Photocuring injection nanometer ink realizes composite 3d Method of printings and printer
Technical field
The present invention relates to 3D printing technique field, and in particular to a kind of mixed ink of injection containing nano particle, quickly
Prepare high accuracy, the forming method of high-performance composite materials 3D devices, and a kind of droplet ejection 3d printers.
Background technology
3D printing (three dimensional printing, 3DP) be Quick-forming (rapid prototyping,
RP) the abbreviation of technology, using material stacking method an advanced technology of product is quickly manufactured.
The major technique of 3D printing at present has:Stereolithography(SLA), fused glass pellet(FDM), laminated solid body processing
(LOM), three dimensional printing(3DP), selective laser sintering(SLS)Deng.
Stereolithography(SLA)It is that this principle of enough rapid curings is molded under ultraviolet light using photosensitive resin
Technique, it is the earliest rapid shaping technique for occurring.Photocureable rapid shaping adopts liquid photosensitive resin for product raw material, tool
Have the advantages that dimensional accuracy is high, surface is smooth, can make Arbitrary surfaces prototype product, but process equipment and processing cost
It is high, cantilever design is needed to produce gas with foreign flavor using supporting, in forming process, being not suitable for office environment makes.
Fused glass pellet(FDM)It is that one kind will be extruded after filamentary material plus heat fusing, a kind of shaping side of accumulation molding
Method.This moulding process is to mix ceramic powders and organic binder bond, and using FDM equipment ceramic green blank is made, and is passed through
Sintering post processing obtains the ceramic member of higher density.The plastic multiple material of this technological forming, but the 3D devices essence of shaping
Degree is poor, it is difficult to which the complicated part of molding structure, vertical direction intensity is little.
Selective laser sintering(SLS)It is the technology being molded using laser selective sintered powder material.This 3D
For working of plastics, the fully sintered polymeric powder of laser finally gives profiled member to printing technique.The sintering temperature of general ceramics is very
Height, it is difficult to laser direct sintering is used, can first by the upper high polymer binder of ceramic powders cladding of infusibility, laser fusion binding agent
To sinter each layer, so as to make ceramic green, by last handling processes such as binding agent removal and sintering, final 3D is just obtained
Ceramic member.
Layer separated growth method(Laminated Object Manufacturing, LOM), it is sheeting superposition work
Skill, first with laser dicing sheet material, then successively accumulation molding.The technique have the large-scale entity component speed of processing it is fast,
The advantages of product hardness and preferable compressive property, have the disadvantage that article surface has obvious step texture, material deterioration inside larger.
3 D-printing(3DP)It is a kind of based on micro-injection principle, solution is selectively sprayed in powder plane, by inlet zone
The method of the powder molding bonded in domain, three dimensional printing technology has become industry of rapid prototyping research and the focus applied.3 D-printing
The advantage of shaping mainly has low cost, operation and maintenance cost are low, be adapted to many materials, shaping speed soon, without the need for supporting construction;
Have the disadvantage element precision and surface quality is poor, product low intensity.
The content of the invention
In order to solve the above problems, photocuring injection nanometer ink of the present invention realizes that composite 3d Method of printing advantages exist
In:1. powder is prepared into nano particle, and being then prepared into photosensitive resin, ink conditioning agent etc. can be adapted to industrial 3D inkjet printings
The ink that machine is used, the precision of the 3D devices for so printing is very high, and forming dimension is big.2. ultraviolet used in forming process
Light source carries out photocuring, it is to avoid during be sintered using light sources such as laser, energy saving.3. the present invention can multiple industry sprays
Black printhead sprays simultaneously, and each ink jet-print head has hundreds of hole forming, and face shaping, shaping speed are similar in forming process
Hurry up, and general SLS and SLM are line shapings.
4. in forming process of the invention, it is not necessary to powdering link, print speed can be made to improve 2 ~ 3 times, powdering process
Print speed can be affected.5. the present invention can print the 3D devices of the materials with high melting point such as large-size ceramic, general 3D printing technique
DLP, SLS, FDM, powder bonding be molded over printing these materials 3D devices when, limited by technology itself, compact dimensions compared with
Little moulding process 6. of the invention, stock utilization is high, reduces production cost, and in the curing process material can keep
Preferable stability of material.7. ultraviolet light source solidifies to print area, by temperature sensor real-time monitoring curing area
The temperature in domain, monitors the nanometer particle ink curing molding state in print area, and the characteristic of product is effectively ensured.
Photocuring injection nanometer ink disclosed by the invention realizes composite 3d Method of printings, mainly including following several
Step:The first step, configures ink:Nanometer ink of the configuration containing nano particle with photosensitive resin, by nanometer ink 3D printing is added
In machine print cartridge.
Modeled by electronic 3-D model simultaneously, if being divided into dried layer X-Y scheme according to the three-dimensional modeling of print device
Shape;Printing path is cooked up according to each layer of shape, the consumption of every layer of material requested is calculated;Print with reference to printing ink
Head quantity, calculates per layer of time-write interval and ink jet-print head regression time, set the ultraviolet light source opening time, and unlatching is determined
When the time more than current layer time-write interval and ink jet-print head regression time summation.
Second step, prints:The ink jet-print head injection nanometer ink by the way of droplet ejection, ultraviolet light source timing is opened
Dynamic, ink jet-print head prints the ground floor of threedimensional model, completes until current layer is printed, and ink jet-print head rises and revert to
Print the surface of initial position.
3rd step, solidification:After the timing that ultraviolet light source is opened is reached, ultraviolet light source is opened, ultraviolet light source
Light direction solidified along the printing path of ground floor, while using infrared temperature sensor real-time monitoring curing area
The temperature in domain, monitors the nanometer particle ink curing molding state in print area, and solidification terminates, and ultraviolet light source is closed.
4th step, repeats according to the mode of two, three liang of steps and successively print and solidification, and to the last one layer of photocuring is complete
Into shaping 3D devices.
5th step, shaped article takes out.
Photocuring injection nanometer ink disclosed by the invention realizes in composite 3d Method of printings that nano particle is ceramics
Powder, glass powder, nylon powder or plastic powders.When the main material of shaping 3D devices is ceramic powders, product before shaping
Need degreasing sintered, 900-1300 DEG C of temperature selection.
Photocuring injection nanometer ink disclosed by the invention realizes that nano-particle diameter is in composite 3d Method of printings
10 ~ 500nm, the size of nano particle is more crucial, and the size of ceramic particle ensures that in print procedure, ink jet-print head will not
There is blocking.For the chemically or physically characteristic of printer model is effectively ensured, it is 70% that nano-particle content accounts for the proportion of nanometer ink
~90%;To ensure effective solidification of per layer of model, it is 10% ~ 30% that the content of photosensitive resin accounts for the proportion of nanometer ink.
Photocuring injection nanometer ink disclosed by the invention is realized in composite 3d Method of printings, during configuration nanometer ink
Appropriate ink conditioning agent can be added;Ink conditioning agent includes surfactant, buffer, metal-chelator, ink conditioning agent
The proportion for accounting for nanometer ink is 0% ~ 5%, and wherein effect of the surfactant in preparation of nano ink mainly has:Keep ink essence
Thin uniform dispersity and do not flocculate;Reduce capillary effect;Froth breaking is acted on.Buffer is in preparation of nano ink
In effect:The pH value of nanometer ink is adjusted, the pH value of nanometer ink has a great impact to the application performance of ink.General feelings
Under condition, the pH value of ink is required 7~9.Metal-chelator effect in the ink is:The conductance of ink can be adjusted
Value, the numerical value of conductance is the height for reflecting salt content in ink.Salt in general ink can damage print cartridge and beat in ink-jet
Crystallization at print head causes plug.
Photocuring disclosed by the invention sprays nanometer ink and realizes in composite 3d Method of printings, described nanometer ink
The speed of injection is 0.1 ~ 1000m/s, forming cavity internal temperature control at 20 ~ 70 DEG C, the power model of described ultraviolet light source
Enclose for 0.5-3w, by the way of irradiation print area printable layer is solidified.
Photocuring injection nanometer ink disclosed by the invention is realized in composite 3d Method of printings, imitated to improve to print
Rate, ink jet-print head quantity be one or more than one, make to be similar in forming process face shaping, shaping speed is fast;In order to
The each layer of surface is realized, more preferable combined with ultraviolet radiation light is consolidated, and prevents ink jet-print head from plug phenomenon, inkjet printing occur
The quantity in the hole that head is provided with is 200 to 2000, forms the effect of droplet ejection.
The invention also discloses a kind of droplet ejection 3d printers, print cartridge is connected in assistant print cartridges, assistant print cartridges by ink pacifies
B/P EGR Back Pressure Transducer EGR and liquid level sensor are equiped with, the piezoelectric microsphere ink jet-print head on assistant print cartridges connection printing head support part is beaten
Print head bracket lower section is provided with ultraviolet light source, and the luminous printer model for pointing to pedestal, irradiating on pedestal of ultraviolet light source is printed
Cheng Zhong, ink jet-print head first completes the printing injection of one layer of ink, and ink jet-print head is printed after completing and returned to after zero position
Rise, subsequent ultraviolet light source solidifies ink material along the path of inkjet printhead movement, temperature sensor real-time monitoring is consolidated
Change the temperature in region, monitor the nanometer particle ink curing molding state in print area, solidification terminates, ultraviolet light source is closed
And return to original position.Printing motor spindle is pedestal, and the print platform that can be lifted, ink jet-print head quantity are provided with pedestal
For one or more than one, the ink jet-print head of ink jet-print head is provided with spray-hole.
The invention also discloses a kind of droplet ejection 3d printers, in order to improve printing effect ink jet-print head quantity for one
It is individual or more than one;In order to realize each layer of surface, more preferable combined with ultraviolet radiation light is consolidated, and prevents ink jet-print head from going out
Existing plug phenomenon, the quantity in the hole that ink jet-print head is provided with is 200 to 2000, forms the effect of droplet ejection.
The invention also discloses a kind of droplet ejection 3d printers, the power bracket of described ultraviolet light source is 0.5-
3w。
Description of the drawings
Fig. 1 realizes composite 3d Method of printings for photocuring injection nanometer ink, and first three walks schematic diagram.
Fig. 2 is a kind of droplet ejection 3d printer arrangement schematic diagrames.
Specific embodiment
Photocuring injection nanometer ink realizes that composite 3d Method of printings carry out 3D by photocuring droplet ejection technology
Print, in piezoelectric ink jet head during jet printing, and then ultraviolet light source solidifies the nanometer ink for ejecting,
Realize melting, sintering and the shaping of nano particle.The moulding process is adapted to ceramics, glass, nylon, plastic or other material.The present invention
Solve that material selection range in existing 3D printing technique is narrow, formed precision is poor, compact dimensions are little, the slow technology of shaping speed is asked
Topic.
Photocuring injection nanometer ink of the present invention realizes that composite 3d Method of printing advantages are:1. powder is prepared into and receives
Rice grain, being then prepared into photosensitive resin, ink conditioning agent etc. can be adapted to the ink that industrial 3D ink-jet printers are used, so
The precision of the 3D devices for printing is very high.2. ultraviolet light source carries out photocuring used in forming process, it is to avoid during make
It is sintered with light sources such as laser, energy saving.3. of the invention is that multiple industrial inkjet printheads spray simultaneously, each ink-jet
Printhead has hundreds of hole forming, and face shaping is similar in forming process, and shaping speed is fast, and general SLS and SLM are lines
Shaping.4. in forming process of the invention, it is not necessary to powdering link, print speed can be made to improve 2 ~ 3 times, meeting during powdering
Affect print speed.5. the present invention can print large-sized 3D ceramic components, general 3D printing technique DLP, SLS, FDM, powder
Last molding bonded is limited when 3D ceramic components are printed by technology itself, the less shaping work 6. of the invention of compact dimensions
Skill, stock utilization is high, reduces production cost, and in the curing process material can keep preferable stability of material.⑦
Ultraviolet light source solidifies to print area, by the temperature of temperature sensor real-time monitoring consolidation zone, monitors print zone
Nanometer particle ink curing molding state in domain, is effectively ensured the characteristic of product.
With reference to shown in accompanying drawing 1, it is following several that photocuring injection nanometer ink realizes that composite 3d Method of printings mainly have
Step, the first step configures ink:Nanometer ink of the configuration containing nano particle with photosensitive resin, by nanometer ink 3D printing is added
In machine print cartridge.
Modeled by electronic 3-D model simultaneously, if being divided into dried layer X-Y scheme according to the three-dimensional modeling of print device
Shape;Printing path is cooked up according to each layer of shape, the consumption of every layer of material requested is calculated;Print with reference to printing ink
Head quantity, calculates per layer of time-write interval and ink jet-print head regression time, set the ultraviolet light source opening time, and unlatching is determined
When the time more than current layer time-write interval and ink jet-print head regression time summation.
Second step, prints:The ink jet-print head injection nanometer ink by the way of droplet ejection, ultraviolet light source timing is opened
Dynamic, ink jet-print head prints the ground floor of threedimensional model, completes until current layer is printed, and ink jet-print head rises and revert to
Print the surface of initial position.
3rd step, solidification:After the timing that ultraviolet light source is opened is reached, ultraviolet light source is opened, ultraviolet light source
Light direction solidified along the printing path of ground floor, while using infrared temperature sensor real-time monitoring curing area
The temperature in domain, monitors the nanometer particle ink curing molding state in print area, and solidification terminates, and ultraviolet light source is closed.
4th step, repeats according to the mode of two, three liang of steps and successively print and solidification, and to the last one layer of photocuring is complete
Into shaping 3D devices.
5th step, shaped article takes out.
Materials processing in nanometer ink for 3D printing is prepared into nano particle, in order that it can be suitable for inkjet printing
Head is printed, wherein a diameter of 10 ~ 500 nanometers of nano particle.The size of nano particle is more crucial, and the size of particle ensures
In print procedure, ink jet-print head is not in blocking, and nano particle is ceramic powders, glass powder, nylon powder or plastics
Powder.
As one kind preferably, when the main material for being molded 3D devices is ceramic powders, product needed degreasing before final molding
Sintering, temperature selects 900-1300 DEG C.
As it is a kind of preferably, improve printing effect ink jet-print head quantity be one or more than one;In order to realize
Even to print each layer, more preferable combined with ultraviolet radiation light is consolidated, and prevents ink jet-print head from plug phenomenon occur, sets on ink jet-print head
The quantity in some holes is 200 to 2000, forms the effect of droplet ejection.
It is low that the nanometer ink of preparation needs to have viscosity, there is preferable mobility, and its cure shrinkage is little, reduces solidification and receives
Contracting causes model deformation, warpage, cracking etc..On the one hand this nanometer ink will adapt to industrial piezoelectric ink jet printing head injection and beat
Print, on the one hand will be adapted to ultraviolet light source solidification.For the chemically or physically characteristic of printer model, nano-particle content is effectively ensured
The proportion for accounting for nanometer ink is 70% ~ 90%;To ensure effective solidification of per layer of model, the content of photosensitive resin accounts for nanometer ink
Proportion is 10% ~ 30%.
In the method that the present invention is provided, if carrying out three-dimensional modeling and three-dimensional entity model being divided into dried layer X-Y scheme
Shape, calculates the shape of each layer of two dimensional surface, cooks up the operation principles such as printing path and step, with traditional 3D printing
Operation principle is consistent with step.Wherein, the process of three-dimensional modeling can be saved, using existing three-dimensional software model is provided.
As a kind of preferred, appropriate ink conditioning agent can be added during configuration nanometer ink;Ink conditioning agent includes surface
Activating agent, buffer, metal-chelator, it is 0% ~ 5% that ink conditioning agent accounts for the proportion of nanometer ink, and wherein surfactant is being matched somebody with somebody
Effect in nanometer ink processed mainly has:Keep the fine uniform dispersity of ink and do not flocculate;Reduce surface tension
Effect;Froth breaking is acted on.Effect of the buffer in preparation of nano ink:Adjust the pH value of nanometer ink, the pH of nanometer ink
Value has a great impact to the application performance of ink.Generally, the pH value of ink is required 7~9.Metal-chelator exists
Effect in ink is:The conductivity values of ink can be adjusted, the numerical value of conductance is the height for reflecting salt content in ink.One
As salt in ink can damage print cartridge and at ink jet-print head crystallization cause plug.
As it is a kind of preferably, the speed of described nanometer ink injection is 0.1 ~ 1000m/s, forming cavity internal temperature control
At 20 ~ 70 DEG C.
As one kind preferably, the power bracket of ultraviolet light source is 0.5-3w, is solidified by the way of irradiation print area
Printable layer.
According to the method that the present invention is provided, by the temperature of temperature sensor real-time monitoring consolidation zone during solidification
Degree, the required solidification temperature of the marking ink of different ratio is different.
In ink jet-print head in course of injection, and then ultraviolet light source solidifies, realize nano particle fusion and into
Type.The moulding process is adapted to ceramics, glass, nylon, plastic or other material.
Specific embodiment one:
Ceramics are prepared as into the nano ceramic powder of a diameter of 100 ± 5nm, the nano ceramic powder and photosensitive resin of preparation, ink
Water modifier is mixed into nano ceramics ink.Wherein match somebody with somebody according to photosensitive resin 10%, ceramic powders 88%, the mixing of ink conditioning agent 2%
Make a nanometer ink.
According to the three-dimensional modeling requirement that print ceramic component, if threedimensional model Slice by slice cutting into dried layer X-Y scheme,
Printing path is cooked up according to each layer of shape, the consumption of every layer of material requested is calculated, single ink jet-print head spray is set
Go out speed 500m/s of nanometer ink, ink jet-print head quantity is 4, and forming cavity temperature is 30 DEG C, calculates every layer of time-write interval
Summation rise time, T time is returned with ink jet-print head, the power of the ultraviolet light source of selection is 1.2W.
Ink-jet starts, ink jet-print head injection nanometer ink, stops printing after elapsed time T, in ink jet-print head recurrence
Rise, ultraviolet light source is opened, along ink jet-print head print path light curing nano ink, the solidification of temperature sensor real-time monitoring
The temperature in region, confirms that solidification is completed, and after the nanometer particle ink curing molding in print area, closes ultraviolet light source.Often
One layer of solidification, platform sends behind, and successively prints in a manner described, successively solidifies, and determines that last layer solidifies successfully, obtains three
Dimensional device.
Carry out degreasing sintered, sintering temperature is 1200 DEG C, obtains resulting devices, obtain product average hardness for 75HV, prolong
It is 3500% to stretch rate, and better than hardness 50-60HV of the common foundry goods of same composition, elongation percentage is 2500% to performance.
Specific embodiment two:
It is a diameter of 300 ± 30nm glass powders by glass preparation, the nano ceramic powder and photosensitive resin of preparation, ink are adjusted
Agent is mixed into nano ceramics ink.Wherein it is hybridly prepared into and receives according to photosensitive resin 25%, glass powder 72%, ink conditioning agent 3%
Meter Mo Shui.
According to the three-dimensional modeling requirement that print glass devices, if threedimensional model Slice by slice cutting into dried layer X-Y scheme,
Printing path is cooked up according to each layer of shape, the consumption of every layer of material requested is calculated, single ink jet-print head spray is set
Go out speed 20m/s of nanometer ink, ink jet-print head quantity is 6, and forming cavity temperature is 60 DEG C, calculates every layer of time-write interval T,
From ultraviolet light source power be 3W.
Ink-jet starts, ink jet-print head injection nanometer ink, stops printing after elapsed time T, in ink jet-print head recurrence
Rise, ultraviolet light source is opened, along ink jet-print head print path light curing nano ink, the solidification of temperature sensor real-time monitoring
The temperature in region, confirms that solidification is completed, and after the nanometer particle ink curing molding in print area, closes ultraviolet light source.Often
One layer of solidification, ink jet-print head rises one layer of printing, and platform is motionless, successively prints in a manner described, successively solidifies, it is determined that finally
One layer solidifies successfully, obtains three-dimension device.
Specific embodiment three:
It is the plastic powders that 10 ~ 80nm of diameter is not waited by glass preparation, the nano ceramic powder and photosensitive resin of preparation, ink are adjusted
Section agent is mixed into nano plastic ink.Wherein it is hybridly prepared into according to photosensitive resin 15%, plastic powders 80%, ink conditioning agent 5%
Nanometer ink.
According to the three-dimensional modeling requirement that print plastic device, if threedimensional model Slice by slice cutting into dried layer X-Y scheme,
Printing path is cooked up according to each layer of shape, the consumption of every layer of material requested is calculated, single ink jet-print head spray is set
Go out speed 5m/s of nanometer ink, ink jet-print head quantity is 1, and forming cavity temperature is 30 DEG C, calculates every layer of time-write interval T,
From ultraviolet light source power be 0.5W.
Ink-jet starts, ink jet-print head injection nanometer ink, stops printing after elapsed time T, in ink jet-print head recurrence
Rise, ultraviolet light source is opened, along ink jet-print head print path light curing nano ink, the solidification of temperature sensor real-time monitoring
The temperature in region, confirms that solidification is completed, and after the nanometer particle ink curing molding in print area, closes ultraviolet light source.Often
One layer of solidification, platform sends behind, and successively prints in a manner described, successively solidifies, and determines that last layer solidifies successfully, obtains three
Dimensional device.
With reference to shown in Fig. 2, the invention discloses a kind of droplet ejection 3d printers, a kind of droplet ejection 3d printer arrangements
Middle print cartridge 1 connects installation in assistant print cartridges 3, assistant print cartridges 3 and is provided with B/P EGR Back Pressure Transducer EGR and liquid level sensor by ink 2, and assistant print cartridges 3 connect
The piezoelectric microsphere ink jet-print head 4 on printing head support part 5 is connect, the lower section of printing head support part 5 is provided with ultraviolet light source 6, outer linear light
Source 6 is luminous luminous downwards, and the lamp holder of ultraviolet light source 6 is pointed to immediately below ink jet-print head, the printer model irradiated on pedestal 9.
Printing motor spindle is pedestal 9, and the print platform 8 that can be lifted is provided with pedestal 9, and the quantity of ink jet-print head 4 is two, ink-jet
The spout of printhead 4 is provided with spray-hole.
The lamp holder of ultraviolet light source 6 is pointed to can be solidified immediately below ink jet-print head along printhead path.
In print procedure, two piezoelectric microsphere ink jet-print heads 4, an injection solid material 7, an injection fid
Material 10, the injection of ink jet-print head 4 nanometer ink, the start by set date of ultraviolet light source 6, ink jet-print head by the way of droplet ejection
4 ground floors for printing threedimensional model, complete until current layer is printed, and ink jet-print head 4 rises and revert to printing initial bit
The surface put.Ultraviolet light source 6 is opened, and the light direction of ultraviolet light source 6 is solidified along the printing path of ground floor,
Until solidification is completed.In every printing and after solidifying one layer of ink, platform declines one layer to print platform 8, such ink jet-print head and
The height that plane will continue to keep fixed is printed, general distance is 2-3mm.Ink jet-print head in print procedure all around
Movement can realize print large scale, high-precision model.
The both sides of ink jet-print head 4 have ultraviolet light source 6, and the power of ultraviolet light source 6 can be according to resin in ink
Content is adjusted.Ultraviolet light source 6 can be moved with the movement of ink jet-print head 4, and ultraviolet light source 6 solidifies and just prints
Region.
The device after solidification is completed is printed, removing is first had to and is removed backing material, then again will be through surface cleaning, de-
Fat, high temperature sintering can just obtain the product of excellent performance.