquid silastic is Bi-component liquid silicone rubber, one-component condensed type liquid silastic or addition
Type liquid silastic.
Preferably, the photosensitive component is by photosensitive resin, acrylic crosslinking agent, acrylic diluents and photoinitiator group
At；The photosensitive resin, acrylic crosslinking agent, acrylic diluents and photoinitiator mass ratio be (10~50): (1~2):
(1~2): (0.5~1).
Preferably, the photosensitive resin is silicone-modified polyacrylate；The silicone-modified polyacrylate packet
Include both-end methacryloxypropyl polysiloxanes and/or methacryloxypropyl hydrocarbyl siloxane.
Preferably, the acrylic crosslinking agent is the acrylate monomer that degree of functionality is greater than 2.
Preferably, the acrylic diluents include butyl acrylate, acrylic acid decylene glycol ester, acrylic acid hexadecanol ester,
Isobornyl acrylate, hydroxyethyl methacrylate, tripropylene glycol diacrylate, 1,6 hexanediol diacrylate, dipropyl
One or more of omega-diol diacrylate, trimethylolpropane trimethacrylate and dipentaerythritol acrylate.
Preferably, the photoinitiator includes 2,4,6-trimethylbenzoyldiphenylphosphine oxide, the vulcanization of 2- isopropyl
One or more of miscellaneous anthrone, bisacylphosphine oxide and 1- hydroxy-cyclohexyl-phenyl ketone.
Preferably, the after cure processing in the step (2) is room temperature vulcanization or high temperature vulcanized.
The present invention provides a kind of straight writing silicon rubber increasing material manufacturing methods of ultraviolet light auxiliary solidification, comprising the following steps:
(1) silicon rubber presoma is subjected to the straight writing of ultraviolet light auxiliary solidification, obtains silicon rubber preformed member；The silicon rubber presoma
It is made of liquid silastic and photosensitive component；(2) the silicon rubber preformed member is subjected to vulcanizing treatment, obtains silicon rubber elastic
Body.The present invention introduces photosensitive component into liquid silastic, assigns quick-setting ability under its ultraviolet light, efficiently solves liquid
Body silicon rubber is difficult to the bottleneck problem of Quick-forming, to realize traditional silicon rubber complex structural member increasing material manufacturing molding；This
The method that invention provides is without being specially synthesized silicon rubber presoma, and method is simple, and applicable silicon rubber type is extensive, with traditional silicon
Rubber curing techniques are compatible, without expensive molding equipment, are easy to implement with excellent mechanical performances, water resistance, high-low temperature resistant
The molding of the silicon rubber complex three-dimensional structures of excellent properties such as property, insulating properties, has a extensive future.
Detailed description of the invention
Ultraviolet light Fig. 1 of the invention solidifies the flow diagram of auxiliary direct write silicon rubber increasing material manufacturing.
Specific embodiment
The present invention provides a kind of straight writing silicon rubber increasing material manufacturing methods of ultraviolet light auxiliary solidification, comprising the following steps:
(1) silicon rubber presoma is subjected to the straight writing of ultraviolet light auxiliary solidification, obtains silicon rubber preformed member；The silicon rubber
Glue presoma is made of liquid silastic and photosensitive component；
(2) the silicon rubber preformed member is subjected to after cure processing, obtains silicone elastomer.
Silicon rubber presoma is carried out the straight writing of ultraviolet light auxiliary solidification by the present invention, obtains silicon rubber preformed member.At this
In invention, the silicon rubber presoma is made of liquid silastic and photosensitive component；The liquid silastic and photosensitive component
Mass ratio is preferably 50~90:10~50, more preferably 60~80:20~40.The present invention can be by adjusting silicon rubber forerunner
The ratio of liquid silastic and photosensitive component adjusts the mechanical performance of silicone elastomer in body, and the ratio of liquid silastic gets over
The mechanical performance of height, gained silicone elastomer is better, in a specific embodiment of the present invention, can be according to specific requirements to silicon
The mechanical performance of rubber elastomer is adjusted.
In the present invention, the liquid silastic is preferably Bi-component liquid silicone rubber, one-component condensed type liquid silicon rubber
Glue or add-on type liquid silicon rubber.Liquid silastic is a kind of sulphurated siliastic system, and good fluidity, vulcanization is fast, the present invention couple
The source of the liquid silastic does not have particular/special requirement, uses common commercial liquid silicon rubber.
In the present invention, the photosensitive component is preferably drawn by photosensitive resin, acrylic crosslinking agent, acrylic diluents and light
Send out agent composition.In the present invention, the photosensitive resin is preferably silicone-modified polyacrylate；Described organic-silicon-modified poly- third
Olefin(e) acid ester preferably includes both-end methacryloxypropyl polysiloxanes and/or methacryloxypropyl hydrocarbyl siloxane.
In the present invention, the acrylic crosslinking agent be preferably degree of functionality be greater than 2 acrylate monomer, more preferably three
Hydroxymethyl-propane triacrylate (TMPTA) or dipentaerythritol acrylate (DPHA).In the present invention, the acrylic acid is handed over
Connection agent can promote the crosslinking curing of photosensitive resin.
In the present invention, the acrylic diluents preferably include butyl acrylate (BA), acrylic acid decylene glycol ester (LA),
Acrylic acid hexadecanol ester (HA), isobornyl acrylate (IBOA), hydroxyethyl methacrylate (HEMA), two propylene of tripropylene glycol
Acid esters (TPGDA), 1,6 hexanediol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), trimethylolpropane
One or more of triacrylate (TMPTA) and dipentaerythritol acrylate (DPHA).In the present invention, the propylene
Sour diluent can reduce the viscosity of silicon rubber presoma, improve curing rate.
In the present invention, the photoinitiator preferably includes 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO),
2- isopropyl vulcanizes miscellaneous anthrone (ITX), in bisacylphosphine oxide (819) and 1- hydroxy-cyclohexyl-phenyl ketone (184)
It is one or more of；In the present invention, the photoinitiator can trigger the crosslinking curing of photosensitive resin under ultraviolet irradiation condition.
In the present invention, the mass ratio of the photosensitive resin, acrylic crosslinking agent, acrylic diluents and photoinitiator is excellent
It is selected as (10~50): (1~2): (1~2): (0.5~1), more preferably (20~40): 1.5:1.5:(0.6~0.8).This hair
Photosensitive component in bright has excellent light-cured performance, and photosensitive component is added in liquid silastic, liquid silicon can be assigned
The cured ability of rubber ultraviolet light efficiently solves the bottleneck problem that liquid silastic is difficult to rapid shaping, realizes traditional silicon
Rubber complex structural member increasing material manufacturing molding.
In the present invention, the photosensitive component is preferably prepared by the following method to obtain:
Photoinitiator, acrylic crosslinking agent and acrylic diluents are mixed and carry out ultrasonic disperse, obtain light-initiated solution；
The light-initiated solution and photosensitive resin are mixed, photosensitive component is obtained.
In the present invention, the ultrasonic disperse preferably carries out under the conditions of low-temperature dark, the temperature of the low-temperature dark condition
Preferably 5~10 DEG C of degree；The present invention does not have particular/special requirement to the condition of the ultrasonic disperse, can be completely molten by photoinitiator
Solution, obtains the solution of homogeneous transparent.
In the present invention, the hybrid mode of the light-initiated solution and photosensitive resin is preferably mechanical stirring mixing, this hair
The bright revolving speed to mechanical stirring mixing does not have particular/special requirement, and component can be uniformly dispersed.
After obtaining photosensitive component, the liquid silastic and photosensitive component are uniformly mixed, silicon of the invention can be obtained
Rubber presoma；The mixing is preferably mechanical stirring.
In the present invention, the ultraviolet light auxiliary solidifies straight book specifically: using ultraviolet during directly writing 3D printing
The method of light irradiation carries out photocuring assistant formation to the silicon rubber presoma of extrusion.The present invention assists solidifying to the ultraviolet light
The actual conditions directly write do not have particular/special requirement, in a specific embodiment of the present invention, each component in silicon rubber presoma
The ratio regular meeting variation that keeps the generations such as the viscosity of silicon rubber presoma, rheological property certain, the present invention preferably according to silicon rubber before
The property of body is driven to determine that ultraviolet light auxiliary solidifies the actual conditions directly write, is carried out according to the experience of those skilled in the art true
It is fixed.The present invention solidifies shape and structure of straight book etc. to ultraviolet light auxiliary also without particular/special requirement, can be arbitrary
The molding of silicon rubber complex three-dimensional structure may be implemented in labyrinth, method provided by the invention.
The equipment that the present invention solidifies auxiliary direct write to the ultraviolet light does not have particular/special requirement, ripe using those skilled in the art
The extrusion 3D printer known.In a specific embodiment of the present invention, the silicon rubber presoma is injected and squeezes out 3D printing
In the barrel of machine, silicon rubber presoma is squeezed out from 3D printing spray head, obtains preformed member on shaped platform after photocuring,
Preformed member is able to maintain good characteristics of macrostructure, will not recurring structure deformation and collapse.In the present invention, the 3D is beaten
The extrusion equipment of print machine is preferably dispenser, and the extrusion way is preferably that nitrogen pushes extrusion, silicon rubber presoma extrudate flow
Amount and the movement speed for squeezing out spray head are adjusted according to the property of Structural Design Requirement and silicon rubber presoma；It is printing
Shi Liyong computer program is controlled, and is printed according to the silastic structure being pre-designed.
The present invention, which solidifies auxiliary direct write by ultraviolet light, makes the silicon rubber presoma of liquid form translucent non-streaming dynamic
Structure.
After obtaining silicon rubber preformed member, the silicon rubber preformed member is carried out after cure processing by the present invention, obtains silicon
Rubber elastomer.In the present invention, the after cure processing is preferably room temperature vulcanization or high temperature vulcanized, in specific reality of the invention
It applies in example, specific conditions of vulcanization is determined according to specific liquid silastic type, with traditional silicon rubber after cure item
Part is identical.The condition of after cure and traditional silicon rubber after cure process compatible in method provided by the invention, it is ensured that increase
The various aspects of performance of material manufacture gained silicone elastomer.The present invention keeps silicon rubber preformed member further by after cure processing
Crosslinking curing improves the mechanical property of silicone elastomer.
Method provided by the invention includes ultraviolet light solidification and vulcanizable cures, is a kind of cured method of second order, the present invention
This cured method of second order can be controllable the silicone elastomer for preparing complex three-dimensional structure.
Method and step provided by the invention is simple, to strong applicabilities such as viscosity, the mobility of printed material, is suitable for various
Commercial liquid silicon rubber system, and without expensive molding equipment, can be used to implement with excellent mechanical performances, water resistance,
The silicon rubber complex three-dimensional shaping structures of the excellent properties such as resistant of high or low temperature, insulating properties, it is easy to spread, it has a extensive future.
Scheme provided by the invention is described in detail below with reference to embodiment, but they cannot be interpreted as pair
The restriction of the scope of the present invention.
Ultraviolet light, which solidifies, in the embodiment of the present invention assists the flow diagram of direct write silicon rubber increasing material manufacturing as shown in Figure 1.
Embodiment 1
(1) silicon rubber presoma is prepared: in terms of mass fraction, the component of silicon rubber presoma are as follows: two-component liquid silicon rubber
80 parts of glue SP-2580 (A:B=1:1), (184) 0.5 parts of 1- hydroxy-cyclohexyl-phenyl ketone, dipentaerythritol acrylate
(DPHA) 1.5 parts, 2 parts of butyl acrylate (BA), 16 parts of both-end methacryloxypropyl polysiloxanes.
1- hydroxy-cyclohexyl-phenyl ketone is added in DPHA and BA mixed liquor, low-temperature dark ultrasonic disperse, until
Solution homogeneous transparent obtains light-initiated solution；Light-initiated solution is added to both-end methacryloxypropyl polysiloxanes
In and mechanical stirring obtain photosensitive component until be uniformly dispersed；Photosensitive component is added into Bi-component liquid silicone rubber, continues
Stirring obtains silicon rubber presoma to substantially uniformity.
(2) ultraviolet light solidifies auxiliary direct write: the silicon rubber presoma injection of preparation is squeezed out to the barrel of 3D printer；It squeezes out
Equipment is dispenser, is pushed and is squeezed out with nitrogen, and it is 0.2mL/min that ink, which squeezes out flow, and the movement speed for squeezing out spray head is 5mm/
S has ultraviolet light auxiliary, ultraviolet light wave a length of 400-450nm, light intensity 10W/cm in print procedure2, utilize computer program control
System prints the silicon rubber of design, obtains preformed member.
(3) after cure is handled: silicon rubber preformed member being heated vulcanizable cures in 200 DEG C of constant temperature ovens, is heated
Time is 5 hours, pipettes to get to the silicon rubber elastic with three-dimensional structure with blade from substrate after natural cooling
Body.
The mechanical property of obtained silicone elastomer is tested, its mechanical strength can be obtained greater than 4MPa, fracture is stretched
Long rate is greater than 100%；
Cyclic tension relaxation experiment is carried out to obtained silicone elastomer, elongation is fixed as 50%, follows as the result is shown
Ring, which stretches relaxation 10 times, will not weaken its mechanical performance.
Embodiment 2
(1) silicon rubber presoma is prepared: in terms of mass fraction, the component of silicon rubber presoma are as follows: RTV one pack system condensed type
BR-900785 parts of liquid silastic, 2- isopropyl vulcanizes miscellaneous 0.5 part of anthrone (ITX), trimethylolpropane trimethacrylate
(TMPTA) 2 parts, 1.5 parts of acrylic acid decylene glycol ester (LA), 11 parts of methacryloxypropyl hydrocarbyl siloxane.
The preparation method and embodiment 1 of silicon rubber presoma are identical.
(2) ultraviolet light solidifies auxiliary direct write: the silicon rubber presoma injection of preparation is squeezed out to the barrel of 3D printer；It squeezes out
Equipment is dispenser, is pushed and is squeezed out with nitrogen, and it is 0.1mL/min that ink, which squeezes out flow, and the movement speed for squeezing out spray head is 2mm/
S has ultraviolet light auxiliary, ultraviolet light wave a length of 400-450, light intensity 20W/cm in print procedure2, controlled using computer program
The silicon rubber for printing design, obtains preformed member.
(3) after cure is handled: silicon rubber preformed member is humidified to heating vulcanizable cures, heating on 40 DEG C of heated at constant temperature platforms
Handling the time is 4 hours, pipettes to get to the silicon rubber bullet with three-dimensional structure with blade from substrate after natural cooling
Property body.
The mechanical property of obtained silicone elastomer is tested, its mechanical strength can be obtained greater than 20MPa, fracture is stretched
Long rate is greater than 5%；
Cyclic tension relaxation experiment is carried out to obtained silicone elastomer, elongation is fixed as 50%, follows as the result is shown
Ring, which stretches relaxation 10 times, will not weaken its mechanical performance.
Embodiment 3
(1) silicon rubber presoma is prepared: in terms of mass fraction, the component of silicon rubber presoma are as follows: add-on type liquid silicon rubber
83 parts of glue NX-015 (A:B=1:1), 1 part of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), dipentaerythritol third
2 parts of olefin(e) acid ester (DPHA), 2 parts of isobornyl acrylate (IBOA), 12 parts of both-end methacryloxypropyl polysiloxanes.
The preparation method and embodiment 1 of silicon rubber presoma are identical.
(2) ultraviolet light solidifies auxiliary direct write: the silicon rubber presoma injection of preparation is squeezed out to the barrel of 3D printer；It squeezes out
Equipment is dispenser, is pushed and is squeezed out with nitrogen, and it is 0.3mL/min that ink, which squeezes out flow, and the movement speed for squeezing out spray head is 2mm/
S has ultraviolet light auxiliary, ultraviolet light wave a length of 400-450, light intensity 20W/cm in print procedure2, controlled using computer program
The silicon rubber for printing design, obtains preformed member.
(3) after cure is handled: silicon rubber preformed member being heated vulcanizable cures in 120 DEG C of constant temperature ovens, is heated
Time is 1 hour, pipettes to get to the silicon rubber elastic with three-dimensional structure with blade from substrate after natural cooling
Body.
The mechanical property of obtained silicone elastomer is tested, its mechanical strength can be obtained greater than 3MPa, fracture is stretched
Long rate is greater than 200%；
Cyclic tension relaxation experiment is carried out to obtained silicone elastomer, elongation is fixed as 50%, follows as the result is shown
Ring, which stretches relaxation 10 times, will not weaken its mechanical performance.
As can be seen from the above embodiments, the applicable material category of increasing material manufacturing method provided by the invention is extensive, solves
Liquid silastic is difficult to the bottleneck problem of rapid shaping, realizes traditional silicon rubber complex structural member increasing material manufacturing molding, and
It is good to obtain silicone elastomer mechanical property.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of ultraviolet light auxiliary solidification is straight to write silicon rubber increasing material manufacturing method, which comprises the following steps:
(1) silicon rubber presoma is subjected to the straight writing of ultraviolet light auxiliary solidification, obtains silicon rubber preformed member；Before the silicon rubber
Body is driven to be made of liquid silastic and photosensitive component；
(2) the silicon rubber preformed member is subjected to after cure processing, obtains silicone elastomer.
2. the method according to claim 1, wherein the mass ratio of the liquid silastic and photosensitive component is 50
~90:10~50.
3. the method according to claim 1, wherein the liquid silastic is Bi-component liquid silicone rubber, list
Component condensed type liquid silastic or add-on type liquid silicon rubber.
4. method according to claim 1 or 2, which is characterized in that the photosensitive component is crosslinked by photosensitive resin, acrylic acid
Agent, acrylic diluents and photoinitiator composition；The photosensitive resin, acrylic crosslinking agent, acrylic diluents and light-initiated
The mass ratio of agent is (10~50): (1~2): (1~2): (0.5~1).
5. according to the method described in claim 4, it is characterized in that, the photosensitive resin is silicone-modified polyacrylate；
The silicone-modified polyacrylate includes both-end methacryloxypropyl polysiloxanes and/or methacryloxypropyl hydrocarbon
Radical siloxane.
6. according to the method described in claim 4, it is characterized in that, the acrylic crosslinking agent is the propylene that degree of functionality is greater than 2
Acid ester monomer.
7. according to the method described in claim 4, it is characterized in that, the acrylic diluents include butyl acrylate, propylene
Sour decylene glycol ester, acrylic acid hexadecanol ester, isobornyl acrylate, hydroxyethyl methacrylate, tripropylene glycol diacrylate,
1,6 hexanediol diacrylate, dipropylene glycol diacrylate, trimethylolpropane trimethacrylate and dipentaerythritol third
One or more of olefin(e) acid ester.
8. according to the method described in claim 4, it is characterized in that, the photoinitiator includes 2,4,6- trimethylbenzoyls
Diphenyl phosphine oxide, 2- isopropyl vulcanize one in miscellaneous anthrone, bisacylphosphine oxide and 1- hydroxy-cyclohexyl-phenyl ketone
Kind is several.
9. the method according to claim 1, wherein the after cure processing in the step (2) is room temperature vulcanization
Or it is high temperature vulcanized.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380556A (en) * | 2016-09-27 | 2017-02-08 | 陕西恒通智能机器有限公司 | High-temperature-resistant high-toughness photo-cured resin for photo-curing 3D printing |
| CN107283819A (en) * | 2017-07-17 | 2017-10-24 | 西安交通大学 | A kind of 3D printing equipment and Method of printing towards HMW silicon rubber |
-
2019
- 2019-01-28 CN CN201910080164.2A patent/CN109762116B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380556A (en) * | 2016-09-27 | 2017-02-08 | 陕西恒通智能机器有限公司 | High-temperature-resistant high-toughness photo-cured resin for photo-curing 3D printing |
| CN107283819A (en) * | 2017-07-17 | 2017-10-24 | 西安交通大学 | A kind of 3D printing equipment and Method of printing towards HMW silicon rubber |
Non-Patent Citations (1)
| Title |
|---|
| TIM FEMMER等: "Print your own membrane: direct rapid prototyping of polydimethylsiloxane", 《LAB ON A CHIP》 * |
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