Method for producing silicone elastomer articles with elevated print quality
10926470 ยท 2021-02-23
Assignee
Inventors
Cpc classification
B29C64/291
PERFORMING OPERATIONS; TRANSPORTING
B33Y10/00
PERFORMING OPERATIONS; TRANSPORTING
B29C64/129
PERFORMING OPERATIONS; TRANSPORTING
B33Y70/00
PERFORMING OPERATIONS; TRANSPORTING
B33Y30/00
PERFORMING OPERATIONS; TRANSPORTING
B29C64/371
PERFORMING OPERATIONS; TRANSPORTING
B29K2083/005
PERFORMING OPERATIONS; TRANSPORTING
B29C64/40
PERFORMING OPERATIONS; TRANSPORTING
B33Y40/20
PERFORMING OPERATIONS; TRANSPORTING
B29C64/124
PERFORMING OPERATIONS; TRANSPORTING
B29C64/393
PERFORMING OPERATIONS; TRANSPORTING
B29C64/106
PERFORMING OPERATIONS; TRANSPORTING
B29C64/112
PERFORMING OPERATIONS; TRANSPORTING
B33Y40/00
PERFORMING OPERATIONS; TRANSPORTING
B33Y50/02
PERFORMING OPERATIONS; TRANSPORTING
International classification
B29C64/124
PERFORMING OPERATIONS; TRANSPORTING
B29C64/291
PERFORMING OPERATIONS; TRANSPORTING
B29C64/106
PERFORMING OPERATIONS; TRANSPORTING
B29C64/112
PERFORMING OPERATIONS; TRANSPORTING
B29C64/371
PERFORMING OPERATIONS; TRANSPORTING
B33Y10/00
PERFORMING OPERATIONS; TRANSPORTING
Abstract
In an additive 3D printing method for production of shaped articles from silicone elastomers, an elastomeric shaped body is built up step by step, by repeatedly precisely positioning portions of the crosslinkable silicone material and crosslinking by means of electromagnetic radiation. Charges that occur on the surface of the print material or on the article are neutralized by means of an ionization system.
Claims
1. A method for layer-by-layer production of a shaped silicone elastomer article, comprising the following steps: 1) by means of a spatially independently controllable 3D printing device, in an x,y working plane, applying crosslinkable silicone print materials in the form of droplets or continuous strands via one or more print nozzles to a spatially independently controllable carrier plate, to an extrinsic component positioned thereon, or to a print material layer applied beforehand, wherein at least one of the print materials comprises a silicone elastomer curable by electromagnetic radiation; 2) by means of at least one spatially independently controllable source of electromagnetic radiation, crosslinking or partly crosslinking the print materials applied, so as to form a layer of the cured or partly cured shaped silicone elastomer article; 3) moving the print nozzle of the 3D printing device or the carrier plate in a z direction in a defined manner, such that a next print material layer can be applied in the x,y working plane; 4) repeating steps 1) to 3) until the shaped silicone elastomer article is fully constructed, wherein steps 1), 2) and 3) are effected independently of one another or coupled to one another simultaneously or successively in any sequence, and wherein the print materials, after leaving the print nozzle and prior to contacting the carrier plate, the extrinsic component, or the print material layer applied beforehand, traverse a discharge region generated by means of an ionization system.
2. The method of claim 1, wherein in addition to a silicone elastomer print material, a second print material which is removable after completion of the shaped silicone elastomer article is applied as a support material.
3. The method of claim 2, wherein the discharge region covers part or all of the surface of the carrier plate, of the extrinsic component, or of a previously applied print material layer.
4. The method of claim 1, wherein the discharge region covers part or all of the surface of the carrier plate, of the extrinsic component, or of a previously applied print material layer.
5. The method of claim 1, wherein a controlled gas flow of ionizable gas is generated proceeding from the ionization system in the direction of the discharge region.
6. The method of claim 1, wherein the outer boundaries of the shaped silicone elastomer article are printed first to form an outlined interior, and then the outlined interior is filled completely or partly with print material.
7. The method of claim 6, characterized in that there is at least one extrinsic component present in the outlined interior.
8. The method of claim 7, wherein silicone the print material applied is subjected fully or partly to mechanical vibration prior to crosslinking or partial crosslinking.
9. The method of claim 1, wherein silicone the print material applied is subjected fully or partly to mechanical vibration prior to crosslinking or partial crosslinking.
10. The method of claim 1, wherein the discharge region is effective to remove electrostatic charges from the droplets or continuous strands applied from the one or more print nozzles.
11. The method of claim 1, wherein the discharge region is ineffective to cause curing of the droplets or continuous strands applied from the one or more print nozzles prior to crosslinking in step 2).
12. The method of claim 1, where the silicone elastomer is a liquid, addition-curable elastomer curable by UV light, and having a viscosity at 25 C. and a shear rate of 0.5 s.sup.1 of at least 200 Pa.Math.s.
13. The method of claim 1, where the silicone elastomer is a liquid, addition-curable elastomer curable thermally, and having a viscosity at 25 C. and a shear rate of 0.5 s.sup.1 of at least 200 Pa.Math.s.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2)
(3)
(4)
(5)
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
(6) The invention relates to a method for layer-by-layer production of shaped silicone elastomer articles comprising the following steps:
(7) 1) By means of a spatially independently controllable 3D printing device, in an x,y working plane, two or more print materials are applied in the form of droplets or continuous strands via one or more print nozzles to a spatially independently controllable carrier plate, to an extrinsic component positioned thereon or to a print material layer applied beforehand, wherein at least one of the print materials comprises a silicone elastomer curable by electromagnetic radiation;
(8) 2) By means of at least one spatially independently controllable source of electromagnetic radiation, the print materials applied are crosslinked or partly crosslinked, so as to form a layer of the cured or partly cured shaped silicone elastomer article;
(9) 3) The print nozzle of the 3D printing device or the carrier plate are moved in the z direction in a defined manner, such that the next print material layer can be applied in the x,y working plane;
(10) 4) Steps 1) to 3) are repeated until the shaped silicone elastomer article is fully constructed,
(11) wherein steps 1), 2) and 3) are effected independently of one another or coupled to one another simultaneously or successively in any sequence,
(12) characterized in that the print materials after leaving the print nozzle traverse a discharge region generated by means of an ionization system.
(13) Preferably, the silicone elastomer used in the method according to the invention is an addition-crosslinking silicone rubber compound. In step 2), this can be crosslinked either thermally and/or by means of UV or UV-VIS light. Silicone rubber compounds of this kind are known, for example, from WO 2016/071241 A1 and in the publications cited therein.
(14) Preferably, the print materials have a viscosity at 25 C. and at a shear rate of 0.5 s.sup.1 of at least 40 Pa.Math.s, more preferably at least 100 Pa.Math.s and most preferably at least 200 Pa.Math.s.
(15) The print materials are preferably deposited at mass throughputs of more than 5 g/h, more preferably at mass throughputs of more than 10 g/h, and especially at mass throughputs of more than 20 g/h.
(16) The viscosity of the silicone rubber compounds can be determined, for example, by means of the test method described hereinafter: using an MCR 302 rheometer from Anton Paar; Graz, Austria according to DIN EN ISO 3219: 1994 and DIN 53019, using a cone-plate system (CP50-2 cone) with an opening angle of 2. The instrument is calibrated with 10000 standard oil from the National Metrology Institute of Germany, Brunswick, Germany. The measurement temperature is 25.00 C.+/0.05 C., the measurement time 3 min. The viscosity figure is the arithmetic mean of three independently conducted individual measurements. The measurement uncertainty in the dynamic viscosity is 1.5%.
(17) Preferably, the method according to the invention is characterized in that, in addition to the silicone elastomer print material, a second print material removable after completion of the shaped silicone elastomer article is applied as a support material. In this context, any desired known support material is usable.
(18) The action of the electromagnetic radiation on the print materials is preferably location-selective or over the full area, pulsed or continuous, and with constant or variable intensity.
(19) In addition, the method according to the invention is preferably characterized in that the discharge region covers part or all of the surface of the carrier plate, of the extrinsic component or of a previously applied print material layer. More particularly, it is advantageous when, in addition to the charging of the print material, charges over the entire print region and/or external bodies or extrinsic components are neutralized. For example, for this purpose, an active ionization electrode, before the printing, can be moved across the print region and also over external bodies and extrinsic components.
(20) The method according to the invention is further preferably characterized in that a controlled gas flow of ionizable gas is generated proceeding from the ionization system in the direction of the discharge region. Preferably, the ionizable gas is compressed air, but other gases or gas mixtures are also usable, such as nitrogen or lean air (i.e. nitrogen-enriched air). The gas flow can generate a directed and better-defined discharge region. Furthermore, a dust removal effect, i.e. reduction in the particle input, is possible. This is of particular relevance for shaped articles that require cleanroom conditions, for example medical articles.
(21) The method according to the invention is further preferably characterized in that the outer boundaries of the shaped silicone elastomer article are printed first and then the outlined interior is filled completely or partly with print material.
(22) The print material applied is preferably subjected fully or partly to mechanical vibration prior to crosslinking or partial crosslinking. Preferably, there is at least one extraneous component here within the outlined interior. The extraneous component can be imprinted into the shaped silicone elastomer article in a form-fitting manner by this method.
(23) Preferably, during the printing, the mechanical motions/vibrations present in the carrier plate and the print body are measured and evaluated.
(24) Above a permissible tolerance range, for example, messages can be generated and/or the print operation can be terminated. This can also be used as a safety measure in order to recognize any mechanical encroachment of personnel onto the carrier plate in the print region.
(25) In addition, the present invention relates to a manufacturing system for use in the method described above, wherein the manufacturing system comprises at least the following components: a spatially independently controllable 3D printer device comprising one or more reservoirs for one or more print materials and at least one print head comprising one or more print nozzles, a spatially independently controllable source of electromagnetic radiation, a spatially independently controllable carrier plate and an ionization system for generation of a discharge region in the region between print nozzles and the carrier plate.
(26) Suitable print nozzles for silicone printing are manufactured by companies such as NORDSON CORP./USA and VERMES MICRODISPENSING GMBH/Germany). These print nozzles enable pressure buildup within the kbar range, which means that amounts of liquid in the p1 to nl range can be expelled within 1-100 s through a nozzle having diameters between 50 and 500 m at a speed of 1-100 m/s. This operation is repeated with a frequency of up to several hundred Hz (these are typical parameter ranges which can differ considerably in the individual case).
(27) Both the 3D printer device and the source of electromagnetic radiation, and also the carrier plate are spatially independently controllable.
(28) In the context of the present invention, spatially independently controllable means that the corresponding device can be moved in all three spatial directions x, y and z, i.e. three-dimensional, in a location-selective manner.
(29) The manufacturing system according to the invention is preferably characterized in that the ionization system comprises one or more spatially independently controllable ionization electrodes.
(30) Preferably, the inclination of the ionization electrode can be adjusted in a location-sensitive manner. This allows the edges to be optimally covered and discharged by the electrodes in comparatively large components.
(31) Suitable ionization systems are obtainable, for example, from the company Haug Ionisationssysteme GmbH & Co. KG/Germany. A system of this kind is typically divided into a discharge power supply and a discharge device, also called an ionization electrode. The discharge power supply transforms the mains voltage available (120/230 V) to a high voltage of up to a few thousand volts. The ionization electrode may assume several forms. Examples that should be mentioned here include elongated rods, annular or ionization electrodes in the form of manual devices. All ionization electrodes have metallic parts (for example tips) which are put under the high voltage and at which the surrounding gas molecules are charged in accordance with the voltage applied.
(32) A specific example of a suitable ionization electrode unit for avoidance of electrostatic charges is a device system from Haug, consisting of a power supply (Haug EN SL LC 230V/50-60 Hz universal power supply with accompanying mains cable) and one or two electrically connected Haug ionization rods (ionization electrodes) from the VS series (e.g. VS 028 300 ionization rod).
(33) The present invention is not restricted to the electrode types described. Also usable are ionization systems and/or ionization electrodes based on other constructions and systems from other manufacturers.
(34) The electrode(s) is/are mounted in the printing device as described in the figures, such that they deionize the region around the nozzle exit for the print material.
(35) The manufacturing system according to the invention is further preferably characterized in that the ionization system has at least one gas connection for an ionizable gas and at least one gas nozzle directed toward the discharge region.
(36) The at least one ionization electrode is preferably arranged in a laterally inclined manner with respect to the print head, so as to cover the full area of the region between the print nozzles and carrier plate. Alternatively, the ionization electrode may be arranged in the form of a ring beneath each print nozzle, in order thus to cover the region beneath each individual print nozzle.
(37) The angle of inclination (angle between the plane of the carrier plate and the transverse axis of the ionization electrode) with ionization systems mounted laterally is preferably in the range from 10 to 80, more preferably in the range from 20 to 60, and especially in the range from 25 to 35.
(38) In addition, the distance between the tip of the ionization electrode and the tip of the nozzle is preferably in a range below 10 cm, more preferably below 5 cm, and especially below 3 cm.
(39) The ionization electrode is independently controllable in spatial terms and preferably in terms of inclination, such that not just the print materials but preferably also the carrier plate and any extrinsic components can be neutralized.
(40) The ionization electrode may be mounted in the vicinity of the metering device; it may optionally also address the entire construction space independently of the metering device, such that any desired point in the construction space can be deionized.
(41) The manufacturing system of the invention preferably further comprises at least one vibration generator. The vibration generator is preferably integrated into at least one holder in the carrier plate. The vibration generator is preferably set up such that vibrations of any desired mechanical amplitudes and frequencies can be generated.
(42) In addition, the manufacturing system according to the invention is preferably characterized in that the 3D printing device comprises at least one confocal measurement system having one or more confocal lenses. Preferably, the confocal lenses and the print nozzles are mounted together on a carriage of a linear actuator and in their entirety form the print head of the 3D printing device.
(43) In addition, the manufacturing system according to the invention is preferably characterized in that it has at least one control unit in which measurement signals obtained by the confocal system can be evaluated and processed further. As described above, it is possible in this way, for example, to measure and, if necessary, further process vibrations and movements of the carrier plate or of the print body.
(44) Preferably, there are one or more positioning geometries for positioning of at least one extrinsic component mounted in the manufacturing system according to the invention, on the carrier plate or onto a previously applied and crosslinked print material layer. These positioning geometries are preferably spacers or positioning points which are attached or mounted on the carrier plate itself or have been produced therefrom by prior printing.
(45) The 3D printing device preferably comprises a movement system for the x,y working plane, wherein the movement system comprises a movement axis movable in the y direction, a movement axis movable in the x direction and a positioning unit. Preferably, there is a holder for the ionization system and the source of electromagnetic radiation mounted on the movement axis movable in x direction.
(46) The present invention further relates to a shaped silicone elastomer article which has been produced by the method described above. Preferably, there is at least one extrinsic component embedded fully or partly, in a form-fitting manner, into this shaped silicone elastomer article.
(47) The shaped silicone elastomer articles according to the invention feature elevated print quality, smooth edges and low deformation. Extrinsic components, even having difficult and poorly accessible surface structures, can be optimally embedded and enclosed in a form-fitting manner.
(48) Moreover, the shaped silicone elastomer articles show a high quality of accordance with the CAD model and improved position and evenness tolerances of the edge faces compared to the CAD model. In addition, better surface roughness is possible (e.g. a mean roughness: R.sub.A<100 m). Surface roughness can be determined, for example, by test methods according to DIN ISO 25178-1:2016-04 and DIN EN ISO 25178-2:2012-09.
(49) The figures show working examples of the invention, although these merely schematically illustrate the subject-matter of the invention. The working examples shown and described hereinafter with reference to the figures should not be regarded as being restrictive of the subject-matter of the invention. A multitude of modifications that are possible within the scope of the claims will be apparent to the person skilled in the art.
(50)
(51) A further embodiment is depicted in
(52) In the case of specific printing processes, print layers and/or shaped articles are generated atop, on (application printing) or surrounding (embedding printing) existing bodies. If these existing/external bodies (extrinsic components) can be electrostatically charged, deflections of the print droplets or strands may arise owing to the abovementioned electrostatic effects. In order to rule this out, prior to the application printing and embedding printing, the ionization electrode as a whole is moved across the entire print region and the external bodies in order to neutralize any existing charges. The magnitude and duration of the discharge prior to the printing are dependent on the size and the physical properties of the surface to be covered.
(53)
(54) The setup and the procedure described in accordance with
(55) Moreover, the bonding of ultrathin silicone films to printed support skeletons or the direct integration of such films as a permeable membrane is employable. Examples here include storage for blood (blood bags), wound dressings for burns with a printed support skeleton (facemask, body moulding, etc.) and wound dressings with a support skeleton in combination with cold plasma (plasma disinfection).
(56) As already described in the paragraphs above, externally added articles, especially silicone articles, become electrostatically charged. This effect is observed to an enhanced degree in the case of electroactive polymers (EAP) or ultrathin silicone films. It is thus necessary here, prior to the positioning of the external silicone articles, to run the ionization electrode across the entire working region and to neutralize the external EAP or silicone articles beforehand. This can be effected with the ionization system installed in the printer according to the invention.
(57) In 3D printing with silicone elastomers, bonding and intermerging and/or complete wetting of edge layers or extrinsic components is extremely important. Especially in the case of printing of relatively large components, specific printing strategies can reduce the printing time. In this case, however, there is increased occurrence of edge layers which have to be embedded in a form-fitting manner. However, the viscosity of silicone elastomers is not always optimal for rapid and reliable wetting or relaxation (self-levelling/diffluence). In the case of printing on extrinsic components, conventional printing (jetting, dispensing) on surfaces with undercuts (pores, very rough surfaces, holes, etc.) is in some cases problematic and inadequate. Shadowed recesses, vertical textured edges and undercuts cannot, as required for construction purposes, be filled up by droplets or strands coming in from above. Instead, the silicone elastomer here has to relax (flow) from the side to the material edge and wet it. This is in some cases associated only with a considerable wait time or unacceptable idle times for the printer. Large relaxation volumes or long relaxation pathways cause long self-relaxation times .sub.s. Even when the body and/or the print materials have been charged, adequate wetting is prevented (very large .sub.eff as a result of very large .sub.io). Various printing methods and extensions are described hereinafter in order to compensate for this.
(58) Fill printing method and vibration relaxation:
(59) A specific embodiment of the 3D printing method according to the invention is the fill printing method. This generates relatively large bodies in a combination of multiple printing strategies and methods. In this method, the outside boundaries are printed by the normal jetting or dispensing method and the hollow interior is subsequently filled. The filling is effected by a movement strategy similar to the dispensing method. The interior is filled strand by strand or point by point from any desired points. In the filling and the filling strategy, adequate wetting of the wall regions has to be ensured. This is of significance especially in the case of printing strand by strand. Large strands (diameter>1 mm) or large droplets (diameter>1 mm) with high viscosity can result in formation of material fronts that cause trapping of air at edge regions (solid/filling material transition). Moreover, the relaxation requires a certain period of time. It would be possible to shorten this with decreasing viscosity of the print material, but this has the disadvantage that voxels placed with the same mass are more rapidly deformed and diffuse at edge regions. One way of influencing the effects mentioned above in a positive manner is to subject the print body to mechanical vibration (reduction of .sub.eff by .sub.vibr). The vibrations ensure faster levelling and, given an optimized filling strategy, lead to optimal wetting of the edge regions. Preference is given here to using piezo elements, compressed air vibrators or vibration motors for generating the vibration. Examples include standard vibration generators in the ultrasound region. For example, the mechanical vibration can be transmitted to the carrier plate (4) by means of a vibration generator (31) integrated within the holder (30).
(60) Edge filling method:
(61) By the edge filling method, it is possible to fully wet and imprint an extrinsic component over its full area.
(62) The following advantages of the invention are apparent over the prior art:
(63) (1) compensation of electrostatic effects in 3D printing with silicone elastomers
(64) (2) deionizing of extrinsic components before and during 3D printing
(65) (3) combination of discharge (ionization) and UV curing in one step
(66) (4) incorporation of vibrations for quicker and defined and complete relaxation of the print materials
(67) (5) imprinting of chargeable or nonchargeable components with undercuts and/or textured surfaces with the aid of the fill printing method, especially with the aid of the edge filling method.
Example
(68) There follows a description of a specific example for the method according to the invention in a manufacturing system according to the invention having a high-voltage electrode and a downstream water-cooled UV-LED bar. The printing space is completely closed and is accessible only via a hatch with a safety switch. The ionization is activated at the start of the printing operation and deactivated at the end of the printing operation. The process sequence corresponds to the sequence shown in
(69) Mechanical vibrations of the carrier plate are recognized by the installed confocal measurement system during the printing process and, if necessary, the printing process is suspended or terminated in the event of excessive vibrations of the carrier plate. This is also used as a safety measure in order to recognize mechanical encroachment of personnel to the printing plate in the printing region.
REFERENCE SIGNS FOR THE FIGURES
(70) 1 print nozzle (e.g. jetting valve or dispensing dosage unit)
(71) 2 print materials (for example in the form of droplets as shown or in the form of an extruded strand)
(72) 3 (individual) layers of the shaped article
(73) 4 carrier plate
(74) 5 high-voltage electrode of the ionization system (e.g. rod-shaped ionization electrode)
(75) 6 tips of the high-voltage electrode of the ionization system
(76) 7 ionization region (discharge region)
(77) 10 side view of manufacturing system with longitudinal electrode inclined by about 30
(78) 11 annular high-voltage electrode (ionization electrode)
(79) 15 side view of manufacturing system with ring electrode
(80) 17 UV light source
(81) 18 additively manufactured shaped article or extrinsic component
(82) 19 print head
(83) 20 confocal lenses (of the confocal measuring unit)
(84) 21 carrier plate movement carriage in the x axis
(85) 23 y movement axis (e.g. linear module)
(86) 24 x movement axis (e.g. linear module)
(87) 25 holder (e.g. a rigid holder for a UV source and/or the ionization electrode and/or a confocal lens)
(88) 26 positioning unit (e.g. step motor with sensor)
(89) 27 top view of manufacturing system
(90) 28 edge region of extrinsic component
(91) 29 support and positioning geometry
(92) 30 holder of the carrier plate
(93) 31 vibration generator
(94) 32 print materials deposited (for example in the form of strands or droplets)
(95) 33 material front 1 (little relaxation)
(96) 34 material front 2 (increasing relaxation)
(97) 35 material front 3 (advanced relaxation)
(98) 36 front of the uppermost printed material layer (corresponding to the top side of the shaped article)
(99) 37 side view of manufacturing system in the operation of the edge filling method
(100) 38 extrinsic component