WO2017189306A1 - 3-dimensional printing - Google Patents

Abstract

The present disclosure relates a method of 3-dimensional printing a printed part. The method comprises printing an inkjet dopant composition at selected locations on a layer of build material comprising polymer particles. The inkjet dopant composition comprises a dopant dispersed or dissolved in a liquid carrier. Polymer particles at selected areas of the layer of build material are then fused to form a fused polymer layer comprising the dopant. The selected areas of the layer of build material include areas of the layer of build material that have not been printed with the inkjet dopant composition.

Description

3-DiMENSIO AL PRINTING'

BACKGROUND

[OOOI3 3-dimensional (3D) printing or additive manufacturing refers to a printing process in which successive layers of material are formed under computer control to create an object. Various methods of 3D printing have been developed, including heat-assisted extrusion, selective laser sintering (SIS), fused deposition modeling (FDM), high speed sintering (HSS) and photolithography.

BRIEF DESCRIPTION OF THE DRAWINGS

£800 1 Various features will be described, by way of example only, with reference to the following figures, in which:

[00031 FIG. 1 is a schematic view of an example of a 3-dimenslona! printing system;

[0004} FIG. 2 is a cross-sectional view of a layer of thermoplastic polymer powder with a dopant printed on a portion of the layer in accordance with examples of the present disclosure;

[ OQ53 F!G, 3 i cross-sectional view of the layer of FIG. 2 after the layer has been fused in accordance with examples of the present disclosure;

[00083 4 is a perspective view of a 3-dimensional printed part having a dopant composite layer, in accordance with examples of the present disclosure; and

[00073 F! 3, 5 is a plan view of the 3-dimensiona! printed part of FIG. 4 where the dopant composite layer is a photoiumsnescenf composite layer in a photoluminescent state, in accordance with examples of the present disclosure.

[000S3 Fie, 8 is an example schematic representation of a GRIN fens stack or assembly that can be prepared in accordance with examples of the present disclosure; and

[00093 F!G. 7 provides an example depicting effective capacitance increase, and;

effective refractive index increase, based on increasing concentration or number density of dielectric nanoparticles printed accordance with the present disclosure. DETAILED DESCRIPTION

[0010] It is to be understood that this disclosure is not limited to the particular process steps and materials disclosed herein because such process steps and materials may vary. It is also to be understood that the terminology used in this disclosure is used for the purpose of describing particular examples only . The terms are not intended to be limiting because the scope of the present disclosure is intended to be limited only by the appended claims and equivalents thereof.

0011| ft is noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the* include plural referents unless the context clearly dictates otherwise.

[00123 As used herein, "liquid vehicle¹' or "ink vehicle^™ refers to a liquid in which additive is placed to form an Inkjet composition. A wide variety of liquid vehicles may be used with the systems and methods of the present disclosure, A variety of different agents, including, surfactants, solvents, co-solvents, anti-kogation agents, buffers, foiocides, sequestering agents, viscosity modifiers, and surface- active agents may be dispersed o dissolved in the liquid vehicle.

[00133 The term "fusing agent" is used herein to describe agents that may be applied to particulate build material, and which may assist in fusing the build materia! to form a layer of a 3D part. Heat may be used to fuse the build material, but the fusing agent can also assis in binding powder together, and/or in generating heat from electromagnetic energy. For example, a fusing composition may include a fusing agent that can bind the build material together in preparation for heating to fuse the materials together, or may be an additive tha becomes energized or heated when exposed to a frequency or frequencies of electromagnetic radiation. Any additive that assists in fusing particulate build material to form the 3D printed part can be used.

[00143 As used herein, "jet," "lettable," "jetting," or the like refers to compositions that are ejected from jetting architecture, such as Inkjet architecture, Inkjet architecture can include thermal or piezo dro on demand architecture, as well as continuous Inkjet architecture. Additionally, such architecture can be configured to print varying drop sizes _» for example, less than SO picolitres (pi), less than 40 p!, less than 30 pL less than 20 pi, less than 10 p!. In some examples, the drop size may be 1 to 40 pi, for example, 3 or 5 to 30 picolitres.

[0015] A "voxel" is the basic volumetric building block used to fabricat three- dimensional objects, Mathematically, a voxel is determined by two spatial parameters in the x~y coordinate plane and a third parameter which determines th voxel's depth, z. Each layer printed has as many voxeis as can be printed, the minimum size of the voxel being limited the drop size of the printed fluid.

0016J As used herein, the term "substantial" or "substantially* when used in reference to a quantity or amount of a material, or a specific characteristic thereof, refers to an amount that is sufficient to provide an effect that the material or characteristic was intended to provide. The exact degree of deviation allowable may in some cases depend on the specific context.

[0017J As used herein, the term "about" is used to provide flexibility to a numerical range endpoint by providing that a given value may be "a little above* or "a iittie beiovv" the endpoint. The degree of flexibility of this term can be dictated by the particular variable and determined based on the associated description herein.

[00183 As used herein, a plurality of items, structural elements, compositional elements, and/or materials may be presented in a common !ist for convenience. However, these lists should be construed as though each member of the list is individually identified as a separate and unique member. Thus, no indi vidua! member of such list should be construed as a de facto equivalent of any other member of the same list solely based on their presentation in a common group without indications to the contrary,

[00193 Concentrations, amounts, and other numerical data may be expressed or presented herein in a range format, It is to be understood that such a range format is used merely for convenience and brevity and thus should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include individual numerical values or sub-ranges encompassed within that range as if each numerical vaiue and sub-range is explicitly recited. As an illustration, a numerical range of "about 1 wf% to about 5 wt%" should be interpreted to include not only the explicitly recited values of about 1 wt% to about 5 wt%, but also include individual values and sub-ranges within the indicated range. Thus, included i this numerical range are individual values such as 2, 3.5, and 4 and sub-ranges such as from 1-3, from 2-4, and from 3-5. etc. This same principle applies to ranges reciting oniy one numerical value. Furthermore, such an Interpretation should apply regardless of the breadth of the range or the characteristics being described. [0020] The present disclosure relates a method of 3-dimensionaS printing a printed part. The method comprises printing an Inkjet dopant composition at selected locations. on a layer of build material comprising poiymer particies. The Inkjet dopant composition comprises a dopant dispersed or dissolved in a liquid canier. Poiymer particles at selected areas of the layer of build materiai are then fused to form a fused polymer layer comprising the dopant. The selected areas of the layer of build materiai include areas of the layer of build materiai that have not been printed with the Inkjet dopant composition,

[0021 J The method may further comprise forming a further layer of build material over the fused polymer layer comprising the dopant. Poiymer particies at selected areas of the further layer of build materiai may be fused to form a fused poiymer layer that is devoid of dopant, Alternatively, an Inkjet dopant composition may be printed on the further layer of build materia! prior to the fusing step. Polymer particles at selected areas of the further layer of build materia! may then be fused to form a further fused polymer layer comprising the dopant,

[00223 The present disclosure also relates to a 3-dimensional printing material set comprising a particulate build materia! comprising thermoplastic polymer particles. The set also comprises an Inkjet dopant composition comprising a dopant dispersed in a liquid carrier. The dopant comprises particles (e.g. nanoparticles) that are selected from at least one of ^' photoiuminesceftt particles, dielectric particies, magnetic particles, ceramic particles, semi-conductor particies, and electrically-conducting particies. The Inkjet dopant composition also comprises an Inkjet fusing composition comprising a fusing agent capable of absorbing electromagnetic radiation to produce heat. In some examples, the thermoplastic polymer particies have an average particle size of 10 to 100 μηι.

[0023] (n S-dimensional printing, a layer of build material comprising poiymer particles may be applied e.g. to a print platform. Selected areas of the layer of build materiai may then be fused to form a solid layer. In some examples, a fusing composition may be printed onto the selected areas of the layer of build material. Fusing agent in the fusing composition may cause the build materia! in the selected areas to fuse to form a solid layer. A new layer of build materiai may then be applied over the solid layer and the process repeated until a complete 3-D part is printed.

[0024] In the present disclosure, it has been found that dopants can be introduced at specific locations within the printed part by Inkjet printing. For example, because droplet size and print location can be controlled, Inkjet compositions containing dopants can be printed in selected amounts at selected locations over the unfused polymer layer. These selected locations may be selected by computer control. Thus, specific voxels may be selected for printing. When the polymer is fused, the dopants become incorporated into the layer at the selected locations. The fused polymer layer containing or incorporating the dopant may foe a doped composite layer or dopant composite layer. Dopants can be selected to provide e.g. conductivity, photoiuminescenee, magnetism, elasticity and/or tensile strength at specific locations, allowing characteristics of the printed part to be tailored at a voxel level . The doped build material may be a doped composite material .

[0025J In some examples, the dopant composition is printed droplet by droplet, wherein each droplet has a volume of 1 to 50 pi, for example, 2 to 30 pi or 6 to 20 pi. This can allow the dopant to be printed, in for example, in patterns (e.g. intricate patterns) throughout the printed part,

[0026] In some examples, the dopant may become embedded in the printed part at selected locations. The dopant may be present at the outer surface of the printed part as well as at at least one location embedded within the printed part. In some examples, the dopant may be present at at Ieasi one location embedded within the printed part. f¾G27J In some examples, the printed part comprises regions comprising the dopant and regions in which the dopant is absent. The regions comprising the dopani may differ in at least one property from the regions in which the dopant is absent, wherein the at least one property is selected from at least one of conductivity, dielectric permittivity, magnetic permeability, refractive index, photoiuminescenee, tensile strength and Young's modulus.

Build material

[0028] Any suitable build material may be employed in the present disclosure. The build material comprises polymer particles or powder, for example, thermoplastic polymer particles or powder. The particles may have an average particle size from 10 to 100 pm, for example, 20 to 80

present disclosure, "average" with respect to properties of particles refers to a number average unless otherwise specified.

Accordingly, "average particle size" refers to a number average particle size.

Additionally, "particle size" refers to the diameter of spherical particles, or to the longest dimension of non-sphericai particles. Particl size may be determined by any suitable method, for example, by dynamic laser scattering or laser diffraction spectroscopy. An example of a^■commercially available instrument suitable for determining particle size may be Masferstzer© by Maivern® Instruments.

[00291 ^ⁿ certain examples, the polymer particles can have a variety of shapes, such as substantially spherical particles onrreguSarly-shaped particles. In some examples, the polymer particles can be capable of being formed into 3D printed parts with a resolution of 10 to 100 pm, for example 20 to 80 pm. As used herein, "resolution" refers to the size of the smallest feature thai can be formed on a 3D printed part. The polymer particles can form layers from about 10 to about 100 pm thick, allowing the fused layers of the printed part to have roughly the same thickness. This can provide a resolution in the z~ axis direction of about 10 to about 100 pm. The polymer particies can aiso have. a sufficiently small particle size and sufficiently regular particle shape to provide about 10 to 100 resolution along the x~axis and y-axis.

[0030J In some examples, the polymer particles can be colorless. For example, the polymer powder can have a white, translucent, or transparent appearance. When used, for example, with a colorless fusing composition, such polyme particles can provide a printed part that is white, translucent, or transparent. In other examples, the polymer particles can be colored for producing colored parts. In still other examples, when the polymer powder is white, translucent, or transparent, color can be imparted to the part by a coloured fusing ink or another colored ink.

[00313 The polymer particles can have melting or softening point from about 7 ^*0 to about 350^CC. In further examples, the polymer can have a melting or softening point from about 150° C to about 20G°C . A variety of thermoplastic polymers with melting points or softening points in these ranges can be used. For exampie, the polymer powder can nylon 8 powder, nylon 9 powder, nylon 11 powder, nylon 12 powder, nylon 66 powder, nylon 812 powder, polyethylene powder, thermoplastic polyurethane powder, polypropylene powder, polyester powder, polycarbonate powder, polyether ketone powder, poiyacrylate powder, polystyrene powder, or combinations thereof. In a specific example, the polymer powder can be nylon 12, which ca have a melting point from about 175°C to about 200°C. In another specific example, the polymer powder can be thermoplastic polyurethane.

[0032] The polymer particles can also in som cases be blended with a filler. The filler can include inorganic particles such as alumina, silica^', or combinations thereof. When the particles fuse together, the filler particles can become embedded in the polymer, forming a composite material. In some examples, the filler can include a free-flow agent, ants-caking agent, or the like. Such agents can prevent packing of the powder particles, coat the powder particles and smooth edges to reduce inter-particle friction, and/or absorb moisture, in some examples, a weight ratio of thermoplastic polymer powder to filler particles can be from 10:1 to 1 :2 or from 5:1 to 1 :1.

Dopant Composition

[0G33| in the present disclosure, a dopant composition is used to introduce a dopant into the printed part. The dopant composition may be InkJet printed onto a laye of build material prior to fusing. In other words, the dopant composition may be printed onto unfuse build material. By Inkjet printing the dopant composition, the dopant

composition may be printed droplet-by-drop!et at specific locations, allowing dopant to be introduced at the voxel-level. Each droplet of dopant composition may have a volume of less than 50 pi, less than 40 pi, less than 30 pi, less than 20 pi, less than 10 pi. In some examples, the droplet size may be 1 to 40 pi, for example, 2, 3, 4 or 5 to 30 pi, for instance. 2, 3, 4 o 5 to 20 pi or 2, 3, 4 or 5 to 10 pi. In some examples, the dopant composition may be applied to unfused build material, for example, prior to application of an fusing composition over the build material.

[00341 Once the dopant composition is printed, the layer of buiid material may be fused at selected areas to a form a fused layer. Fusing may be performed under computer o digital control. These selected areas include areas that have been printed with the dopant composition and areas that are free from the dopant composition. In this way, dopant may be incorporated into the resulting fused layer at pre-determined locations in a pre-determined pattern. This can allow the properties of the printed part to be controlled and varied. For example, by selecting appropriate dopants and tailoring their concentration and/or location at each layer of build material, properties such as electrical conductivity, heat conductivity, magnetic properties, mechanical properties {e.g. tensile strength) or optical properties can be tailored accordingly.

[00353 n some examples, fusing may be carried out by applying a fusing composition to selected areas of the layer of build material and subjecting the build material to heat or electromagnetic radiation. The application of heat or electromagnetic radiation may cause the polymer of the build material to melt or soften in the areas where the fusing composition has been applied. The selected areas over which the fusing composition is applied may include areas that are printed with a dopant composition as well as areas 3 that are unprlnted or devoid of dopant composition.

[0036] The volume of dopant composition that is printed on the particulate build materia! may be varied. For exampie, when using a single dopant composition wit one concentration of dopant, applying more ink to a given voxel can result in a greater mass fraction of dopant, increasing mass fraction of dopant can be carried out by ejecting higher drop volumes, ejecting more drops at a given voxel, or by printing multiple passes of fluid at a single voxel location, tn another exampie, multiple dopant compositions can b prepared with different concentrations of dopants. The multiple dopant compositions can likewise he printed at different fluid volumes as well for additional flexibility.

£00373 ^"Ffte concentration of dopant throughout the printed part may be varied gradually, for example, to create a concentration gradient of dopant in at least one region of the printed pari. As a result, at least one property^' of the printed part may vary along a gradient. Fo example, the electrics! conductivity, heat conductivity, magnetic properties or optica! properties of the part may vary along a gradient in at least one region of the printed part. Alternatively,, the dopant may be printed at a fixed concentration such that the concentration of dopant is substantially constant throughout all dopant-printed areas of the printed part.

I0038J When the dopant composition is printed onto a layer of the build material, the dopant composition can penetrate into build material. As a result, the dopant (e.g.

particles, for instance, nanoparticies) can deposit on particles of the build material and/or deposit in the interstices between polymer particles. At large enough mass fractions, the microscopic physical properties of the doped voxel can be modified. By placing dopants, for exampie at predetermined concentration or at various concentrations (laterally and/or vertically) at a gradient along the structure being printed, parts having specific physical properties at specific locations can be produced. The concentration (e.g., mass fraction) of the dopant, or the pattern of dopant being printed, or both, can provide unique physical properties. Because these dopants can be printed digitally, they can be printed at any concentration and/or pattern desired to obtain a physical property (e.g. optica!, photoluminescent, magnetic, or electrical properties), for instance, at one or more specific locations within the printed pari,

[0039] In some examples, the dopant composition can include a fusing agent. In other examples, the photoluminescent ink can be printed with a separate fusing composition to facilitate fusing of the thermoplastic polymer. In either case, the temperature of the build material can be raised above the melting or softening point of the thermoplastic polymer so as to facilitate the fusing process.

[0040J Any suitable dopant may be employed. Sn some examples, the dopant takes the form of solid particles, for instance, nanopartscles. These particles may be dispersed in a liquid carrier, for example, in the presence of a surfactant. Suitable particles include photoluminescent particles, dielectric particles, magnetic particles, ceramic particles, semi-conductor particles, and electricaily-conducfjng particles polymer particles.

[0041] In some examples, the dopant is a photosensitive dopant. The photosensitive dopant may be a charge transport molecule. Examples of photosensitive dopants include p-diethylaminobenzaldehyde diphenyihydrazone, anti-9-isopropy!carbazole-3- carbal-dehyde diphenyihydrazone or tri-p-tolylamine. When exposed to a predetermined wavelength of electromagnetic radiation, photosensitive dopants undergo an irreversible molecular reconfiguration, which can change the electrical properties of the dopant, for example, by turning them on or off. Where a photosensitive dopant is used, therefore, it ma be possible to expose certain regions of the doped build material either in an unfused or fused state to predetermined wavelengths of electromagnetic radiation to turn the electrical properties of the dopant on or off. The predetermined wavelengths of electromagnetic radiation may be applied using a laser operated, for example, under laser control to induce the irreversible molecular reconfiguration in certain regions of the build material.

[00423 In some examples, the dopant is not a photosensitive dopant. Thus, m some examples, the dopant is not a charg transport molecule. In some examples, the dopant is not p-diethylaminobenzaldehyde diphenyihydrazone, anti-S-isopropyicarbazoSe-S- carbal-dehyde diphenyihydrazone or tri-p-toiy!amsne.

[0043] Suitable particles may have a particle size in the range of 1 to 200 nm.

Nanoparticles may have a particle size of 1 to TOO nm. in some examples, nanopartscles having a particle size of 1 to 80 nm, for example, 2 to SO nm or 3 to 20 nm are employed.

[00443 The dopant may be present in the dopant composition in an amount of 0,01 wt% to 10 wt%. In one example, the concentration of dopant in the dopant composition can be from 0.05 wt% to S wt%. In another example, the concentration can be from 0.1 wt% to 5 wt%. in yet another example, th concentration can be from 0.1 wt% to 3 wt%. In a particular example, the concentration can be from 0.5 wt% to 1.6 wt%.

p 4Sj Where the dopant is a photoluminescent agent, any agent that exhibits photoluminescence may be employed, "Photoiuminescence," as used herein, refers t an emission of light by a substance as a result of the absorbance of a photon by that substance. More specifically, absorption of a photon by a photo!uminescentagent can induce photoexcitation of the photoiuminescent agent. Photoexcitation refers to the excitation of electrons within the photoiuminescent agent due to the absorption of the photon. The photoexcitation of the photoiuminescent agent can be followed by a relaxation event, where the excited electrons relax back to a lower energy state. The relaxation of the excited electrons can be accompanied by the emission of a photon from the photoiuminescent agent. Typically, the photoiuminescent agent can absorb photons at a different wavelength of electromagnetic radiation than the wavelength of the emitted photon.

[0046} In some examples, these photoiuminescent agents can be "tuned" to photoexcit at wavelengths within the Ultra violet (UV) range and to photoiuminesce within the visible range. This can allow the photoiuminescent agent to remain covert until irradiated with a photoexciting wavelength of electromagnetic radiation. In other examples, the

photoiuminescent agent can be "tuned" to photoexcite at one wavelength within the visible range and to emit at a different wavelength within the visible range.

£00473 Non-limiting examples of photoiuminescent agents can include a

photoiuminescent pigment, a photoiuminescent dye, a quantum dot. the like, or combinations thereof, in some examples, the photoiuminescent agent can include a fluorescent agent, a phosphorescent agent, or a combination thereof. In some examples, photoiuminescent dyes can be enclosed within, distributed throughout, or otherwise associated with a particl (e.g. nanopartide}. in some examples, photoiuminescent pigments can include a photoiuminescent particle (e.g. nanoparticle). For example, a photoiuminescent pigment or dye can be coupled to a surface of a particle (e.g.

nanoparticle), embedded within the particle (e.g. nanoparticle), distributed throughout the particle (e.g. nanoparticle), or otherwise associated with a particle (e.g. nanoparticle).

[0048] Numerous photoiuminescent pigment and/or dyes can be used. Non-limiting examples can include europium doped strontium aluminates, thallium doped sodium iodides, activated alkaline earth metal sulfides, activated alkaline earth metal silicates, rhodamines, acridines, fluorines, cyanines, oxazines, phenanthridines, pyrrolopyrroSes, ben20xazo.ies, benzothiazoles, azo pigments, azo-metal complexes,

hisacetoacetaryiides, azomethines, ary!rrsethines, benzimidazolones, dtazopyrazoicnes, qulnacridones, qusnones, fSavanthrones, persnortes, isoindolines, isoindolinones, peryienes, phthalocyanines, metal-potha!acyanine complexes, porphyrins, metal- porphyrin complexes, polyenes, po!ymethines, sqyaraines, or combinations thereof. In one specific example, a photoluminescent dye can be fluorescein. Sn another specific example, a photoluminescent dye can be rbodamine 8. As previously described, dyes or pigments can be associated with nanopartictes. Non-limiting commercially available examples can include Fluoresbrite® microspheres, such as YG Carboxylate

Microspheres, YO Carboxylate Microspheres, NYG Carboxylate Microspheres, B8 Carboxylate Microspheres, and EU Carboxylate Microspheres available from

Polysciences, Inc.

[0049] Where the photoluminescent agent is a particulate (e.g., a photoluminescent pigment, photoluminescent nanoparticle, etc.), the photoluminescent agent can have a particle size from about 10 nm to about 400 nm or 500 nm, or from about 20 nm to about 200 nm or 300 nm, or from about 30 nm to about 70 nm or 120 nm.

JOOSOJ Quantum dots can also be used as a photoluminescent agent. Quantum dots can be very small semiconductor particles thai typically have a particle size of about 20 nm or less. Quantum dots can be made of a variety of semiconductor materials. For example, quantum dots can be made of a single element, such as silicon, germanium, and the like. Alternatively, quantum dots can be compounds of materials, such as indium phosphide, indium arsenide, zinc sulfide, lead sulfide, cadmium sulfide, lead selenide, cadmium selenide, the like, or combinations thereof. Other quantum dots that can be used include MH-VI quantum dots, including, for example CiilnS* or CulnSe_¾ quantum dots, where x may be 1 or 2. Non-limiting commercially available quantum dots can include Indium Phosphide Zinc Sulfide Quantum Dots in Water and Cadmium Selenide Zinc Sulfide Quantum Dots in Water from !MN-Labs, and Na.noDOT™ CIS-50Q and

NanoDOT™ CSS-700 from Voxtei, Inc.

[0OS1J Quantum dots can be prepared in a number of ways. For example, th quantum dots can be made of a single component with uniform composition throughout (e.g., silicone, zinc sulfide, etc.}. The photoiumineseence of these quantum dots can be tunable merely by adjusting the size of the quantum dot. In other examples, the quantum dots can foe prepared with a core material having a Sower band gap surrounded by a shell material having a higher band gap. As one example, the core materia! can be cadmium selenide and the shell materia! can be zinc sulfide. The photoiuminescence o these quantum dots can be tunable based on both particle size and the specific combination of core and/or shell materials, in other examples, the quantum dots can be prepared by alloying different quantum dots particles together, such as indium phosphide and zinc sulfide, or cadmium selenide and zinc sulfide, or any other suitable alloy of quantum dot particles. These quantum dots can also be tuned based on both size and the specific semiconductor used,

[0052| As previously described, quantum dots can typicaiiy have a particie size of about 20 nm or less. Generally, the larger the particle size of the quantum dot, the longer the photoiuminescent emission wavelength will be. Conversely, the smaller the particie size of the quantum dot, the shorter the photoSuminescent emission wavelength will be. In some examples, the quantum dote can have a particle size from about 2 nm to about 10 nm_* In other examples, the quantum dots can have a particle size from about 4 nm to about 8 nm. in other examples, the quantum dots can have a particle size from about 8 nm to about 14 nm.

[0053] In some examples, the dopants are dielectric particles (e.g. nanoparticies).

Dielectric particles may be used to alter the dielectric properties (e.g. capacitance) of a printed part at pre-determined locations. Because of the physical relationship between a material's dielectric constant and its refractive index, the optical properties {e.g.

refractive index) of a printed part may be varied by incorporating dielectric nanoparticies into the printed part at specific locations. Thus, by printing dielectric particles at specific locations, the local refractive index of each voxel can be varied. This may have applicability in Sens manufacture. For example, droplets of dopant composition comprising dielectric particles can be printed at the voxel level on a layer of polymer build material, and then the layer can be fused, thus forming a lens layer. This lens layer can be built upon to form a lens or a lens stack with optical spacers. By changi g the density of dielectric particles locally at the voxel level, the refractive index at various locations can also be changed, in other words, dielectric particies can be printed at the voxel level to predictably shift the effective dielectric constant of a polymer build material by controlling the mass fraction of dielectric particies per voxel. A gradient refractive inde (GRI ) lens may be formed by varying the effective refractive index (using different concentrations of dielectric particles) within each layer as appropriate to form the GRIN Sens. Lenses or lens stacks can be prepared by additive layering until a desired optical structure is^■formed. For optical (e.g. lens) applications, the build material may be formed of transparent polymer particles.

[0054] Example dielectric particles that can be used include, but are not limited to, SaTiOs, PMH-PT (e.g., 65/35), PbNbaOe, PLZT (e.g., 7/80/40), Si0_2t Ai₂0₃, Ta₂0₅, TiOz, SrTiO¾ Zr<¾, HfO¾. HfSiCM, La_aO¾ Y_SQ₃, a~ A10¾ GaCusTUGia, and/or La^Sro-aNiOi, to name a few. The particle size of the dielectric particles may be, for example from 1 nm to 100 nm, or from 1 nm to 50 nm, or from 5 nm to 30 nm, or from 20 nm to 100 nm, or from 50 nm to 100 nm in average particle size,

[00553 The dopant composition may comprise a liquid vehicle, in some examples, the liquid vehicle formulation can include water or consist of water.

[0056] In some examples, an additional co-solvent may also be present. In certain examples, a high boiling point co-solvent can be included in the dopant composition. The high boiling point co-soivent can be an organic co-soivent thai boils at a temperature higher than the temperature of the powder bed during printing. I some examples, the high boiling point co-solvent cars have a boiling point above 250 °C, In still further examples, the high boiiing point co-solvent can be present at a concentration from about 1 wt% to about 4 wt%.

[00571 Classes of co-solvents that can be used can include organic co-solvents including aliphatic alcohols,, aromatic alcohols, diois, glycol ethers, poiyglycoi ethers, caprolactams, formamides, acetamsdes, and long chain alcohols, Examples of such compounds include primary aliphatic alcohols, secondary aliphatic alcohols, 1 ,2- alcohols, 1 ,3-aScoho!s, 1 ,5-alcohols, ethylene glycol alkyi ethers, propylene glycol alky! ethers, higher homologs (Ce-Cis) of polyethylene glycol aikyi ethers, N-alkyi

caprolactams, unsubstituted caprolactams, both substituted and unsubstituted formamides, both substituted and unsubstituted acetamides, and the fike. Specific examples of solvents that can be used include, but are not limited to, 2~pyrro!idinone, N~ methylpyrro!idone, 2~hydiOxyethyl~2~pyfrolidone, 2-methyl-1 ,3-propanediol, fetraethylene glycol, 1 ,8-hexanediol, 1,5-hexanedioi and 1 ,5-pentanediol.

[0058] A surfactant, or combi ation of surfactants, can also be present in the dopant composition. Examples of surfactants include alky! polyethylene oxides, alky! phenyl polyethylene oxides, polyethylene oxide block copolymers, acetyleoic polyethylene oxides, polyethylene oxide (di)esters, polyethylene oxide amines, protonated

polyethylene oxide amines, protonated polyethylene oxide amides, dimethicone copo!yois, substituted amine oxides, and the like. The amount of surfactant added to the formulation of this disclosure may range from 0.01 wt% to 20 wt%. Suitable surfactants can include, but are not limited to, liponic esters such as Tergitol™ 15-S-12, Tergitol™ 15-S-7 available from Dow Chemical Company, LEG-1 and LEG-7; Triton™ X-100; Triton™ X-405 available from Dow Chemical Compan ; and sodium dodecyisulfate.

[00533 Various other additives can be employed t© optimize the properties of the dopant compositions for specific applications. Examples of these additives are those added to inhibit the growth of harmful microorganisms. These additives may be b cides, fungicides, and other microbial agents, which are routinely used in ink formulations. Examples of suitable microbial agents include, but are not limited to, NUGSEPT® (Nudex, Inc.), UCARCIDE™ (Union carbide Corp.), VANCIDE® .(R.T. VanderbiSi Co.), PROXEL® (iC! America), and combinations thereof.

[0060 Sequestering agents, such as EDTA (ethylene diamine tetra acetic acid), may be included to eliminate the deleterious effects of heavy metai impurities. Buffers may aiso b used to control the pH of the composition. Viscosity modifiers may also be present. Such additives can be present at from 0.01 wt% to 20 wt%,

Fusing Composition

[0061] Where a fusing composition is employed, the fusing composition (or "fusing ink") can contain a fusing agent that is capable of absorbing electromagnetic radiation to produce heat. The fusing agent can be colored or colorless, in some exarnpi.es, the fusing agent can be carbon black, near-infrared absorbing dyes, nea -infrared absorbing pigments, tungsten bronzes, molybdenum bronzes, metai nanoparticies, or combinations thereof.

|0062] The fusing composition may be Inkjet printed onto selected areas of the iayer of build material prior to fusing. The fusing composition may be applied to areas of the layer of buiid material that have been printed with dopant composition, a well as to areas of the iayer of build materia! that have not been printed with dopant composition. The fusing agent can have a temperature boosting capacity sufficient to increase the temperature of the polymer powder above the melting or softening point of the polymer powder. When the fusing ink is printed on a portion of the poiymer powder, the fusing agent can heat the printed portion to a temperature at or above the melting or softening point, while the portions of the polymer powder unprinted with fusing ink remain below the melting or softening point. This can allow the formation of a solid 30 printed part, while the loose powder can be easily separated from the finished printed part. Any dopant printed on the poiymer powder prior to application of the fusing composition may also become incorporated into the printed part.

[0063] The fusing agent may be an infrared absorbing, for example, a near-infrared absorbing dye. Examples of near-infrared absorbing dyes include tetraaryldiamine dyes, cyanine dyes, pthaSocyanine dyes, dithiolene dyes, and others. In further examples, the fusing agent can be a near-infrared absorbing conjugated poiymer such as poly{3,4- ethylenedsoxythiophene5-po y{sfyrenesuifonate) (PEDOT;PSS), a po!ytbSophene, polyfp- phenylene sulfide}, a polyansiine, a polyCpyrrole), a po!y(acetylene), poly{p-phenyfene vinylene), polyparaphenylene, or combinations thereof. As used herein, "conjugated" refers to alternating double and single bonds between atoms in a molecule. Thus, "conjugated polymer" refers to a poiymer that has a backbone with alternating double and single bonds, in many cases, the fusing agent can have a peak absorption wavelength in the range of 800 hm to 1400 nm,

[00643 ~^he fusing agent may also be an infrared absorbing, for example, a near-infrared absorbing pigment. A variety of near-infrared pigments can aiso be used. Non-limiting examples can include phosphates having a variety of counterions such as copper, zinc, iron, mag esium_s calcium, strontium, the like, and combinations thereof. Non-iimiting specific examples of phosphates can include s aO?, Jv PzCte, MsPgQio, Ms{P0 )¾

{Ρ(¾·>2, Μ2Ρ4ΟΊ.2» and combinations thereof, where represents a counterion having an oxidation state of +2, such as those listed above or a combination thereof. For example, ΜζΡ βτ can include compounds such as CuaPaO?, Cu MgPaQ?, Cu/ZnP₂0?, or any other suitable combination of counterions. It is noted that the phosphates described herei are not limited to counterions having a +2 oxidation state. Other phosphate counterions can also be used to prepare other suitable near-infrared pigments,

[00653 Additional examples of near-infrared pigments ca include siiicates. The siiicates can have the same or similar counterions as the phosphates. One non-iimiting example can include zSiQ*. MaS Os, and other silicates where M is a counterion having an oxidation state of +2. For example, the silicate MjSiaOs can include MgaSiiOs,

SVSg/CaSisOs, gCuSfeOe, CuzSbOs, Cu ZfiSfeOe, or other suitable combination of counterions. It is noted that the silicates described herein are not limited to counterions having a +2 oxidation state. Other siiicate counterions can also be used to prepare other suitable near-infrared pigments.

[0066] The amount of fusing agent in the fusing composition can vary depending o the type of fusing agent. In some examples, the concentration of fusing agent in the fusing composition can be from 0.1 wt% to 20 wt%. In one example, the concentration of fusing agent i the fusing ink can be from 0.1 wi% to 15 t%. in another example, the concentration can be from 0,1 wt% to 8 ^' wi%< in yet another example, the concentration can be from 0.5 wt% to 2 wt%. In a particular example, the concentration can be from 0.5 wt% to 1.2 wt%. [00673 in some examples, the fusing Ink can have a black or gray color due to the use of carbon black as the fusing agent. However, in other examples the fusing ink can be colorless or nearly colorless. The concentration of the fusing agent can be adjusted to provide a fusing ink in which the visible color of the fusing ink is not substantially altered by the fusing agent. Although some of the above described fusing agents can have low absorbance in the visible light range, the absorbance is usually greater than zero.

Therefore, the fusing agents can typically absorb some visible light, but their color in the visible spectrum can be minimal enough that it does not substantially impact th fusing composition's ability to take on another color when a colorant is added. The fusing agents in concentrated form can have a visible color, but the concentration of the fusing agents in the fusing ink can be adjusted so that the fusing agents may not be present in such high amounts that they alter the visible color of the fusing ink. For example, a fusing agent with a very Sow absorbance of visible light wavelengths can be included in greater concentrations compared to a fusing agent with a relatively higher absorbance of visible light. These concentrations can be adjusted based on a specific application with some experimentation.

[00683 In further examples, the concentration of the fusing agent can be high enough that the fusing agent impacts the color of the fusing ink, but Sow enough that when the ink is printed on the build material comprising the polymer particles or powder, the fusing agent does not impact the color of the powder. The concentration of the fusing agent can be balanced with the amount of fusing ink to be printed on the polymer powder so that the total amount of fusing agent printed onto the polymer powder can be low enough that the visible color of the polymer powder is not impacted. In one example, the fusing agent can have a concentration in the fusing ink such that after the fusing ink is printed onto the polymer powder, the amount of fusing agent in the polymer powder is from 0.0003 wt to 5 wt% with respect to the weight of the polymer powder,

[00693 Th fusing agent can have a temperature boosting capacity sufficient to increase the temperature of the polymer powder above the melting or softening point of the polymer powder. As used herein, "temperature boosting capacity'¹ refers to the ability of a fusing agent to convert electromagnetic radiation e.g. infrared or near-infrared light energy into thermal energy to increase the temperature of the printed polymer powder over and above the temperature of the unprinted portion of the polymer powder.

Typically, the polymer powder particles can be fused together when the temperature increases to the melting or softenin temperature of the poiymer. As used herein, "melting poinf refers to the temperature at which a polymer transitions from a crystalline phase to a pliable, amorphous phase. Some polymers do not have a single melting point, but rather have a range of temperatures over which the polymers soften. This range can be segregated into a lower softening range, a middle softening range, and an upper softening range. In the lower and middle softening ranges, the particles can coalesce io form a part while the remaining polymer powder remains loose. If the upper softening range is used, the whole powder bed can become a cake. The "softening point," as used herein, refers to the temperature at which the polymer particles coalesce while the remaining powder remains separate and loose. When the fusing ink is printed on a portion of the polymer powder, the fusing agent can heat the printed portion to temperature at or above the melting or softening point, while the unprinted portions of the polymer powder remain below the melting or softening point. This ai!ows the formation of a solid 3D printed part, while the loose powder can be easily separated from the finished printed part.

[00703 Although melting point and softening point are often described as the

temperatures for coalescing the polymer powder, in some cases the polymer particles can coalesce together at temperatures slightly below the melting point or softening point. Therefore, as used herein "melting point" and "softening point" can include temperatures slightly lower, such as up to about 20°C lower, than the actual melting point or softening point

[0071] In one example, the fusing agent can have a temperature boosting capacit from about 10-C to about 7Q*C for a polymer with a melting or softening point from about 100^'JC to about 350^aC. If the powder bed is at a temperature within about 1G°C to about 70^SC of the melting or softening point, then such a fusing agent can boost the

temperature of the printed powder up to the melting or softening point, while the unprinted powder remains at a lower temperature. In some examples, the powder bed can be preheated to a temperature from about 1 GX to about 70°C lower than the melting or softening point of the polymer. The fusing composition can then be printed onto the powde and the powder feed can be irradiated with a near-infrared Sight to coalesce the printed portion of the powder,

[0072] The fusing composition may comprise a liquid vehicle. The fusing agent may be dispersed in the liquid vehicle. In some examples, the liquid vehicle formulation can include water or consist of water.

[0073} In some examples, an additional co-solvent may also be present. In certain examples, a high^' boiling point co-solvent can be induded in the fusing composition. The high boiling point. co-solvent can he an organic co-solvent thai boils at a temperature higher than the temperature of the powder bed during printing, in some examples, the high boiiing point co-solvent can have a boiiing point above 250 °G. In stil! further examples, the high boiiing point co-solvent can be present at a concentration from about 1 wi% to about 4 t%.

[0074| Classes of co-solvents that can be used can include organic co-solvents including aliphatic alcohols, aromatic aicohols, diols, glycol ethers, poiygfyeo! ethers, caproiactams, formamides, acetamides, and long chain alcohols. Examples of such compounds include primary aliphatic alcohols, secondary aliphatic alcohols, 1 ,2- alcohols, 1 ,3-aicohols, 1 ,5-aicohois, ethylene glycol alky! ethers, propylene glycol aikyl ethers, higher homoiogs (Ce-Cw) of polyethylene glycol aikyl ethers, N~alkyi

caproiactams, unsubstituted caproiactams. both substituted and unsubstituted formamides, both substituted and unsubstituted acetamsdes, and the like. Specific examples of solvents that can be used include, but are not limited to, 2-pyrrolidinone, - methyipyrro!idone, 2-hydroxyethyi-2-pyrrolidone, 2~methy!-1 ,3-pro anediol, tetraeiliylene glycol, 1 ,8-hexanediol, 1 ,5-hexanediol and 1 ,5~pentanediol.

[007S] A surfactant, or combination of surfactants, can also be present in the fusing composition. Examples of surfactants include alkyi polyethylene oxides, aikyl phenyl polyethylene oxides, polyethylene oxide block copolymers, acetylenic polyethylene oxides, polyethylene oxide (di Jesters, polyethylene oxide amines, protonated

polyethylene oxide amines, protonated polyethylene oxide a ides; dimethieone copoiyols, substituted amine oxides, and the like. The amount of surfactant added to the formulation of this disclosure may range from 0,01 wt% to 20 wt%. Suitable surfactants can include, but are not limited to, lipontc esters such as Tergitol™ 15-8-12, Terglto!™ 1S-S-7 available from Dow Chemical Company, LEG-1 and LEG-7; Triton™ X-100; Triton™ X-405 available from Dow Chemical Company ; and sodium dodecySsu!fate,

[0076] Various other additives can be employed to optimize the properties of the fusing compositions for specific applications. Examples of these additives are those added to inhibit the growth of harmful microorganisms. These additives may be biocides, fungicides, and other microbial agents, which are routinely used in ink formulations. Examples of suitable microbial agents include, but are not limited to, NUOSEPT®

(Nudex, inc.), UGARC!DE™ (Union carbide Corp.), VANG!DE® (R.T. Vanderbilt Co.), PROXEL® (!C! America), and combinations thereof. [00773 Sequestering agents, such as EDTA (ethylene diamine tefra acetic acid), may be included to eliminate the deleterious effects of heavy metal impurities. Buffers may also be used to control the pH of the composition. Viscosity modifiers may also be present. Such additives can be present at from 0.01 wt% to 20 w %.

Colorant

[0078} In addition to dopant, colorant may be applied to the build material. Colorant may be applied to at least the outer surface of the printed part. The colorant may be visible to the naked eye and may be employed in sufficient amounts to impart a discernible colour to the printed part. The coloran may be a visible dye or a visible pigment,

[0079] Such colorants may be applied by printing an inkjet ink composition comprising a colorant onto the build material The colored Inkjet ink may be applied to at least portion of a layer of unfused polymer particles to impart colour to the printed part. A colored ink jet ink can include any suitable colorant, including dyes and/or pigments. This can allow for printing of full-color 3-dimensional parts. Suitable inkjet inks include cyan, magenta, yellow, and black inks. Coloured inkjet ink compositions ma be provided together with the build material, dopant composition and fusing composition as part of the 3~dimensionai printing materia! set.

[0080] Alternatively or additionally, colorants may be incorporated into the dopant composition and/or fusing composition described above. In some examples, the colorant can be present in an amount from 0.5 wt% to 10 wt% i the compositions. In one example, the colorant can be present in an amount from 1 wt% to 5 wt%. In another example, the colorant can be present in an amount from 5 wt% to 10 wt%.

[00-81] In some examples, the colorant can be a dye. The dye may be nonionic, cationic, anionic, or a mixture of ^"nonsonic, cationic, and/or anionic dyes. Specific examples of dyes that may be used include, but are not limited to, Sulforhodamine B, Acid Blue 1 3, Acid Blue 29, Acid Red 4, Rose Bengal, Acid Yellow 17, Acid Yellow 29, Acid Yellow 42, Acridine Yellow G, Acid Yellow 23, Acid Slue 9, Nitro Blue Tetrazolium Chloride

onohydrate or Nitro BT, Rhodamine 6G, Rhodamine 123, Rhodamine B, Rhodamine B Ssocyanate, Safranine D, Azure B_s and Azure B Eosinate, which are available from Sigma-ASdrich Chemical Company (St Louis, Mo ). Examples of anionic, water-soluble dyes include, but are not limited to, Direct Yellow 132, Direct Blue 199, Magenta 377 (available from !lford ACS, Switzerland), alone or together with Acid Red 52, Examples of water-insoluble dyes include azo, xanthene, methine, poSymethine, and anthraquinone dyes. Specific examples of water-insoiubie dyes include Grasoi® Blue GH, Grasoi® Pink, and Grasoi® Yeiiow dyes avaitabie from Ciba-Geigy Corp. Black dyes may include, but are not limited to. Direct Biack 154, Direct Biack 188, Fast .Black 2, Direct Black 171 , Direct Black 19, Acid Black 1 , Acid Black 191 , Mobay Black 5P, and Add Black 2,

[0082] ^ⁿ other examples, the coiorant can be a pigment. The pigment can be self- dispersed with a polymer, oligomer, or small molecule; or can be dispersed with a separate dispersanl Suitable pigments include, but are not limited to, the following pigments available from BASF: Pa!iogen®) Orange, Heiiogen® Biue L 6901 F,

Heiiogen®} Biue NBD 7010, Heiiogen® Blue 7090, Heiiogen® Blue L 7 Q1F,

Paliogen®) Blue L 6470, Heiiogen®) Green 8683, and Heiiogen® Green L 9140. The following biack pigments are available from Cabot: Monarch® 1400, Monarch® 1300, Monarch®) 1100, Monarch® 1000, Monarch®) 900, Monarch® 880, Monarch® 800, and Monarch®) 700. The following pigments are available from CiBA: Chromophtai®} Yellow 3G, Chromophial®) Yellow GR, Chromophtai®) Yellow 8G, Igrazin® Yeiiow SGT, Sgralite® Rubine 4BL, Monastrai® Magenta, Monastrai® Scarlet, Monastrai® Violet R, Monastrai® Red B, and Monastral® Violet Maroon B. The following pigments are available from Degussa: Printex® U, Printex® V, Printex® 140U, Printex® 140V, Colo Black FW 200, Color Biack FW 2, Coior Black FW 2V, Color Black FW 1 , Color Black FW 18, Coior Black S 160, Color Black S 170, Special Biack 6, Special Black 5, Special Black 4A, and Special Black 4. The following pigment is available from DuPoni: Tipure®) R-101. The following pigments are available from Heubach: Daiamar® Yeiiow YT-858-D and Heueophthal Blue G XBT-583D. The foSiowing pigments are available from Clariant Permanent Yeiiow GR, Permanent Yellow G, Permanent Yellow DHG, Permanent Yeiiow NCG-71 , Permanent Yellow GG, Hansa Yeiiow RA, Hansa Brilliant Yeiiow 5GX- 02, Hansa Yel!ow-X, Novoperm® Yellow HR, Novoperm® Yellow FGL, Hansa Brilliant Yeiiow 10GX, Permanent Yeiiow G3R-01 , Hostaperm® Yellow H4G, Hostaperm® Yellow H3G, Hostaperm® Orange GR, Hostaperm® Scarlet GO, and Permanent Rubine F8B, The following pigments are available from Mobay; Quindo® Magenta, indofast® BrlHsant Scarlet, Quindo® Red R670G, Quindo® Red R67 3, and Indofast® Violet The following pigments are available from Sun Chemical: L 74-1357 Yellow, L7S-1331 Yellow* and 175-2577 Yellow. The following pigments are available from Columbian: Raven® 7000, Raven® 5750, Raven® 5250, Raven® 5000, and Raven® 3500, The following pigment is available from Sun Chemical: LHO9303 Black. Any other pigment and/or dye can be used that is useful in modifying the coior of the above descri ed inks and/or ultimately, the printed part.

Ptinit^'ng System

[0083] The method of the present disclosure may be performed using a 3-dimensionat printing system. An example of a S-dimensional printing system 100 is shown in FIG, 1. The system may include a powder bed 1 0 including build material in the form of, for example, a thermoplastic polymer powder 115. in the example shown, the powder bed has a moveable floor 1 0 that allows the powder bed to be lowered after each layer of the 3-dimens^'iona! part is printed. The 3-dimensional printed part can include a doped layer 126, including a doped portion 125, applied to a surface of a part body 127. The system also includes an Inkjet printer 130 that includes a first Inkjet pen 135 in

communication with a reservoir of a dopant ink 140. The first Inkjet pen can print th dopant ink onto the powder bed. A second Inkjet pen 145 is in communication with a reservoir of a fusing ink 50. The second nkjet pen can print the fusing ink onto the powder bed. After the fusing ink has been printed onto the powder bed, a fusing lamp 180 can be used to expose the powder bed to electromagnetic radiation sufficient to fuse the powder that has been printed with the fusing inks>

[0084] To achieve good selectivity between the fused and unfused portions of the powder bed, the fusing inks can absorb enough energy to boost, the temperature of the e.g. thermoplastic polymer powder above the melting or softening point of the polymer, while imprinted portions of the powder bed remain below the melting or softening point. In some examples, the 3-dimensional printing system can include preheaters for preheating the thermoplastic polymer powder to a temperature near the melting or softening point. In one example, the system can include a print bed heater to heat the print bed during printing. The preheat temperature used can depend on the type of thermoplastic polymer used. In some examples, the print bed heater can heat the print bed to a temperature from 130 to 160 °C. The system can also include a supply bed, where polymer particles can b stored before being spread in a layer onto the print bed. The supply bed can have a supply bed heater. In some examples, the supply bed heater can heat the supply bed to a temperature from 90 °C to 1 0 X,

[00853 Suitable fusing lamps for use in the 3~dimensionat printing system can include commercially available infrared lamps and halogen lamps. The fusing Samp can be a stationary lamp or a moving lamp. For example, the lamp can be mounted on a track to move horizontally across the powder bed. Such a fusing lamp can make multiple passes over the bed depending on the amount of exposure needed to coalesce each printed layer. The fusing Samp can irradiate the entire powder bed with a substantial Sy uniform amount of energy. This can selectively coalesce the printed portions with fusing inks leaving the unprinted portions of the poiymer powder below the melting or softening point

[0O86J In one example, the fusing Samp can be matched with the fusing agents in the fusing inks so that the fusing Samp emits wavelengths of light that match the peak absorption wavelengths of the fusing agents, A fusing agent with a narrow peak e.g. at a particular near-infrared wavelength can be used with a fusing Samp that emits a narrow range of wavelengths at approximately the peak wavelength of the fusing agent.

Similarly, a fusing agent that absorbs e.g. a broad range of near-infrared wavelengths can be used with a fusing lamp that emits a broad range of wavelengths. Matching the fusing agent and the fusing Samp in this way can increase th efficiency of coalescing the polymer particles with the fusing agent printed thereon, while the unprinted polymer particles do not absorb as much light and remain at a lower temperature.

[00871 Depending on the amount of fusing agent present, the absorbance of the fusing agent, the preheat temperature, and the melting or softening point of the polymer, an appropriate amount of irradiation can be supplied from the fusing lamp, in some examples, the fusing iamp. can irradiate each layer from about 0.5 to about 10 seconds per pass.

[0O88J The incorporation of dopant into a 3-dimensional printed part described herein is illustrated, by way of example, in FIGs. 2-3, FIGs, 2-3 are cross sectional views of a layer of polymer powder build material that ha been printed wit a dopant composition and a fusing composition. FIG. 2 shows the powder layer 200 after being printed but before being cured, and FIG, 3 shows the coalesced powder layer 300 after being cured. In FIG. 2, a first portion 210 of the powder layer 200 has been printed with a dopant composition containing dopant 220 and with fusing ink containing fusing agent 225. The dopant 220 penetrates into the spaces between the powder particles 230. A second portion 240 of the powder layer has been printed with a fusing ink including a fusing agent 225, but without dopant 220. Thus, as shown, only a portion of the printed layer includes the dopant 220, It should be noted that these figures are not necessarily drawn to scale, and the relative sizes of powder particles and dopant particles can differ from those shown.

[00891 As shown in FIG. 3, when the powder layer 300 is fused or cured by exposure to electromagnetic radiation, the dispersed dopant 320 can be entrapped throughout a portion of a matrix 335 formed by fusing, agent hi the ink and the powder particles in the first portion 310. Thus, the dopant entrapped In the matrix of fused polymer powder can form a doped composite layer. In the second portion 340 of the powder layer, the powder particles are fused in the absence of dopant. It should be noted thai FIGS. 2 and 3. show only a 2-dimensional cross-section of a portion of a doped composite layer. Further, the dopant is illustrated in FIGs. 2 and 3 as completely penetrating the layer of polymer build material. However, this is not necessary. In some examples, the dopant can extend into the composite layer to a depth greater than about 20%, about 50%. about 70%, or about 90% of the thickness of the layer.

[00903 " some examples, the amount of dopant dispensed onto the powder bed can be adjusted by printing the dopant composition in multiple passes. In one example, a single pass of an- Inkjet printhead can be sufficient Alternatively, additional passes can be applied to increase the amount of dopant applied. In further examples, the amount of dopant dispensed can be adjusted by adjusting the drop weight of the inkjet printhead either through resistor design or by changing firing parameters. Thus, with a greater drop weight, a greater amount of the dopant can be printed with each drop fired. However, in some cases jetting too large an amount of ink in a single pass can lead to lower print quality because of ink spreading. Therefore, in some examples multiple passes can be used to print more of the photo! uminesceni ink with bette print quality.

[0O91J F!G. 4 shows an example of a 3-dimensional printed part 400 that includes a part body 410 and a doped/dopant composite layer 420 applied to a surface of the part body. Th dopant composite layer includes a dopant composite portion 425 having a dopant (e.g. photoiuminescent agent) dispersed in a matrix ef fused thermoplastic polymer powder. St is noted thai the dopant can be present both beneath the surface 415 and at the surface of the dopant composite layer. It is also noted that the illustrated 3- dimensional printed part can be printed in a number of orientations, such as with the doped composite portion facing up, facing sideways, etc.

P092j However, as illustrated in FIG. 5, the dopant (e.g. photoiuminescent) composite portion 525 of 3-dimensional printed part 500 can be clearly distinguished from non- doped (e.g. non~photo!uminescent portions) of the dopant (e.g. photoiuminescent) composite layer, in one example, the dopant composite portion is a photoiuminescent composite portion that photoJu iriesces after photoexcitation to reveal a quick response or G code, in alternative examples, the dopant composite portion may be a

photoiuminescent composite portion that can phataluminesce to present a bar code, a serial number, a trademark, a tradename, instructions, other words, the like, or a combination thereof.

[OGS33 In an aiternative example, the 3~dsmensionaS printed part 500 can be printed such that the GR code can be cieariy visible under ambient lighting and can be decoded using standard QR code algorithms. However, features 522a, 522b, and 522c can each be printed to have different dopant e.g. photoiuminescent features. For example, these features can be printed with photoSuminescent agents that photoexcit at different wavelengths of electromagnetic radiation, with different amounts of photoiuminescent agent to provide different photoiuminescent intensities, with different mixtures of photoiuminescent agents, etc., or a combination thereof. This can provide additional information encoded in the spatial attributes of the luminescent composite that can only be readable during specific photoiuminescent events. Thus, these QR codes can be read using standard QR code algorithms under ambient Sighting, but can be read using a specific QR code algorithm during photoluminescence to provide additional information. The same concept can also be employed with bar codes and other identifying or serialization information. Thus, photoiuminescent inks can provide increased information paySoads for printed security and serialization features.

[0094] FIG, 8 if!ustrates schematically a GRIN iens stack or assembly thai can be prepared in accordance with examples of the present disclosure. For example, a traditional lens assembly is shown at a) that includes various types of traditional glass Senses 44, including converging lenses, diverging lenses, and optical spacers, etc. Also shown is air spac 42 between each lens on the assembly, which is typical of curved lens assemblies where spatial relationships and curvature profiles provide desired optical properties. On the other hand, in accordance with the present disclosure, a GRI lens stack or assembly is shown at b) which can simulate the optical properties of the more traditional lens stack shown at a). However, the layered and printed lenses are printed to form a monolithic lens structure, as shown at c). Essentially, each of the optical lens shapes shown at a) may be recreated b printing layers 30 (shown thicker than may be applicable in practice) with dielectric nanopartlc!es as the dopant. The dielectric nanoparticles are printed at varying densities within each layer to form doped SensSets 34 and undoped portions 32, Additionally, rather than having air space between the lenses, spacers can be printed without dielectric nanopartictes, for example (note that there is space between the various Senses), in the schematic structure shown at b) and c), the "^'tenses" ar shown using dashed lines to denote that these GRIN Senses are printed to behave functionally like their counterpart lenses shown at a), but may not actually have the same physical shape as the curved Sens. Similar optic characteristics can be achieved by printing varying densities in a gradient along the x-axis, as shown schematically at b).

[009SJ Advantages of printing GRIN Senses using this method may include the elimination of Sens placement, mechanical alignment and assembly costs, since th assembly may he printed as a single monolithic part. Optical fidelity may also be improved because there would be lower error related to precise lens placement.

Furthermore, voxel-scale correction of edge aberration defects can be likewise reduced. Because these Senses can be printed digitally , customisation and rapid design changes can be carried out without the fabrication of ne molds. Furthermore, this technology can be extended into more complex optica! systems and sensors, e.g., embedded spectrometers.

[0096] FIG. 7 provides an example of how the effective capacitance (C = eo e_r A d) may Increase with an increasing concentration or mass fraction of dielectric nanoparticles with respect to the particulate build materia!, in this equation, C is effective capacitance, eo is permittivity of vacuum (a fundamental physical constant), e_f is relative dielectric constant (a physical property of the material), A is the capacitor's area, and d is the capacitors thickness. Notably, in this example, a poiyamide 12 (ΡΆ-12) powder was used with Ti<¾ dielectric nanopartictes. PA- 12 was used in this example to show that there is a relationship between dielectric nanoparticle number density and effective capacitance (and thus, effective refractive index), in alternative examples, materials e.g. polymethyl methacryiate or polycarbonate or other optically transparent or translucent polymers may foe used in place of PA-12. By modifying the number density of TiC¾ dielectric nanoparticSes in the build material, the effective capacitance can be varied, as shown (by wa of example) in FIG, 7. These dat were determined by measuring (at 1 MHz) the complex impedance as a function of frequency. As can be seen from FIG. 7, the slop indicates a clear dependence of the effective capacitance on Ti<¾ mass fraction (or concentration of dielectric nanopartictes). EXAMPLES

[0Q97| The following illustrates several examples of the present disclosure. However, it is to be understood that the following are only illustrative of the application of the principles of the present disclosure. Numerous modifications and alternative

compositions, methods, and systems may be devised without departing from the spirit and scope of the present disclosure. The appended claims are intended to cover such modifications and arrangements.

Example 1

[0098} A 3~dlmensional printing system was used to print a 3~dimensionai printed part having a photolumineseent composite layer on a surface of the part body, A

photoiuminescent ink (as dopant composition) and fusing ink were printed from two separate ink jet pens. Two separate photoiumi escent inks were used. The first photolumineseent ink included 3 wt% fluorescein in an aqueous ink vehicle and the second photolumineseent ink included 0.25 wt% rhodami se B in an aqueous ink vehicle. The fusing Ink included 5 wt% carbon black in an aqueous ink vehicle.

|0099] The inks were jetted onto a bed of nylon (PA12) particles (Vestoslnt® x1556). The nylon particles had an average particie size of approximately 50 pm. The layer thickness was approximately 100 pm. Each layer was printed with on of the two separate photo!uminescent inks in pre-designated photolumineseent composite areas. The carbon black fusing ink was printed in both the photolumineseent composite areas and in other body portions. The inks were printed at contone levels of 266 for the photolumineseent inks and 80 for the fusing ink. A single pass of each of the inks was performed for the photolumineseent composite layer. After the single pass, a curing pass was performed,

[00100] The printer powder supply and powder bed were filled with the nylon particles. The supply temperature was set at 110 °C and the print tied temperature was set at 130 ^"C. A heater under the print bed was set at 150 °C. The print speed was set at 10 inches per second (ips) and the cure speed was set at 7 ips. Curing was performed using two 300 W bulbs placed approximately 1 cm away from the surface of the powder bed.

[00101] The 3-dimensional printed part included printed photoiuminescent features that were relatively unobservable under ambient lighting. However, under UV light, the photoluminescent emission from the photoluminescent features became very prominent. The edges of the printed photoluminescent features were very dear, providing clearly distinguishable luminescent features under UV light. In particular, the photoluminescent features included circles, hexagons, and triangles.

Example 2

[00102! The same general printing parameters as described in Example 1 were used to print another 3-dimensionai printed part having a photoluminescent composite layer on a surface of the part body. The 3-dimensionai printed part was pnnted in predesignated areas with separate photoluminescent inks including 1.3 wt% Carboxy YG 100 nm nanospheres in an aqueous vehicle, 2.6 wt% Carboxy YG 100 nm nanospheres in an aqueous vehicle, 2.5 wt% Carboxy YO 400 nm nanospheres in an aqueous vehicle, 2.7 wf% Carboxy NYO 200 nm nanospheres in an aqueous vehicle, 2,6 wt% Carboxy YG 200 nm nanospheres in an aqueous vehicle, 2.6 wt% Carboxy 8B 100 nm nanospheres in an aqueous vehicle, and 1.0 wt% Carboxy EU 200 nm nanospheres in an aqueous vehicle, respectively, each available from Polysclences, Inc.

[00103] Some of the features printed with the different photoluminescent inks were marginally observable under ambient lighting. However, these features could likely be masked using a specific colorant in combination with a particular phoioiuminescent ink. Under UV light, the phoioiuminescent features were clearly visible, some with stronger photo!uminescence than others. The 2.5 wt% Carboxy YO 400 nm nanosphere ink and the 1.0 wt% Carboxy EU 200 nm nanosphere ink both had relatively strong pSiotoiuminescence in comparison with the other photoluminescent inks under the specific wavelength of UV light used to photoexcite the various photoluminescent features.

Example 3

[00104] The same general printing parameters as described in Example 1 were used to print yet another 3-dimensionai printed part having a phofoSumsnescent composite layer on a surface of the part body . The 3-dimensionaS printed part was printed in predesignated areas with separate photoluminescent inks including 1 wt% thP ZnS quantum dots (oleylamine iigand) in an aqueous vehicle {available from NM- Labs), 0.1 wt% inP/ZnS quantum dots (earboxylic acid Iigand) in an aqueous vehicie (available from NN-Labs), and 1 wt% NanoDOT™ CIS-700 in an aqueous vehicie

(available from Voxte!).

[001 OS] The features printed with the different photoiumineseeni inks were largely unobservabie under ambient lighting. However, under UV Sight, the photoiumineseeni features were clearly visible, some with stronger photoiuminescence than others. The 1 wt% NanoDOT™ C!S-700 had relatively strong photo!uminescenee in comparison with the other photo! uminesceni inks under the specific wavelength of UV tight used to photoexcit the various photoiumineseeni features.

Example 4

[001063 *ⁿ ^is Example, a 3-dimensiona! printing system can be used to print various 3-dimensionai printed parts having a photoiuminescent security feature encapsulated within the part body beneath a surface layer, Specifically,

photoiuminescent inks and fusing inks were printed from separate ink jet pens. The photoiumineseeni inks used had formulations as follows:

I ink #1 - 3 .0% Fluorescein j Component Weight (g) for 25 g Ink J

Water 18.31 I

Organic Co-so!vent Vehicie 5.94

Fluorescein, Na+ salt 0.75 I

Ink #2 - 0,5% hodamine 8

Component Weight (g) for 25 g Ink j

Water 18.94 I

Organic Co-solvent Vehicie 5.94 Rhodamine B 0.13

ink #3 * 3.0% Fluorescein

Component Weight (g) for 25 g Ink

Water 18.46

Organic Co-solvent Vehicle 5.75 I

Non-ionic Wetting Agent 0.04

Fluorescein, Na+ sait 0.75

[001071 The fusing ink was formulated as foifows:

Weight % Weight for of 10 kg fnk

1 Components in ink formulation component

Organic Co-solvent Vehicle 20.00 2000.00 ϊ Anionic Surfactant 0 50 50.00

Nonionic Surfactants _____

1 Poiymer Dispersant 0.01 1.00 [ Chelating Agent ____________

1 Biocides 0,32 32,00 I

1 Carbon black 5.00 2500.00

Di Water 73.33 5333.00 Total Fluid 10000.00

[00108] The inks were jetted onto a bed of nylon (PA12) particles (Vesiosint® x1558, available from Evonik). The nylon particles had an average particle size of approximately 50 μηι. The layer thickness was approximately 100 m. Each 3- dimensional printed part was printed with a subsurface particle layer having a security feature. On these layers the photolumineseent ink was printed into a security area to form the security feature using a contone level of 255, a print resolution of 1200 x 1200, and a drop weight of 9 ng to achieve a print density of about 1 mg solids/cubic centimeter (cc) for the rhodarriihe B inks and about 6 mg soSids/cc for the fluorescein inks. The fusing Ink was printed in both the security area and non-security areas of the subsurface particle layer using a contone level of 80, a resolution of 1200 x 1200, and a drop weight of 1 .5 ng to achieve a print densit of about 4 mg soiids cc. A single pass of each of the inks was performed for the photolumi nescent com posit© layer. After the single pass, a curing pass was performed.

£00 003 A surface particle layer was printed on top of the subsurface fused layer. The surface particle layer included a masking area or feaiure printed over the subsurface security feature, as well as non-masking areas. The non-masking areas of the surface particle layer were prepared i the same manner as the non-security areas of the subsurface particle layer. The masking area was printed by reducing the contone level of the fusing ink to 40, while using the same resolution and drop weight as in other areas. This was sufficient to decrease the print density in the masking area to about 2 mg solids/cc,

[0011 ] The printer powder supply and powde bed were filled with the nylon particles. The supply temperature was set at 1 0 °C and the print bed temperature was set at 130 °C. A heater under the print bed was set at 150 °C. The print speed was set at 10 Inches per second (ips) and the cure speed was set at 7 ips. Curing was performed using two 300 W bulbs placed approximately 1 em away from the surface of the powder bed.

[00111] The security features encapsulated within the 3-dimensionai printed parts were unobservabie under ambient lighting. However, under UV irradiation, the photoiumi nascent emission from the photaSuminesoerst features became reasonably visible in ambient iighting. However, using UV irradiation in a dark room resulted in a very prominent phoioiuminescent security feature that was visible through the masking area.

Claims

Claims

1 , A method of S-dimensionai printing a printed part, the method comprising

printing an inkjet dopant composition at selected locations on a layer of build materia! comprising polymer particles, wherein the inkjet dopant composition comprises a dopant dispersed or dissolved in liquid carrier; and

fusing polymer particles at selected areas of the layer of build material to form a fused polymer !ayer comprising the dopant,

wherein the selected areas of the layer of build material include areas of the layer of build material that have not been printed with the inkjet dopant composition.

2, A method as claimed in claim 1 , which further comprises printing an inkjet fusing composition onto selected areas of the layer of build materia! prior fo fusing.

3, A method as claimed in claim 1 _« wherein the dopant comprises dopant particles.

4. A method as claimed in claim 3, wherein the dopant particles are selected from photoluminescent particles, dielectric particles, magnetic particles, ceramic particles, semi-conductor particles, and electricaily-conducting particles. 5. A method as claimed in claim 3, wherein the dopant particles have a particle si2e of i to 200 nm.

8. A method as claimed in claim 1 , wherein th printed part comprises regions comprising the dopant and regions in which the dopant is absent

7, A method as claimed in claim 6, wherein the regions comprising the dopant differ in at least one property from the regions in which the dopant is absent, wherein the at least one property is selected from at least one of conductivity, dielectric permittivity, magnetic permeability, refractive index, photoluminescence, tensile strength and Young's modulus.

8. A method as claimed in claim 1 , which further comprises forming a further layer of build material over the fused polymer layer; printing an Inkjet dopant composition at selected locations on the further layer of build material; and fusing polymer particles at selected areas of the further layer of build material to form a further fused polymer layer comprising the dopant

9. A method as claimed in claim 1 , which further comprises forming a further layer of build material over the fused polymer layer, and fusing polymer particles at selected areas of the further layer of build material to form a fused polymer layer that is devoid of dopant.

10. A method as claimed in claim 1 , wherein the printed Inkjet dopant composition flows into at least some of the interstice between adjacent polymer particles in the layer of build material.

11. A method as claimed in claim 10, wherein the printed inkjef dopant composition penetrates into at least part of the depth of the layer of build material.

12. A method as claimed in claim 1 , wherein the Inkjet dopant composition is printed droplet by droplet, wherein each droplet has a volume of 5 to 20 pL

13. A method as claimed in claim 1 , wherein the build materia! comprises polymer particles are thermoplastic polymer particles selected from at least one of a poSyamide, a poiyurethaoe, a polycarbonate, a polystyrene and poiyo!efin.

14. A 3-dimensional printing material set comprising

a particulate build material comprising thermoplastic polymer particles; an snkjet dopant composition comprising a dopant dispersed in a liquid carrier; wherein the dopant comprises particies that are selected from at least on of photoluminescent particles, dielectric particles, magnetic particies, ceramic particies, semi-conductor particles, electrically-conducting particies and polymer nanopartides; and an snkjet fusing composition comprising a fusing agent capable of absorbing electromagnetic radiation to produce heat

15, A 3 - dimensional printing material set further comprising an Inkjet ink composition comprising at least one colorant.