Method and apparatus for 3D printing

Abstract

A printing system (1400, 1500) is disclosed for printing of a three-dimensional (3D) object by superposition of compacted layers. The system comprises: a) a transport mechanism (12, 630) comprising a movable carrier (600) adapted to displace a backing surface (10, 620) along a direction of travel; b) an adhesive application module (14, 30, 700, 1000) adapted to render tacky desired foreground regions of the backing surface, or of a compacted layer previously formed thereon; c) a first dispensing module (16, 34, 2000) for applying model particles to adhere selectively to the regions rendered tacky; d) a second dispensing module (20, 38, 740, 2000) for applying a support material to coat at least regions of the backing surface, or of a compacted layer previously formed thereon, not coated with the model particles; and e) at least one compacting module (40, 42, 3000) for compressing the model particles and / or the support material to form thereon a compacted layer or a part thereof; the transport mechanism serving to displace the movable carrier to pass cyclically through the adhesive application, dispensing and compacting modules so as to form superposed compacted layers on the movable carrier. Methods for 3D printing using such systems and components thereof, as well as suitable compositions are also described.

Description

[0001] METHOD AND APPARATUS FOR 3D PRINTING

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims Paris Convention priority from Great Britain patent applications GB 2313841.5 filed on September 11, 2023, and GB 2400528.2 filed on January 15, 2024, the entire disclosures of which are hereby incorporated by reference, as if fully set forth herein.

[0004] FIELD

[0005] The present disclosure relates to a method and apparatus for three-dimensional (3D) printing, including components and consumables therefor.

[0006] BACKGROUND

[0007] Various methods have hitherto been proposed for digital manufacture of 3D objects, which fall into two categories, namely subtractive and additive. In the former, material is removed from an initial solid blank to leave behind the desired finished article. This method is used for example to make dental crowns and fillings. The present invention is concerned with the additive method, in which the end-product is built up layer by layer, with each of all but the lowest layer being deposited onto, and bonded to, a layer beneath it.

[0008] The additive method of 3D printing has been used for plastics materials, ceramics and metals, the method of deposition of each layer and the method of binding of each layer to the one beneath it being dependent upon the material from which the end-product is to be formed.

[0009] To form a desired object by the additive method of manufacture, it is known to deposit stacked layers of two types of materials. A first type includes the material from which the object is to be formed and is termed herein the model material. The second type provides support for the formation of subsequent layers and is herein termed the support material. Upon completion of the printing process, or any other desired post-printing finishing process, the support material can be removed, and the remaining shape of model material can be referred to as the “green” printed part or the green model. If the model material is itself constituted of particles of the material intended to form the desired object (e.g., metal or ceramic) and a binder as used in Binder Jetting (BJT), Material Extrusion (MEX), Material Jetting (MJT) and Vat Photopolymerization (VPP) technologies, the binder would be mostly eliminated at the end of the 3D printing. This step is known as debinding, which may be either thermal, solvent based, or catalytic, depending on the binder. Following debinding, the remaining shape, which may still contain sufficient amount of binder to provide enough structural integrity, is referred to as the “brown” printed part or the brown model.

[0010] Depending on the amounts of binder eliminated and shapes and / or density of the remaining particles, the brown model can be relatively porous. The brown model can be further treated, according to the type of model material being used, to provide to the treated end-product desired mechanical properties (e.g., can be cured, melted, or sintered to consolidate the powder material to the desired final density, etc.).

[0011] Existing additive manufacture processes are relatively slow and energy-consuming, hence expensive, and mainly relevant for prototyping, or manufacturing of spare parts and such uses that would excuse the relatively high cost.

[0012] To form items of relatively high resolution, particles of relatively small size need to be used, in which case it may take a high number of layers to form an object having dimensions in other orders of magnitude. Moreover, applying relatively small particles as dry powders can be problematic, as the particles may remain suspended in the air rather than attached to a substrate.

[0013] One solution, termed nanoparticle jetting, involves as its name suggests, the alternating jetting of droplets of “model ink” and “support ink” in respective regions of a layer being formed on the substrate. For a solid material to be amenable to ink jetting, its size should preferably be below 1 micrometer (pm). Thus, this process is expensive, both for the preparation of suitable inks and the need to dry each layer, before a new one can be applied. Moreover, it could be extremely time consuming for the preparation of relatively large objects.

[0014] To facilitate the attachment of powder particles to a substrate, without having to disperse them in a liquid, relatively large particles should be used (which can be at the expense of detailed resolution). In this method, a bed of powder particles, the bed having a thickness of 30- 500 pm, for individual particles typically larger than 20-30 pm and usually in the 70-100 pm range, is targeted where desired with a glue acting material. This process is known as binder jetting and may require a relatively large amount of binder to enrobe the particles to be jointly adhered. In this process, the bed is constituted of similar particles that have a dual role, a) serving as model particles, where glued by a jetted binder and b) serving as support particles everywhere else. This may impose conflicting demands on the particles and be wasteful, even if under some circumstances the support particles could be recycled following their removal. Moreover, larger particles and / or larger amounts of binder (the removal of which being often challenging) yields aggregations of particles having relatively large voids therebetween. Too large voids may reduce the bulk density of the particles in the model to an extent detrimental to its function.

[0015] The present invention lends itself to the manufacture inter alia of printed circuit boards (PCB), which are currently manufactured by one of the following main approaches.

[0016] In a first approach, a foil of conductive material (typically copper) is laminated onto a dielectric board and an image is formed by coating the laminated copper foil with a resist material that can be etched to leave a desired circuit layout. The conductivity that can be achieved by this method is very good, as one starts with a foil of conducting material. However, this method is very wasteful and limited to relatively simple structures.

[0017] In a second approach, more complex structures can be formed by jetting a would-be conductive ink on a dielectric board directly according to the desired circuit layout. While this approach reduces the waste of material, it is still relatively slow and limited in the conductivity which can be achieved after sintering of the particles jetted in the ink. Typically, the conductivity of a PCB prepared by such printing method does not exceed -30% IACS, this abbreviation standing for International Annealed Copper Standard and the number preceding “IACS” being the percentage of conductivity relative to copper, which is considered to be 100% conductive.

[0018] SUMMARY

[0019] According to the present disclosure, there is provided in a first aspect a printing system for printing of a three-dimensional object by superposition of compacted layers as hereinafter set forth in more detail and claimed in Claim 1 of the appended claims and claims depending therefrom.

[0020] According to the present disclosure, there is provided in a second aspect a method of 3D printing which comprises forming a plurality of superposed compacted layers as hereinafter set forth in more detail and claimed in Claim 19 of the appended claims and claims depending therefrom.

[0021] The printing system comprises: a) a transport mechanism comprising a movable carrier adapted to displace a backing surface along a direction of travel; b) an adhesive application module adapted to render tacky desired regions of the backing surface, or of a compacted layer previously formed thereon; c) a first dispensing module for applying model particles to adhere selectively to the regions rendered tacky; d) a second dispensing module for applying a support material to coat at least regions of the backing surface, or of a compacted layer previously formed thereon, not coated with the model particles; and e) at least one compacting module for compressing the model particles and / or the support material to form thereon a compacted layer or a part thereof; the transport mechanism serving to displace the movable carrier to pass cyclically through the adhesive application, dispensing and compacting modules so as to form superposed compacted layers on the movable carrier.

[0022] In some embodiments, the second dispensing module is configured to apply a support material in the form of support particles, the second dispensing module further comprising an adhesive forming unit adapted to form a background adhesive in regions of the backing surface, or of a compacted layer previously formed thereon, uncoated by the model particles. The background adhesive forming unit can be selected in accordance with the adhesive application module and the means used thereby to form a tacky adhesive image. If the module applying the adhesive intended to adhere the model particles is configured to apply a layer of adhesive over the entire backing surface (or underlying layer), said module further comprising a device adapted to selectively render tacky desired regions of the adhesive layer (foreground adhesive regions), then the adhesive forming unit of the second dispensing module can be a heater capable of rendering tacky regions of the previously applied adhesive not already coated with model particles (the background adhesive regions). Alternatively, if the module applying the adhesive intended to adhere the model particles is configured to selectively apply a layer of adhesive only in the desired foreground adhesive regions, then the adhesive forming unit of the second dispensing module can also be capable of selectively applying a same or different adhesive to the background adhesive regions to be coated by the support particles.

[0023] In some embodiments, at least one of the adhesive application module and the adhesive forming unit of the printing system comprises a plurality (e.g., 50, 100, 128, 150, 180, 200, 256, 300, 360, 400, 512, 600, 720, 800, 1024, 1200, 1600, 1440, 2048, 2880, etc. and any intermediate value) of individually controllable jetting nozzles forming a liquid writing unit adapted to jet an adhesive liquid according to the predetermined patterns of the desired region or in complementary regions surrounding the predetermined patterns, respectively, said adhesive application module and / or adhesive forming unit optionally further comprising a drying unit adapted to render the adhesive liquid tacky, the adhesive liquid of the adhesive application module and the adhesive forming unit optionally being different. In some cases, the jetting nozzles constituting a liquid writing unit can be arranged in arrays. Furthermore, their individual controllability may not only refer to switching them on or off, but also to the volume of liquid that can be jetted towards any particular point, such variations being also referred to as grey levels. Nozzles able to produce 3 different sizes of droplets in addition to being off are said to have 4 grey levels.

[0024] The size of the droplets of adhesive liquid can be varied from layer to layer, for example, if different particles (e.g., of different size) are to be applied and retained by the adhesive image formed during a particular cycle. Alternatively, or additionally, the size of the droplets of adhesive liquid can be varied within a specific adhesive image intended for a single stack of compactable particles. For illustration, as an adhesive image may dry faster at its contour than within inner areas of continuous adhesive, it can be desired to jet at the exposed perimeter of the image droplets having a volume relatively higher (e.g., twice larger) than droplets deposited more internally.

[0025] In some embodiments, at least one of the adhesive application module and the adhesive forming unit of the printing system comprises a plurality of individually controllable jetting nozzles forming an activator writing unit adapted to jet an adhesive activating liquid upon a thin layer of adhesive according to the predetermined pattern of the region desired tacky or in complementary regions surrounding the predetermined pattern, respectively.

[0026] Instead of, or in addition to, being followed by a downstream activator writing unit, the adhesive application module and the adhesive forming unit may be preceded by an upstream adhesive priming unit. The adhesive priming unit may be used to improve the quality of the adhesive image to be subsequently formed, allowing it to faithfully reproduce the intended image (e.g., avoiding spreading of the adhesive that would modify the shape of the image, such as by widening traces, or conversely avoiding beading of the adhesive that may decrease adherence of the image (and the particles to be applied thereto), also distorting the adhesive image as compared to the intended one). In other words, the adhesive priming unit (if included in the printing system) may serve to modify the surface energy of the superficies being primed in accordance with the surface tension of the adhesive liquid (e.g., form a contact angle between 40° and 70°), so that, upon contact with the primed surface, the adhesive liquid neither spreads nor beads significantly, the resulting adhesive image being substantially as intended in shape and thickness. The adhesive priming unit can be adapted to modify the entire surface being primed and be based on physical treatment (e.g., corona plasma) or chemical treatment (e.g., applying a priming coat). Alternatively, the adhesive priming unit can selectively apply a priming liquid in regions to be thereafter targeted by the adhesive liquid. Such an adhesive priming unit can, in principle, be constructed in a manner similar to a selective adhesive forming unit or activator writing unit, with a plurality of individually controllable nozzles adapted to jet a priming liquid where desired. A priming liquid may include any substance capable of modifying the surface energy of an underlying surface while being compatible with the adhesive and particles to be applied thereon. For instance, positively charged substances (e.g., polyethylene imines) can be used for anchoring negatively charged adhesives.

[0027] By the above-mentioned methods of pre-treatment, priming regions to which an adhesive liquid would be subsequently deposited are formed so as to increase the proper attachment of the adhesive within the borders of the sought adhesive image. Alternatively, or additionally, one may treat the regions surrounding the intended adhesive image so as to repulse the adhesive liquid from said areas, forcing it to remain within the borders of the intended adhesive image. This alternative approach for improving the print quality of the adhesive image can be viewed as a masking technique and a module adapted to implement it can be referred to as a masking module. While adhesive priming can be adequate, when desired, for lines having a width of 25 pm or more, it is believed that the adhesive masking method can be advantageous for even narrower lines having a width of only 10-20 pm.

[0028] Were the nozzles of such modules or unit to be operated in a continuous manner so as to form a line (e.g., of adhesive or activating liquid), the width of the line might be, for instance, of 50 pm or more, and a spacing between adjacent line of at least 50 pm.

[0029] In some embodiments, at least one of the adhesive application module and the adhesive forming unit comprises a plurality of individually controllable electromagnetic (EM) radiation emitting elements forming a writing unit adapted to heat a thin layer of thermoplastic adhesive according to the predetermined pattern of the region desired tacky or in complementary regions surrounding the predetermined pattern, respectively. While the writing unit can be directed to heat an adhesive layer directly applied to the backing surface (or to an underlay), it may alternatively be directed to enable selective transfer of adhesive regions. In such embodiments, the thin layer of thermoplastic adhesive according to the predetermined pattern is first formed as a mirror image on a transfer member, the adhesive application module further comprising said transfer member and a transfer station at which the mirror image is transferred from the transfer member to the backing surface or a layer formed thereon, the thin layer of thermoplastic adhesive, towards which the writing unit is directed, being formed on the transfer member.

[0030] In some embodiments, the individually controllable electromagnetic (EM) radiation emitting elements of the writing unit are laser beam emitting elements, the plurality of laser beam emitting elements optionally being constituted of one or more arrays of vertical -cavity surface-emitting lasers (VCSELs).

[0031] Were the radiation emitting elements of such modules or unit to be operated in a continuous manner so as to form a line (e.g., of tacky adhesive), the width of the line might be, for instance, of 20 pm of more, and a spacing between adjacent lines of at least 20 pm, enabling the formation of patterns with denser and / or thinner traces than ink-jetting equipment.

[0032] The radiation of each emitting element can be controlled so as to modulate the degree of impinging heat in a manner comparable to the controllability of the volume of a droplet that can be jetted by an individual nozzle. Thus, by analogy, the EM radiation emitting elements may, as nozzles, be said to have grey levels. In some cases, the writing units may be configured to have 4 grey levels or more, 8 grey levels or more, 16 grey levels or more, or 32 grey levels or more.

[0033] In some embodiments, the arrays of nozzles, or of EM radiation emitting elements, constituting the writing unit can be aligned or otherwise arranged so as to form scalable writing bars, also termed imaging bars, adapted for relatively wide formats of up to 30 cm, up to 60 cm, up to 90 cm, or up to 120 cm.

[0034] In some embodiments, the writing unit is adapted to form images (e.g., of jetted adhesive or of heat spots) having a relatively high resolution of at least 300 dots per inch (DPI). In some cases, the writing unit can provide for a resolution of at least 600 DPI, at least 900 DPI, or at least 1,200 DPI. (Image resolution is almost universally quoted in DPI; as one inch is a little more than 2.5 cm, each 100 DPI equates to about 40 dots per centimeter.)

[0035] In some embodiments, the dispensing modules, first or second when adapted to apply particles, each comprises one or more powder containers, each configured to contain same or different (e.g., model) particles, each powder container being connected via one or more passageways to a respective applicator adapted to apply the model (or the support) particles upon the tacky adhesive image formed in the desired regions of the backing surface, or of a compacted layer previously formed thereon. The applicator can be a contact-less applicator, such as a spray blowing the particles towards the tacky adhesive without contacting it, or can alternatively be a periodically contacting applicator. While a contact-less applicator sprinkling particles can be easier to operate, it typically requires removal of particles scattered on unintended areas, hence the inclusion of a cleaning device and optionally of a recycling device, if waste of valuable particles is to be reduced or avoided. In some embodiments, the cleaning device if including a moving cleaning member due to contact the particles, may also serve to concomitantly rub the particles in the adhesive image. Otherwise, the use of a contact-less applicator of particles may require the assistance of a rubbing module to render uniform the coat of particles stacked on the adhesive image.

[0036] In contrast, an applicator of particles intermittently contacting an adhesive image so as to effect a more selective transfer only to tacky regions may require a more complex operation and control, involving for instance cyclical engagement and disengagement of moving parts, but could advantageously facilitate subsequent cleaning of surplus particles having parasitically transferred or even entirely eliminate the requirement for such a cleaning step or device.

[0037] In some embodiments, the applicator of a module adapted to dispense particles by controlled contact consists of one or more rollers, the roller adjacent to the movable carrier, also referred to as an applicator cylinder, being configured to rotate in the direction of travel of the backing surface whilst slipping with respect to an upstream cylinder transferring particles thereto, the applicating cylinder having substantially no slippage with respect to the backing surface.

[0038] In some embodiments, the second dispensing module is configured to apply a support material in liquid form, the second dispensing module further comprising a solidifying unit adapted to solidify the applied liquid support material. If the liquid support material can be solidified by drying, the solidifying unit can be a dryer capable of removing the liquid vehicle of the support material. If the support material is a curable liquid which can be solidified by curing upon exposure to predetermined factors (e.g., UV light), then the solidifying unit can be a curing unit exposing the liquid to the factors adapted to harden it.

[0039] The second dispensing module can be configured to apply a liquid support material in a non-selective manner over the entire surface of the layer, excess being wiped away from the regions already coated by the model particles, for instance with a doctor blade, a squeegee, or any like device adapted to level a liquid. The liquid levelling member can be disposed statically with respect to the X-direction of motion of the substrate, the relative displacement of the substrate in the printing direction providing for the wiping effect. Alternatively, the liquid levelling member can be movable (typically, but not exclusively, in a direction opposite and / or transverse to the printing direction).

[0040] When two levelling members are used to equalize the surface of the (e.g., curable) liquid, they need not be the same. For instance, one can be static in the X-direction, while the second can be movable, e.g., in a transverse Y-direction whilst the substrate proceeds to a downstream station in the printing direction. Having two levelling members (e.g., each in relative motion with the substrate in a distinct direction) may accelerate the formation of a layer of liquid having a relatively uniform thickness and / or may improve the distribution / homogeneity of solid additives (e.g., mechanical reinforcement or dielectric fibers) optionally comprised therein. Alternatively, or additionally, the liquid levelling member(s) can be vibrated to facilitate the removal of excess liquid, to randomize the distribution of materials (e.g., fibers) that would otherwise be predominantly arranged according to the direction of travel of the backing surface and / or evening of the liquid surface.

[0041] A similar accelerating effect with respect to the levelling of the liquid (and optionally the uniformizing of its features) can be obtained, when appropriate, by rotating the platform supporting the substrate. Excess liquid can be collected and discarded or recycled, if feasible.

[0042] Alternatively, the second dispensing module can be configured to apply the liquid support material selectively in regions uncoated by the model particles, the module including for instance a digitally controlled jetting head.

[0043] Jetting heads comprising nozzles are typically suited for liquids having a relatively low viscosity not exceeding 200 milliPascal. second (mPa.s being equivalent to a centipoise) at room temperature (e.g., circa 23°C), the viscosity of such jettable liquids often being less than 100 mPa.s, less than 50 mPa.s, less than 25 mPa.s, or less than 10 mPa.s. Some dispensers having larger nozzles or openings (e.g., injectors, extruders) can be capable of dispensing thicker liquids having viscosities of up to 1,000 mPa.s or even up to 10,000 mPa.s at room temperature, dispensing being often performed at an elevated temperature allowing a relative thinning of the liquid. As used herein, a material is said to be liquid regardless of its viscosity at working temperature (e.g., even if otherwise qualifying as a paste) to differentiate it from a solid material substantially devoid of a liquid carrier, (e.g., particles).

[0044] In some embodiments, the printing system may comprise two compacting modules, each disposed downstream of a respective dispensing module and adapted to compress the materials dispensed thereby. Regardless of the number of compacting modules included in the printing system, each may comprise a) a rotatable compactor controllably urged towards the backing surface to be in rolling contact with the model particles and / or the support material of each to be compacted layer; b) a countersurface supporting the movable carrier and a backing surface thereon at least at the point of rolling contact with the compactor; and c) a heating element adapted to heat at least one of the backing surface and the layer(s) formed thereon. In some embodiments, the compacting module may further comprise a device providing vibration to the rotatable compactor.

[0045] In some embodiments, the printing system further comprises a levelling module adapted to ensure that the layer formed thereby has an even continuous surface and / or has a desired thickness. The levelling module can be selected to remove at least part of any material protruding over a desired flat surface and / or exceeding the thickness sought for the layer. The levelling module can include a milling, grinding, and / or abrading device and means of removing the excess material taken away from a layer by such device. For illustration, the levelling device can be disposed in a chamber further including suction means to eliminate the residues milled, ground, and / or abraded away. The desired flatness or thickness of a layer can be achieved by relative motion between the layer and the levelling module in a direction transverse to the printing direction to an extent determining the flatness / thickness of the layer being levelled. For illustration, and considering a flat horizontal backing surface, the levelling module can be raised to a height above an intended outermost surface of the layer being formed corresponding to its desired thickness, or the backing surface can be lowered to a similar extent, or each could be partially moved respectively up and down, the total relative displacement corresponding to the thickness of the new layer to be levelled.

[0046] The printing system may further comprise any suitable sensors adapted to monitor and control the 3D printing process and the parts (e.g., modules) implementing steps thereof. Sensors can be temperature sensors, pressure sensors, motion sensors, distance sensors, level sensors, flow sensors, torque sensors, vibration sensors, presence sensors and the like, as adapted to the parameter to be monitored and controlled by the relevant feedforward or feedback mechanism. In some embodiments, the printing system further comprises an alignment sensor to align a positioning of the tacky adhesive image of each cycle with respect to edges of, or fiducial markers on, the backing surface.

[0047] In some embodiments, the transport mechanism further comprises a motor, a driving unit adapted to displace the movable carrier (e.g., horizontally, vertically, rotationally about a horizontal or a vertical axis, etc.), a control unit, a monitoring unit, a power supply and a process control software (e.g., to control speed, direction of displacement, distance between modules and backing surface or outermost surface of last superposed layer, temperature and any like parameter suitable for the operability of each module). The transport mechanism may further comprise a heater facilitating heat activation of heat activatable adhesives.

[0048] In some embodiments, the printing system further comprises a pre-treating module adapted to treat the backing surface upstream of the adhesive application module. For illustration, the pre-treating module can be selected and configured to apply a sacrificial layer or otherwise treat the backing surface to facilitate subsequent operations, such as the separation of the superposed compacted layers upon completion of printing or furthering the adhesivity of the first layer to be formed on the backing surface.

[0049] In some embodiments, the printing system further comprises a cleaning module adapted to remove excess model particles and / or support material from unintended regions, the cleaning module optionally comprising a brush, a soft roll, or a sponge, the cleaning module optionally being in a confined environment to permit gas flow or suction.

[0050] In some embodiments, the printing system further comprises a model enhancer module comprising an applicator configured to apply to voids between model particles a model enhancer liquid and a unit for treating the model enhancer liquid.

[0051] In some embodiments, the printing system further comprises a detaching module for detaching the superposed compacted layers from the backing surface.

[0052] In some embodiments, the printing system further comprises a post-printing module for treating the, optionally detached, superposed compacted layers so as to form the three- dimensional object, the treatment being at least one of i) separating the compacted model particles from the support material, the post printing module comprising at least one of a mechanical disrupter, a chemical disintegrator, an air knife and a suction port; and ii) consolidating the model particles of the superposed compacted layers, or a part separated therefrom, the consolidation being by application of energy, the post-printing module accordingly comprising an energy source selected from the group consisting of: ultraviolet (UV) source, infrared (IR) source, electron beam source, and a heat source.

[0053] In some embodiments, the printing system further comprises a controlled environment compartment which optionally provides a covered space around at least one of the adhesive applicator module, the first dispensing module, the second dispensing module, the compacting module(s), and the optional foregoing modules, the at least one covered space being bounded by the movable carrier and optionally providing a gas controlled environment.

[0054] Compositions that can be used inter alia in the present methods and / or printing systems are also disclosed to illustrate how the invention can be practiced.

[0055] Features of different embodiments of the foregoing aspects and additional benefits of the present disclosure are set out in the following detailed description taken in conjunction with the figures, non-limiting examples and clauses, and in the appended dependent claims.

[0056] BRIEF DESCRIPTION OF THE DRAWINGS

[0057] The invention will now be described further, by way of example, with reference to the accompanying drawings, where like reference numerals or characters (or last digits thereof) indicate corresponding or like components. The description, together with the figures, makes apparent to a person having ordinary skill in the art how some embodiments of the disclosure may be practiced. The figures are for the purpose of illustrative discussion and no attempt is made to show structural details of an embodiment in more detail than is necessary for a fundamental understanding of the disclosure. For the sake of clarity and convenience of presentation, some objects depicted in the figures are not necessarily shown to scale.

[0058] In the Figures:

[0059] Fig, 1 is a schematic representation of a first apparatus for 3D printing of an article;

[0060] Fig, 2 is a schematic representation of a second apparatus for 3D printing of an article;

[0061] Figs. 3 to 7 show schematically the sequence of steps and implementing modules employed in forming a 3D article by different embodiments of the invention;

[0062] Fig, 8 shows illustrations of the post-processing of an article after all its different layers have been deposited;

[0063] Fig, 9 shows in the form of a flowchart various sequences of steps that can be employed in forming a 3D article by different embodiments of the invention;

[0064] Fig, 10 illustrates a device adapted to non-selectively apply a thin layer of adhesive;

[0065] Fig, 11 illustrates in cross-sectional side view a device adapted to deposit particles on a transferring surface from which particles can be detached by thin layers of tacky adhesive;

[0066] Fig, 12 provides in perspective view an applicator of particles similar in principles to the device shown in Fig. 11; Fig, 13A displays a top view of a single coat of layers of particles as applied to an adhesive image by a conventional dispenser, whereas Fig, 13B displays a comparative top view of a coat of particles alternatively applied using an applicator according to the present teachings, such as illustrated in Figs. 11 and 12;

[0067] Fig, 14 shows a perspective view of a brush that may be used to remove surplus particles according to one embodiment of the present teachings;

[0068] Fig, 15 illustrates a cleaning device as may be used to remove surplus particles according to one embodiment, the cleaning device including a rotatable brush optionally constructed as shown in Fig. 14;

[0069] Fig, 16 illustrates a device adapted to compact particles on a supporting surface;

[0070] Fig, 17 illustrates a device adapted to level a solid outer surface in superposed layers;

[0071] Fig, 18 illustrates how devices, such as illustrated in Figs. 10-12 and 14-17, can be arranged to form a 3D printing system able to form a stack of layers including regions of compacted first particles when the substrate and its transport mechanism are non-planar;

[0072] Fig, 19 provides an exemplary alternative arrangement of devices, when the 3D printing system is intended for planar substrates and transport mechanisms;

[0073] Fig, 20 displays pictures captured by microscopy of particles according to embodiments of the present teachings (panels A-C) and of cross-sections through layers formed from said particles following their compaction (panels D-E) and their subsequent sintering (panel F);

[0074] Fig, 21 displays pictures captured by microscopy of particles that may serve as additives to curable liquids capable of serving as dielectric support material, panel A showing the rodshaped particles before being added to the curable liquid and panel B showing a cured version of the same; and

[0075] Fig, 22A displays part of a pattern that can be printed to form a PCB as fed to a printing system according to a particular embodiment of the disclosure, whereas Fig, 22B displays a top view of a printed version of the same pattern after three cycles.

[0076] DETAILED DESCRIPTION

[0077] The method of 3D printing of the present invention comprises forming a plurality of stacked layers, in which at least each intermediate layer is formed of contiguous regions of two or more different materials (e.g., particles having different compositions or properties and / or different adhesive compositions) that cover the whole of the area bounded only by the outer perimeter of each intermediate layer. In other words, the individual layers do not have any holes in them, though the perimeters of adjacent layers do not need to be the same. Consequently, during formation of each layer, there is a continuous underlying layer onto which material can be applied.

[0078] Fig. 1 schematically shows an apparatus for carrying out a method of a first embodiment of the invention. A substrate 10 is mounted on a transport mechanism shaped as a drum 12 that transports it sequentially through different processing stations. In a first station 14 a thin adhesive layer is selectively applied to regions onto which first particles are to be adhered, said regions (which need not be contiguous for any single type of material) being also termed first regions or foreground regions. The selective application may for example be carried out by jetting of an adhesive composition to the first regions. While the adhesive is tacky, the substrate passes through a second station 16 where first particles are made to adhere only to regions that have been coated with an adhesive. This process is then essentially repeated for second particles by passing the substrate through a third station 18 where a second adhesive coating is selectively applied to second regions (also called background regions or remaining regions) of the substrate 10 and then through a fourth station 20 where second particles are adhered only to regions coated with the second adhesive. If desired, the process can be repeated for third particles. Once all the different particles forming the various regions of a layer have been applied to the substrate 10, it is passed through a station 22 where the particles are compacted, and optionally levelled, to create a flat continuous surface onto which a new layer of particles can be applied. Such a compacting station may additionally be found after previous types of particles have been adhered to selectively applied regions of thin adhesive layer preceding the completion of a layer. In the setup illustrated in Fig. 1, such a situation would be depicted by the presence of two compacting stations, one downstream of station 16 and upstream of station 18, and the other as currently illustrated by station 22 downstream of station 20 and upstream of station 14. If the compaction achieved downstream of the last compacting station passed through during any given cycle is such that the flat continuous surface has an average roughness Ra of 3 pm or less (as could have been achieved by milling), separate levelling may not be necessary. Yet, in some embodiments, an even smoother surface (e.g., having an average roughness Ra of 2 pm or less, 1 pm or less, or 0.5 pm or less), may be required of the continuous intermediate layer, in which case a separate levelling station (not shown in present figure) may be further included downstream of station 22 and upstream of station 14 where a new cycle can be initiated. Depending on the desired degree of smoothness, the levelling station can include a milling device (for Ra of about 3.5 pm or less), a grinding device (for Ra of about 1.5 pm or less) or an abrading device (also known as a polishing device) (for Ra of about 0.5 pm or less).

[0079] The topographic properties of a surface compacted and / or levelled by a compacting module or a levelling module as herein described can be monitored by any suitable method. For illustration, optical sensors suitable for distance measurements, light detection and ranging (LiDAR), 3D mapping, and laser scanning of the surface being assessed, or cameras capturing such information, may be used in connection with computerized analysis systems translating the sensors output into a sought measurement. Control systems may further be used to modify an operational parameter of the 3D printing system in response to the measured property (e.g., surface topography measured by laser triangulation).

[0080] After completion of multiple cycles according to similar principles, there is formed a stack as shown at (A) in Fig. 8. Within this stack, the first particles, shown around the centreline, may be made of a metal or a ceramic and the second particles, surrounding the first particles, may be formed of a plastics material. To complete the production of an article made of the first particles, the stack may be consolidated as shown at (B) in Fig. 8, such as by sintering, to fuse the different layers of the first particles to one another and finally, as shown at (C) in Fig. 8, the second particles may be removed to leave behind only the desired article. It will be seen from this exemplary figure that the first particles are those serving to form the desired article and will therefore also be termed herein model particles, while the second particles serve only to allow the model particles to be deposited wherever necessary and are herein also termed support particles.

[0081] The support particles can be made of material different from the model particles in order to permit their removal by a physical or chemical process. The manner of the removal will depend on the choice of support particles. For example, the support particles may dissolve in a solvent in which the model particles are not soluble, to permit chemical removal of the support particles, or they may have a lower melting point, allowing their removal by application of heat to which the model particles would be resistant.

[0082] Alternatively, or additionally, the regions made of different materials may include different adhesives, the particles themselves optionally being made of a same material. For illustration, a first adhesive intended to adhere the first particles can be rendered tacky at a first temperature and a second adhesive intended to adhere the second particles can be rendered tacky at a second temperature. This alone may permit the joint application (at a same station and / or concomitantly) of the first adhesive and second adhesive, each in its respective intended region, the first adhesive being activatable at a first temperature (e.g., 80°C) sufficiently lower than the second temperature (e.g., 120°C) so that the second adhesive remains “inactive” when the first particles are applied to the first adhesive at its first temperature. The temperature may then be raised to reach the second temperature, thereby activating the second adhesive in regions uncoated by the first particles, the regions now rendered tacky being then able to adhere second particles. If the regions made of different materials differ from one another inter alia or only by the choice of the adhesives, then the adhesives can additionally be selected to facilitate or prevent removal of one type of particles’ coating over the other, the adhesives having different solubility / resistance towards a removing solvent. For instance, the first adhesive can be water-insoluble and the second adhesive water soluble, water being used to separate particles bound in the different regions upon completion of superposition of all compacted layers.

[0083] It should be noted that removal of the support material is not essential as it may form part of the end-product. For example, in the manufacture of a circuit board, the support particles may form the insulating substrate while the model particles may form the desired electrical conductors.

[0084] Fig- 2 differs from Fig. 1 in that instead of adhesives being applied to selective regions according to the particles to be coated thereby, an adhesive coating is applied to the entire substrate 10 and then selectively activated, such as by exposure to radiation or a suitable chemical agent. Thus, in the apparatus schematically depicted in Fig. 2 there is only one adhesive application station 30 where an adhesive is applied but is not tacky (or tacky enough) by the time it reaches a first activator station 32 where selected regions of the adhesive (e.g., first or foreground regions) are activated to remain tacky until desired particles are applied thereto. After first particle are applied to the activated regions of the adhesive by a station 34, the remaining regions of the adhesive (e.g., second or background regions) are activated in an adhesive activating station 36 to remain tacky till desired particles are applied thereto and are coated with second particles in station 38. As with the previous embodiment, the final station 40 serves to compact (and optionally level) all the particles constituting a layer to provide a continuous surface for the next deposition cycle and, similarly, such a compacting station may additionally be found downstream of station 34 and upstream of stations 36 being an adhesive activator or 38 being a dispenser of second particles.

[0085] In both embodiments, the compaction (optionally achieving levelling) can be carried out by passing the coated substrate between rollers urged against one another with a desired force but movable relative to one another to allow for the height of the substrate to increase from cycle to cycle. Compaction can be performed at at least 25 MPa, at least 50 MPa, at least 75 MPa, or at least 100 MPa; the applied pressure typically not exceeding 500 MPa, and being of up to 400 MPa, or 300 MPa. Compaction can furthermore be performed at a temperature higher than room temperature, such as at 50°C or more, the temperature of compaction being selected in accordance with the thermal resistance of the materials being compacted. Typically, if heat is applied during compaction, it does not exceed 150°C.

[0086] The embodiments of Figs. 1 and 2, which build an article onto a part-cylindrical substrate, are well suited to manufacture of flexible circuit boards, as the substrate can be bent after removal from the drum. To construct an article that is not necessarily flexible and that needs to have a flat base requires a different transport mechanism to move the substrate cyclically between different processing stations. It is possible for example, to replace the drum by an annular horizontal support surface that rotates about a vertical axis. As a further alternative, the substrate may be placed on a flat plate that is suspended from two continuous chains and each station may comprise features to retain the plate in a predetermined position during processing, to ensure correct alignment of the different regions.

[0087] Though it has been assumed above that both the model and the support materials are made of particles, it would be possible for the support regions to be applied as a liquid that is then solidified (e.g., dried or cured if a curable liquid, such as a radiation curable resin that can be solidified by ultraviolet (UV), visible or IR light, electron beam (EB), or thermal energy). Liquid may be selectively applied to the support regions, such as by jetting, or one may coat with a liquid the entire substrate (including regions already coated with particles) and, following curing at a curing station, the solidified (e.g., cured) support materials may be removed from regions coated with model particles. In this case, a separate levelling device adapted to remove surplus support material will be required in addition to the compacting station adapted to compress the regions coated with model particles. The levelling device of the separate levelling station may, for example, employ an abrasive having a hardness greater than that of the cured support material but lower than that of the compacted model particles. While for the sake of efficient stacking of layers it may be desired to remove as little as possible from the regions of compacted model particles, this is not essential. It may, on the contrary, be desirable to expose the model particles compacted in an underlying layer to model particles to be freshly applied in a subsequent layer. This can be the case when model particles of adjacent layers are to be applied in overlapping regions, the exposure of the model particles of a previous layer facilitating later binding to model particles of a following layer in a consolidation process. When such exposure is required (e.g., for the additive manufacturing of a PCB), the levelling of the intermediate layer may be such as to achieve an average roughness Ra of 500 nm or less, 400 nm or less, 300 nm or less, or 200 nm or less.

[0088] Figs. 3 to 7 illustrate schematically different apparatus for implementing different embodiments of the method of the invention, wherein an arrow indicates the direction (X) of the process for completing the formation of a single layer of the stack. While illustrated with a transport mechanism adapted for a flat planar backing surface for stacked layers having a flat base, this should not be construed as limiting.

[0089] Fig- 3 shows the steps performed by the embodiment of Fig. 2 and uses the same reference numerals. A thin adhesive applicator 30 is followed by a selective adhesive activator 32. After passing through the model particle dispenser 34 while the selectively activated adhesive is still tacky, the substrate passes beneath a background adhesive activator 36 and a support particle dispenser 38 while the activated background adhesive is still tacky, before reaching the compacting station 40. While the second adhesive activator 36 can selectively activate (e.g., by selective irradiation or jetting of an activating chemical) the second regions of the substrate to be thereafter coated by second particles, this is not essential. For instance, if the thin layer of adhesive applied by applicator 30 over the entire surface of the substrate due to form a subsequent layer is heat activatable, then activation of the adhesive layer in the background regions not coated by model particles can be achieved by applying heat to the entire substrate, the model particles in the coated first regions blocking access to subsequently applied support particles.

[0090] Fig. 4 differs from Fig. 3 only in that it comprises two compaction stations, the model particles being compacted in a station 42 before activation of the background adhesive (at 36), deposition of support particles (at 38) on the exposed regions of the activated adhesive, and compaction of the support particles to the substrate in compacting station 40, where the model particles may be further compacted.

[0091] In Fig. 5, which is based on the embodiment of Fig. 1 and uses the same reference numerals, the adhesive for the model particles is applied by a selective applicator 14A that is followed by an optional activator 14B that is not selective which can be used to increase, maintain or restore tackiness of the selective adhesive image. Likewise, the adhesive for the support particles is a selective applicator 18A that is followed by an optional activator 18B that is not selective. Otherwise, the process is the same as in Fig. 3. For illustration, selective applicators 14A and 18A may apply a thin layer of same or different heat activatable adhesives, which can optionally be non-selectively activated by heat at stations 14B and 18B, to the extent necessary to increase or renew their tackiness for adhering to the model or support particles respectively downstream dispensed.

[0092] While in the present figure, the selective applicators of adhesives have been illustrated as being each downstream followed by a respective dispenser of particles 16 or 20, this arrangement should not be construed as limiting. For instance, if the adhesive compositions are distinct, e.g., the first adhesive being activatable at a first temperature and the second adhesive being activatable at a second temperature greater than the first (and being inactive at the first temperature), then applicators 14A and 18A may be adjacent one another so as to form at once a layer with different regions of distinct adhesives. The first particles may then be applied by particle dispenser 16 at the first temperature (optionally with the assistance of heater 14B), this temperature rendering tacky only the regions of the first adhesive, and the second particles may be thereafter applied by particle dispenser 20 at the second temperature (optionally with the assistance of heater 18B), this higher temperature rendering tacky the regions of the second adhesive. As the regions of the first adhesive are by then already coated by the first particles, the second particles will only adhere to the second activated adhesive. In this case, the different adhesive compositions, even if jointly applied before entering a first dispenser of particles, may be viewed as serving the purpose of “differential” adhesion to a backing surface or underlying layer during the formation of the superposed layers.

[0093] Alternatively, or additionally, the different adhesives may serve the purpose of “differential” removal of the different materials, if desired, following completion of superposition of the layers. For instance, the first adhesive can be insoluble in a “removing solvent” whereas the second adhesive would be soluble in the same solvent. Again, adhesive applicators 14A and 18A can be adjacent one another forming at once the different regions of distinct adhesives. Furthermore, in this case, the particles serving as model or support can be the same, since their removal may rely on the distinct adhesives binding them. Then, in such embodiment, a single particle dispenser 16 may suffice (optionally with the assistance of a device activating the layer comprising the distinct adhesives, e.g., heater 14B).

[0094] As readily appreciated from these exemplary alternatives, an intermediate layer is said to be made of different materials in different regions of the layer, a) if the “building” material, whether particles or solidifiable liquids, are of different chemical and / or physical composition; b) if the “connecting” material, namely the adhesive compositions, similarly have different chemical and / or physical properties; or c) both.

[0095] Fig. 6 illustrates an embodiment in which the support material is applied in liquid form. The first four processes in this embodiment can be the same as in Fig. 4 and have been allocated the same reference numerals. Following application and compaction of the model particles, in the station designated 60 a liquid resin is applied over the entire surface of the substrate. A squeegee 62 removes most of the liquid overlying the compacted model particles while leaving a film of the liquid resin over the remainder of the substrate. Following curing of the liquid resin in the station designated 64 the substrate passes through a levelling station 66 in which any cured resin overlying the compacted model particles is removed by milling, grinding, and / or abrasion, the material so eliminated being sucked away. If desired, an excess of model particles may be applied during the first four processes and the levelling may remove some of the model particles as well as the overlying cured resin. While levelling is described in this figure as being performed on a cured resin, such a step may alternatively be performed when the materials forming an intermediate layer are all in the form of particles. Taking Fig. 6 for illustration, in this case station 60 would dispense support particles, squeegee 62 would ensure the support particles fill the regions of the substrate not previously coated by the model particles, station 64 would in turn ensure all particles are compacted before entering the levelling station 66.

[0096] While Figs. 1 to 6 have schematically illustrated different methods and some alternative apparatuses for their implementation showing that all layers of the stack can be formed on a common transport mechanism (e.g., adapted to convey a flat planar or a curved backing surface and growing substrate), this should not be construed as limiting. For instance, some layers can be formed on a separate surface before being transferred to the transport mechanism onto an initially vacant surface or on layers previously formed thereon or transferred thereto from additional separate surfaces.

[0097] Fig- 7 illustrates such an embodiment and differs from Fig. 6 in that there are two thin adhesive applicators. A first thin adhesive applicator 30a is configured to coat non-selectively the entire surface of the substrate transported by the flat transport mechanism 52 illustrated horizontally in the figure. A second thin adhesive applicator 30b is configured to non- selectively coat a separate surface, shown as drum 54, the downstream selective adhesive activator 32 and model particle dispenser 34 being now adjacent to and operative on drum 54 so as to form thereon a layer including regions selectively coated with model particles. These regions of model particles are transferred in mirror image from drum 54 to the thin adhesive applied on the upper surface conveyed by the flat transport mechanism 52 at the nip 56 therebetween. This relocation of the layer at the transfer nip 56 can take place if the thin adhesive applied by applicator 30a to form a flat adhesive is still tacky, and the model particles have a greater adhesion to the flat adhesive than to the adhesive to which they were initially adhered to on the surface of the drum. If this is not the case, an additional adhesive activator (not shown) can be included downstream of the thin adhesive applicator 30a and upstream of the nip 56 to ensure that the thin layer of adhesive be tacky enough to detach the regions of model particles from the drum to effect their transfer. While a compacting station 42 is shown downstream of the transfer nip 56, this may not be necessary if the pressure applied to effect transfer at the nip can additionally achieve a desired compaction of the model particles. The following processes can be as illustrated in Fig. 6, the support material being applied as a liquid resin in the station designated 60, most of the liquid overlying the compacted model particles being removed by squeegee 62 while leaving a film of the liquid resin over the remainder of the substrate which is solidified in the station designated 64. The substrate then passes through a levelling station 66. Alternatively (and not shown in Fig. 7), the support material can be applied in the form of particles, in which case the processes following compaction of the transferred model particles can be as illustrated for instance in Fig. 4.

[0098] While Figs. 1 to 7 have for simplicity schematically illustrated different 3D printing methods and some exemplary printing systems for their implementation showing layers formed of two different types of material, this should not be construed as limiting. As can be appreciated, some steps of the method may be repeated for additional (e.g., a third, a fourth, and so on) material, the apparatus accordingly including additional corresponding devices adapted to the performance of such steps for the materials desired in addition to the first and second one. A set of devices adapted to the performance of any of the steps described herein, such as enabling the formation of regions of a specified material on the backing surface, can be referred to as a sub-system. Hence, if a third material is to be applied similarly to a second material, the apparatus may further comprise a sub-system identical to the one selected for the application of the second material. However, they need not be identical, as some devices of such two sub-systems can be redundant and omitted in one of the two sub-systems.

[0099] Alternatively, the additional material can be applied by any other equipment, means or devices, suitable for said material and / or its intended purpose in the layer or stack thereof, the method being accordingly adapted to further comprise appropriate steps. For illustration, when manufacturing PCBs, the substrate may be capable of conveying a plurality of patterns of (e.g., first) conductive materials. The patterns formed on a common substrate can be the same or different. In such a case, a manufacturing process would ultimately include the division of the substrate into sections, each split region bearing the individual patterns constituting the sought chips. In the present method, separation between adjacent patterns formed on a common substrate can be facilitated or fully achieved by use of an additional “separating” material during the formation of the stack of layers. For instance, once layers of particles made of an electrically conductive material have been applied in repeated cycles and compacted to form the shape of the desired circuit of each future chip, a separating material can be applied to surround this pattern at any specified distance therefrom, the outline of the separating material from top view being same or different than the outer shape of the pattern surrounded thereby. For example, if the pattern from top view can be approximated to a rectangle, the separating material can be deposited to form a larger rectangle or a circle having a diameter larger than the longest dimension of the rectangular pattern each encompassing the regions to be separated from one another.

[0100] If the patterns are the same or have a similar outer shape and dimensions (e.g., regardless of the topography of the inner circuit), the separating material is typically applied midway between two adjacent patterns outermost contours. The separating material can, depending on the shapes of the patterns, be shared by adjacent patterns in part of their perimeters. For example, if the patterns from top view can be approximated to rectangles, the separating material can be deposited at a distance of only one edge to separate adjacent rectangular patterns.

[0101] If the patterns have different outer shapes (e.g., a square, a rectangle, a circle, a triangle, etc.), the separating material can be applied at any distance from an outermost contour of one pattern / shape as long as it does not intersect with an adjacent pattern or the separating material surrounding the second pattern / shape. The separating material can be applied by a movable dispensing injector, static nozzles of suitable jetting equipment or any like device capable of forming, around the patterns, “walls” or “fences” of sufficient height (ie., at least matching the height of the pattern). Then, a curable liquid can be applied as aforesaid to cover the plurality of patterns and their separating walls. Following curing, the cured outer surface can be levelled to at least expose the tips of the separating walls. The separating material can advantageously be made of a substance that can be removed with relative ease. The separating material needs be adapted to the formation of the walls (e.g., maintain a desired height), optionally compatible with the curing method of the curable material (e.g., both being UV curable at similar wavelengths) but can, for instance, be thereafter capable of being removed by a suitable solvent (e.g., by water, if water-soluble). In this case, a same, or different, separating material can be used to form a sacrificial layer prior to the formation of the patterns on the common substrate, so that the removal of the separating material(s) result in the physical separation (splitting) of the patterns individually “encapsulated” in the cured material (e.g., in a dielectric cured epoxy).

[0102] As readily appreciated, while in preceding paragraphs an additional material (e.g., other than model or support as can be applied by the previously described methods or devices) further included in the present methods in reliance on additional dedicated dispensers was illustrated by a separating material due to be removed so as to physically detach patterns from neighboring ones formed on a same substrate, such method steps, or dedicated equipment, are not limited to these sole substances / purposes. For illustration, the additional material may be intended to remain where deposited, only serving to fence the patterns one from the functional and / or visual effect of another without necessarily physically detaching them. In such a case, the material can be termed a fencing material, but any other nomenclature can be used to similarly refer to a material suited for the named function of their presence which can also be purely ornamental.

[0103] Such an additional material, depending on the specific role it is to provide with respect to the stacked layers, can either be applied to continuously surround regions of first materials or be disposed in only parts of such “perimeter” of the first materials. Alternatively, the additional material can be applied to existing regions of model or support materials. For illustration, the additional material can be jetted on model particles to facilitate their later consolidation or can be jetted on support material to achieve any desirable effect (e.g., adding a coloring agent to a solidifiable liquid).

[0104] Regardless of the number of materials that may be used to generate any intermediate layer, the form in which they are applied (e.g., as particles or a jettable liquid) and of the way by which each such material is applied or transferred to form such a layer, the present method is believed to achieve such additive manufacturing in a relatively fast manner. The efficiency of such a process, its productivity over time, can be provided in volume of materials than can be formed by unit of time, for instance in cubic centimeter per hour (cm3 / h) or liter per hour (1 / h) under the operating conditions (e.g., speed of the transport mechanism) selected for the 3D printing system of relevance. In some cases, the present printing methods and / or apparatuses enable a 3D build speed of at least 5 cm3 / h, at least 10 cm3 / h, at least 25 cm3 / h, at least 50 cm3 / h, at least 100 cm3 / h, at least 200 cm3 / h, at least 300 cm3 / h, or at least 400 cm3 / h for manufacturing of superposed layers involving a liquid, such as can be required for the preparation of PCBs or similar electronic circuits. When the present printing methods and / or apparatuses rely on solid materials substantially devoid of a liquid carrier, the 3D build speed can be further increased and be of at least 0.5 1 / h, at least 1 1 / h, at least 2 1 / h, at least 4 1 / h, at least 6 1 / h, at least 8 1 / h, or at least 10 1 / h.

[0105] Fig- 9 shows in the form of a flowchart various sequences of steps that can be employed in forming a 3D article, as exemplified in preceding figures illustrating different embodiments of the present teachings. In a first step Sil, a tacky image having a selective shape is formed as a thin layer of adhesive on a backing surface (e.g., a bare surface of a transport mechanism or the outermost surface of a growing substrate made of previously applied layers). Such a step of forming a tacky image in a first region of a layer can be carried out by three main approaches referred to as alternative steps Sila, SI lb and Sllc. In the approach designated by step Sila, the surface upon which the tacky image is to be formed is entirely coated with a thin layer of adhesive and regions of the layer corresponding to the desired image are selectively activated (e.g., by physical of chemical means adapted to the adhesive of the layer). This approach is illustrated by stations 30 and 32 in Figs. 3, 4 and 6. In the alternative approach designated by step Sllc, the tacky image is formed on an underlying surface by selectively depositing a thin layer of adhesive according to a desired shape. If, for illustration, the adhesive is ink-jetted to the backing surface as a liquid, then the formation of the tacky image may include at least partial removal of the liquid carrier, the partly dried image having a desirable tackiness by the time it is used to attach particles dispensed thereover. This approach is illustrated by station 14A in Fig. 5. In the alternative approach designated by step Sllb, the tacky image is formed either by selectively activating or selectively depositing a thin adhesive layer in regions of the backing surface to be coated with model particles. The tacky image is first formed on different surfaces (in manners similar to those already described for Sila and Sllc) and only then transferred to the backing surface, this situation being illustrated in Fig. 7.

[0106] Regardless of the steps used to form the selective tacky image of Sil, the adhesive image (also called the foreground adhesive) is then exposed to the particles to be adhered thereto. For brevity, particles made of a first material can also be referred to as “first particles”. While the first particles applied to the selective tacky image in step S12 have been previously described as being the model particles, this should not be construed as limiting. As readily appreciated, the first particles to be applied to suitable regions of a layer can alternatively be support particles. Particles made of a second material can also be referred to as “second particles”, and so on.

[0107] In a following step designated S13, the first particles can be compacted by application of pressure (with or without heat) such as illustrated by station 42 in Figs. 4, 6 and 7. This step can be optional, as shown by the omission of such a compacting station from Fig. 3 and 5, wherein a unique compacting station 40 or 22 is present downstream of a station at which regions of background adhesive are coated with second particles.

[0108] In a following step designated S14, a thin layer of adhesive is formed in the regions of the backing surface not previously coated by the first particles, (ie., in regions other than the first region). Such a step of forming a thin adhesive layer in previously uncoated background regions can be carried out by three main approaches referred to as alternative steps S14a, S14b and S14c, the selection of which may depend on the approach selected for step Sil as explained below.

[0109] The step designated by S14a can follow the application of first particles (e.g., model particles) to a tacky image formed according to step Sila, in which a thin layer of adhesive entirely coating an underlying surface is selectively activated to yield the first region (in which the first particles can be optionally compacted). In such a case, as the background regions not coated by the particles are already coated by a thin layer of adhesive, it suffices for step S14a to activate the adhesive in the background regions. Such an activation of the thin adhesive layer can be selective (e.g., by physical of chemical means targeting only the areas not previously coated by particles) or can be non-selectively applied to the entire layer, based on the understanding that first regions already coated by first particles would not be “reactivated” to lose their adhered particles. This approach is illustrated by station 36 in Figs. 3 and 4.

[0110] The step designated by S14b can follow the application of first particles to a tacky image selectively formed and / or transferred according to step SI lb or Sllc to yield the first (optionally compacted) region. In such a case, as the background regions not coated by the particles are also devoid of a thin layer of adhesive, step S14b requires such selective application of a thin layer of adhesive. Step S14b can be performed like step Sllc, but the adhesives need not be the same. In such a case, the adhesive selectively deposited or transferred to adhere the first particles to the foreground regions can be referred to as the first adhesive, while the adhesive selectively deposited or transferred to adhere the second particles to the background regions can be referred to as the second adhesive. This approach in which a background adhesive region is selectively formed following the application of first particles is illustrated by station 18A in Fig. 5.

[0111] Regardless of the method by which the background adhesive region is selectively formed, e.g., according to step S14a or S14b, when the second material is in the form of particles, the second particles are applied to adhere to the background adhesive. Second particles can be applied (e.g., by a support particle dispenser 38) to overcoat the entire backing surface, being urged into the regions not previously coated, and removed from the coated ones, by a squeegee or like device. Such a step is designated S15A in the figure. In a following step designated S16A, the second particles can be compacted by application of pressure (with or without heat) such as illustrated by station 40 or 22 in Figs. 3-5.

[0112] In an alternative approach the second material is in the form of a liquid. The step designated by S14c can follow the application of first particles to a tacky image formed according to any of steps Sila, SI lb and Sllc to yield the first region, though starting from step Sila can be wasteful in material, though easier in implementation. Therefore, step S14c is typically preceded by the compaction of the first particles in step S13. If the second material is applied as a liquid overcoating the entire surface (including the first regions where the first particles are already adhered and compacted), as can be formed by using a squeegee to level the liquid to a thickness commensurate with the heights of the particles in the first regions, then the following stages first include a step designated S15B in which the liquid second material is solidified. For instance, if the liquid applied in S14c is a curable resin, then it can be cured by the suitable curing agent in S15B or if the applied liquid of second material is a molten wax, then it can be solidified by cooling. In a step designated S16B excess of solid second material is removed so as provide an even continuous surface to the completed layer. In this step, part of the first particles coating the first regions can be removed, the tips of the particles being milled away or abraded, depending on the method used for levelling. This approach is illustrated by the stations downstream of 42 in Figs. 6 and 7.

[0113] The flowchart does not display all optional steps herein disclosed that can be further included in the method for printing a 3D-object according to the present teachings. For illustration, the entire process may begin by the application of a sacrificial layer to ease final separation of the object from its substrate, if desired. Other optional steps include for illustration: a) the cleaning of a surface following application and / or compaction of particles (e.g., to remove surplus particles) and / or following levelling of the layer (e.g., to remove debris); b) the pretreatment of a surface (or selected regions therein) for improving the quality of a subsequently deposited adhesive image, such a step being referred to as an adhesive priming step when increasing the adherence of the adhesive in the desired image or an adhesive masking step when decreasing the adherence of the adhesive in negative areas of the desired image; and c) the selective deposition of a third material, either in between patterns of the first material (e.g., to ease division of the substrate into individual patterns) or on the patterns of the first and / or second material (e.g., to improve their intended functionality).

[0114] Each of the above sequence of steps leading to the formation of one layer in which at least the particles of the first material are compacted can be repeated as necessary to obtain a desired stack of superposed layers (as mentioned in steps S17A or S17B, depending on the preceding steps).

[0115] Once the layers including regions of at least particles of first material being compacted have been superposed one on the other to form a 3D-object, or a part thereof, the stack may optionally be detached from the backing surface upon which the layers were prepared. Alternatively, or additionally, if steps were included to form borders of separating material around individual patterns formed on a common backing surface, the patterns may be physically separated from one another, such a step being optionally performed at different premises and / or by distinct entities.

[0116] The materials providing at least for the first particles (hence the first regions of each intermediate layer) can be functionalized (e.g., by consolidation, as in debinding processes, sintering or any like treatment adapted to render the object functional). This functionalization, denoted in the figure by optional step S18 can further optionally include removing parts of the layers (e.g., second particles in second regions, separating materials in border regions) not intended to remain in the final object (or part thereof) and or cleaning of the remaining parts.

[0117] Features of the various exemplary processes described above will now be considered individually in more detail, some enabling devices and suitable compositions being also described.

[0118] Adhesive Application

[0119] It is possible to use a relatively low amount of adhesive, the layer required to retain the stack of particles typically having a thickness corresponding to about a fifth to a tenth of the average size of the particles and the layer optionally remaining between printing layers following compacting not exceeding 1 pm. This not only reduces costs, but also the adverse effects associated with the presence of excessive binder on the quality of the end-product. While the elimination of adhesive is expected to be more difficult from relatively narrow voids, as compared to relatively larger ones, the compaction step nevertheless facilitates the debinding process. First, the small size of the voids by itself ensures that only a minute amount of adhesive material would require elimination between particles that would only at most deform to disc shape. If the model particles are made of a crushable conglomerate of particles, the crushing of the powder “open” larger passage for the elimination of the adhesive. If necessary, the debinding (elimination of the adhesive) can be done layer by layer, or after the stacking of a limited number of layers, rather than at the end of the process when passages out are more limited and occluded in part by repeated compactions.

[0120] Adhesive can be selectively applied to desired regions of a layer by any device suitable for ink-jetting. Such devices are known to persons skilled in the printing industry relying on ink-jetting and need not be further detailed herein. Since in this case, the adhesive is applied relatively liquid (with a viscosity adapted to the jetting method and vice versa), it may be desired to dry the adhesive partially, by removing part of the liquid carrier. The drying may take place after the selective application of the adhesive liquid, before and / or after the application of particles, the drying being such that the adhesive remains sufficiently tacky to attach the particles, and sufficiently deprived of liquid for the compaction of the particles not to inadvertently displace them by slippage.

[0121] Alternatively, an adhesive can be applied to entirely coat the surface of an underlying layer within the perimeter of the layer to be subsequently formed, regions of the adhesive being later selectively rendered tacky by suitable activation. An exemplary device configured for this purpose is schematically illustrated in Fig. 10.

[0122] Fig. 10 shows an adhesive applicator 1000, such as depicted by station 30 e.g., in Fig. 2, the applicator comprising a rotatable cylinder 100 upon which a sleeve 102 made of a release material, such as a silicone elastomer, is mounted and secured by any suitable system, such as shown herein by numeral 104. Heating elements can be located in and / or about the cylinder so as to maintain a desirable temperature on its outer surface 106 (e.g., on the surface of the silicone sleeve). Such a heating device is depicted as a central heater 108 in the present figure. In operation, cylinder 100 is in rolling contact with dipping cylinder 110 which rotates in chamber 112 within a bath of molten adhesive 114. The adhesive is maintained in relatively liquid molten state by means of a heater 116 positioned in the walls of the melting chamber 112, the chamber also including a thermocouple or any like instrument 118 adapted to measure temperature, so as to monitor the temperature of bath 114 and control the heat applied thereto by heater 116 to maintain the adhesive in suitably molten form. Rollers 120 can be disposed in contact with dipping cylinder 110 to ensure that the adhesive coat formed on the cylinder following its rotation within the bath of molten adhesive 114 is uniform over the surface of the cylinder 110, rollers 120 being also capable of removing excess coating if any, surplus still liquid adhesive dripping back to the bath. A roller 122 having a similar function may be positioned downstream of the nip where the dipping cylinder 110 comes into contact with cylinder 100 to transfer to its surface 106 a thin layer of adhesive.

[0123] Downstream of the nip is a metering device 130 consisting of a metering blade 132 which can be heated by a heater 134 located in a body 136 of the metering device, the body further including a mechanism 138 for pivoting and / or displacing the metering blade with respect to the outer surface 106 of cylinder 100 so as to ensure that a uniform distance is maintained between the blade 132 and the outer surface 106, hence an adhesive coat having a predetermined thickness is formed on sleeve 102 of cylinder 100 downstream of the metering device 130. Temperature sensors 140, such as infra-red (IR) sensors, may be positioned around cylinder 100 to measure the temperature of its outer surface 106, before its coating with a molten adhesive (e.g., upstream of cylinder 110), after its coating with a metered layer of adhesive (e.g., downstream of metering device 130) or both to monitor and control temperature as needed. The thin layer of adhesive of known thickness can then be transferred from cylinder 100 to the surface to be coated therewith at a nip 150. This can be achieved by urging cylinder 100 towards the relevant surface by way of a pneumatic piston 124 capable of pressing chamber 112, its cylinder 110 and in turn cylinder 100 to form intimate contact with the intended surface. In the present figure, the applicator of the adhesive is illustrated in contact with a partial surface of a curved drum 12, as depicted in Fig. 2, but it may alternatively be in contact with a planar backing surface as shown inter alia in Fig. 3 (see station 30).

[0124] The adhesive applicator can be preceded by a module adapted, selectively or otherwise, to treat, chemically or physically, regions of the substrate upon which the adhesive is to be deposited as an adhesive image. If present, this module can be termed an adhesive priming module. If the priming treatment involves a chemical substance to be applied selectively to desired regions of a layer, the adhesive priming module can include any device suitable for inkjetting. If the adhesive priming substance is to be applied on the entire surface of a preceding layer, a module similar in principle to the exemplified adhesive applicator 1000, can be used. If the priming treatment is physical, a device capable of discharging corona plasma can be disposed upstream of any suitable adhesive applicator. The pretreatment of the surface can alternatively seek to decrease the presence of the adhesive in undesired areas surrounding the intended image (which can be referred to as the negative image). In such a case, the module preceding the adhesive applicator can be referred to as an adhesive masking module.

[0125] Particle Applicator

[0126] Here, an active adhesive image (selectively formed or activated) is brought into contact with (e.g., model) particles dispensed by a dispenser capable of reliably providing an even layer of particles, without necessarily forming a monolayer, but forming a coating of densely packed and uniformly distributed particles. The dispenser may in principle be similar to a dispenser of particles as used in xerography, into which one may optionally introduce a rubbing effect to enhance the uniform attachment of the particles transferred to the glue. The rubbing effect can be achieved by controlling slipping between a transfer roller and the applicator, or between any two cylinders disposed upstream of the applicator, the applicator having itself substantially no slippage with the substrate. As moving parts are rarely ideally entirely devoid of any slippage, as used herein a slippage between any two surfaces is said to be essentially null when the relative speed between the two surfaces is 2% or less of the fastest, or 1% or less, or 0.5% or less.

[0127] While in theory, only the particles coming in direct contact with the adhesive layer would transfer, prospectively forming a “single particle deep” layer of particles on the activated glue, in practice additional particles stick to the first layer due to cohesivity (e.g., as resulting from the presence of attractive van der Waals interactions between the particles, the cohesion typically increasing with decreasing particle size). The particles would however not transfer to “inactivated” regions of the adhesive or to regions lacking an adhesive.

[0128] If parasitic transfer should nevertheless occur, the particles having inadvertently transferred to unintended areas of the inactivated adhesive layer / uncoated tray could be removed by gentle suction or blowing away, optionally assisted with mechanical means of dislodgment of loosely attached particles (e.g., with a rotating brush or sponge). A mechanism or station adapted to such a purpose in a printing system according to the present teachings can be referred to as a cleaning device, module or station (e.g., depicted as 730 in Fig. 19) to be later detailed.

[0129] An exemplary device configured for the application of particles to tacky adhesive images is schematically partially illustrated in the side view of Fig. 11, an alternative perspective view emphasizing different details being shown in Fig. 12. The dispenser of particles 2000 is formed of a chamber 200 and a housing 260. Particles may be supplied to the chamber by way of cartridges 210 loaded into adapted cavities of the housing, the cartridges or the recesses into which they are lodged including mechanisms 212 (e.g., paddles) and 214 (e.g., flexible sweeps) for mixing the particles and for smearing the mixed particles onto the surfaces to be contacted thereby. In some cases, the smearing mechanisms 214 are sufficient to also achieve mixing of the particles, so that additional mechanisms 212 dedicated to mixing can be omitted. For instance, smearing of the particles can be performed by e.g., four sweeps regularly distanced around a pivot and made of very thin metal shims, consisting for instance of stainless steel having a thickness of about 0.065 mm.

[0130] In operation of the applicator, the mixing and / or smearing mechanisms (which are typically secured to an axis disposed at the center of the cavity or cartridge) rotate constantly at a controllable desired speed. The particles may alternatively be supplied from a reservoir of particles in communication with the supply cavity(ies) via supply pipe(s), the particles being delivered by way of gravitation or any suitable mechanical device (e.g., a single ortwin screw(s) extruder).

[0131] As the particles are supplied from cartridges or (e.g., tube-shaped) cavities in the housing, the openings facing a subsequent component of the dispenser are designed so as to permit sufficient exposure and contact with the particles, while preventing surplus presence in a downstream chamber. A component downstream of the particle supply and disposed at least in part in a chamber of the applicator can be referred to as a transfer member, a transfer cylinder or a transfer roller. To ensure sufficient exposure of the surface of a transfer cylinder to the particles being supplied, the length of the opening is typically corresponding to the length of the cylinder or outer surface to which the particles are to be applied for subsequent transfer. To facilitate contact, the width of the opening may permit rotation of at least a part of the transfer cylinder surface within the cavity or the cartridge. The opening may also be dimensioned in accordance with the dimensions of the radially extending smearing mechanisms 214 due to spread the mixed particles on the outer surface of the transfer cylinder during its partial rotation through the supply cavity / cartridge. Considering rotating flexible sweeps for illustration, while schematically represented as straight lines in Fig. 11, in practice such strips bend in contact with the walls of the particle supply cavities or cartridges, the openings’ dimensions being such that the strips retain sufficient curvature upon contacting with a transfer surface circulating through the opening to effect smearing of the particles. Typically, the openings in the particle supply cavities or cartridges have an area corresponding to at least 15% of the circumferential area of the surface of the downstream transfer cylinder, the area of opening generally being between 17.5% and 22.5% of the area of the downstream cylinder. While the dimensions of the opening typically remain constant in operation of the dispenser, in an alternative architecture the effective dimensions of the opening may be controlled (e.g., using a sliding lid altering the width of the opening), the communication between the supply of particles and a subsequent transfer cylinder being even closed when desired.

[0132] The particles (e.g., from each cartridge) are smeared upon a respective sleeve 222 which can be made of a sponge-like material (e.g., consisting of a closed cell foam) mounted on a rigid axial support 220, the combination being referred to herein as a roller, or cylinder 220. Alternatively, the outer surfaces of the cylinders 220 may be made of a silicone elastomer. The particles are then transferred from the primary transfer cylinders 220 to a common secondary transfer cylinder 230 which can have an outer surface made of a release material, such as can be provided by a silicone sleeve 232 mounted on the cylinder 230. In contrast with the parts of the applicator of particles 2000 previously described, which were all entirely disposed within the boundaries of housing 260, the transfer cylinder 230, which is able to releasably transfer particles out of the housing, is only partly disposed within the chamber 200.

[0133] Blades 240a and 240b are disposed at the rim of the aperture in the housing through which cylinder 230 can cyclically rotate. These blades may not only ensure the formation of a uniform layer of particles on the outer surface of sleeve 232, but also prevent egress of particles from chamber 200. The blades can each be controllably disposed to form any desired gap with the outer surface of sleeve 232 on cylinder 230. They can be made of a same or different material (e.g., a metal or a plastic polymer), have a same or different flexibility (a contacting levelling blade being typically more flexible than a gap-forming sealing one), and / or have a same or different shape, such blades being known to the skilled persons. Typically, at least one of the blades (e.g., 240a) has a tip forming an acute angle, a slope of which being in contact with the outermost layer of particles on the coat formed on transfer cylinder 230 so as to level the coat of particles upon exit from the housing. A blade (e.g., 240b) only serving to reduce egress of free particles from the housing need not contact the coat, being disposed with a small spacing therefrom. Such a sealing blade may have a round tip.

[0134] In the event that blades 240a and 240b fulfil slightly different functions as exemplified above, the one predominantly serving for levelling and the one predominantly serving for sealing would be positioned on the housing according to the direction of rotation of cylinder 230. In order to be sufficiently flexible so as to permit efficient levelling, the levelling blade can be made of a relatively thin metal shim, such as from stainless steel having a thickness between 0.1 and 0.5 mm. A blade intended to partially seal the housing of the applicator need not have a same degree of flexibility and can be made from materials relatively more rigid and / or with a relatively larger thickness reducing the bendability of the blade. For illustration, blades intended only for sealing can be made of polycarbonate having a thickness between 1 and 2 mm, e.g., being of 1.5 mm.

[0135] In the perspective view of Fig. 12, a few cogwheels 270 secured to the shafts of respective e.g., transfer) cylinders disposed in the housing 260 of the applicator 2000 are visible. They may engage additional toothed wheels hidden in the present figure by the gear 272 connected by a transmission belt 274 to a motor 276. Depending on the respective sizes of the cogwheels associated with each rotating cylinder and / or optionally interconnecting them, the speed and / or direction of the motion of the mixing and smearing mechanisms of the supply cavity(ies) and of each transfer cylinder, as transmitted by the motor, can be controlled.

[0136] As better seen in Fig. 18 to be later detailed, transfer cylinder 230 can then transfer the particles to a similarly constructed applicator 250 also having on its outer surface a release material, such as can be provided by a silicone sleeve 252 mounted on the cylinder 250. The cylinder 230 and the applicator 250 need not be the same, neither in dimensions nor in the properties of their outer surfaces. For illustration, the hardness of the silicone sleeve 252 may be lower than the hardness of the silicone sleeve 232, to facilitate transfer of particles from the last transfer cylinder partially circulating within the dispenser housing to the applicator cylinder (entirely found externally to the dispenser housing). The applicator cylinder can then be urged, for instance using a pneumatic or hydraulic piston 254, into contact with a surface including tacky regions of adhesive to be coated by the particles. The outer surface 252 of the applicator cylinder 250 actually urged into rolling contact with the surface of the substrate for particles to transfer to the adhesive coated areas of the substrate can also be referred to as a continuous blanket. The continuous blanket of the applicator can, instead of a sleeve mountable on a cylinder, form a belt (preferably seam-less) circulating over two or more rollers including a driving one. Hence, the applicator can be a rotating cylinder or a circulating belt, a drive mechanism for urging a surface of the applicator into rolling contact with the surface of the substrate being accordingly selected. For illustration, while the drive mechanism may entirely displace cylinder 250 or one of the rollers supporting a belt, it may alternatively move an impression cylinder located within the perimeter of the circulating belt, on a rear side thereof. The continuous blanket (and any other outer surface made of an elastomer facilitating release) can be made of any suitable materials and prepared by any appropriate method. By way of example, a flexible blanket or sleeve can comprise in their release surface elastomers formulated as disclosed inter alia in WO 2018 / 100541 and cast as detailed in WO 2017 / 208155 to the same Applicant. By way of non-limiting example, the elastomeric sleeves can be prepared by centrifugal casting elastomers including or consisting of silicone-based polymers in a drum having dimensions (e.g., diameter, length) adapted to the sought sleeves or belt, said materials being suitable to release particles transiently transferring therefrom. Suitable silicone polymers can be selected from liquid silicone resins (LSR), room temperature vulcanization (RTV) silicones, vinyl methyl silicone (VMQ), phenyl silicone rubber (PMQ, PVMQ), fluorosilicone rubber (FMQ, FMVQ), and polydialkyl siloxanes (PDAS) capable, alone or in combination, of providing once cured a mechanically resilient silicone matrix. The silicone polymers can be addition-curable or condensation-curable, depending on their particular chemistry, and can be formulated to include any desirable and suitable additive (e.g., cross-linkers, catalysts, curing inhibitors, etc.). The silicone polymers can also be mixed with elastomers of different chemical families (e.g., polyurethanes) to further tailor the properties of the sleeves as desired. Persons knowledgeable in the art of elastomeric blankets can readily adapt the exact composition of the fluid polymer to be centrifugally casted to the desired properties (e.g., hardness) of the sleeve, the mixing, defoaming, spinning and curing (e.g., temperature) conditions being also derivable from the properties sought of the cured product.

[0137] For instance, the continuous blanket and the sleeves of the transfer rollers can be prepared from a two-parts LSR, the relative proportion of each part in the formulation being casted into a continuous, seam -less, sleeve setting inter alia the final hardness of the sleeve. Taking for illustration, two-compartments LSR commercialized by KCC Silicones as SL9508A for Part A and SL9508B for Part B, a weight-to-weight ratio of Part A to Part B of 10: 1 yields a silicone SL9508AB having a Shore A hardness of 50 when cast and cured as detailed herein-below. Increasing the relative amount of Part A to Part B decreases the hardness of the resulting cured silicone polymer. In this particular example, Part A:Part B ratios of 20: 1, 30: 1, 35: 1, 40: 1 and 50: 1, respectively result in silicone elastomers having a hardness of 40, 30, 24, 15 and 9 Shore A, any desirable other values being obtained by suitably modifying the ratios between the two parts. The hardness of the cured elastomer can be determined by routine analysis, such as described in ASTM D 2240. While the property monitored for the elastomer can be a physical property (e.g., its hardness as determined on a suitably prepared sample), the different proportions of components of two-parts LSR may also result in changes in chemical properties of the elastomer. In the present illustration, SL9508A contributes vinyl groups while SL9508B additionally contributes hydride groups, the final amounts of which can be modified according to the respective proportion of each part in the final elastomer.

[0138] Following the aforesaid principles, a continuous blanket of an applicator cylinder or sleeves of upstream disposed transfer cylinders can be prepared, for example, by mixing SL9508A with SL9508B at any ratio of parts providing a desirable hardness, the mixed LSR being first cast-centrifuged for 10 to 15 minutes at 1200 to 1400 revolutions per minute (rpm) at room temperature so as to build an even tubular structure on the inner walls of a smooth casting drum (e.g., made of Aluminum 6061 and having an average roughness Ra between 0.2 pm and 1.6 pm). The tube-like liquid elastomer is then cured for 1 to 2 hours at 80°C whilst the drum is rotating at 500 to 1000 rpm (depending on the ratio elected for the two parts). The sleeve is then (actively or passively) cooled to room temperature under the same ongoing spinning conditions. The sleeve sufficiently cured and cold can be then gently detached from the surface of the drum inner walls and transferred for final curing to an oven set at 170°C for 30 minutes. The fully cured sleeve (e.g., 232, 252), typically having a cured thickness of about 2 to 3 mm, can then be mounted on a cylinder (e.g., 230, 250).

[0139] When the continuous blanket is urged into contact with the substrate at least selectively coated with an active adhesive so as to transfer particles thereto (e.g., by moving downward in Fig. 18), the dispenser 2000 can be disengaged from the applicator cylinder 250. This can be achieved by any mechanism (schematically represented by double arrows 256) able to displace the housing 260 away (or towards) the continuous blanket, so that a gap is formed (or closed) between the outer surface of the last transfer cylinder (e.g., 230) and the blanket on the applicator. Once the applicator disengages from the substrate, the dispenser may reengage with the surface of the continuous blanket so as to replenish the coat of particles in regions partially depleted by the preceding transfer. To facilitate the reformation of a homogenous coat of particles on the continuous blanket, it can be advantageous to set the last transfer cylinder coming into contact with the outer surface of the applicator to be in relative slippage therewith, e.g., by having a different linear speed, to favorize a rubbing effect on the particles. As used herein, the term “rubbing” with respect to the particles is to be understood broadly to encompass any action on the particles that may further homogenize at least one property of the particle coating (whether on the transfer surface or the adhesive regions), be it the thickness of the layer, the orientation of the particles, their distribution on the surface, their size or any other like characteristic of the particles forming the coat. Typically, a rubbing effect can be achieved when two surfaces are in motion one relative to the other (e.g., the linear speed of the relatively faster surface being at least 10% higher than the linear speed of the relatively slower surface, or at least 15% higher, or at least 20% higher), the resulting friction causing the arrangement of the particles into a relatively even coat of stacked particles. In one prototype of particle dispenser as shown in Fig. 11, the transfer and applicator rollers have been set to have a maximal relative speed of 200%, the two surfaces in rolling contact being optionally counter-rotating. A rubbing effect was observed when the speed of the faster rotating surface was within a range of 110% to 200% of the slower rotating surface, but it may suffice that the speed of the faster surface be within the range of 110% to 150%, or 110 to 125% of the slower one.

[0140] While in the particle applicator exemplified in these figures, two cavities are depicted to provide a supply of particles (e.g., optionally by way of cartridges insertable in the relevant cavities), this should not be construed as limiting. The applicator may alternatively include only one supply of particles or more than two. When two or more supply of particles are included, the particles supplied thereby can be the same (e.g., to accelerate or increase coverage) or different (e.g, in size and / or composition of matter).

[0141] Considering the path followed by particles supplied by a single source, the present illustrations depict a series of two transfer cylinders (220 and 230) when the applicator is used in connection with an external applicator cylinder 250 (see Fig. 18); or with a single transfer cylinder (220) when the last cylinder (230) partly circulating out of the housing may serve as applicator cylinder (see Fig. 19). This should not be construed as limiting and any other number of transfer cylinders may be used along the path between one supply of particles and the last cylinder due to act as applicator cylinder, as long as permissible in the housing.

[0142] Typically, all cylinders arranged to transfer particles between the supply and the final applicator are selected to have outer surfaces facilitating such transfer one from the other. For illustration, an upstream primary transfer cylinder (e.g, 220) can have a sponge-like outer surface and a subsequent downstream secondary transfer (or applicator) cylinder (e.g., 230 or 250) can have a releasy outer surface, or an upstream transfer cylinder can have a releasy outer surface with a predetermined hardness (e.g., within a range of 20-50 Shore A) and a subsequent downstream transfer (or applicator) cylinder may have a releasy outer surface with a relatively lower hardness (e.g., being 10 Shore A smaller than a preceding roller). Conveniently the outer surfaces of any of the cylinders involved in the dispensing of the particles can be provided in the form of a sleeve to be mounted on a cylindrical support, so they can be replaced with ease in case of need. Alternatively, an entire cylinder can be replaced by a new one when desired.

[0143] When two or more supply of particles are included, the paths followed by their respective particles need not be the same. For illustration, they may have a different number of transfer cylinders, which may additionally differ in individual properties, direction and speed of rotation etc. By way of example, when two or more transfer cylinders are used in parallel to transfer particles to a common cylinder, one of the upstream transfer cylinders can be configured to have the same linear speed as the common cylinder (z.e., transferring the particles with essentially no slippage to increase efficiency of transfer), whereas a second upstream transfer cylinder can be configured to have a different linear speed and / or direction of rotation, the slippage resulting with respect to the common cylinder providing a rubbing effect (e.g., to increase homogeneity of the coat of particles to be further transferred). The relative velocity and direction of rotation between any two cylinders can, for illustration, be set according to the dimensions of the toothed wheels associated with their respective axis of rotation and the presence of intermediate cogwheels therebetween. The degree of slippage between any two cylinders effecting transfer of particles from one to the other may inter alia affect the properties (e.g., thickness) of the coat of particles ultimately transferring, the cohesivity between the particles also contributing to the prospective end-result. Particles smaller than 100 pm are believed to display sufficient cohesion to form a stack, the smaller the particles the higher the expected cohesion.

[0144] Without wishing to be bound by any particular theory, it is believed that the adhesive image may also control the thickness of the coat of particles that would transfer and adhere thereto. Depending on the thickness of the adhesive image and the viscosity of the glue, particles being inserted therein during transfer may displace the adhesive away (e.g., upwardly) from its supporting surface, the adhesive material so lifted by an initial set of particles being then able to detach a subsequent set of particles and so on, until there is no more adhesive (or active one) capable of transferring particles from the continuous blanket to the substrate. To ensure that no adhesive may adversely transfer from the substrate to the blanket, the number of overlying layers of particles on the blanket typically exceeds the number of layers that may transfer to the adhesive image being considered.

[0145] Typically, the number of layers of particles forming a coat on any transfer cylinder or applicator before application, or on the adhesive image after a single transfer can be estimated by measuring the average thickness of the coat and comparing to the average thickness of the constituent particles, such dimensions being determined by any suitable standard methods (e.g., microscope analysis). While the coats of particles may rarely be only one particle thick, they typically are vastly at least two particles thick, and predominantly at least three particles thick. Importantly, for the sake of 3D printing, the particles should preferably be packed relatively densely in the coat of particles. As the particles are to be compacted (reducing gaps therebetween), a coverage by 100% of particles of any surface being considered (as can be assessed by top-view image analysis) may not be necessary (even if achievable). In some embodiments, the proportion of the e.g., blanket) surface that is covered by the layers of particles forming the transferable or transferred coat may need only be 95% or less, or 90% or less. That being said, the present dispenser may suitably achieve a coverage of 75% or more, 80% or more, or 85% or more. In some cases, the coverage of any surface of transfer (donating or receiving the particles) can be comprised between 75% and 100%, 80% and 95 % or 85% and 95%.

[0146] Fig. 13 shows how an applicator of particles according to the present teachings provides an improved coverage of particles. The figure shows top view captured by optical microscopy (Olympus OLS 4000 LEXT, at a magnification of x20) of particles applied on an adhesive image, the picture on the left side (Fig. 13 A) showing the coverage achieved by a conventional dispenser of particles, such as a toner cartridge including a sponge roller and an elastomeric one but deprived of rubbing effect, whereas the picture on the right side (Fig. 13B) shows the coverage achieved by an applicator as discussed with reference to Figs. 11 and 12, the present applicator being operated to include a rubbing effect and the transfer of the particles to the adhesive image being achieved by rolling contact with cylinder 230 serving as applicator.

[0147] A same layer of adhesive (including a polyamide resin, such as Uni-Rez™ 2224 commercialized by Kraton, supplemented with 10 wt.% rosin gum, such as Foral™ AX-E commercialized by Eastman) having a thickness of about 4 pm was applied on a transparent foil of PET as substrate and pre-heated to 115°C to remain tacky whilst particles are applied thereto. Polyamide particles having an average diameter (Dvso) of about 40-50 pm and a predominant distribution of size between 10 and 100 pm (commercially available from BASF as Ultrasint® PA11) were supplied to each device being compared. The PET foil was transported below the dispensers at a distance enabling contact with the outermost roll of each device and the adhesive image now coated with the particles applied thereto was brushed with a rotating brush 190 disposed in a cleaning device 2020, as illustrated in Figs. 14 and 15 to be later detailed. Top views of the coats of particles were then captured. With the conventional dispenser, a coverage of less than 75% was achieved when the PET foil conveying the adhesive image was transported at a speed of 100 mm / s relative to the dispenser, see Fig. 13A, the percentage of coverage being estimated by suitable image analysis based on a larger field of view. Increasing the speed of the adhesive image detracted from the coverage that could be achieved.

[0148] At the same substrate speed of 100 mm / s, the present dispenser including a rubbing effect provided a particles coverage of about 100%. The rubbing effect was achieved by setting one of the transfer rollers to be at a relative linear speed at least 10% higher than that of the applicator surface, the linear speed of the applicator corresponding to the linear speed of the substrate. Speed of the substrate was step-wisely increased up to ten-fold and the coverage remained at about 100% at all tested speeds, as can be seen in Fig. 13B which shows the results obtained at 1 m / s. A similarly high coverage was observed when the cylinder serving as applicator was mounted with elastomeric sleeves having hardnesses of 50 Shore A, 40 Shore A, 30 Shore A, 24 Shore A, and 15 Shore A (prepared from LSR as previously described).

[0149] Thus, the inclusion of rubbing between the transfer rollers of the present applicator of particles not only enhanced the coverage of particles that may be achieved on the adhesive image, but also significantly increased the speed at which such improvement can be obtained. Understandingly, dispensers of particles conventionally used in 2D printing or copying industry do not need to achieve high coverage, human brains automatically compensating for lower ink coverage (even not exceeding 50%) so that we may perceive a full image regardless of true density of ink spots on the printing substrate and the relative amount of interstices.

[0150] Similar experiments were performed with particles made of different materials and / or having a different particle size distribution, and the particle applicator of the invention (as discussed with reference to Figs. 11 and 12) was found similarly effective. For instance, spherical metallic particles made of copper coated with silver (at 10 vol.%) having an average diameter (Dvso) of about 10 pm and a predominant distribution of size between 4 and 22 pm (commercially available from Fukuda as Cu - HWQ - 10 pm) were supplied to the present applicator and tested for transfer to a similar adhesive layer applied on a PET support, the adhesive now having a thickness of about 2 pm. The extent of transfer (e.g., coverage of particles) was tested as previously detailed at various speeds from sleeves 232 having hardnesses of 50 Shore A, 40 Shore A, 30 Shore A, 24 Shore A, and 15 Shore A. A particles coverage of about 100% was observed regardless of the hardness of the sleeve and at all speeds tested from 100 mm / s up to 400 mm / s. The same particles of plastics and metals were tested in similar experiments, the linear speed of the applicator surface (and of the PET substrate) being set at 500 mm / s and the rubbing being achieved by a relative speed of an upstream transfer roller corresponding to 10%, 17% or 200% of said speed. The outer surface 232 of the applicator 230 had a hardness of 40 Shore A. The adhesives layers tested were about 2 pm thick for the copper particles coated with silver and about 4 pm thick for the polyamide particles. The adhesive layers applied on the substrate were pre-heated to 80°C so as to be tacky upon rolling contact. The adhesives so tested included a polyimide binder, Uni-Rez™ 2215 or Uni-Rez™ 2224, a copolyester, Dynacoll® 7360, or a rosin gum combined with pentaerythritol tetrastearate (9: 1), all binders including 10 wt.% of carbon black pigments (Printex® 35 by Orion) to alternatively enable their activation by EM radiation. All adhesives tested with the aforesaid particles as dispensed by the present dispenser enabled a coverage of at least 90%.

[0151] It is reminded that while the above-described dispenser of particles 2000 involving contact between the surface of an applicator bearing the particles and an adhesive image can be advantageous, particles may alternatively be applied without such direct contact. An alternative dispenser disposed at 5 mm above the substrate and in which particles were instead jetted towards the substrate was tested at a flow rate of 25 g / s and found suitable. In this case, the coverage of particles was estimated following removal of surplus particles by a rotating brush having a linear speed of at least 200 mm / s. As the cleaning was performed shortly after the application of the particles to the tacky adhesive, it is believed that it contributed to the rubbing of the particles on the adhesive image. A coverage of more than 90% was achieved.

[0152] Additional details on apparatuses adapted to apply particles to an adhesive surface as may be used in the present systems for 3D printing, or in any other manufacturing process requiring application of particles, are provided in the following clauses.

[0153] Removal of Surplus Particles

[0154] Depending on the method selected to apply particles on an adhesive image, it may be desired to include a cleaning step (e.g., after application and / or compaction of the particles) so that the particles may substantially only be found in the desired regions of each layer on the substrate. A cleaning device for removing surplus particles, in particular from unintended areas of the substrate, can be contact-less (e.g., removing superfluous particles by suction) or configured to intermittently engage in a controlled manner the surface to be “cleaned” by contact with a dislodging component of the device. Taking for illustration a rotating brush 190 that may serve as displacing member, an exemplary one is schematically illustrated in perspective view in Fig. 14. The bristles 192 can be secured in a (e.g., cylindrical) brush body 194 and disposed in clusters linearly aligned with the axis of rotation 196 of the brush (e.g., forming a plan therewith), or being relatively staggered in the direction of rotation as shown in the figure, or in any other desirable arrangement of the bristle packs achieving a satisfactory density of bristle tips on the surface to be cleaned during its passage through the cleaning device. Advantageously, the clusters of bristles can be arranged on the rotating brush so as to form “compartments” between aligned rows reducing egress of dislodged particles from the cleaning device and facilitating their removal by suction. The lateral outflow of dislodged particles can be prevented by suitable seals positioned at the longitudinal ends of the rotating brush and / or at the perimeter of the housing of the brush.

[0155] The bristles can be made of any material sufficiently stiff to dislodge particles loosely attached or inadvertently present in unintended areas, while remaining sufficiently soft to avoid a) deleterious displacement of particles cohesively stacked on the adhesive image; b) distortion of the adhesive image and particles thereon with respect to the underlying surface; and c) damaging of any regions of the surface contacted by the bristles during the rotation of the brush. Advantageously, the bristles and the brushes made therewith, together with their controlled operability (e.g., distance from the surface, speed of rotation, angle between bristles and surface, bristle-free length upon contact etc. can maintain a delicate balance allowing (further) rubbing of particles on the adhesive image without adverse effects, whereby the packing of the particles can be improved and / or the particles’ coverage on the adhesive image increased. A side view of an exemplary cleaning device 2020 comprising a rotatable brush 190 within a housing 201 is provided in Fig. 15, the device additionally including suction means 202 to remove surplus particles and a mechanism 203 for approaching or retreating the brush, to permit or prevent contact between the bristles and the surface to be, or already, cleaned. The mechanism 203 may include a motor 204 capable of displacing the housing 201 (and the brush rotating therein) by way of intermediate connectors 205 also secured to a part 206 travelling along rails formed in the fixed structure 207 supporting the subsystems of the present printing apparatus. The perimeter of the open part of the housing allowing the circulation of the rotating brush 190 for contact with the surface to be cleaned may include arrays of bristles 208, advantageously, but not necessarily, made of the same material as the bristles of the rotating brush. The arrays 208 may serve to further clean the surface from loose particles, but more importantly may serve to relatively seal the volume encompassed by the cleaning device 2020 so as to limit egress of cleaned particles into the environment of the sub-system. In the present figure, arrays of bristles 208 are shown for clarity on the lateral side of the housing 201 at the back of the drawing and in side-view on the exit side of the cleaning device (the substrate moving from left to right in this figure).

[0156] The bristles and the brush can be made of any durable material capable of resisting abrasion, wear and fatigue, or any other cause of damage to the structural integrity of the bristles, under the conditions (e.g., temperature, speed, pressure perceived by the bristles and bending effect thereon, surfaces to be cleaned, etc.) at which the cleaning device is operated. Thus, they should advantageously have high stiffness (and preferably high stiffness-to-weight ratio) and high tensile strength (and preferably high strength-to-weight ratio). If the printing system, and in particular the cleaning device, is to be operated at a temperature above ambient temperature, the brush and its bristles should additionally display tolerance to the elevated temperature, preferably having low thermal expansion.

[0157] The material of the bristles can be selected in accordance with the material of the particles to be cleaned therewith so as to reduce or eliminate sticking of surplus particles to the bristles, which could in turn reduce the efficacy of the cleaning device. The composition of other regions of a layer may also be taken into consideration, when formed of cured liquids instead of particles. For illustration, when the particles (or non-particulated regions) are made of plastic materials, it can be beneficial to use bristles made of anti-static materials to eliminate any static electricity that may build-up and the adverse electrostatic adhesion it may undesirably generate.

[0158] The combination of suction of the removed particles with their physical dislodgment (as above exemplified) is believed to be advantageous when a cleaning device is desired. In one embodiment, the bristles can be fine filaments (e.g., having a diameter of 50 pm or less, 25 pm or less, or 12.5 pm or less, and typically of 1 pm or more, 2 pm or more, or 5 pm or more). When made of carbon, the fine bristles can also be termed carbon fibers.

[0159] Compaction

[0160] By using a relatively significant force urging a hard roller to compact the powders on the substrate, one can achieve very good compacting, even deformation of the powder particles when made of deformable materials, resulting in a relatively high density of the green printed model. Such greater density can have significant technological advantages, for instance if the model particles are made of a metal to be sintered to develop a desired function.

[0161] As the layers add up, the pressure applied at the nip to compact the particles should be gradually decreased, otherwise the stack of compacted layers, or part of it, may detach from the substrate or from previously formed layers, a process termed “delamination”. There are three main modes of compacting, each being able to control the pressure and prevent delamination in a different manner. All share a compacting roller, in rolling contact with the layers to be compacted to the substrate. The compaction and its extent (which may for example exceed the ultimate tensile strength of the particles being compacted) can be controlled by several parameters, which include inter alia the size of the compacting roller, its hardness (or other surface properties), the force applied to the compacting roller, the temperature applied at compaction (which also depends on the materials to be compacted and the backing surface), the coexistence of additional compacting enhancing powers (e.g., vibration of the compacting roller or ultrasonication of the particles to increase their packing) etc.

[0162] In a first approach, pressure can be controlled according to the force applied to the substrate and the layers of particles building-up thereon. The force can be applied, for instance, by a hydraulic or a pneumatic press urging the compacting roller towards the substrate, the force being decreased as the layers pile up.

[0163] In a second approach, the pressure perceived by the outermost layer being compacted can be decreased by increasing the size of the gap between the rollers, to accommodate the growing thickness of the layers, the thickness of each depending on the particles being used, the number of particles stacked in the thickness direction, and typically not exceeding 50 pm.

[0164] In these two approaches, the compacting roller can be rotated by mere friction with the printed object uppermost surface, having a substantially null relative linear velocity as compared to the substrate.

[0165] In a third approach, the compacting roller can be independently driven by a motor setting a relative velocity with the substrate, which can be adjusted to reduce shear forces perceived by the object. Controlling (and preventing) slipping between layers may also reduce the risks of delamination.

[0166] In all cases, heat can be applied at the nip of compaction to reduce yield strength and increase the plasticity of the material being layered, increasing temperature therefore allows decreasing the force applied by the heated pressure roller.

[0167] An exemplary device configured for the compaction of particles to an underlying thin adhesive layer is schematically illustrated in Fig. 16. The compacting device 3000 includes a pneumatic piston 300 capable of urging a compacting roller 310 into contact with regions or layers of particles on a substrate conveyed and supported by a suitable transport mechanism the compacting roller and the surface compacted therewith forming a compacting nip 330. The compacting roller is typically made of a material harder than the particles or surfaces to be compacted thereby.

[0168] In the present figure, the compacting roller 310 is illustrated in contact with a partial surface of a curved drum 12, as depicted in Fig. 2, but it may alternatively be in contact with a planar backing surface. If the backing surface is planar and rotatable about a vertical axis, then the compacting roller may be frustoconical, so that there should be no relative slip between the surface of the compacting roller and the backing surface in any part of the nip between them.

[0169] The compacting roller 310 may include heating elements in and / or around it, such as illustrated by internal heater 312. The temperature of the outer surface of the compacting roller can be monitored by any suitable device, such as by an IR sensor 314 which in turn may send data to a controller of the heater so as to achieve a desired temperature. There may also be provided a blade 320 for removing from the surface of the compacting roller any residual particles that would have unduly transferred thereto during compaction.

[0170] It is believed that the present compaction step and the device allowing its implementation can significantly reduce the presence of voids between the compacted particles, voids constituting only 20% or less, 15% or less, 10% or less of the volume of the compacted layer. This can translate in even lower presence of voids if the particles are later consolidated or functionalized, e.g., by sintering, a region of compacted particles containing less than 10% of voids being expected for illustration to contain less than 5% of voids once sintered. The presence of voids and their extent can be estimated by routine experimentation, such as by image analysis of suitable cross-sections or by evaluation of the density of a sample as compared to the density of the same volume of material in bulk continuous form, the difference being attributed to the voids.

[0171] Levelling

[0172] As previously explained, if the compaction achieved downstream of the last compacting station passed through during any given cycle or number of cycles is such that a resulting even continuous surface is substantially flat (e.g., having an average roughness Ra of 3 pm or less), separate levelling may not be necessary. Yet, when smoother surfaces are required, a device capable of levelling a solid outer surface of superposed layers can be incorporated in the printing system. Levelling devices can involve physical interaction with the surface being levelled, alone or together with a chemical interaction, and a levelling module may include one or more such devices. In case multiple levelling devices are present in a levelling module, they can be independently or jointly operated according to the smoothness desired of the surface being levelled. For example, a first levelling device might include a rotating levelling member, such as a fly cutter, a cartridge with inserts, or an end mill cutter, which typically permits milling of the surface to an average roughness Ra between 200 nm and 10 pm. A second levelling device may use polishing or grinding wheels as levelling members, such wheels or pads mountable thereon typically achieving an average roughness Ra between 50 nm and 1 pm.

[0173] The levelling module, regardless of the type and number of devices adapted to form a flat continuous surface, may further include equipment configured to remove the abraded materials, typically by suction, which can be assisted by means for dislodging the debris, such as air knives or liquid jets. For illustration, a levelling module may include a cyclone-type suction system.

[0174] A physical levelling device can be as schematically illustrated in Fig. 17. The levelling device 4000 includes a levelling disc 400 rotatable in a plane parallel to the outer surface to be levelled therewith. The levelling disc can be made of any material having a hardness adapted to mill, grind or polish the materials constituting the layers. If desired, the levelling disc may include inserts of even harder materials. The levelling disc can be rotated by a motor 410, such as a spindle motor, the disc being brought into contact with the outer surface of the layers (or regions thereof) by a lowering or lifting mechanism 420 adapted to control the position of the disc along a Z-direction in accordance with a desired distance from the surface to be levelled. The levelling device 4000 also includes a suction chamber 430 and all related parts (e.g., pipes, pumps, filters, pressure regulators, etc. allowing to readily eliminate the debris being formed during levelling.

[0175] Printing Systems

[0176] Having provided schematic layouts for devices suitable to implement steps of the present 3D printing method, their exemplary arrangements into printing systems are depicted in Figs. 18 and 19. Fig. 18 displays for clarity only a part of the devices as may be arranged in a printing system 1400 to form stack of layers as previously illustrated in Fig. 2, the transport mechanism of the substrate (hence, its backing surface) being a drum. In this figure the transport mechanism drum 12 rotates counterclockwise along a circular path, the first station being the adhesive applicator 1000, the thin layer of adhesive applied thereby to the outer surface of drum 12 being selectively activated by device 500. Device 500 can be a laser emitting device such as detailed in the Applicant’s earlier patent applications WO 2016 / 189510, WO 2016 / 189511 and WO 2019 / 030694, capable of selectively heating and rendering tacky regions of a thermally activatable adhesive. The layer of adhesive including its selectively activated regions is then brought into contact with particles applied thereto by a particle applicator 2000, following which the particles having adhered to the activated adhesive may be compacted by a compacting device 3000. For sake of clarity, this figure lacks stations 36, 38 and 40 as shown in Fig. 2. Double arrows positioned next to pneumatic pistons 124, 254 and 300, indicate that the outermost cylinder of the devices including these pistons may be brought into contact with, or away from, the transporting drum and the layers being built thereon, the same controlled engagement / disengagement of the dispenser 2000 being illustrated by double arrows 256. In Fig. 18, adhesive applicating cylinder 100 of device 1000 and compacting roller 310 of compacting device 3000 are shown engaged with drum 12, whereas particle applicator cylinder 250 of particle dispensing device 2000 is shown disengaged from the transport drum 12.

[0177] In Fig. 19, in contrast to Fig. 18, the transport mechanism of a printing system 1500 is planar. In this figure, in which the direction of printing is from left to right, a platform 600 that can be controlled to move back and forth on guiding rails 610 (and forming therewith a transport mechanism 630) is illustrated with a substrate 620 thereon. The substrate is passed by the transport mechanism 630 through a first station 700 at which an adhesive can be selectively applied to desired regions of the substrate. The station 700 may comprise an inkjet head capable of moving in any direction parallel to the plan of the substrate (e.g., typically in a scanning direction perpendicular to the printing direction), but may alternatively comprise a static print bar constituted from a plurality of inkjet heads, the nozzles (or arrays of nozzles) of the inkjet heads spanning the width of the substrate in a direction traverse to the printing direction. Inkjet heads are known and need not be detailed herein. They can be purchased from several reputable manufacturers, amongst them Eastman, Epson, Fujifilm Dimatix, Konica Minolta, Kyocera, Ricoh, Toshiba, Seiko and Xaar, each having models adapted to any desired viscosity and jetting method (including the controllable varying of droplet volume). Depending on the inkjet head, the adhesive liquid to be jetted thereby and the particles to be adhered thereto, lines may be formed to have a width of 50 pm or more, the minimal spacing between adjacent lines being typically of at least 50 pm.

[0178] Following the formation of the desired image of adhesive, the substrate is transported to a second station at which particles of a first material can be applied to the adhesive. The device capable of transferring the particles to the adhesive can be the particle applicator 2000 previously detailed. In the present illustration, cylinder 230 which acted as a last transfer cylinder preceding the applicator cylinder 250 in Fig. 18 can now directly serve to transfer the particles to the adhesive and de facto serve as applicator cylinder, its outer surface 232 serving as the continuous blanket. The mechanism 256 which previously served to disengage the dispenser from an external applicator cylinder 250 whilst it was urged into contact with the substrate, may now serve to urge the applicator cylinder 230 into contact with the substrate, so that layers of particles may transfer from blanket surface 232 to the adhesive image formed at the first station.

[0179] The substrate partially coated with the adhesive and the particles thereon can proceed to a third station 710 at which excess liquid from the adhesive can be removed. Device 710 can be a drier, heating the substrate by convection or radiation (e.g., IR). While a single device 710 is illustrated in this figure downstream of applicator 2000, a second one may be positioned upstream of the applicator of particles if the adhesive selectively applied by the inkjet head(s) 700 is too liquid / insufficiently tacky to retain the particles upon passing beneath the applicator 2000.

[0180] Following its drying, by one or more driers 710, the substrate and the particles adhered thereto arrive at the compacting nip formed by urging the compacting device 3000 against the platform 600. The layer including the compacted stack of particles can then be sintered by any suitable sintering device 720, the sintering being performed either for each cycle, for every few cycles, or upon completion of all cycles of additive manufacturing. In the latter case, the sintering device 720 need not be included in the printing system 1500 and can be an off-line device. If needed, following compaction and optional sintering, the substrate can be cleaned by a cleaning device 730, configured to remove particles having parasitically transferred to and / or sintered on unintended regions of the substrate. An additional, or alternative, cleaning device 730 (not shown in the figure) can be disposed upstream of the compacting device 3000 and downstream of the optional dryer 710. The cleaning device 730 can be as previously detailed with reference to exemplary sub-system 2020.

[0181] In the apparatus exemplified in this figure, the second material is applied in liquid form by a suitable applicator 740 which may further include a squeegee 742 to ensure that the curable liquid uniformly coats the surface of the substrate. While in the present illustration, the squeegee 742 would wipe the liquid in direction opposite the printing direction as the substrate proceeds to a following station, alternatively it (or an additional squeegee) can be movable and configured to wipe the liquid in a direction transverse to the printing direction. The substrate then proceeds to a curing station 750, the exact curing device being selected in accordance with the liquid material to be cured (e.g., the device including a UV source when the liquid is UV-curable). Finally, the upper surface of the substrate can be milled, ground or abraded by a levelling device 760, such as detailed with respect to exemplary sub-system 4000, following which the levelled surface can be inspected by an inspecting device 770 before being sent back to the first station for a new cycle and a new layer.

[0182] While not apparent in the figure, an encoder is provided in the transport mechanism, allowing the substrate to be correctly positioned with respect to the inkjet head(s) for the adhesive of a subsequent cycle / layer to be properly registered with respect to the adhesive selectively applied in a previous cycle / layer. Alternatively, or additionally, proper registration between cycles (or between stations, if selective) can be achieved by optical sensors suitably disposed in the apparatus to monitor signals (e.g., fiducial marks) indicative of positioning of the substrate with respect to any device due to interact therewith.

[0183] As new layers are formed, the distance between the outermost layer being formed and the stations and devices interacting therewith is modified. A desired gap (or lack thereof) can be maintained by moving the substrate 620 on the platform 600 up or down in a Z-direction, to a Z-level as desired, alternatively, or additionally, the devices (e.g., 2000, 3000, 730, 740-742, and 760) can be displaced up or down to achieve the desired distance. For instance, while the compacting device 3000 and the levelling device 760 are positioned to contact the uppermost surface of the substrate or layers formed thereon when the transport mechanism is moving in the printing direction, these same devices could be lifted to avoid contact in the reverse direction when the substrate is brought back to home position in order to start a new cycle.

[0184] While in Fig. 19 the various devices and stations of the apparatus are depicted in a linear arrangement considering their projection on the X-Y-plane, this should not be construed as limiting, an elliptical, oval or circular arrangement being also envisioned. In other words, considering a line in the plane of the drawing as being along an X-axis, the transport mechanism can displace the substrate either to the right or to the left in the present drawing, and additionally to locations that may be in the front or in the back of the drawing sheet (along a Y-axis transverse to the X-axis). Furthermore, the transport mechanism may include elements capable of lifting or lowering the substrate along a Z-axis, as may be required when the substrate is aligned with specific stations and devices therein, along the path it cyclically follows to form the superposition of compacted layers. Alternatively, or additionally, in some stations the devices can be adapted to be displaced in any of the X-, Y- or Z-direction, to remain at a desired relative positioning with respect to the substrate. For illustration, a dispenser of a liquid can be movable in a Y-direction transverse to the direction of printing and a compacting roller or a levelling disc can be movable in a Z- direction.

[0185] Regardless of the type of transport mechanisms (e.g., planar or not) used for apparatuses and printing systems according to the present teachings, they may displace the substrate at a linear speed of at least 0.5 meter per second (m / s), at least 1 m / s, at least 2 m / s, or at least 3 m / s. Advantageously, the afore-described exemplary apparatuses enable relatively high throughput additive manufacturing.

[0186] In common with their conventional additive manufacturing counterparts, the present apparatuses may include digital data feeding equipment and controls which enable slicing a computer model of a desired 3D object into thin cross sections, translating the result into two- dimensional position data and feeding the data to control equipment which fabricates the corresponding 3D structure in a registered layered manner. Hardware, software, firmware, or combinations thereof using an operating system, as well computer object data formats adapted for such Computer-Aided Design (CAD) are known and need not be detailed herein. For clarity, such computer assisted manufacturing (CAM) systems and other conventional equipment (such as supply systems for the different building materials) are omitted in the figures.

[0187] Consumables

[0188] Of the three main approaches introduced above regarding the operation of a compacting device 3000, the first one “force control” is the relatively easier one to implement from an engineering point of view, but the relatively more limited with respect to prevention of delamination. Surprisingly, it has been found that modifying the constitution of the particles may also prevent “delamination” from the substrate, by modifying the forces that would be required for compaction.

[0189] Specifically, instead of using particles entirely made of the desired material at a hardness that could render the layers built therefrom “oversensitive” to the pressure, the particles can be made-up of the intended constituents of the final material (providing a master alloy, mixed or treated powders to reduce yield strength and increase plasticity), some being intentionally selected to be relatively softer, the relatively harder cores being then “protected” by the softer constituents and the resulting layers of particles being compressible at relatively lower pressures preventing detachment.

[0190] Alternatively, the particles can be made-up of aggregates of micro and nanoparticles of the intended material, a pressure which can be relatively moderate crushing the aggregates into their sub-particulate constituents. Interestingly, such “composite particles” are not only advantageous during printing of the model and the compaction of the layers, but also for some future end-products. For instance, the “composite particles” could undergo sintering under conditions relatively milder than “conventional particles”. Alternatively, or additionally, the “composite particles” may provide a superior effect as compared to conventional ones, if similarly post treated. For illustration, composite particles could be sintered at a lower temperature to provide a same conductivity as regular particles, but could alternatively provide a superior conductivity if sintered under the same conditions.

[0191] An effect similar to the use of “composite” particles, can be obtained by applying nanoparticles into the voids remaining following the compaction of the model particles. This can be achieved by ink jetting followed by sintering of the nanoparticles. While the feasibility of this method has been experimentally established, from a commercial standpoint jetting a liquid material requires the subsequent elimination of the liquid carrier, such drying accordingly slowing down the process. It is believed that instead of jetting ink that typically contains no more than 10% nanoparticles, one could jet a slightly more viscous slurry, containing for example 20% of nanoparticles, the nanoparticles migrating from the slurry to the interparticulate voids by capillarity, and the ink of the nanoparticles being applied by roll or blade coating.

[0192] For simplicity, model or support powders that are predominantly constituted of elementary particles of materials that can be deformed during compaction according to the present teachings can be referred to as deformable powders or particles. Deformable particles can be made of a single material (e.g., a metal, a homo-polymer) or of a mix of materials (e.g., an alloy, a co-polymer). Model or support powders that predominantly include non-deformable elementary particles assembled (e.g., with a binder) in clusters that can be dismantled during compaction can be referred to as crushable powders or particles. They can be made of a single material with a narrow particle size distribution (PSD) (e.g., particles of ceramic having relatively homogeneous dimensions assembled with a binder) or of a mix of distinct PSDs and / or materials (e.g., microparticles of a first metal and nanoparticles of a second metal). The powders’ grains, which can be made of one or more elementary particles, may have a longest dimension in a range of 1 pm to 100 pm. As the grains are often relatively globular, their longest dimension can typically be determined as their average diameters. In some embodiments, the average longest dimension or diameter of grains suitable for additive manufacturing by the present methods is 75 pm or less, 50 pm or less, 40 pm or less, 30 pm or less, 20 pm or less, or 10 pm or less. In some embodiments, the average longest dimension or diameter of the grains is 2.5 pm or more, 5 pm or more, 7.5 pm or more, or 9 pm or more. In some embodiments, the average longest dimension or diameter of the grains is between 2.5 pm and 75 pm, between 5 pm and 50 pm, between 7.5 pm and 40 pm, or between 9 pm and 30 pm.

[0193] The elementary particles constituting the powders’ grain may have their longest dimension in a range of 5 nm to 10 pm, particles having a longest dimension not exceeding 1 pm, being typically smaller than 500 nm can be referred to as nanoparticles, larger particles being conversely termed microparticles. As the individual particles are often relatively globular, their longest dimension can typically be determined as their average diameters. In some embodiments, the average longest dimension or diameter of particles that may be used individually or as part of larger grains in the present methods is 5 pm or less, 4 pm or less, 3 pm or less, 2 pm or less, 1 pm or less, 500 nm or less, 250 nm or less, or 100 nm or less. In some embodiments, the average longest dimension or diameter of the particles is 10 nm or more, 50 nm or more, or 75 nm or more, if the particles are nanoparticles not exceeding 1 pm; or 1 pm or more, 2.5 pm or more, or 5 pm or more, if the particles are microparticles. In some embodiments, the particles can be nanoparticles having an average longest dimension or diameter between 5 nm and 1000 nm, between 10 nm and 500 nm, between 50 nm and 250 nm, or between 10 nm and 100 nm. The particles can also be microparticles having an average longest dimension or diameter between 1 pm and 10 pm, between 1 pm and 5 pm, between 1 pm and 2.5 pm, provided in any event that the size of the individual particle does not exceed the desired size of the grain.

[0194] The dimensions and average size of particles (e.g., nanoparticles, microparticles or powder grains) can be assessed by any known technique, such as microscopy (e.g., SEM, TEM, FIB, laser confocal microscope) and analysis of images captured at an appropriate magnification. Dynamic Light scattering (DLS) or Light Scattering (LS) can be used for sampling larger populations, providing values statistically more significant. DLS is more suited for relatively smaller particles (e.g., of up to 6 pm) and LS for relatively larger particles (e.g., of up to 3.5 mm). In DLS or LS techniques, the particles are approximated to spheres of equivalent behavior, this method being therefore particularly suitable for globular particles, and the size can be provided in terms of hydrodynamic diameter. DLS or LS also allows assessing the size distribution of a population of particles, the results being typically provided in terms of the hydrodynamic diameter for a given percentage (e.g., 10%, 50% and 90%) of the cumulative particle size distribution, either in terms of numbers of particles or volumes. The size of the grains or particles can be assessed by this method on a sample suspended in a suitable liquid (e.g., water optionally supplemented with a dispersant), in which case their average diameter can be estimated by the median hydrodynamic diameter D50 (maximum hydrodynamic diameter below which 50% of the sample volume (Dv50) or the number (DN50) of particles exists). DIO and D90 (by volume or by number) provide the range within which a predominant portion of the population of particles exists and may serve to estimate if a population of particles is, or not, of relatively uniform size. In some embodiments, the values as measured by DLS or LS refer to Dv values.

[0195] In some embodiments, the size of the particles is relatively uniform (or their size distribution is relatively narrow and / or relatively symmetrical with respect to a median value of the population). Such relative size uniformity is believed to increase the reproducibility of the printing method. Size uniformity is however not essential as some variations may assist in achieving a better packing of the particles once compacted on the substrate, smaller ones being able to fill voids in between larger ones, hence resulting in a denser coverage of any particular layer by the materials applied in the respective regions.

[0196] If the particles are to be functionalized (e.g., sintered) for the operability of the 3D object formed therewith, their improved packing (as may result from the deformability of the grains or their crushability into densely packed particles of same or different PSDs and / or materials) may facilitate such functionalization, and in turn optionally improve a property of the resulting object (e.g., a conductivity of a PCB).

[0197] A particle size distribution is said to be relatively narrow if at least one of the following conditions applies:

[0198] A) If the particles are nanoparticles, the difference between the hydrodynamic diameter of 90% of the nanoparticles and the hydrodynamic diameter of 10% of the same is equal to or less than 250 nm, equal to or less than 200 nm, equal to or less than 150 nm, or equal to or less than 100 nm, which can be mathematically expressed by: (D90 - D10) < 250 nm and so on; B) If the particles are microparticles or grains, the difference between the hydrodynamic diameter of 90% of the microparticles or grains and the hydrodynamic diameter of 10% of the same is equal to or less than 2.5 pm, equal to or less than 2.0 pm, equal to or less than 1.5 pm, or equal to or less than 1.0 pm, which can be mathematically expressed by: (D90 - DIO) < 2.50 pm and so on;

[0199] C) The ratio between a) the difference between the hydrodynamic diameter of 90% of the nanoparticles, microparticles or grains and the hydrodynamic diameter of 10% of the same; and b) the hydrodynamic diameter of 50% of the same, is no more than 2.5, no more than 2.0, no more than 1.5, or even no more than 1.0, which can be mathematically expressed by: (D90 - D10) / D50 < 2.5 and so on; and

[0200] D) The poly dispersity index of the nanoparticles, microparticles or grains is equal to or less than 0.5, equal to or less than 0.4, equal to or less than 0.3, or equal to or less than 0.2, which can be mathematically expressed by: PDI = o2 / d2< 0.5 and so on, wherein is the standard deviation of the particles distribution and d is the mean size of the particles, the PDI optionally being equal to 0.01 or more, 0.05 or more, or 0.1 or more.

[0201] The PDI information is generally readily obtained from the instrument used to measure the hydrodynamic diameter of the particles being considered.

[0202] Materials suitable for additive manufacturing, including powders, adhesives and curable liquids, are known but shall be exemplified in a non-limiting manner in the following, as many more similar or equivalent materials can be used in the practice or testing of embodiments of the invention.

[0203] Composition of the Particles

[0204] The materials to be selected for the formation of the model particles, should take into consideration not only the intended function, but also prospective post-printing processes. For instance, if the method is used to form a pattern due to remain on a substrate (e.g., a board for printed circuitry), then the materials should be “formulated” according to the temperature each substrate could withstand for the sintering of the particles of conductive material. For example, glass-filled epoxy boards, such as FR4, are relatively heat sensitive, so that sintering of metallic particles stacked thereon should not exceed 220°C. In such case, it is preferable to use model particles constituted of both micro and nano-particles of metal. While their overall conglomerated size could be similar to regular powders, the fact that their individual constituents would be relatively smaller enables their sintering at relatively lower temperature. Sintering, however, need not only be thermal and could alternatively (or additionally) be achieved by laser / sonication / induction / microwave sintering. One could combine a layer- by-layer sintering to achieve preliminary bonding, then finalize with sintering of the stack of particles, the final sintering step being optionally less demanding, if intermediate sintering was performed every layer or every few layers.

[0205] Delamination can occur if internal stresses exceed the cohesion forces in the printed layers and between them. To avoid delamination, one can use the following materials: agglomerated powders where each particle is composed of nano / micro particles with binder, under certain pressures the powder will crush into the previous printed layer, this composite material that include major powder, binder and voids can absorb extra energy and prevent delamination. Another type of “composite” particles that may reduce the risks of delamination can consist of at least two different types of materials (e.g., soft and hard), where the soft materials can absorb the energy and deform where the hard powder can function as gap control for the compacting roller. Finally, in some applications, the thickness of the adhesive layer can be increased to absorb the compacting roller energy to prevent delamination.

[0206] This process has been tested for model particles made of metals (aluminium, copper, silver-coated copper, ferrous metals, stainless steel, titanium alloys), plastics (polyamide, polyethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS)) and ceramics (alumina, silicon carbide, tungsten carbide zirconia, titanium hydride and ferrum carbonate).

[0207] Fig. 20 shows photos captured by scanning electron microscopy (SEM) of particles according to embodiments of the present teachings and of cross-sections through compacted layers formed therefrom, taken using a Focused Ion Beam (FIB) setting of the microscope. Fig. 20A is a photo of deformable particles made of the alloy AlSiioMg, the particles initially having a globular shape with an average diameter Dv50 of about 40 pm, while Fig. 20D is a cross-sectional photo of layers, each formed by compaction at a pressure of about 300 MPa, of the same particles using an apparatus as schematically illustrated in Fig. 18, the drum 12 rotatably transporting the substrate and the layers sequentially built on having a linear speed of 1 m / s. The grains previously globular now appear as flattened discs, which look like a brick wall in the section.

[0208] Fig. 20B is a photo of crushable grains made of particles of silica having a relatively uniform PSD with a Dv50 of about 1 pm and a PDI of 0.2, the particles being bound into grains by polyvinylpyrrolidone (PVP) at 2 wt.%. The grains have on average a longest dimension of about 50 pm. Fig. 20E shows layers compacted from the same particles at a pressure of about 100 megaPascal (MPa) under otherwise similar operating conditions of the apparatus, the crushability of the grains into their elementary particles blurring the borders between different layers.

[0209] Fig. 20C is a photo of crushable grains made of two types of particles both in materials and PSDs. First the grains are constituted of micro-particles of copper coated with a thin envelop of silver, these particles having an average diameter of about 1 pm, and secondly of nanoparticles of silver having an average diameter of about 50 nm, the two types of particles being bound to form crushable grains of about 8 pm. Fig. 20F shows sintered layers following compaction of the same particles at a pressure of about 100 MPa under otherwise similar operating conditions of the apparatus, the crushability of the grains into elementary particles of different size providing for a mosaic of larger particles, with nanoparticles intercalated in the voids. The conductivity of a line prepared by this method, following a sintering at about 220°C for 5 minutes, was measured and found to amount to 50% of the ideal conductivity of pure copper as established under similar conditions.

[0210] The binder can be selected from a group consisting substances that may be removed with relative ease when desired while being sufficiently resilient when necessary for the present process. Suitable binders can be polymers, such a polyvinyl pyrrolidones (PVP), polyvinyl alcohols (PVA), polyvinyl butyrals (PVB), polyamides (PA), polyacryl amide (PAM), poly(N- isoprolylacrylamide)s (PNIPAM), poly(acrylic acid)s (PAA), polymethacrylates (PMMA), polypropylenes (PP), polyethylenes (PE), poly(ethylene oxide)s (PEO), polyethylene terephthalates (PET), polyethylene glycols (PEG), sulfonated polyesters and poly(2-ethyl-2- oxazoline) (PEOX). They can also be selected from sugars, oligosaccharides and polysaccharides, such as glucose, maltose, cellulose, hydroxyethyl cellulose, cellulose acetate, amylose, chitosan, carnauba wax, agar agar, acrawax, and starch. A binder can further be combinations of the foregoing materials.

[0211] While the materials adapted for the present 3D printing method have been described mainly as particular solid matters or curable liquids, this should not be construed as limiting. For instance, some particles (typically nanoparticles of metals) may be replaced by salts (e.g., copper nitrate hydroxide or copper sulfate, for copper) or by precursors (e.g., Metal -Organic- Decomposition (MOD)). MOD materials can precipitate as metal nanoparticles upon heating and may then serve as “binders” to larger particles, enhancing the mechanical strength of the region including the MOD and / or improving its function (e.g., electric conductivity following sintering). Thus, while for brevity it might be referred herein to materials by specific chemical names, salts or precursors of the same are encompassed, when relevant.

[0212] Additional details on crushable particles as may be used in the present method or system for 3D printing, or in any other manufacturing process requiring such particles, are provided in the following clauses.

[0213] Composition of the Curable Liquids

[0214] When the support material can remain in the end-product, it may be provided in the form of a liquid which can undergo hardening, in addition to the form of grains or particles. Materials may relatively solidify by building more complex structures starting from simpler ones (which can be liquid at the time they are applied to the substrate). A classic example is provided by pre-polymers which may form larger (e.g., thermosetting) polymers by ongoing cross-linking, a polymerization process also known as curing. Curing of curable materials can be induced by chemical additives (also called curing agents) or by physical means (e.g., light, heat, radiation).

[0215] Chemically curable materials can be epoxy resins, their typical curing agents including polyamines, polyamides, anhydrides, imidazoles and phenols; polyester resins, their typical curing agents including styrene monomers, MEKP (Methyl Ethyl Ketone Peroxide), and cobalt naphthenate: polyurethane resins, their typical curing agents including isocyanates and polyols; acrylic resins, their typical curing agents including free radical initiators such as peroxides or azo compounds; silicone resins, their typical curing agents including silanes and organometallic compounds; phenolic resins, their typical curing agents including formaldehyde-based resins or other phenolic compounds; vinyl ester resins, their typical curing agents including peroxides and amines; cyanate ester resins their typical curing agents including anhydrides; and diallyl phthalate (DAP) resins, their typical curing agents including peroxides. Other specialty curing agents can be used with the afore-said chemically curable resins. Resins that can be cured by using peroxides, azo compounds, or like initiators are often polymerizing through a free radical mechanism, and may therefore alternatively be referred to as free radical curable resins.

[0216] Physically curable materials can be resins that harden through different mechanisms when exposed to specific types of energy, the resins being for instance heat curable, UV-curable, photo-curable, and e-beam curable. UV-curable resins include acrylate and methacrylate-based oligomers and photo-initiators that are acrylate or methacrylate derivatives; photo-curable resins include cationic epoxy resins and vinyl ether resins, their polymerization upon exposure to light being initiated by photoinitiators, such as diaryliodonium salts or sulfonium salts; e- beam curable resins can be epoxy resins and acrylic or methacrylic resins.

[0217] The curable liquid can be adapted to the model particles, and compatible therewith, and can additionally be selected to suitably adhere to an underlying surface and preferably rapidly solidify when sufficiently exposed in the present methods to the relevant curing agent and / or curing energy. The compatibility of the curable liquids with the model particles understandingly includes the compatibility of the liquids with steps of the method intended for the particles. For illustration, if the particles are to be sintered at an elevated temperature, then the curable liquids and their cured counterparts should be selected to be heat resistant at least up to the temperature of sintering. Likewise, if additional parts are to be attached to a stack of layers prepared as herein taught with cured regions set to remain in the final product, the curable liquids and their cured counterparts should be selected to be adapted to their future attachment (e.g., being heat resistant at least up to the temperature of soldering of electronic components to a PCB to form an integrated circuit).

[0218] The curable liquids may further contain any desirable additive as can be selected according to an optional further function of the cured liquid, in addition to supporting other materials (e.g., compacted particles), the additional role being sought during the manufacturing process and / or thereafter. Additives to curable liquids can, depending on their nature, either be consumed during the curing process or be stable therethrough, so as to remain present in the cured material. Additives can: serve for the formulation of the curable liquids (e.g., rheology modifiers, surfactants, etc.); be facilitators of the curing process (e.g., initiators, catalysts, crosslinkers, etc.); be protective agents to the model particles by blocking permeation of deleterious environmental factors (e.g., anti-oxidants, dessicants, etc.); or contribute to any sought chemical and / or physical property of the curable liquid and / or of the cured material resulting therefrom (e.g., thermal and / or electrical conductivity, or lack thereof, mechanical, optical, magnetic properties, flame retardation, etc.). The additives can be soluble in the curable liquids or dispersible therein.

[0219] By way of non-limiting examples, mechanical properties of a cured material can be modulated by the addition of reinforcement fillers (such as glass fibers or silica particles). Reinforcement fillers (or any other solid additive) can be added to the curable liquids in any desired form (e.g., globular, rod-like, platelet-like, elongated fibers, etc.), such additives typically having at least one dimension (e.g., a rod having a diameter) in the nanometer range and being often referred to as nanofillers The dimensions of solid fillers, if any present in the curable liquids, can be selected in accordance with the method of application of the liquid during the manufacturing of the stacked layers. Vice versa, the method of application of the curable liquids can be selected in accordance with their composition.

[0220] For illustration, silica can be added in the form of nanorods to a curable epoxy resin to serve for the manufacturing of a PCB. Particles of silica may contribute, among others, to the coefficient of thermal expansion (CTE, as can be measured as a change in ncrease in length, area, or volume in response to temperature) of the cured resin, the modulation of which to match or be close to the CTE of the model material being often desired. Moreover, silica may increase the mechanical strength (e.g., compressive strength, tensile strength or flexural strength) of the cured resin and desirably affect its dielectric properties.

[0221] Mention is made of the delicate balance between a desire to use curable compositions with a concentration of a suitable filler high enough to achieve a sought goal, while maintaining the viscosity sufficiently low to retain workability (e.g., ease of application) and a brief enough processing speed. Considering prospective self-levelling to illustrate the latter, highly viscous compositions would be relatively flow-resistant and may significantly delay the natural formation of a smooth layer as compared to a more liquid (e.g., curable) composition, the lower viscosity of which shortening the time it takes to equilibrate as a smooth and even surface.

[0222] The silica can be purchased as chopped or unchopped fibers (e.g., such as Unifrax E- Glass® E-08-F) or prepared as nanofibers according to known methods, such as disclosed by Tepekiran et al. in Aerosol Science And Technology, Vol. 53, Issue No. 8, pp 921-932 (2019), the nanofilaments being subsequently manually ground using a mortar and pestle to yield nanorods or short fibers having on average a diameter between about 100 nm and 1,000 nm and a length between about 0.5 pm and 10-15 pm. Such silica nanorods were added to a UV-curable epoxy resin, Optimax® 8046-LV from Novachem Corporation at a significantly high weight percentage of 50 wt.%, poured on a rigid epoxy support having a thickness of 100 pm, the curable epoxy having a wet thickness of 30 pm, and the silica-filled epoxy was cured for 2 seconds under a UV-lamp having a wavelength of 395 nm (manufactured by Zhongshan Enbo Optoelectronics). A micrograph of such nanorods (milled fibers) as captured by FIB-SEM microscopy are shown in Fig. 21A before their embedment in the resin and in Fig. 21B in the cured resin.

[0223] The dielectric constant or relative permittivity (DA) of the silica filled epoxy was measured by parallel plate capacitor method (such as described in ASTM DI 50) on a sample similarly prepared but with a cured epoxy thickness of 2 mm. A 2 mm thick pellet having a diameter of 13 mm was extracted from the cured silica filled coating, placed between conductive plates to yield a dielectric constant of 4.7 as measured at a frequency of 100 kHz and a temperature of 25°C. For comparison, a reference sample made of an FR4 sheet purchased from Vector Electronics was tested in the same way and found to have a highly similar dielectric constant of 4.6, demonstrating that the present methods, which enable a filler loading high enough to desirably modulate the properties of the cured solid, provide for the manufacturing of structures having dielectric constants comparable to commercialized product.

[0224] In general, conventional FR4-boards typically have a dielectric constant between 3.5 and 5.5, or between 3.8 to 4.8, depending on the fiber glass weave style, the thickness of the board and of conductive copper, its resin content, temperature, moisture and frequency (typically set between 1 MHz to 10 GHz).

[0225] In a separate experiment, the same Unifrax E-Glass® E-08-F glass fibers were milled using a mortar-mill into short fibers having an average length of 15 pm and incorporated at 50 wt.% into an alternative UV-curable epoxy resin, commercialized as EPV 9411 by Polymer G. The composition had a dynamic viscosity of 267 mPa s at 50°C, at which the fiber- supplemented curable liquid was poured, smeared and levelled into thin layers having a thickness of about 30 pm. Each layer was cured for 2 seconds under UV-light with wavelength of 395nm. This process was repeated to create specimens with a total thickness of about 2 mm.

[0226] One specimen was punched into a pellet having a diameter of 13 mm to assess its dielectric constant as previously described, which was found to be of 4.7.

[0227] Another fiber-supplemented specimen was tested for flexural strength in the direction of smearing (according to ASTM D6272) and displayed a strength of 212 MPa. For comparison, a reference specimen prepared by casting to have similar dimensions, but no glass fibers, displayed a flexural strength of 132 MPa.

[0228] The coefficient of linear thermal expansion (CLTE) of the specimen with the glass fibers and its reference was measured by thermomechanical analysis performed from 25°C to 200°C. The measurements performed in the direction of smearing of the curable liquid resulted in a CLTE of the fiber-supplemented specimen of 26xl0'6K’1, while in the perpendicular direction the CLTE of the specimen was found to be 88xl0'6K'1. Without wishing to be bound by any particular theory, the distinct CLTEs observed in the different directions of the specimen are believed to result from the relative alignment of the fibers according to the smearing involved in its formation. For comparison, the CLTE for the reference sample lacking any filler was found to be 120x1 O'6K'1.

[0229] Therefore, it is seen that high loading of glass fibers into a curable liquid provides for a cured material having superior flexural strength and reduced CTLE, as compared to the same material cured in absence of any filler. Advantageously, the dielectric constants are suitable for the preparation of 3D printed articles such as PCBs.

[0230] The relatively high loading is enabled by the dimensions of the fibers following their milling. If one were to try to incorporate even as little as 0.1 wt.% of the fibers as supplied into a liquid, this would result in an amorphous mass and not in a liquid of measurable viscosity. By the present method, wherein the fibers are relatively shorter than in their supplied form, adding 0.1 wt.% of the fiber to a curable liquid of interest does not significantly affect the dynamic viscosity, such that the viscosity of the supplemented liquid is no more than 1.2-fold the viscosity of the liquid without any filler. This was confirmed by incorporating 0.1 wt.% of the milled glass fibers (E-Glass® E-08-F) into Optimax® 8046-LV or EPV 9411 and measuring the dynamic viscosity (with or without the fibers) at a temperature at which the liquid is sufficiently flowable for application. At 50°C the dynamic viscosity of Optimax® 8046-LV was of about 71 mPa.s, this viscosity being unaffected by the addition of the glass fibers. At the same temperature, the dynamic viscosity of EPV 9411 was of about 62 mPa.s, the viscosity only mildly increasing to 65 mPa.s in presence of the glass fibers.

[0231] Similarly suitable cured materials were prepared by supplementing with 50 wt.% glass fibers prepared as previously discussed the following curable liquids EPV 3408 CO, EPV 938, EPV 8100 (of Polymer G); SunTronic® U6415 JET 9525 (of SunChem); Prelect UVD110 (of Agfa); which were tested as single material; and Ebecryl® 83, Ebecryl® 160, Ebecryl® 270, Ebecryl® 600, Ebecryl® 605, Ebecryl® 605 / 40, Ebecryl® 641, Ebecryl® 3203, Ebecryl® 3600, Ebecryl® 3703, Ebecryl® 3708, Ebecryl® LEO 10551, and Ebecryl® LED 03 (of Allnex); which were tested in various combinations one with another.

[0232] The suitability of all curable compositions as currently supplemented with 50 wt.% of milled fibers of E-glass, which was preliminarily established in laboratory settings with manual application of the liquid as detailed for EPV 9411 and Optimax® 8046-LV, was confirmed in the automated printing system described with reference to Fig. 19. This second series of experiments was performed with curable compositions which have been stored since their preparations for periods of up to three months at 4°C. Notably, and despite the very high loading of milled fibers, the curable compositions retained flowable viscosities at their temperature of application and displayed no deleterious separations between the filler and the liquid medium. This suggests a stability of the present curable compositions which is unexpected of liquids highly loaded in solid materials.

[0233] An additional or alternative additive that can be added to a curable liquid may be a coloring agent selected in accordance with a color conventionally associated with the products due to include the cured liquid. Thus, the cured material can be transparent or opaque, and clear or colored. The coloring agent, if present, which could provide for any desirable shade, should not affect the performance of the material once cured. Colors can be selected according to the shades of the compacted particles upon which the curable liquid is to be cast, so as to achieve contrast, brightness or any other visual effect in the finished product including the layers stacked according to the present teachings.

[0234] Taking printed circuit boards for illustration, the first material of the particles can be electrically conductive and deposited to form a pattern including traces and pads for additional electronic components, while the curable liquid can be selected to remain in the final product in which it may serve as solder mask. In this case, the different colors that can be added to the curable liquid may be used to distinguish the solder masks, facilitate the identification of the PCBs and ease their assemblies. While green has been predominantly used in solder masks of PCBs, colors other than green (e.g., red, blue, white, black, yellow, and purple) have recently been introduced in the preparation of solder masks to serve as PCB color codes.

[0235] Compositions highly loaded with fillers according to the present teachings may not only be used for permanent fencing or encapsulation as herein detailed, but may also, in dependence upon the fillers and base materials selected for their preparation and their relative proportions, serve for the preparation of temporary sacrificial layers or separating materials, as shall be detailed in the following.

[0236] Additional details on curable compositions as may be used in the present method or system for 3D printing, or in any other manufacturing process requiring such curable compositions, are provided in the following clauses.

[0237] Adhesive Compositions

[0238] The initial requirements common to any composition suitable for the formation of a thin adhesive layer to be thermally activated (e.g., selectively for the foreground image or non- selectively for the background image) are: a) it can be melted to a suitable viscosity for application as a thin layer (e.g. , having a dynamic viscosity of no more than 1 Pascal-second (Pa.S) at 150°C and a shear stress of 1000 sec'1); b) it should have an open-time sufficiently short (e.g., < 1 sec, 0.5 sec or 0.2 sec) to readily solidify as a thin layer of even thickness on an application roller made of silicon (e.g., 102) and / or to prevent parasitic attachment of particles in inactivated regions of the adhesive; c) it is sufficiently cohesive to transfer as a uniform layer from the application roller to the support or compacted layers previously applied thereon; d) it should have an open-time sufficiently long (e.g., up to 0.5 sec, 0.25 sec or 0.1 sec) to remain tacky between the time the layer is activated and the time it is contacted by the particles to be attached thereon.

[0239] Additional requirements may depend on the intended use of the 3D printed object, as residual amounts of adhesive may remain in the end-product, in which case the adhesive compositions may additionally be required to be compatible with such use. Fundamentally, a material or a chemical composition is compatible with another composition or with a method if it does not prevent its activity or performance, or if it does not reduce it to an extent that would significantly affect the intended purpose. Such compatibility may be from a chemical standpoint, for instance, materials having respective moieties or active groups that may desirably interact with one another, for illustration, adhesive materials being relatively acid on their own (e.g., rosin gums), by way of suitable additives (e.g., organic acids), or both, can beneficially reduce the amount of metal oxide that may surround metal particles, such decrease in the presence of an oxide relatively to the unoxidized metal typically increasing the conductivity once the particles are sintered. From a physical standpoint the compatibility of materials may relate, for instance, to the adhesive composition having a softening temperature and / or a debindability (ease of elimination) adapted to the printing process or operating conditions of the printing apparatus, or two materials intended to form contiguous regions having a similar coefficient of thermal expansion. From the standpoint of an intended use in a present process, an adhesive composition would be compatible if, for instance, being capable of absorbing the radiation of laser emitting elements intended for its activation or not impairing the consolidation of the layers or their functionalization, such as permitting proper sintering, conductivity, RF or dielectric properties, as may be desired. Some adhesive materials may by themselves be capable of fulfilling a particular set of desirable requirements, but in some embodiments (or for adhesives lacking a particular capacity) the adhesive compositions may be supplemented with suitable additives to enable or enhance a desired property or compatibility as above exemplified. For instance, an additive can facilitate the activation of activatable adhesives by the elected method of activation, can facilitate the consolidation (e.g., sintering) of the stacked layers by the method elected for this purpose or can adapt the property of a region made therewith to a sought value. For illustration, a radiation absorbing agent can be added to facilitate radiation triggered activation, a sintering additive can be added to facilitate sintering or a filler can be added to bring CTE of the stacked layers to a desired level.

[0240] In a test developed to select suitable adhesive compositions, a substrate (e.g., a PCB board, a transparent glass slide, etc. is coated with a thin layer of the material being tested and exposed to laser emission adapted to prospectively render it tacky, and the irradiated sample is then brought into contact with a layer of particles to be detached from a blanket support having a releasy outer surface made of polydimethyl siloxane (PDMS). The substrate is then separated from the blanket and the ability of the tested activatable adhesive composition to detach and retain the particles is determined. A similar test can be performed with any other desirable method of activation or deposition of the adhesive candidate.

[0241] Adhesive compositions, in particular activatable ones, may comprise at least one of a natural or a synthetic polymer (e.g., a polyacrylate, a polyalkene (also known as polyolefin, such as a polyethylene, a polypropylene), a polyamide, a polycarbonate, a polyester, a polyketone, a thermoplastic polyurethane (TPU) or a gum of natural origin, such as gum Arabic, gum rosin etc., or any like thermoplastic material), if desired a plasticizer (e.g., fatty compounds, phtalates, resins, waxes, etc.) added to ensure the composition would have a required tackiness once activated, and any other optional additive which may facilitate activation. For instance, if the selectively activating device (e.g., as illustrated by referral 500 in Fig. 18) is a laser emitting device where the laser emit in the near-infrared (NIR) light range then the adhesive composition can be supplemented with (absorbance types) carbon black, dyes, pigments, cesium tungsten oxide, lanthanum hexaboride, nanoparticles of metals having an average size not exceeding 100 nm, such as nanoparticles of stainless steel 316L, carbon coated nickel copper, copper and nickel, or like additives, which may enhance its absorption in the NIR range at which the lasers operate. This was experimentally confirmed by the Applicant who tested carbon black at 20 wt.% and 30 wt.%, cesium tungsten oxide at 34 wt.%, lanthanum hexaboride at 45 wt.%, and nanoparticles of stainless steel 316L at 50 wt.%, the absorption enhancers being incorporated in various adhesive compositions, all being found activatable at energy levels of 0.6 Joule per square centimeter.

[0242] Similar principles may be followed (and materials used) for the preparation of liquid adhesive compositions which can be selectively applied where desired and for the preparation of binders adapted to maintain elementary particles as crushable powders’ grains. However, as the selectively applicable liquid and the binder need not be responsive to a specific trigger, as are the activatable adhesive compositions, additional materials may be used for this particular purpose. For illustration, while thermoplastic materials are preferred for the activatable adhesive compositions and can be used for the jettable counterparts or for the binders, the latter may also include thermosetting polymers.

[0243] In a test carried out by the Applicant, an adhesive suitable for the formation of a continuous thin layer was prepared from a commercially available flexographic printing ink, Uni-Rez™ 2224 (a polyamide resin) supplemented with 10 wt.% rosin gum (Foral™ AX-E) and 10-30 wt.% of radiation absorbers. Another suitable adhesive was found to be a hot melt adhesive Dynacoll® 7360 (which is a saturated copolyester).

[0244] Additional suitable adhesives have been already described with respect to the feasibility of the particle dispenser to apply particles thereon and more materials are listed as binders to the particles to be later detailed.

[0245] The thickness of the adhesive layer may be adapted to the size of the particles to be attached thereon, and for instance could be only 0.5-2 pm or 0.5-1 pm thick for particles of about 10 pm, and 2-4 pm to 2-3 pm thick for particles of about 40 pm, the general rule of thumb being that the thickness of an adhesive image is about a tenth to a fifth of the average size of the particles. It is preferred that the thickness of the adhesive layer does not to exceed 10 pm, being typically of no more than 7 pm. This allows very small amount of glue to be used which is beneficial for the debinding process and allow the preparation of more accurate models.

[0246] In embodiments where the adhesive is selectively applied for the model and support particles, it is possible to use different adhesive compositions. For example, the adhesive used for the support particles may be water soluble while that used for the model particles is not soluble in water. The same approach may be applied to composite particles, with model particles relying on a first kind of (e.g., water-insoluble) binder and the composite support particles relying on a second type of (e.g., water-soluble) binder. Selectively applicable adhesive compositions should have a viscosity adapted to their method of application, for instance enabling their jetting, this being typically achieved by the inclusion of a liquid (e.g., a solvent) lowering the relative presence of adhesive solids. The nature of the solvent used for the preparation of a selectively applicable liquid adhesive composition may depend on the nature of the material dissolved therein which would provide the required tackiness upon at least partial evaporation of the solvent. If the adhesive material is a water-soluble thermoplastic polymer such as polyvinylpyrrolidone (PVP) or polyacrylic acid (PAA), the solvent can be water, short chain alcohols of no more than six carbon atoms (e.g., methanol, ethanol, isopropyl alcohol, etc.} which tend to rapidly evaporate, long chain alcohols (also known as fatty alcohols, which are often considered as plasticizers since their relatively lower rate of evaporation allows them to sufficiently remain with the polymer to lower the temperature at which it would become or remain tacky) and glycol derivatives (e.g., ethylene glycol, diethylene glycol (DEG), diethylene glycol butyl ether (DEGBE), dipropylene glycol methyl ether (DPM), etc. . Materials that can serve to impart adhesive properties to a jettable liquid are known and include, in addition to the resins and polymers already mentioned as activatable adhesives or binders, phenolic resins, such as cresols, novolacs and bakelites, and PVP, to name a few.

[0247] Similar principles apply when the selectively applicable composition is other than exclusively adhesive for the attachment of future particles, for instance, if intended to deliver model particles made of a conductive material in order to 3D print a circuit due to be electrically conductive. Taking commonly used silver inks for illustration, such compositions typically contain 20-50% wt.% of silver nanoparticles having an average diameter of 20-100 nm dispersed in an aqueous or organic solvent, the liquid further including any co-solvent, dispersant or additive required to stabilize the ink, facilitate its application (e.g., by jetting) or enhance its adhesion to the targeted surface and interactions with same or other particles. The constituents of the liquid carriers of such commercially available conductive inks can be as previously described with respect to the liquid adhesives.

[0248] The support particles can also be selected in accordance with the model particles. They should provide for easy removal, if so desired, upon completion of manufacturing and be, for instance, soluble in a desired solvent (preferably in water) or eliminated by burning at a temperature not affecting the model particles (e.g., salts, silica SiCE, ferrous carbonate FeCCh, calcium carbonate CaCCh). To the extent that the removal is not complete, residues of the support particles “contaminating” the model particles, such “contaminants” should be compatible with the intended function of the 3D shaped model. For instance, if the product is a PCB, residues of support particles should not affect conductivity of the model areas and their radio frequency (RF) properties, such as surface conductivity, surface roughness etc.

[0249] Understandingly, removal of a material, if so desired upon completion of manufacturing of the superposed layers should be indifferent to the method used to apply the removable material (e.g., as particles, as solidifiable liquid).

[0250] Interestingly, alternance of layers of support material being removable with support material being stable under the conditions set for removal may permit the fabrication of thin sheets of support material in between areas formed of model particles. If the layer of remaining support is thin enough and / or made of a soft enough material (e.g., a polymer), such layer can be flexible. In such a case, the present method may allow the manufacturing of 3D objects having relatively solid parts connected to relatively flexible ones, permitting for illustration the synchronous manufacturing of rigid-flex PCBs. Regardless of the type of objects to be manufactured, the present method advantageously allows to print the substrate (e.g., a flexible or rigid one) prior to (or during) the superposition of layers including the model particles.

[0251] For the manufacture of printed circuit boards, the model material could be electrically conductive (optionally following a treatment step, such as sintering) and the support material could be electrically insulating (e.g., epoxies, including glass or ceramic filled epoxies, ceramics, polyimide, polytetrafluoroethylene (PTFE) and combinations thereof, so as to separate and isolate the shapes of conductors formed on the PCB substrate. The support materials, which may remain for a PCB end-product, apart from being insulating should possess other properties required for desired PCB functioning such as dielectric constant, dielectric loss, temperature stability of the properties etc. In that case, residues of model particles and / or of adhesives in the support areas should not damage these properties.

[0252] Depending on the materials used for the model particles, the process may serve for the manufacturing of different 3D objects, and vice versa. Taking for illustration printed electronics, the material resulting from the compaction of the support material (e.g., particles) may remain in the end-product (even if sintered).

[0253] Micro particles of copper pressed between 100-300 MPa at the printing stage and followed during post processing with application of a pressure between 20-50 MPa at temperature between 250-350°C has been found to achieve 25-35 % of copper bulk conductivity. By using silver coated copper powder with same conditions, a conductivity of between 30-40% of bulk copper conductivity (i.e. > 30% IACS) can be achieved.

[0254] In order for post-processing of printed circuit boards to be able to use lower pressures and temperatures while achieving the required high conductivity, it has been found desirable to use as particles aggregates of nanoparticles. Even aggregates of microparticles (e.g., of copper) with nanoparticles (e.g., of silver) have been found advantageous to achieve a relatively higher conductivity of more than 35% of bulk copper (upon sintering of the model particles).

[0255] In some cases, conductive traces that can be prepared by the present 3D printing methods, and / or in the 3D printing systems enabling inter alia their implementation, all with the materials as herein taught, can have (following suitable consolidation, such as by sintering) a conductivity relatively high. In some embodiments, the conductivity of the traces can be of 30% IACS or more, 35% IACS or more, 40% IACS or more, 45% IACS or more, 50% IACS or more, or 55% IACS or more.

[0256] For products where the substrate and the support are temporary for the duration of the manufacturing, it should be selected to be compatible with later separation of the manufactured object. In such case, the support would be selected to have both suitable mechanical properties (to sustain the pressure ± heat) and release capability, or be coated with a sacrificial layer enabling later separation of the object.

[0257] When the particles are composed of aggregates a binder might be needed. When the binder of some of the intended particles or the adhesive of each layer is to remain in the endproduct, their composition should be accordingly selected and adapted. For illustration, if the model particles are made of a plastics material that would be hardened at a temperature insufficient to eliminate the adhesive in-between, then the adhesive might also provide desirable mechanical properties to the resulting object.

[0258] Sacrificial Compositions

[0259] When separation of the object formed by the present 3D printing methods is desired, application of a sacrificial layer on the backing surface can precede the cyclical formation of layers including the compacted particles. This step, however, is not essential when separation can be achieved mechanically without adverse effect to the base of the 3D printed object being disconnected from the backing surface upon which it was produced. The sacrificial layer can be formed by a pre-treating module configured to dispense a sacrificial liquid so as to form a coat of uniform thickness on the backing (e.g., metallic) platform, the suitable module further comprising a drier to eliminate the liquid (e.g., a solvent in which suitable materials are dispersed or dissolved), so that the sacrificial layer formed thereby is substantially dry and flat when entering a first cycle of particle deposition.

[0260] Alternatively, the sacrificial layer can be prepared separately according to the dimensions of the platform and / or of the object to be additively manufactured thereon. The layer can then be solidified (e.g., dried, cured or cooled, if made of a thermoplastic polymer) so as to form a flat sacrificial support (e.g., having a thickness of 500 pm or less, 250 pm or less, 100 pm or less, or 50 pm or less) to be placed on the backing surface at the beginning of the manufacturing process. Such ready-to-use sacrificial supports can be dispensed individually at the commencement of the process by suitable dispensers.

[0261] In case the sacrificial layer is supplied in form of a separately prepared sacrificial support, it may be advantageous to include in the platform means to retain the sacrificial support in position. For illustration, a sacrificial support can be secured on a porous backing surface by way of suction applied from the rear side of the support.

[0262] As the base surface of a 3D printed object to be formed thereon may reproduce the topography of the outermost surface of the sacrificial layer or support, in cases where the base surface is to meet specific requirements, it can be advantageous for the sacrificial surface to enable or facilitate obtaining such properties. For illustration, if the base surface is to be flat and relatively smooth (e.g., as may be required of PCBs), it can be beneficial to use a sacrificial layer or support that is similarly flat and smooth. Thus, a module configured to form a solid sacrificial layer or dispense a sacrificial support (if not previously prepared with desirable surface properties) may further include levelling members selected to provide a sought smoothness. Alternatively, the solid sacrificial layer or support dispensed by such a module can be transported to a levelling module of the printing system before being subjected to a first cycle of application of particles thereon.

[0263] As already explained, to enable later separation, the sacrificial layer or support should preferably be easily soluble in a solvent (e.g., water) chemically inert with respect to the object being separated. But, as other materials previously detailed, the sacrificial layer (whether formed inline from a liquid or secured as a sacrificial support prepared offline) should furthermore be made of substances compatible with the process (e.g., pressure and temperature) and the particles or curable liquids to be subsequently applied thereon. It is reminded that similar principles apply to compositions that can be used to separate regions through slices of the 3D printed object. Thus, compositions intended to transiently isolate areas that may be later detached one from the other to form discrete articles out of the printed object, can be identical to sacrificial compositions as herein described.

[0264] The sacrificial layer must ensure that the layers building-up thereon are adhered sufficiently to the backing surface to sustain compaction (and levelling, when applied) at the temperatures at which the 3D printing is performed. For illustration, if regions of the object are to include a cured liquid having a hardness in the Shore C or even Shore D range, then the sacrificial layer or support should preferably have a comparable or higher hardness at the printing temperature of compaction, to mechanically resist to this step so as to avoid deformation of the layers by local or total collapse of the sacrificial layer.

[0265] Materials suitable for the preparation of the sacrificial liquid or sacrificial support may depend on the printing conditions being considered and materials envisioned. For example, one may use water-soluble polyvinyl alcohol (PVA) of appropriate grades for this purpose.

[0266] Materials previously listed as suitable adhesives or binders may also serve for the present purpose. However, since the sacrificial layer or support is required to withstand repeated compaction while substantially retaining its original dimensions, the materials that may be used alone for the sake of an adhesive composition or a particle binder may now need to be supplemented with fillers to augment their mechanical resilience.

[0267] Fillers can be ceramics (e.g., alumina, silica, zirconia, zirconium(IV) silicate, etc.), minerals (e.g., calcium carbonate, clays, sodium chloride, talc, etc.), polysaccharides (e.g., cellulose, chitosan, lignin, starch, etc.), or any other material known as suitable for this mechanical reinforcing purpose. The fillers can be provided in any shape adapted to their function (e.g., beads or fibers). Notably, their presence in a sacrificial composition can be relatively significant, being for illustration of 30 wt.% or more, 50 wt.% or more, or even 70 wt.% or more. In case the fillers are shaped as fibers, they can be prepared according to the principles already detailed for curable compositions similarly containing a relatively high amount of fibers.

[0268] Sacrificial compositions may, as other substances already described, also contain additives such as plasticizers, dispersants, rheology modifiers, stabilizers, lubricants, pH modifiers and like conventional additives, which need not be further detailed.

[0269] If the flowability of the sacrificial composition is insufficient at their temperature of inline application or off-line preparation, a (e.g., volatile) solvent can be added to facilitate their spreading, the solvent being later eliminated by evaporation prior to the application of particles and compaction thereof.

[0270] The following sacrificial compositions were prepared both in-line in a printing apparatus as illustrated in Fig. 18 and off-line for feeding to a printing apparatus as illustrated in Fig. 19. All were found suitable for the ongoing stacking and compacting of layers thereupon, and for their later separation from the base of the additively manufactured object, even following sintering at temperatures ranging from 200°C to 1500°C, depending on the particles used in the subsequently applied layers.

[0271] The polyvinyl alcohols (PVA) tested included Poval™ 3-86, Poval™ L-508, Elvanol™ 85-82, Elvanol™ 71-30, Mowiflex™ C-17, and Mowiflex™ H-15, and the polyvinyl butyral (PVB) materials tested included Mowital™ B60H and Mowital™ B16H, all available from Kuraray. Additional binding materials tested included polyvinyl pyrrolidone (PVP) as commercialized by BASF as Luvitec® K90 and rosin gum commercialized as Foral™ AX-E.

[0272] The fillers tested in combination with the above listed binding materials (and their relative concentration in the sacrificial compositions) included calcium carbonate (50 wt.%), cellulose (33 wt.%), chitosan (80 wt.%, 90 wt.%), corn starch (25 wt.%, 33 wt.%, 50 wt.%, 66 wt.%), lignin (3 wt.%), silica (50 wt.%), sodium chloride (43 wt.%, 73 wt.%), and zirconium silicate (91 wt.%).

[0273] Working Examples

[0274] Having detailed various embodiments of the 3D printing methods and systems of the invention, and the materials that can be used therewith, manufacturing examples are now provided.

[0275] In a printing system as shown in Fig. 18, a thermally activatable adhesive composition containing 40 wt.% of Uni-Rez® 2224, 20 wt.% of NiPex® 150 by Orion and Foral™ AX-E was applied at a predetermined thickness of 1.5 pm, 2 pm or 2.5 pm from the bath of applicator 1000 heated to 80°C. The heated adhesive was applied to entirely cover the surface of drum 12 which was rotated at a linear speed of 0.5 m / s.

[0276] Particles were supplied by dispenser 2000 by periodically urging the applicator 250 into contact with the tacky adhesive. In a first series of experiments, initial layers were prepared by application of crushable particles prepared in-house and consisting of 91 wt.% of ZrSiCU bound by 9 wt.% of PVP, the particles having an average diameter of about 25 pm. Each application was followed by the compaction of the applied particles at 100 MPa and 25°C by compacting device 3000. After 10 cycles, the particles of zirconium silicate were replaced by particles of polyamide, Ultrasint® PA11, which were similarly applied and compacted to form 30 more layers on the 10 layers of zircon. Cross-sections were prepared and analyzed by microscope, all displaying a particle density of at least 90% regardless of the thickness of adhesive utilized.

[0277] In a second series of experiments, 20 layers were prepared by application of the crushable particles including ZrSiC , the compaction of the applied particles being now tested at 200 MPa, 300 MPa, or 400 MPa, and 25°C. The following layers (30 in total) were prepared by application and compaction of various particles of aluminium and alloys thereof, namely aluminium 6061, AlSilOMg and AlSi20Mg, as well as mixtures thereof, all having an average diameter of about 25 pm. Cross-sections of all compacted samples so prepared displayed a particle density of at least 90% regardless of the applied pressure, some mixtures of aluminum- based materials enabling such high density of particles at even lower compacting pressures of 50 or 100 MPa. Typically, the layers compacted at each cycle had an average thickness between 16 pm and 20 pm in all experiments.

[0278] In a printing system as shown in Fig. 19, a thermally curable adhesive composition containing 40 wt.% of silver nanoparticles having an average particle size of 30-50 nm in an aqueous dispersion compatible for ink jetting was jetted on a substrate 620 made of rigid epoxy at a station 700 using Samba® 3GL printheads of Fujifilm Dimatix with droplets of 5 picoliter. The adhesive liquid was jetted to form a pattern as partially shown in top view in Fig. 22A, the wet thickness of the adhesive pattern being of about 5 pm at each jetting cycle. Particles having an average diameter of approximately 10 pm and made of copper coated with silver at 10 wt.% were applied on the adhesive, while still tacky, using a particle dispenser as illustrated by 2000. Particles found in regions other than intended were brushed off at a cleaning station 730 including a cleaning device 2020. The particles found on the adhesive pattern were compacted by a compacting device 3000 at a pressure of 100 MPa and a temperature of 30°C after each cycle of particles deposition. Following two repeats of the foregoing steps up to a total number of three cycles, a UV curable resin was applied by liquid applicator 740 and levelled with a squeegee 742 to cover the pattern of compacted particles. The UV curable resin was made of epoxy (Optimax® 8046-LV) supplemented with 50 wt.% of spherical silica powder having a measured average diameter of about 1.8 pm (for a nominal diameter set to be of about 2.5 pm, as provided for SS-T-2.5 silica powder manufactured by China New Energy). The pattern including the curable liquid was cured for 2 seconds at a curing station 750 using a UV lamp emitting at a wavelength of 395 nm. The cured product was polished using a face milling machine with 14 inserts of polycrystalline cubic diamond equally spaced on a disc having a diameter of 160 mm (manufactured by Iscar) as a levelling device 760 to level the outer surface to a roughness Raof less than 500 nm as determined by Laser Measuring Microscopy (LEXT OLS5000, Olympus) as inspecting device 770, the pattern of particles of conductive material remaining embedded and protected by the cured epoxy. The cured and polished product was then placed in an oven at 250°C for 5 minutes in order to sinter the particles and render the pattern electrically conductive. The pattern obtained at this stage is partially shown in top view in Fig. 22B The traces formed in this experiment had a width of 370 pm, the spacing between the closest adjacent traces being of 230 pm.

[0279] The conductivity of the resulting traces was found to correspond to about 60% of the conductivity of bulk copper as conventionally measured by a four probe method. This degree of conductivity (i.e. -60% IACS) for a trace prepared by additive manufacturing is impressive, being twice the values often reported for the electrical conductivity traditionally obtained by approaches deemed similar. The resistivity across layers of conductive material stacked one on top of the other was found by the same method to be essentially null, supporting a near ideal contact between the superposed layers as expected from the present method and materials used therein.

[0280] Using the same materials, two distinct circuits were printed one above the other and interconnected by intermediate vias formed using a similar 3D printing method. A first circuit according to a first pattern including traces and contact pads was formed by five cycles of application of particles of conductive material upon an adhesive image selectively deposited according to the desired pattern. The particles were compacted after each cycle. A curable epoxy liquid supplemented with silica particles was then poured and levelled with a suitable squeegee so as to fill the background regions. The substrate including the first pattern of compacted particles surrounded by the support liquid was then cured and the outermost surface was grinded as previously described. The total thickness of the first circuit after grinding was of about 32 pm.

[0281] The vias were then formed in alignment with desired contact pads on top of the first circuit by ten cycles of the same method, particles being compacted after each cycle, addition of curable liquid, curing and grinding of the outermost surface being performed each five cycles of deposition of the conductive particles. The total thickness of the vias embedded in the insulating support was of about 75-80 pm after last grinding. The second circuit following a second pattern of traces was then formed on the outermost surface of the substrate by three cycles of application of particles of conductive material upon an adhesive image selectively deposited according to the desired second pattern, whilst in proper alignment with the vias due to connect the second circuit to the first. Particles were compacted after each cycle, the curable liquid being added and cured as last step. The total thickness of the second circuit without grinding was of about 22 pm.

[0282] The substrate including the two circuits and the intermediate vias was then placed in an oven at 250°C for 5 minutes in order to sinter the particles and render the pattern electrically conductive, as later confirmed.

[0283] A benefit offered by the proposed method of 3D manufacture resides in the relatively low energy consumption as compared to more conventional 3D printing methods. For example, the known binder jetting method, which relies on the adhesive being mixed with the material to be selectively deposited, typically requires high amount of energy to eliminate the liquid carrier of the jetted material. In technologies involving lasers, such as Selective Laser Melting (SLM), Selective Laser Sintering (SLS), or Laser Metal Deposition (LMD), the energy required to melt or sinter a powder made of metal or polymer is significantly higher than the energy needed by a laser to heat a thin layer of adhesive.

[0284] In addition to the features that are set out in the appended claims, the present specification has disclosed several further features that are believed to be inventive in their own right, and in order that these features may subsequently be patented separately, by way of divisional applications, they are set out below in the following clauses.

[0285] 1. A method of 3D printing which comprises forming a plurality of superposed layers within which at least each intermediate layer formed on an underlying layer is composed, within an area bounded only by an outer perimeter, of one or more materials, wherein each intermediate layer that comprises more than one material is formed by: a) depositing at least one coating of a first material on selected first regions within the outer perimeter by:

[0286] (i) selectively applying an adhesive to, or selectively activating an adhesive in, the selected first regions, and

[0287] (ii) adhering particles to the adhesive in the selected first regions; b) subsequently depositing a coating having a different composition from the previously applied coating(s) on all remaining regions within the outer perimeter of the intermediate layer not occupied by the first material; and c) compacting at least the particles of the first material of each layer prior to the deposition of an overlying layer; whereby an even continuous surface is formed onto which the overlying layer can be deposited.

[0288] 2. The method as in clause 1, wherein coating of the remaining regions of each intermediate layer is achieved by application or activation of an adhesive within said remaining regions and adhesion of particles thereto, at least one of the adhesive and the particles of the coating applied to said remaining regions being different from the adhesive and the particles of coating applied to the first regions.

[0289] 3. The method as in clause 2, wherein the particles of the remaining regions are compacted during and / or after compaction of the particles of the selected first regions, the compaction of all particles serving to provide the even continuous surface.

[0290] 4. The method as in clause 1, wherein coating of the remaining regions of each intermediate layer is achieved by application of a second material as a liquid within the perimeter, the liquid second material being applied after one or more cycles of deposition of the first material.

[0291] 5. The method as in clause 4, wherein following application of the liquid second material, the second material is solidified optionally following active levelling of the liquid with one or more levelling members, at least one levelling member being further optionally vibrated during levelling.

[0292] 6. The method as in clause 5, wherein the liquid second material is a curable resin that is solidified by curing.

[0293] 7. The method as in any one of clauses 1-6, wherein the step of ensuring that the coatings constituting the intermediate layer provide an even continuous surface includes removing at least part of any coating of remaining regions overlying the selected first regions, by milling, grinding, and / or abrasion.

[0294] 8. The method as in any one of clauses 1-7, wherein the coating of the regions is deposited in one cycle and at least the particles of the first material are adhered to a selectively activated adhesive applied to the entire surface of the underlying layer, and wherein the selective activation is a chemical and / or a physical activation, the latter comprising application of energy by heat conduction or radiation.

[0295] 9. The method as in any one of clauses 1-7, wherein at least the particles of the first material deposited in the selected first regions of each cycle are adhered to an adhesive that is selectively applied to the underlying layer or an underlying coating by jetting, by use of a mask, or by transfer of a selective adhesive image.

[0296] 10. The method as in any one of clauses 1-9, wherein prior to applying an adhesive at least on the selected first regions, and / or on the remaining regions, an adhesive priming substance is applied at least on said regions.

[0297] 11. The method as in any one of clauses 1-10, wherein prior to applying an adhesive at least on the selected first regions, and / or on the remaining regions, an adhesive masking substance is applied at least in areas adjacent to said regions.

[0298] 12. The method as in any one of clauses 1-11, wherein following application of particles to an activated adhesive and / or compaction of the particles, surplus particles not in direct contact with the adhesive are removed.

[0299] 13. The method as in any one of clauses 1-12, wherein compacting of regions formed by application of particles includes applying a pressure in a range of 1 to 300 MegaPascal (MPa), the applied pressure being optionally controllably modified for each coating or layer being compacted.

[0300] 14. The method as in clause 13, wherein energy is applied during compaction to raise the temperature of the particles to be compacted to at least one temperature in the range of 20°C to 500°C, the applied heat being optionally controllably modified for each coating or layer being compacted.

[0301] 15. The method as in any one of clauses 1-14, wherein compacting is effected by a rotating cylinder controllably urged into rolling contact with the coating(s) to be compacted, the compressive force applied to the particles being optionally sufficient to cause plastic deformation of the particles in at least a part of the intermediate layer and the rotating cylinder being further optionally vibrated during compaction.

[0302] 16. The method as in any one of clauses 1-15, wherein any adhesive applied to an underlying layer to adhere particles thereto is applied in a thickness of 10 pm or less, 5 pm or less, 2 pm or less, 1 pm or less, or 0.5 pm or less 17. The method as in any one of clauses 1-16, wherein any adhesive applied to any underlying layer or any underlying coating to adhere particles thereto, is heat activatable and comprises a thermoplastic polymer and optionally an agent adapted to absorb EM radiation and / or an agent adapted to facilitate consolidation of the particles.

[0303] 18. The method as in any one of clauses 1-17, wherein the materials applied in the form of particles are selected from the group comprising metals, ceramics, carbides, salts, and plastics materials.

[0304] 19. The method as in any one of clauses 1-18, wherein materials applied in the form of particles have a particle size with an average longest dimension not exceeding 200 pm or 100 pm.

[0305] 20. The method as in any one of clauses 1-19, wherein materials applied in the form of particles comprise clusters of individual particles including nanoparticles having an average longest dimension no greater than 200 nm and a binder.

[0306] 21. The method as in any one of clauses 1-20, wherein the particles of at least one of the materials applied in particle form are composite particles, including two or more materials agglomerated, encapsulated, or coated one within the other.

[0307] 22. The method as in any one of clauses 1-21, further comprising applying a sacrificial first layer or disposing a sacrificial support onto a surface prior to forming a first intermediate layer.

[0308] 23. The method as in any one of clauses 1-22, wherein when the layers superposed in a Z- direction comprise in a plan perpendicular to the Z-direction a plurality of separated patterns, each pattern being in distinct first regions, the method further comprises applying a separating material between the patterns, the separating material optionally being a removable material, further optionally being the same as a material adapted to form a sacrificial first layer onto a surface prior to forming a first intermediate layer.

[0309] 24. The method as in clause 23, wherein the separating material is applied after compacting the particles of the first material and prior to applying a second material as a liquid within the perimeter, the separating material and the liquid second material optionally being each independently a curable resin solidifiable by curing.

[0310] 25. The method as in any one of clauses 1-24, wherein following formation of all the layers, one of the materials is removed to leave a three-dimensional shape composed of the remaining materials and having voids corresponding to regions previously occupied by the removed material.

[0311] 26. The method as in clause 25, wherein the one material is removed by at least one of: a) a chemical treatment, the chemical treatment optionally adapted to solubilize the said one material; and b) a physical treatment, the physical treatment optionally including a mechanical treatment to dislodge particles of the said one material, or a thermal treatment to melt the said one material.

[0312] 27. The method as in any one of clauses 1-26, further comprising consolidating the particles of the first material one with the others, the consolidation being by application of energy, said energy being optionally applied following the compacting of only some of the superposed layers.

[0313] 28. The method as in clause 27, wherein the first particles are consolidated whilst attached to a backing surface and the backing surface is optionally a rigid and / or flexible substrate adapted for the manufacturing of electronic components selected from a group including printed circuit boards (PCBs), integrated circuits (IC), radio frequency identification (RFID) tags, capacitors, batteries, Liquid Crystal Displays (LCDs), wave guides, thin film devices and solar cells.

[0314] 29. The method as in clause 28, wherein the rigid and / or flexible substrate are manufactured according to any preceding clause prior to or during the compacting of the superposed layers or a part thereof.

[0315] 30. A particle application apparatus for applying particles to a substrate (10) which is coated in at least selected areas with an adhesive, the apparatus comprising: a) an applicator having the form of a cylinder (250) or a belt, b) a drive mechanism (254) for urging a surface of the applicator into rolling contact with the surface of the substrate, and c) a particle dispenser (2000) for applying to at least a section of the applicator surface that is to make rolling contact with the substrate a uniform multilayer coating of the particles to be applied to the substrate, wherein the cohesion between the overlying layers of particles coating the surface of the applicator is less than the cohesion of the particles to the adhesive on the substrate, the latter cohesion being in turn less than the cohesion between the adhesive and the substrate, whereby particles are transferred from the applicator to the adhesive coated areas of the substrate without transfer of adhesive from the substrate to the applicator.

[0316] 31. The particle application apparatus as in clause 30, wherein the particle dispenser (2000) comprises at least one particle supply (210), and at least one transfer cylinder (230) for transferring particles from the, or a respective, particle supply, onto the surface of the applicator, prior to the surface coming into the contact with the substrate.

[0317] 32. The particle application apparatus as in clause 31, wherein the, or each, particle supply comprises a cartridge insertable into a respective supply chamber.

[0318] 33. The particle application apparatus as in clause 31 or 32, in which the particle dispenser comprises at least one primary transfer cylinder (220) receiving particles from the, or a respective, particle supply (210) and a secondary transfer cylinder (230) receiving particles from the primary transfer cylinder(s) and transferring the particles to the applicator (250).

[0319] 34. The particle application apparatus as in clause 33, wherein at least the surface (222) of the or each primary transfer cylinder (220) is made of a sponge-like material.

[0320] 35. The particle application apparatus as in clause 33 or 34, wherein the, or each, supply chamber and / or cartridge includes one or more members (212, 214) for mixing the particles, at least one of the members (214) being movable and extending so as to contact the surface (222) of associated primary transfer cylinders (220), whereby the mixed particles are evenly smeared to form a homogeneous coating of particles on the surface of the primary transfer cylinder.

[0321] 36. The particle application apparatus as in any one of clauses 33-35, wherein the particle dispenser comprises a housing (260) common to all the particle supplies and transfer cylinders, and wherein the secondary transfer cylinder comprises a cylinder disposed (230) in a respective chamber (200) in the housing so as to protrude partially through an opening in the housing, in order to contact the applicator (250), the latter being disposed outside the housing.

[0322] 37. The particle application apparatus as in clause 36, wherein at least one levelling blade (240) is disposed adjacent to the opening in the housing (260), the or each levelling blade controllably contacting the surface (232) of the secondary transfer cylinder (230) or particles thereon.

[0323] 38. The particle application apparatus as in clause 37, wherein the or each levelling blade (240) is configured to prevent egress of particles from the housing (260). 39. The particle application apparatus as in any one of clauses 36-38, wherein the hardness of the surface of the applicator (250) is lower than that of the surface (232) of the secondary transfer cylinder (230).

[0324] 40. The particle application apparatus as in clause 33 or 39, wherein the hardness of the surface of the applicator (250) is lower than that of the surface (232) of the secondary transfer cylinder (230) that is lower than that of the surface (222) of the primary transfer cylinder (220).

[0325] 41. The particle application apparatus as in any one of clauses 30-40, wherein, in operation, the applicator surface (252) is configured to rotate or circulate at a linear speed substantially identical to the linear speed of the substrate (10) upon rolling contact therebetween, so as to avoid slippage between the applicator (250) and the substrate.

[0326] 42. The particle application apparatus as in any one of clauses 31-41, wherein, in operation, the applicator surface (252) is rotated or circulated at an absolute linear speed at least 10% higher or lower than the linear speed of at least one of the transfer cylinders (220, 230), so as to enable slippage between surfaces upstream of the applicator (250) and rubbing of the particles prior to rolling contact between the applicator (250) and the substrate (10).

[0327] 43. The particle application apparatus as in any one of clauses 30-42, further comprising a drive mechanism (256) for urging the particle dispenser (2000) into rolling contact with a surface (252) of the applicator (250), wherein, in operation, the drive mechanism (256) is configured to disengage the dispenser from the applicator whilst the drive mechanism (254) is urging a surface of the applicator into rolling contact with the surface of the substrate.

[0328] 44. A particle application apparatus for applying particles to a substrate (10) which is coated in at least selected areas with an adhesive, the apparatus comprising: a) an applicator having the form of a cylinder (230) configured to make rolling contact with the surface of the substrate, b) a drive mechanism (256) for urging a surface (232) of the applicator into rolling contact with the surface of the substrate, and c) a particle dispenser for applying to at least a section of the applicator surface that is to make rolling contact with the substrate a uniform multilayer coating of the particles to be applied to the substrate, wherein the cohesion between the overlying layers of particles coating the surface of the applicator is less than the cohesion of the particles to the adhesive on the substrate, the latter cohesion being in turn less than the cohesion between the adhesive and the substrate, whereby particles are transferred from the applicator to the adhesive coated areas of the substrate without transfer of adhesive from the substrate to the applicator.45. The particle application apparatus as in clause 44, wherein the applicator cylinder (230) is mounted within a housing (260) further containing at least one particle supply (210), and at least one transfer cylinder (220) for transferring particles from the, or a respective, particle supply, onto the surface (232) of the applicator.

[0329] 46. The particle application apparatus as in clause 45, wherein the applicator cylinder (230) is disposed in a respective chamber (200) in the housing (260) so as to protrude partially through an opening in the housing, in order to contact the substrate (10).

[0330] 47. The particle application apparatus as in clause 45 or 46, wherein the, or each, particle supply comprises a cartridge insertable into a respective supply chamber.

[0331] 48. The particle application apparatus as in any one of clauses 45-47, wherein at least the surface (222) of the or each transfer cylinder (220) is made of a sponge-like material.

[0332] 49. The particle application apparatus as in clause 47 or 48, wherein the, or each, supply chamber and / or cartridge includes one or more members (212, 214) for mixing the particles, at least one of the members (214) being movable and extending so as to contact the surface (222) of associated transfer cylinders (220), whereby the mixed particles are evenly smeared to form a homogeneous coating of particles on the surface of the transfer cylinder.

[0333] 50. The particle application apparatus as in any one of clauses 46-49, wherein at least one levelling blade (240) is disposed adjacent to the opening in the housing (260), the or each levelling blade controllably contacting the surface (232) of the applicator (230) or particles thereon.

[0334] 51. The particle application apparatus as in clause 50, wherein the or each levelling blade (240) is configured to prevent egress of particles from the housing.

[0335] 52. The particle application apparatus as in any one of clauses 48-51, wherein the hardness of the surface (232) of the applicator (230) is smaller than that of the surface (222) of the transfer cylinders (220).

[0336] 53. The particle application apparatus as in any one of clauses 44-52, wherein, in operation, the applicator surface (232) is configured to rotate or circulate at a linear speed substantially identical to the linear speed of the substrate (10) upon rolling contact, so as to avoid slippage between the applicator (230) and the substrate. 54. The particle application apparatus as in any one of clauses 45-53, wherein, in operation, the applicator surface (232) is rotated or circulated at an absolute linear speed at least 10% higher or lower than the linear speed of at least one of the transfer cylinders (220), so as to enable slippage between surfaces upstream of the applicator (230) and rubbing of the particles prior to rolling contact between the applicator and the substrate (10).

[0337] 55. Powder grains (e.g., for additive manufacturing), each powder grain being made of at least particles of a first material, particles of a second material and a binder maintaining said particles as powder grains, wherein: a) the powder grains have on average an equivalent diameter Doin a range of 1 micrometer (pm) to 100 pm; b) the particles of the first material have a first particle size distribution with an average diameter Dvi50 between 500 nanometer (nm) and 5 pm; c) the particles of the second material have a second particle size distribution with an average diameter Dv250 between 20 nm and 100 nm; a unitless ratio between Dvi50 and Dv250 (Dvi50 / Dv25ff) being in the range of 5 to 15; the particle size distribution being determined by laser diffractometry or by analysis of microscopy images and at least one of the first and second materials being optionally adapted to form model or support regions in a layer formable by additive manufacturing.

[0338] 56. The powder grains as in clause 55, the grains being deformable under modest pressure of 20 MPa and temperature of 50°C, such that grains deformed under said conditions have on average an equivalent diameter DD equal to or smaller than 60% of Do.

[0339] 57. The powder grains as in clause 55 or 56, wherein the first particle size distribution of the particles of the first material has a DvilO between 100 nm and 1 pm; and a Dvi90 between 1 pm and 10 pm.

[0340] 58. The powder grains as in clause 57, wherein the first particle size distribution of the particles of the first material further fulfils at least one: i- (D vi90-D vilff)ID vi50 is in a range of 0.2 to 2.0, 0.3 to 1.6, or 0.4 to 1.2; ii- (D vi90-D vi5ff)ID vi50 is in a range of 0.1 to 1.4, 0.15 to 1.2, or 0.2 to 1.0; and iii- vi50 is in a range of 0.1 to 1.4, 0.15 to 1.2, or 0.2 to 1.0. 59. The powder grains as in any one of clauses 55-58, wherein the second particle size distribution of the particles of the second material has a Dv210 between 10 nm and 30 nm; and a DV290 between 50 nm and 200 nm.

[0341] 60. The powder grains as in clause 59, wherein the second particle size distribution of the particles of the second material further fulfils at least one: i- (D V290-D v210)U) v250 is in a range of 0.3 to 3.0, 0.3 to 2.5, or 0.3 to 2.0; ii- (D V290-DV250 D v250 is in a range of 0.25 to 2.0, 0.4 to 1.8, or 0.5 to 1.5; and iii- (D V250-D y21 )U) y250 is in a range of 0.25 to 2.0, 0.4 to 1.8, or 0.5 to 1.5.

[0342] 61. The powder grains as in any one of clauses 55-60, wherein by total volume of the powder grains, the particles of the first material constitute between 40 vol.% and 60 vol.%, the particles of the second material constitute between 10 vol.% and 40 vol.%, and the binder constitute between 10 vol.% and 30 vol.%.

[0343] 62. The powder grains as in any one of clauses 55-61, wherein the binder is included at a proportion of 15% to 35% of the sum of the volume of the particles of the first and second material.

[0344] 63. The powder grains as in any one of clauses 55-62, wherein the first and second material are independently selected from a group consisting of metals (such as aluminum, carbonized iron, copper, gold, nickel, platinum silver, stainless steel, and tin), metal oxides (such as cupric oxide (CuO), cuprous oxide (CU2O), and ferric oxide (Fe2O3)), carbides (such as boron carbide (B4C), silicon carbide (SiC), titanium carbide (TiC), tungsten carbide (WC), and tungsten carbide cobalt (WCCo)), ceramics (such as alumina (AI2O3), boron nitride (BN), ferrous oxide (FeO), silicon nitride (Si3N4), titanium dioxide (TiCE), zirconia (ZrCh) and zirconium silicate (ZrSiC )) and combinations thereof, the melting temperature of the second material being lower than the melting temperature of the first material.

[0345] 64. The powder grains as in any one of clauses 55-63, wherein the binder is selected from a group consisting of polymers, such a polyvinyl pyrrolidones (PVP), polyvinyl alcohols (PVA), polyvinyl butyrals (PVB), polyamides (PA), polyacryl amide (PAM), poly(N- isoprolylacrylamide)s (PNIPAM), poly(acrylic acid)s (PAA), polymethacrylates (PMMA), polypropylenes (PP), polyethylenes (PE), poly(ethylene oxide)s (PEO), polyethylene terephthalates (PET), polyethylene glycols (PEG), sulfonated polyesters and poly(2-ethyl-2- oxazoline) (PEOX); sugars, oligosaccharides and polysaccharides, such as glucose, maltose, cellulose, hydroxy ethyl cellulose, cellulose acetate, amylose, chitosan, carnauba wax, agar agar, acrawax, and starch; and combinations thereof.

[0346] 65. The powder grains as in any one of clauses 55-64, further comprising at least one additive the presence of all additives not exceeding 5 vol.% by total volume of the powder grains, the, or each, additive being selected from a group consisting of plasticizers, surfactants, anti-oxidants, sintering facilitators, preservatives, pH modifiers, and organic acids.

[0347] 66. The powder grains as in any one of clauses 55-65, the particles of the second material being sinterable at a sintering temperature sufficiently low to substantially retain all of the binder during the sintering period of the grains.

[0348] 67. The powder grains as in clause 66, wherein the binder is substantially retained in the grains when subjected to sintering at a temperature of 200°C for 15 minutes.

[0349] 68. The powder grains as in any one of clauses 55-67, wherein at least one of the grains and the constituting particles are spheroidal.

[0350] 69. The powder grains as in any one of clauses 55-68, obtainable by spherical granulation of the particles of the first and second material with the binder whilst dispersed in a liquid, followed by elimination of said liquid, or by milling of a mixture comprising said materials, the mixture being substantially devoid of any liquid during milling.

[0351] 70. The powder grains as in any one of clauses 55-69, the grains having a porosity of less than 50%, less than 40%, less than 30% or less than 20%, as measurable by BET.

[0352] 71. The powder grains as in any one of clauses 55-70, the grains having a specific surface area between 50 and 500 m2 / g.

[0353] 72. The powder grains as in any one of clauses 55-71, for use in a particle application apparatus as in any one of clauses 30-54 and / or in a method as in any one of clauses 1-29 or appended method claims, the powder grains being crushable and optionally further deformable.

[0354] 73. A composition comprising a liquid and fibers having an average diameter Davenot exceeding 10 pm and a unitless aspect ratio HA between the average lengths Laveand diameters DaVe of the fibers comprised between 5 and 20, the fibers being present at a weight concentration by total weight of the composition between 40 wt.% and 60 wt.%, between 44 wt.% and 60 wt.%, or between 47 wt.% and 60 wt.%, the composition having a dynamic viscosity of 400 mPa s (one millipascal-second) or less, at at least one temperature between 40°C and 120°C, as measured using a Brookfield type viscometer, the liquid being optionally curable and the composition curable.

[0355] 74. The composition as in clause 73, wherein the average diameter Daveof the fibers is between 150 nm and 10 pm, between 150 nm and 7 pm or between 150 nm and 5 pm, the average length Laveis between 1 pm and 50 pm, and the aspect ratio (ASP= LaVe / Dure) is between 5 and 15, between 7 and 15, or between 7 and 12.

[0356] 75. The composition as in clause 73 or 74, wherein in presence of 0.1 wt.% of the fibers, the liquid has a viscosity not exceeding 1.2-fold the viscosity of the liquid in absence of the fibers, as measured at at least one temperature between 40°C and 120°C using a Brookfield type viscometer.

[0357] 76. The composition as in any one of clauses 73-75, the composition having a dynamic viscosity of 300 mPa s or less, 200 mPa s or less, or 100 mPa s or less, at at least one temperature between 40°C and 120°C, as measured using a Brookfield type viscometer.

[0358] 77. The composition as in any one of clauses 73-76, wherein the liquid is curable and after spreading of the curable composition and full curing thereof, the cured composition has, in a direction of spreading, a linear coefficient of thermal expansion CLTE between 5 xlO'6K'1and 30xl0'6K’1, between 10 xlO'6K'1and 30xl0'6K’1, or between 15 xlO'6K'1and 30xl0'6K’1, as measured by thermomechanical analysis.

[0359] 78. The composition as in any one of clauses 73-77, wherein the fibers include two populations, a first population of fibers having a first average diameter Di between 150 nm and 500 nm, between 150 nm and 400 nm, or between 150 nm and 350 nm; and a second population of fibers having a second average diameter D2 between 500 nm and 10 pm, between 500 nm and 8 pm, or between 500 nm and 6.5 pm; a unitless ratio DR between the average diameters D2 and Di (D2 / D1) being in the range of 3 to 70, in the range of 3 to 50 or in the range of 3 to 30; a size of the fibers being determined by analysis of microscopy images and averaged for at least 300 fibers.

[0360] 79. The composition as in clause 78, wherein the first population of fibers have a first average length Li between 1 pm and 30 pm, between 3 pm and 25 pm, or between 3 pm and 20 pm; and the second population of fibers have a second average length L2 between 5 pm and 50 pm, or between 5 pm and 40 pm; a unitless ratio LR between L2 and Li (L2 / L1) being in the range of 1 to 40, or in the range of 1 to 30. 80. The composition as in any one of clauses 73-79, wherein the liquid is curable and selected from a group consisting of modified or unmodified epoxy compounds (including epoxy acrylates), acrylates (including mono-, di- and tri-acrylates); urethane acrylates; polyether acrylates; vinyl ethers; polycyclic aromatic hydrocarbons; and combinations thereof.

[0361] 81. The composition as in clause 81 being a curable composition, wherein the modified or unmodified: a) epoxy compounds and epoxy acrylates are selected from a group comprising bisphenol- A based epoxy acrylate; amine modified bisphenol-A based epoxy acrylate, bisphenol-A diglycidyl ether di-acrylate, epoxyacrylate oligomers, epoxycyclohexylmethyl epoxycyclohexane and carboxylate7-oxabicyclo[4.1.0]hept-3-ylmethyl-7-oxabicyclo[4.1.0]heptane- 3 -carboxylate; b) mono-, di- and tri-acrylates are selected from a group comprising isobornyl acrylate, hexanediol diacrylate, tripropylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, and ethoxylated trimethylolpropane triacrylate; c) urethane acrylates are selected from a group comprising aliphatic urethane acrylate, aliphatic urethane diacrylate and aliphatic polyester urethane diacrylate; d) polyether acrylates are selected from a group comprising amine modified polyether acrylate, amine modified polyether diacrylate, and propoxylated (2PO) neopentyl glycol diacrylate; e) vinyl ethers are selected from a group comprising vinyl ether, diethylene-glycol divinyl ether, vinyloxyethoxy ethyl acrylate; and f) polycyclic aromatic hydrocarbons are selected from a group comprising benzocyclobutenes, benzocyclobutadienes, benzocyclooctatetraenes and derivatives thereof.

[0362] 82. The composition as in any one of clauses 73-81, wherein the fibers or the populations of fibers are each independently selected from fibers consisting of carbon, ceramics (including alumina and glass), natural polymers (including cellulose, chitosan and lignin), synthetic polymers (including polyesters, polypropylenes, fluoropolymers, such as polytetrafluoroethylene (PTFE), and polyamides, such as aramid and nylon, and combinations thereof.

[0363] 83. The composition as in any one of clauses 73-82, wherein the one or more populations of fibers are fibers consisting of glass, the glass fibers being selected from a group comprising E-glass, D-glass, and TEOS-based electro-spun glass. 84. The composition as in any one of clauses 73-83, further comprising beads having an average diameter not exceeding 5 pm and a unitless aspect ratio between the average longest and smallest dimensions comprised between 1 and 3, the beads optionally being present at a weight concentration by total weight of the composition of up to 10 wt.%.

[0364] 85. The composition as in clause 84, wherein the beads consist of glass, cellulose, ceramics, PTFE and combinations thereof.

[0365] 86. The composition as in any one of clauses 73-85, wherein the fibers have a specific surface area of at least 1.5 m2 / g and at most 20 m2 / g as measured by BET.

[0366] 87. The composition as in any one of clauses 73-86, wherein the fibers are made of a material having a specific gravity of at least 0.5 g / cm3and at most 5 g / cm3, at least 0.5 g / cm3and at most 2.5 g / cm3, or at least 1 g / cm3and at most 2.5 g / cm3.

[0367] 88. The composition as in any one of clauses 73-87, wherein the liquid is curable and after spreading of the curable composition and full curing thereof, the cured composition has, in a direction of spreading, a flexural strength between 200 MPa and 300 MPa, between 200 MPa and 400 MPa, or between 200 MPa and 500 MPa, as measured according to ASTM D6272.

[0368] 89. The composition as in any one of clauses 73-88, wherein the fibers are selected to provide to an object prepared therewith at least one property selected from mechanical reinforcement, thermal insulation or conduction, electrical insulation or conduction, modulation of thermal expansion, and radiation blocking or adsorption.

[0369] 90. The composition as in any one of clauses 73-89, further comprising at least one additive the presence of all additives not exceeding 10 wt.% by total weight of the composition, each additive being selected from a group consisting of curing initiators, curing catalysts, curing inhibitors, fire retardants, adhesion promoters, and viscosity modifiers, the additive being adapted to the curing method of the liquid if curable.

[0370] 91. The composition as in any one of clauses 73-90, wherein the liquid is curable by application of energy selected from heat, eBeam, IR and UV radiation.

[0371] 92. The composition as in any one of clauses 73-91, for use in additive manufacturing, the composition being either a curable composition remaining in cured form in a manufactured object, optionally serving as a fencing material or an insulating casing for a conductive pattern, or a temporary composition, optionally serving as removable support, separating material, sacrificial layer or support. 93. The composition as in any one of clauses 73-92, for use in a method as in any one of clauses 4-29, the composition serving as liquid second material.

[0372] 94. A process of forming a three-dimensional object comprising the steps of selectively forming and curing a layer of a curable composition as in any one of clause 73-92, whereby cured regions are formed on an underlying surface, and cyclically repeating the steps of selectively forming and curing a layer of said composition a plurality of times to obtain a three- dimensional object comprising a stack of cured regions.

[0373] 95. The process as in clause 94, further comprising prior to the formation of cured regions in each cycle steps including: a) selectively applying particles in selected areas of an underlying surface; and b) compacting the applied particles.

[0374] 96. The process as in clause 94 or 95, wherein the particles are applied with a particle application apparatus as in any one of clauses 30-54.

[0375] 97. The process as in any one of clauses 94-96, further comprising following the formation of cured regions in each cycle, steps including: levelling of the cured regions and / or of the selected areas of compacted particles, whereby a continuous flat surface is formed, optionally for a subsequent cycle.

[0376] 98. A three-dimensional object, or one or more parts thereof, including compacted layers of particles.

[0377] 99. A three-dimensional object, or one or more parts thereof, formed by a method as in any one of clauses 1-29 or appended method claims or by a process as in any one of clauses 94- 97 or using a printing system as claimed in any one of the appended system claims, the object or parts thereof including at least regions comprising compacted layers of particles or stacks of cured regions.

[0378] 100. The three-dimensional object, or one or more parts thereof, as in clause 98 or 99 wherein particles constituting the compacted layers are as in any one of clauses 55-72, and / or the cured regions are made of a composition as in any one of clauses 73-92.

[0379] 101. The three-dimensional object, or one or more parts thereof, as in any one of clauses 98-100 comprising compacted layers of particles and stacks of cured regions in complementary areas, wherein the particles consist of a conductive material and the cured regions are made of an insulating material, the particles forming at least one circuit embedded in the insulating material. 102. A printed circuit board comprising at least one circuit of conductive material embedded in an insulating substance as in any one of clauses 98-101, two or more circuits, if present, being optionally connected one to another by vias formed by a method as in any one of clauses 1-29 or appended method claims.

[0380] It is appreciated that certain features of the disclosure, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the disclosure, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination or as suitable in any other described embodiment of the disclosure. Certain features described in the context of various embodiments are not to be considered essential features of those embodiments, unless the embodiment is inoperative without those elements. None of the specifically disclosed embodiments should be considered limiting, being provided for the sake of illustration. Many other alternatives, modifications and variations of such embodiments will occur to those skilled in the art based upon Applicant’s disclosure herein. Accordingly, it is intended to embrace all such alternatives, modifications and variations and to be bound only by the spirit and scope of the disclosure and any change which comes within their meaning and range of equivalency.

[0381] In the description and claims of the present disclosure, each of the verbs “comprise”, “include” and “have”, and conjugates thereof, are used to indicate that the object or objects of the verb are not necessarily a complete listing of features, members, steps, components, elements or parts of the subject or subjects of the verb. Nevertheless, it is contemplated that the compositions of the present teachings also consist essentially of, or consist of, the recited components, that the methods of the present teachings also consist essentially of, or consist of, the recited process steps, and that the apparatus or system of the present teachings also consist essentially of, or consist of, the recited devices.

[0382] Positional or motional terms such as “upper”, “lower”, “right”, “left”, “bottom”, “below”, “lowered”, “low”, “top”, “above”, “elevated”, “high”, “vertical”, “horizontal”, “front”, “back”, “backward”, “forward”, “upstream” and “downstream”, as well as grammatical variations thereof, may be used herein for exemplary purposes only, to illustrate the relative positioning, placement or displacement of certain components, to indicate a first and a second component in present illustrations or to do both. Such terms do not necessarily indicate that, for example, a “bottom” component is below a “top” component, as such directions, components or both may be flipped, rotated, moved in space, placed in a diagonal orientation or position, placed horizontally or vertically, or similarly modified.

[0383] As used herein, the singular form “a”, “an” and “the” include plural references and mean “at least one” or “one or more” unless the context clearly dictates otherwise. As used herein, the term at least one of A and B is intended to mean either A or B, and may mean, in some embodiments, A and B. Unless otherwise stated, the use of the expression “and / or” between the last two members of a list of options for selection indicates that a selection of one or more of the listed options is appropriate and may be made.

[0384] The word “exemplary” is used herein to mean “serving as an example, instance or illustration”. Any embodiment described as “exemplary” is not necessarily to be construed as preferred or advantageous over other embodiments and / or to exclude the incorporation of features from other embodiments.

[0385] As used herein, unless otherwise stated, adjectives such as “substantially”, “approximately” and “about” that modify a condition or relationship characteristic of a feature or features of an embodiment of the presently disclosed subject matter, are to be understood to mean that the condition or characteristic is defined to within tolerances that are acceptable for operation of the embodiment for an application for which it is intended, or within variations expected from the measurement being performed and / or from the measuring instrument being used. For example, when the term “about” or “approximately” precedes a numerical value, it may indicate + / -15%, or + / -10%, or even only + / -5%, or any other suitable + / - variation within such ranges, and in some instances may indicate the precise value. Furthermore, unless otherwise stated, the terms (e.g., numbers) used in an embodiment of the presently disclosed subject matter, even without such adjectives, should be construed as having tolerances which may depart from the precise meaning of the relevant term but would enable the embodiment or a relevant portion thereof to operate and function as described, and / or as understood by a person skilled in the art.

[0386] To the extent necessary to understand or complete the present disclosure, all publications, patents, and patent applications mentioned herein, including in particular the applications of the Applicant, are expressly incorporated by reference in their entirety as is fully set forth herein.

[0387] Certain marks referenced herein may be common law or registered trademarks of third parties. Use of these marks is by way of example and shall not be construed as descriptive or limit the scope of this disclosure to material associated only with such marks.

Claims

CLAIMS1. A printing system (1400, 1500) for printing of a three-dimensional object by superposition of compacted layers, the system comprising: a) a transport mechanism (12, 52, 630) comprising a movable carrier (600) adapted to displace a backing surface (10, 620) along a direction of travel; b) an adhesive application module (14, 30, 700, 1000) adapted to render tacky desired foreground regions of the backing surface, or of a compacted layer previously formed thereon; c) a first dispensing module (16, 34, 2000) for applying model particles to adhere selectively to the regions rendered tacky; d) a second dispensing module (20, 38, 740, 2000) for applying a support material to coat at least regions of the backing surface, or of a compacted layer previously formed thereon, not coated with the model particles; and e) at least one compacting module (40, 42, 3000) for compressing the model particles and / or the support material to form thereon a compacted layer or a part thereof; the transport mechanism serving to displace the movable carrier to pass cyclically through the adhesive application, dispensing and compacting modules so as to form superposed compacted layers on the movable carrier.

2. The printing system as claimed in claim 1, wherein the movable carrier (600) of the transport mechanism (12, 52, 630) is configured to displace the backing surface (10, 620) in at least one of a positive and negative direction along i) a linear X-axis parallel to the direction of travel, or an elliptical, oval or circular path, said path having at least one axis of symmetry substantially parallel to the X-axis, ii) a direction along a Y-axis traverse to the direction of travel, and iii) a direction along a Z-axis normal to a plane or curved surface comprising the X- and Y- axes.

3. The printing system as claimed in claim 1 or claim 2, wherein the adhesive application module (14, 30, 700, 1000) comprises one of a) a plurality of jetting nozzles adapted to eject an adhesive liquid onto the foreground regions, b) a plurality of EM radiation emitting elements adapted to selectively render tacky a thin film of dry adhesive formed on the backing surface, and c) a transfer member adapted to convey a mirror adhesive image transferable to the backing surface, each said adhesive application module being configured to form or transfer a desired adhesive image in the foreground regions, the adhesive image having a thickness of 10 pm orless, 5 pm or less, 2 pm or less, 1 pm or less, or 0.5 pm or less.

4. The printing system as claimed in any one of claim 1 to claim 3, the printing system further comprising a convection or radiation heater (14B, 18B, 710) located downstream of at least the adhesive application module (14, 30, 700, 1000), the heater being set to maintain a desired tackiness in the foreground regions suitable to adhere the model particles and / or to at least partially consolidate the superposed model particles by at least partial elimination of adhesive therebetween.

5. The printing system as claimed in any one of claim 1 to claim 4, the printing system further comprising an adhesive activator (14B, 32, 36) located downstream of at least the adhesive application module (14A, 30, 700, 1000), a physical and / or chemical activation provided by said adhesive activator being set to provide a desired tackiness to previously applied or transferred adhesive suitable to adhere particles dispensed downstream of the adhesive activator.

6. The printing system as claimed in any one of claim 1 to claim 5, the printing system further comprising an adhesive priming unit located upstream of at least the adhesive application module (14A, 30, 700, 1000), and being set to improve the adherence of the adhesive to an underlying surface.

7. The printing system as claimed in any one of claim 1 to claim 7, wherein the, or each, compacting module (40, 42, 3000) comprises an optionally heated rotating cylinder (310) configured to be controllably urged into rolling contact with at least the regions of the backing surface coated with the model particles, the rotating cylinder (310) being capable of applying a pressure in a range of 1 to 300 MegaPascal (MPa), at at least one temperature in the range of 20°C to 500°C.

8. The printing system as claimed in any one of claim 1 to claim 7, further comprising a cleaning device (730, 2020) for removing excess particles not in direct contact with the tacky regions.

9. The printing system as claimed in any one of claim 1 to claim 8, wherein the second dispensing module (20, 38, 2000) is adapted to apply the support material as support particles in background regions of the backing surface complementary to the foreground regions, said second dispensing module being located downstream of a second adhesive application module (18A) or of an adhesive activator (18B, 32, 36), each being adapted to render tacky the background regions.

10. The printing system as claimed in claim 9, wherein at least one of the adhesive application module (14, 30, 700), the second adhesive application module (18A) and the adhesive activator (14B, 18B, 32, 36) disposed downstream of the foregoing modules comprises a plurality of jetting nozzles capable of selectively forming or activating the desired adhesive images in the foreground or background regions.

11. The printing system as claimed in claim 9 or claim 10, wherein at least one of the adhesive application module (14, 30, 700), the second adhesive application module (18A) and the adhesive activator (14B, 18B, 32, 36) disposed downstream of the foregoing modules comprises a plurality of EM radiation emitting elements capable of selectively forming or activating the desired adhesive images in the foreground or background regions.

12. The printing system as claimed in any one of claim 9 to claim 11, wherein the adhesive activator (14B, 18B, 32, 36) is a conduction or radiation heater adapted to non-selectively activate an adhesive image previously formed in foreground and / or background regions of the backing surface.

13. The printing system as claimed in any one of claim 1 to claim 8, wherein the second dispensing module (740) is adapted to apply the support material as a curable liquid after one or more cycles of applying the model particles, said second dispensing module optionally comprising a liquid levelling device (742) to level the liquid.

14. The printing system as claimed in claim 13, further comprising a curing station (64, 750) adapted to cure the curable support liquid into a solid support.

15. The printing system as claimed in any one of claim 1 to claim 14, further comprising an additional dispenser adapted to apply an additional material on model particles, on support material, thereupon, thereunder and / or therebetween.

16. The printing system as claimed in claim 15, wherein the additional dispenser is adapted to selectively apply a separating material, said dispenser being operative A) to apply a sacrificial layer or dispense a sacrificial support prior to a first cycle of application of model particles, and / or B) to apply separating borders externally to the foreground regions of model particles after one or more cycles of applying said particles and prior to applying the support material.

17. The printing system as claimed in any one of claim 1 to claim 16, further comprising a levelling device (66, 760, 4000) adapted to mill, grind, or polish an outer surface of a compacted layer to provide an even continuous surface between each cycle and / or following a last cycle, said levelling being optionally set to expose model particles compacted in apreceding cycle.

18. The printing system as claimed in any one of claim 1 to claim 17, further comprising at least one of an inspecting device (770) and a consolidating device, the consolidating device optionally being a sintering device (720).

19. A method of 3D printing which comprises forming a plurality of superposed layers within which at least each intermediate layer formed on an underlying layer is composed, within an area bounded only by an outer perimeter, of one or more materials, wherein each intermediate layer that comprises more than one material is formed by: a) depositing at least one coating of a first material on selected first regions within the outer perimeter by:(i) selectively applying an adhesive to, or selectively activating an adhesive in, the selected first regions, and(ii) adhering particles to the adhesive in the selected first regions; b) subsequently depositing a coating having a different composition from the previously applied coating(s) on all remaining regions within the outer perimeter of the intermediate layer not occupied by the first material; c) compacting at least the particles of the first material of each layer prior to the deposition of an overlying layer; and d) following application of the coatings over all the regions within the outer perimeter, ensuring that the coatings constituting the intermediate layer provide an even continuous surface onto which the overlying layer can be deposited.

20. The method as claimed in claim 19, wherein coating of the remaining regions of each intermediate layer is achieved by application or activation of an adhesive within said remaining regions and adhesion of particles thereto, at least one of the adhesive and the particles of the coating applied to said remaining regions being different from the adhesive and the particles of coating applied to the first regions.

21. The method as claimed in claim 20, wherein the particles of the remaining regions are compacted during and / or after compaction of the particles of the selected first regions, the compaction of all particles serving to provide the even continuous surface.

22. The method as claimed in claim 19, wherein coating of the remaining regions of each intermediate layer is achieved by application of a second material as a liquid within theperimeter, the liquid second material being applied after one or more cycles of deposition of the first material.

23. The method as claimed in claim 22, wherein following application of the liquid second material, the second material is solidified optionally following active levelling of the liquid with one or more levelling members, at least one levelling member being further optionally vibrated during levelling; the liquid second material optionally being a curable resin that is solidified by curing.

24. The method as claimed in any one of claim 19 to claim 23, wherein the step of ensuring that the coatings constituting the intermediate layer provide an even continuous surface includes removing at least part of any coating of remaining regions overlying the selected first regions, by milling, grinding, and / or abrasion.

25. The method as claimed in any one of claim 19 to claim 24, wherein the coating of the regions is deposited in one cycle and at least the particles of the first material are adhered to a selectively activated adhesive applied to the entire surface of the underlying layer, and wherein the selective activation is a chemical and / or a physical activation, the latter comprising application of energy by heat conduction or radiation.

26. The method as claimed in any one of claim 19 to claim 24, wherein at least the particles of the first material deposited in the selected first regions of each cycle are adhered to an adhesive that is selectively applied to the underlying layer or an underlying coating by jetting, by use of a mask, or by transfer of a selective adhesive image.

27. The method as claimed in any one of claim 19 to claim 26, wherein prior to applying an adhesive at least on the selected first regions, and / or on the remaining regions, an adhesive priming substance is applied at least on said regionsand / or an adhesive masking substance is applied at least in areas adjacent to said regions.

29. The method as claimed in any one of claim 19 to claim 28, wherein following application of particles to an activated adhesive and / or compaction of the particles, surplus particles not in direct contact with the adhesive are removed.

30. The method as claimed in any one of claim 19 to claim 29, wherein compacting of regions formed by application of particles includes applying a pressure in a range of 1 to 300 MegaPascal (MPa), the compaction optionally including raising the temperature of the particles to be compacted to at least one temperature in the range of 20°C to 500°C, the applied pressure and / or heat being optionally controllably modified for each coating or layer being compacted.

31. The method as claimed in any one of claim 19 to claim 30, wherein compacting is effected by a rotating cylinder controllably urged into rolling contact with the coating(s) to be compacted, the compressive force applied to the particles being optionally sufficient to cause plastic deformation of the particles in at least a part of the intermediate layer and the rotating cylinder being further optionally vibrated during compaction.

32. The method as claimed in any one of claim 19 to claim 31, further comprising applying a sacrificial first layer or disposing a sacrificial support onto a surface prior to forming a first intermediate layer.

33. The method as claimed in any one of claim 19 to claim 32, wherein when the layers superposed in a Z-direction comprise in a plan perpendicular to the Z-direction a plurality of separated patterns, each pattern being in distinct first regions, the method further comprises applying a separating material between the patterns, the separating material optionally being a removable material, further optionally being the same as a material adapted to form a sacrificial first layer onto a surface prior to forming a first intermediate layer.

34. The method as claimed in any one of claim 19 to claim 33, wherein following formation of all the layers, one of the materials is removed to leave a three-dimensional shape composed of the remaining materials and having voids corresponding to regions previously occupied by the removed material.

35. The method as claimed in claim 34, wherein the one material is removed by at least one of: a) a chemical treatment, the chemical treatment optionally adapted to solubilize the said one material; and b) a physical treatment, the physical treatment optionally including a mechanical treatment to dislodge particles of the said one material, or a thermal treatment to melt the said one material.

36. The method as claimed in any one of claim 19 to claim 35, further comprising consolidating the particles of the first material one with the others, the consolidation being by application of energy, said energy being optionally applied following the compacting of only some of the superposed layers.

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