THREE-DIMENSIONAL PRINTING WITH DIHYDRAZIDE ANTIOXIDANTS

BACKGROUND

Methods of three-dimensional (3D) digital printing, a type of additive manufacturing, have continued to be developed over the last few decades. However, systems for 3D printing have historically been very expensive, though those expenses have been coming down to more affordable levels recently. In general, 3D printing technology can shorten the product development cycle by allowing rapid creation of prototype models for reviewing and testing. Unfortunately, the concept has been somewhat limited with respect to commercial production capabilities because the range of materials used in 3D printing is likewise limited. Accordingly, it can be difficult to 3D print functional parts with desired properties such as mechanical strength, visual appearance, and so on. Nevertheless, several commercial sectors such as aviation and the medical industry have benefitted from the ability to rapidly prototype and customize parts for customers.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view of an example multi-fluid kit for three-dimensional printing in accordance with examples of the present disclosure.

FIG. 2 is a schematic view of another example multi-fluid kit for three-dimensional printing in accordance with examples of the present disclosure.

FIG. 3 is a schematic view an example three-dimensional printing kit in accordance with examples of the present disclosure.

FIG. 4 is a schematic view of another example three-dimensional printing kit in accordance with examples of the present disclosure.

FIG. 5 is a schematic view of yet another example three-dimensional printing kit in accordance with examples of the present disclosure.

FIGS. 6A-6C show a schematic view of an example three-dimensional printing process using an example three-dimensional printing kit in accordance with examples of the present disclosure.

FIG. 7 is a flowchart illustrating an example method of making a three-dimensional printed article in accordance with examples of the present disclosure.

The figures depict several examples of the presently disclosed technology. However, it should be understood that the present technology is not limited to the examples depicted.

DETAILED DESCRIPTION

The present disclosure describes multi-fluid kits for three-dimensional printing, three-dimensional printing kits, and methods of making three-dimensional printed articles. In one example, a multi-fluid kit for three-dimensional printing can include a fusing agent and a second fluid agent. The fusing agent can include water, a polar organic solvent having a boiling point from about 200° C. to about 320° C., and a radiation absorber. The radiation absorber can absorb radiation energy and convert the radiation energy to heat. The fusing agent or the second fluid agent can include a dihydrazide anti-oxidant. In a particular example, the second fluid agent can be a detailing agent including a detailing compound, wherein the detailing compound reduces a temperature of powder bed material onto which the detailing agent is applied. In another example, the second fluid agent can be an antioxidant agent including water and the dihydrazide antioxidant, and the multi-fluid kit can also include a separate detailing agent including a detailing compound, wherein the detailing compound reduces a temperature of powder bed material onto which the detailing agent is applied. In some examples, the dihydrazide antioxidant can be present in the fusing agent or the second fluid agent in an amount from about 0.1 wt % to about 10 wt % with respect to a total weight of the fusing agent or the second fluid agent, respectively. In other examples, the dihydrazide antioxidant can be present in the fusing agent and the second fluid agent. In another example, the second fluid agent can also include a polar organic solvent having a boiling point from about 200° C. to about 320° C.

The present disclosure also describes three-dimensional printing kits that include powder bed material and fluid agents as in the multi-fluid kits. In one example, a three-dimensional printing kit can include a powder bed material that includes polymer particles and a fluid agent to selectively apply to the powder bed material. The fluid agent can include water and a polar organic solvent having a boiling point from about 200° C. to about 320° C. A dihydrazide antioxidant can be included either in the powder bed material or in the fluid agent. In a certain example, the fluid agent can be a fusing agent including the dihydrazide antioxidant and a radiation absorber to absorb radiation energy and convert the radiation energy to heat. In another example, the three-dimensional printing kit can include a separate fusing agent including a radiation absorber to absorb radiation energy and convert the radiation energy to heat, and the fluid agent can be a detailing agent including a detailing compound to reduce a temperature of powder bed material onto which the detailing agent is applied. The dihydrazide antioxidant can be included in the fusing agent, the detailing agent, or a separate antioxidant agent in an amount from about 0.1 wt % to about 10 wt % based on a total weight of the fusing agent, the detailing agent, or the separate antioxidant agent, respectively. In some examples, the dihydrazide antioxidant can include adipic dihydrazide, carbohydrazide, oxalyl dihydrazide, succinic dihydrazide, isophthalic dihydrazide, azelaic dihydrazide, sebacic dihydrazide, dodecanedioic dihydrazide, terephthalic dihydrazide, oxbisbenzene sulfonylhydrazide, or a combination thereof. In further examples, the dihydrazide antioxidant can be included in the powder bed material in an amount from about 0.05 wt % to about 5 wt % based on a total weight of the powder bed material. In certain examples, the polymer particles can include polyamide 6, polyamide 9, polyamide 11, polyamide 12, polyamide 6,6, polyamide 6,12, polyethylene, thermoplastic polyurethane, polypropylene, polyester, polycarbonate, polyether ketone, polyacrylate, polystyrene powder, wax, or a combination thereof, and the dihydrazide antioxidant can include adipic dihydrazide, carbohydrazide, oxalyl dihydrazide, succinic dihydrazide, isophthalic dihydrazide, azelaic dihydrazide, sebacic dihydrazide, dodecanedioic dihydrazide, terephthalic dihydrazide, oxbisbenzene sulfonylhydrazide, or a combination thereof.

The present disclosure also describes methods of making three-dimensional printed articles. In one example, a method of making a three-dimensional printed article can include iteratively applying individual build material layers including polymer particles to a powder bed. A fusing agent can be selectively jetted onto the individual build material layers based on a three-dimensional object model. The fusing agent can include water, a polar organic solvent having a boiling point from about 200° C. to about 320° C., and a radiation absorber. A dihydrazide antioxidant can be introduced to the polymer particles. The powder bed can be exposed to energy to selectively fuse the polymer particles in contact with the radiation absorber to form a fused polymer matrix at individual build material layers. In a certain example, the dihydrazide antioxidant can be introduced by mixing the dihydrazide antioxidant into the polymer particles before applying the individual build material layers. The dihydrazide antioxidant can be mixed into the polymer particles in an amount from about 0.05 wt % to about 5 wt % with respect to a total weight of the powder bed material. In another example, the dihydrazide antioxidant can be included in the fusing agent or a second fluid agent, and the dihydrazide antioxidant can be introduced to the polymer particles by jetting the fusing agent or the second fluid agent onto the polymer particles.

The materials and methods described herein can be used to make 3D printed articles while avoiding negative interactions that have been found to occur between the powder bed material and the fluid agents used in the methods. It has unexpectedly been found that the fluid agents (such as fusing agents, detailing agents, etc.) used in certain 3D printing processes can react with or otherwise interact with ingredients in the powder bed material. In some cases, these interactions can cause oxidation, yellowing, and other material degradation in the powder bed material. For example, certain ingredients in fusing agents and detailing agents can react with ingredients in the powder bed material to produce chromophores that give an undesired color to the powder bed material. The ingredients of the powder bed material that interact with the fluid agents can be the polymer of the powder bed material or additives that may be present in the powder bed material. To complicate this matter, in many cases polymer powders can be supplied by suppliers with unspecified additives such as antioxidants, flow aids, fillers, anti-static agents, and so on. The identity and amounts of the additives may not be known to the end user, and therefore it can be difficult to formulate fluid agents for 3D printing that can reduce these negative interactions.

The ingredients in the fusing agents and detailing agents that participates in the negative interactions can include high boiling polar organic solvents in some examples. Polar organic solvents with a boiling point from about 200° C. to about 320° C. can be included in fusing agents and detailing agents in order to increase the jettability of these agents. Fluid ejectors, such as inkjet printheads, can be susceptible to clogging. The volatile solvents in the fluid agents can evaporate from the nozzles of the fluid ejectors, which can cause the fluid agents to dry and clog the nozzles. Including high boiling point polar organic solvents into the agents can reduce evaporation of the nozzle and thereby reduce nozzle clogging. Therefore, removing the high boiling polar organic solvents from the fusing agent and detailing agent is not desirable.

It has been found that the negative interactions between the high boiling polar organic solvents in the fluid agents and the ingredients in the powder bed material can be reduced or eliminated by adding a dihydrazide antioxidant. The dihydrazide antioxidant can help reduce yellowing, oxidation, and other interactions with a variety of different polymer powders containing different additives. Additionally, the dihydrazides can perform this function without causing negative side effects to the 3D printing process. Without being bound to a particular mechanism, in some examples the dihydrazides can scavenge molecular oxygen from the 3D printing materials and break down to form innocuous byproducts. The dihydrazides can prevent negative interactions between the fluid agents the powder bed material when the dihydrazides are added either to a fluid agent or to the powder bed material.

Multi-Fluid Kits for Three-Dimensional Printing

With this description in mind, FIG. 1 shows a schematic of an example multi-fluid kit for three-dimensional printing 100. The kit includes a fusing agent 110 and a second fluid agent 120. The fusing agent can include water, a polar organic solvent having a boiling point from about 200° C. to about 320° C., and a radiation absorber. The radiation absorber can absorb radiation energy and convert the radiation energy to heat. The fusing agent or the second fluid agent can include a dihydrazide antioxidant. As explained above, the dihydrazide antioxidant can prevent or reduce interactions between the polar organic solvent and ingredients in the powder bed material.

As used herein, “polar organic solvents” can include organic solvents made up of molecules that have a net dipole moment or in which portions of the molecule have a dipole moment, allowing the solvent to dissolve polar compounds. The polar organic solvent can be a polar protic solvent or a polar aprotic solvent. Examples of polar organic solvents that can be used can include diethylene glycol, triethylene glycol, tetraethylene glycol, C3 to C6 diols, 2-pyrrolidone, hydroxyethyl-2-pyrrolidone, 2-methyl-1,3 propanediol, poly(propylene glycol) with 1, 2, 3, or 4 propylene glycol units, glycerol, and others. In some examples, the polar organic solvent can be present in an amount from about 0.1 wt % to about 20 wt % with respect to the total weight of the fusing agent.

The dihydrazide antioxidant can generally be any compound that includes two hydrazide groups which can help reduce interactions between the fluid agents and the powder bed materials described herein. In some examples, the dihydrazide can include sulfonohydrazide groups, while in other examples, the dihydrazide can include carbohydrazide groups. In certain examples, the dihydrazide can be a water soluble or water dispersible dihydrazide. As used herein, “water soluble” refers to materials that can be dissolved in water to form a solution that does not separate into multiple phases at a concentration from about 5 wt % to about 99 wt % of the dissolved material with respect to the entire weight of the solution. As used herein, “water-dispersible” refers to materials that can form a stable dispersion in water without settling at a concentration from about 5 wt % to about 99 wt % of the dispersed material with respect to the entire weight of the dispersion. The dispersible material can be dispersed either on its own or with a dispersant. Non-limiting examples of dihydrazide antioxidants can include adipic dihydrazide, carbohydrazide, oxalyl dihydrazide, succinic dihydrazide, isophthalic dihydrazide, azelaic dihydrazide, sebacic dihydrazide, dodecanedioic dihydrazide, terephthalic dihydrazide, oxbisbenzene sulfonylhydrazide, and combinations thereof.

As mentioned above, the dihydrazide antioxidant can be included in either the fusing agent or in the second fluid agent. In either case, when the dihydrazide antioxidant and the polar organic solvent in the fusing agent are both applied together onto a powder bed, the dihydrazide antioxidant can help prevent interactions between the polar organic solvent and the powder bed material. In certain examples, the dihydrazide antioxidant can be included in an amount from about 0.1 wt % to about 10 wt % in either the fusing agent or the second fluid agent. In further examples, the dihydrazide antioxidant can be included in an amount from about 1 wt % to about 6 wt % in either the fusing agent or the second fluid agent. In still further examples, the dihydrazide antioxidant can be included in both the fusing agent and the second fluid agent, in identical amounts or in different amounts.

In some examples, the second fluid agent can be a detailing agent. The detailing agent can include a detailing compound, which is a compound that can reduce the temperature of powder bed material onto which the detailing agent is applied. In some examples, the detailing agent can be applied around edges of the area where the fusing agent is applied. This can prevent powder bed material around the edges from caking due to heat from the area where the fusing agent was applied. The detailing agent can also be applied in the same area where fusing was applied in order to control the temperature and prevent excessively high temperatures when the powder bed material is fused. In some examples, the dihydrazide antioxidant can be included in the fusing agent, the detailing agent, or both. Additionally, in some examples the detailing agent can include a polar organic solvent having a boiling point from about 200° C. to about 320° C. This polar organic solvent can be the same as or different from the polar organic solvent in the fusing agent.

In another example, the second fluid agent can be an antioxidant agent that includes water and the dihydrazide antioxidant. The multi-fluid kit can also include a separate detailing agent in addition to the antioxidant agent. The antioxidant agent may be selectively jetted in any areas where it is desired to reduce or prevent interactions between the polar organic solvent and the powder bed material. FIG. 2 shows a schematic of such a multi-fluid kit 200. This multi-fluid kit includes a fusing agent 210, an antioxidant agent 220, and a detailing agent 230.

Three-Dimensional Printing Kits

The present disclosure also describes three-dimensional printing kits. In some examples, the three-dimensional printing kits can include materials that can be used in the three-dimensional printing processes described herein. FIG. 3 shows a schematic illustration of one example three-dimensional printing kit 300 in accordance with examples of the present disclosure. The kit includes a powder bed material 340 including polymer particles and a fluid agent 320 to selectively apply to the powder bed material. The fluid agent includes water and a polar organic solvent having a boiling point from about 200° C. to about 320° C. A dihydrazide antioxidant is included either in the powder bed material or in the fluid agent. In further examples, the fluid agent can be a fusing agent, a detailing agent, or an antioxidant agent as described above.

In further examples, a three-dimensional printing kit can include multiple fluid agents, such as any combination of a fusing agent, a detailing agent, and an antioxidant agent. FIG. 4 is a schematic illustration of one example three-dimensional printing kit 400 that includes a powder bed material 440, a fusing agent 410, and a detailing agent 430. The dihydrazide antioxidant can be included in the fusing agent, detailing agent, or in the powder bed material. Additionally, the fusing agent and/or the detailing agent can include a polar organic solvent having a boiling point from about 200° C. to about 320° C. as described above.

FIG. 5 is a schematic illustration of yet another example three-dimensional printing kit 500 that includes a powder bed material 540, a fusing agent 510, an antioxidant agent 520, and a detailing agent 530. In this example, the antioxidant agent can include water and the dihydrazide antioxidant. In certain examples, the fusing agent and/or the detailing agent can also include the dihydrazide antioxidant. In other examples, the powder bed material can include the dihydrazide antioxidant. Additionally, any of the fusing agent, antioxidant agent, and detailing agent can include a polar organic solvent having a boiling point from about 200° C. to about 320° C.

When the dihydrazide antioxidant is included in a fluid agent such as a fusing agent, antioxidant agent, or detailing agent, the dihydrazide antioxidant can be present in an amount from about 0.1 wt % to about 10 wt % based on the total weight of the fluid agent. In further examples, the dihydrazide can be present in an amount from about 1 wt % to about 6 wt %. In other examples, the dihydrazide antioxidant can be included in the powder bed material. For example, the dihydrazide antioxidant can be mixed with the powder bed material before using the powder bed material in a 3D printing process. When the dihydrazide antioxidant is included in the powder bed material, the dihydrazide antioxidant can be present in an amount from about 0.05 wt % to about 5 wt % based on the total weight of the powder bed material. In further examples, the dihydrazide antioxidant can be present in an amount from about 0.5 wt % to about 3 wt %.

To illustrate the use of the three-dimensional printing kits and multi-fluid kits described herein, FIGS. 6A-6C illustrate one example of using a three-dimensional printing kit to form a 3D printed article. In FIG. 6A, a fusing agent 610 and a detailing agent 630 are jetted onto a layer of powder bed material 640. The fusing agent is jetted from a fusing agent ejector 612 and the detailing agent is jetted from a detailing agent ejector 632. These fluid ejectors can move across the layer of powder bed material to selectively jet fusing agent on areas that are to be fused, while the detailing agent can be jetted onto areas that are to be cooled. As explained above, the fusing agent and/or detailing agent can include a polar organic solvent having a boiling point from about 200° C. to about 320° C. Additionally, a dihydrazide antioxidant can be included in the fusing agent, detailing agent, powder bed material, or a combination thereof. A radiation source 650 can also move across the layer of powder bed material.

FIG. 6B shows the layer of powder bed material 640 after the fusing agent 610 has been jetted onto an area of the layer that is to be fused. Additionally, the detailing agent 630 has been jetted onto areas adjacent to the edges of the area to be fused. In this figure, the radiation source 650 is shown emitting radiation 652 toward the layer of polymer particles. The fusing agent can include a radiation absorber that can absorb this radiation and convert the radiation energy to heat.

FIG. 6C shows the layer of powder bed material 640 with a fused portion 642 where the fusing agent was jetted. This portion has reached a sufficient temperature to fuse the polymer particles together to form a solid polymer matrix. The area where the detailing agent was jetted remains as loose polymer particles.

Powder Bed Material

In certain examples, the powder bed material can include polymer particles having a variety of shapes, such as substantially spherical particles or irregularly-shaped particles. In some examples, the polymer powder can be capable of being formed into 3D printed objects with a resolution of about 20 μm to about 100 μm, about 30 μm to about 90 μm, or about 40 μm to about 80 μm. As used herein, “resolution” refers to the size of the smallest feature that can be formed on a 3D printed object. The polymer powder can form layers from about 20 μm to about 100 μm thick, allowing the fused layers of the printed part to have roughly the same thickness. This can provide a resolution in the z-axis (i.e., depth) direction of about 20 μm to about 100 μm. The polymer powder can also have a sufficiently small particle size and sufficiently regular particle shape to provide about 20 μm to about 100 μm resolution along the x-axis and y-axis (i.e., the axes parallel to the top surface of the powder bed). For example, the polymer powder can have an average particle size from about 20 μm to about 100 μm. In other examples, the average particle size can be from about 20 μm to about 50 μm. Other resolutions along these axes can be from about 30 μm to about 90 μm or from 40 μm to about 80 μm.

The polymer powder can have a melting or softening point from about 70° C. to about 350° C. In further examples, the polymer can have a melting or softening point from about 150° C. to about 200° C. A variety of thermoplastic polymers with melting points or softening points in these ranges can be used. For example, the polymer powder can be polyamide 6 powder, polyamide 9 powder, polyamide 11 powder, polyamide 12 powder, polyamide 6,6 powder, polyamide 6,12 powder, polyethylene powder, wax, thermoplastic polyurethane powder, acrylonitrile butadiene styrene powder, amorphous polyamide powder, polymethylmethacrylate powder, ethylene-vinyl acetate powder, polyarylate powder, aromatic polyesters, silicone rubber, polypropylene powder, polyester powder, or mixtures thereof. In a specific example, the polymer powder can be polyamide 12, which can have a melting point from about 175° C. to about 200° C. In another specific example, the polymer powder can be thermoplastic polyurethane.

The thermoplastic polymer particles can also in some cases be blended with a filler. The filler can include inorganic particles such as alumina, silica, fibers, carbon nanotubes, or combinations thereof. When the thermoplastic polymer 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, anti-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 further examples, a filler can be encapsulated in polymer to form polymer encapsulated particles. For example, glass beads can be encapsulate in a polymer such as a polyamide to form polymer encapsulated particles. In some examples, a weight ratio of thermoplastic polymer to filler in the powder bed material can be from about 100:1 to about 1:2 or from about 5:1 to about 1:1.

Fusing Agents

The multi-fluid kits and three-dimensional printing kits described herein can include a fusing agent to be applied to the polymer build material. The fusing agent can include a radiation absorber that can absorb radiant energy and convert the energy to heat. In certain examples, the fusing agent can be used with a powder bed material in a particular 3D printing process. A thin layer of powder bed material can be formed, and then the fusing agent can be selectively applied to areas of the powder bed material that are desired to be consolidated to become part of the solid 3D printed object. The fusing agent can be applied, for example, by printing such as with a fluid ejector or fluid jet printhead. Fluid jet printheads can jet the fusing agent in a similar way to an inkjet printhead jetting ink. Accordingly, the fusing agent can be applied with great precision to certain areas of the powder bed material that are desired to form a layer of the final 3D printed object. After applying the fusing agent, the powder bed material can be irradiated with radiant energy. The radiation absorber from the fusing agent can absorb this energy and convert it to heat, thereby heating any polymer particles in contact with the radiation absorber. An appropriate amount of radiant energy can be applied so that the area of the powder bed material that was printed with the fusing agent heats up enough to melt the polymer particles to consolidate the particles into a solid layer, while the powder bed material that was not printed with the fusing agent remains as a loose powder with separate particles.

In some examples, the amount of radiant energy applied, the amount fusing agent applied to the powder bed, the concentration of radiation absorber in the fusing agent, and the preheating temperature of the powder bed (i.e., the temperature of the powder bed material prior to printing the fusing agent and irradiating) can be tuned to ensure that the portions of the powder bed printed with the fusing agent will be fused to form a solid layer and the unprinted portions of the powder bed will remain a loose powder. These variables can be referred to as parts of the “print mode” of the 3D printing system. Generally, the print mode can include any variables or parameters that can be controlled during 3D printing to affect the outcome of the 3D printing process.

Generally, the process of forming a single layer by applying fusing agent and irradiating the powder bed can be repeated with additional layers of fresh powder bed material to form additional layers of the 3D printed article, thereby building up the final object one layer at a time. In this process, the powder bed material surrounding the 3D printed article can act as a support material for the object. When the 3D printing is complete, the article can be removed from the powder bed and any loose powder on the article can be removed.

Accordingly, in some examples, the fusing agent can include a radiation absorber that is capable of absorbing electromagnetic radiation to produce heat. The radiation absorber can be colored or colorless. In various examples, the radiation absorber can be a pigment such as carbon black pigment, glass fiber, titanium dioxide, clay, mica, talc, barium sulfate, calcium carbonate, a near-infrared absorbing dye, a near-infrared absorbing pigment, a conjugated polymer, a dispersant, or combinations thereof. Examples of near-infrared absorbing dyes include aminium dyes, tetraaryldiamine dyes, cyanine dyes, pthalocyanine dyes, dithiolene dyes, and others. In further examples, radiation absorber can be a near-infrared absorbing conjugated polymer such as poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS), a polythiophene, poly(p-phenylene sulfide), a polyaniline, a poly(pyrrole), a poly(acetylene), poly(p-phenylene 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 polymer that has a backbone with alternating double and single bonds. In many cases, the radiation absorber can have a peak absorption wavelength in the range of about 800 nm to about 1400 nm.

A variety of near-infrared pigments can also be used. Non-limiting examples can include phosphates having a variety of counterions such as copper, zinc, iron, magnesium, calcium, strontium, the like, and combinations thereof. Non-limiting specific examples of phosphates can include M₂P₂O₇, M₄P₂O₉, M₅P₂O₁₀, M₃(PO₄)₂, M(PO₃)₂, M₂P₄O₁₂, and combinations thereof, where M represents a counterion having an oxidation state of +2, such as those listed above or a combination thereof. For example, M₂P₂O₇can include compounds such as Cu₂P₂O₇, Cu/MgP₂O₇, Cu/ZnP₂O₇, or any other suitable combination of counterions. It is noted that the phosphates described herein are not limited to counterions having a +2 oxidation state. Other phosphate counterions can also be used to prepare other suitable near-infrared pigments.

Additional near-infrared pigments can include silicates. Silicates can have the same or similar counterions as phosphates. One non-limiting example can include M₂SiO₄, M₂Si₂O₆, and other silicates where M is a counterion having an oxidation state of +2. For example, the silicate M₂Si₂O₆can include Mg₂Si₂O₆, Mg/CaSi₂O₅, MgCuSi₂O₆, Cu₂Si₂Oe, Cu/ZnSi₂O₆, 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 silicate counterions can also be used to prepare other suitable near-infrared pigments.

In further examples, the radiation absorber can include a metal dithiolene complex. Transition metal dithiolene complexes can exhibit a strong absorption band in the 600 nm to 1600 nm region of the electromagnetic spectrum. In some examples, the central metal atom can be any metal that can form square planer complexes. Non-limiting specific examples include complexes based on nickel, palladium, and platinum.

A dispersant can be included in the fusing agent in some examples. Dispersants can help disperse the radiation absorbing pigments described above. In some examples, the dispersant itself can also absorb radiation. Non-limiting examples of dispersants that can be included as a radiation absorber, either alone or together with a pigment, can include polyoxyethylene glycol octylphenol ethers, ethoxylated aliphatic alcohols, carboxylic esters, polyethylene glycol ester, anhydrosorbitol ester, carboxylic amide, polyoxyethylene fatty acid amide, poly (ethylene glycol) p-isooctyl-phenyl ether, sodium polyacrylate, and combinations thereof.

The amount of radiation absorber in the fusing agent can vary depending on the type of radiation absorber. In some examples, the concentration of radiation absorber in the fusing agent can be from about 0.1 wt % to about 20 wt %. In one example, the concentration of radiation absorber in the fusing agent can be from about 0.1 wt % to about 15 wt %. In another example, the concentration can be from about 0.1 wt % to about 8 wt %. In yet another example, the concentration can be from about 0.5 wt % to about 2 wt %. In a particular example, the concentration can be from about 0.5 wt % to about 1.2 wt %. In one example, the radiation absorber can have a concentration in the fusing agent such that after the fusing agent is jetted onto the polymer powder, the amount of radiation absorber in the polymer powder can be from about 0.0003 wt % to about 10 wt %, or from about 0.005 wt % to about 5 wt %, with respect to the weight of the polymer powder.

In some examples, the fusing agent can be jetted onto the polymer powder build material using a fluid jetting device, such as inkjet printing architecture. Accordingly, in some examples, the fusing agent can be formulated to give the fusing agent good jetting performance. Ingredients that can be included in the fusing agent to provide good jetting performance can include a liquid vehicle. Thermal jetting can function by heating the fusing agent to form a vapor bubble that displaces fluid around the bubble, and thereby forces a droplet of fluid out of a jet nozzle. Thus, in some examples the liquid vehicle can include a sufficient amount of an evaporating liquid that can form vapor bubbles when heated. The evaporating liquid can be a solvent such as water, an alcohol, an ether, or a combination thereof.

In some examples, the liquid vehicle formulation can include a co-solvent or co-solvents present in total at from about 1 wt % to about 50 wt %, depending on the jetting architecture. Further, a non-ionic, cationic, and/or anionic surfactant can be present, ranging from about 0.01 wt % to about 5 wt %. In one example, the surfactant can be present in an amount from about 1 wt % to about 5 wt %. The liquid vehicle can include dispersants in an amount from about 0.5 wt % to about 3 wt %. The balance of the formulation can be purified water, and/or other vehicle components such as biocides, viscosity modifiers, materials for pH adjustment, sequestering agents, preservatives, and the like. In one example, the liquid vehicle can be predominantly water.

In some examples, a water-dispersible or water-soluble radiation absorber can be used with an aqueous vehicle. Because the radiation absorber is dispersible or soluble in water, an organic co-solvent may not be present, as it may not be included to solubilize the radiation absorber. Therefore, in some examples the fluids can be substantially free of organic solvent, e.g., predominantly water. However, in other examples a co-solvent can be used to help disperse other dyes or pigments, or enhance the jetting properties of the respective fluids. In still further examples, a non-aqueous vehicle can be used with an organic-soluble or organic-dispersible fusing agent.

Classes of co-solvents that can be used can include organic co-solvents including aliphatic alcohols, aromatic alcohols, diols, glycol ethers, polyglycol ethers, caprolactams, formamides, acetamides, and long chain alcohols. Examples of such compounds include 1-aliphatic alcohols, secondary aliphatic alcohols, 1,2-alcohols, 1,3-alcohols, 1,5-alcohols, ethylene glycol alkyl ethers, propylene glycol alkyl ethers, higher homologs (C₆-C₁₂) of polyethylene glycol alkyl ethers, N-alkyl caprolactams, unsubstituted caprolactams, both substituted and unsubstituted formamides, both substituted and unsubstituted acetamides, and the like. Specific examples of solvents that can be used include, but are not limited to, 2-pyrrolidinone, N-methylpyrrolidone, 2-hydroxyethyl-2-pyrrolidone, 2-methyl-1,3-propanediol, tetraethylene glycol, 1,6-hexanediol, 1,5-hexanediol and 1,5-pentanediol.

Regarding the surfactant that may be present, a surfactant or surfactants can be used, such as alkyl polyethylene oxides, alkyl phenyl polyethylene oxides, polyethylene oxide block copolymers, acetylenic polyethylene oxides, polyethylene oxide (di)esters, polyethylene oxide amines, protonated polyethylene oxide amines, protonated polyethylene oxide amides, dimethicone copolyols, substituted amine oxides, and the like. The amount of surfactant added to the fusing agent may range from about 0.01 wt % to about 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 (Michigan), LEG-1 and LEG-7; Triton™ X-100, Triton™ X-405 available from Dow Chemical Company (Michigan); and sodium dodecylsulfate.

Various other additives can be employed to enhance certain properties of the fusing agent 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 can be used in various formulations. Examples of suitable microbial agents include, but are not limited to, NUOSEPT® (Nudex, Inc., New Jersey), UCARCIDE™ (Union carbide Corp., Texas), VANCIDE® (R.T. Vanderbilt Co., Connecticut), PROXEL® (ICI Americas, New Jersey), and combinations thereof.

Sequestering agents, such as EDTA (ethylene diamine tetra acetic acid), may be included to eliminate the deleterious effects of heavy metal impurities, and buffer solutions may be used to control the pH of the fluid. From about 0.01 wt % to about 2 wt %, for example, can be used. Viscosity modifiers and buffers may also be present, as well as other additives to modify properties of the fluid as desired. Such additives can be present at from about 0.01 wt % to about 20 wt %.

In some examples, the fusing agent can include a polar organic solvent having a boiling point from about 200° C. to about 320° C. in an amount from about 0.1 wt % to about 20 wt % with respect to the total weight of the fusing agent. In further examples, the fusing agent can include a dihydrazide antioxidant in an amount from about 0.1 wt % to about 10 wt %. In still further examples, the fusing agent can include both the polar organic solvent having a boiling point from about 200° C. to about 320° C. and the dihydrazide antioxidant.

Antioxidant Agents

In some examples, the multi-fluid kits or three-dimensional printing kits can include an antioxidant agent. Generally, the antioxidant agent can be a fluid agent that includes a dihydrazide antioxidant. In some examples, the antioxidant agent may not perform the functions of either a fusing agent or a detailing agent. In further examples, the antioxidant agent can be included in a multi-fluid kit or a three-dimensional printing kit in which the other fluid agents do not include the dihydrazide antioxidant.

In some examples, the antioxidant agent can include a polar organic solvent having a boiling point from about 200° C. to about 320° C. in an amount from about 0.1 wt % to about 20 wt % with respect to the total weight of the antioxidant agent. In further examples, the antioxidant agent can include a dihydrazide antioxidant in an amount from about 0.1 wt % to about 10 wt %. In still further examples, the antioxidant agent can include both the polar organic solvent having a boiling point from about 200° C. to about 320° C. and the dihydrazide antioxidant.

The antioxidant agent can also include ingredients to allow the antioxidant agent to be jetted by a fluid jet printhead. In some examples, the antioxidant agent can include jettability imparting ingredients such as those in the fusing agent described above. These ingredients can include a liquid vehicle, surfactant, dispersant, co-solvent, biocides, viscosity modifiers, materials for pH adjustment, sequestering agents, preservatives, and so on. These ingredients can be included in any of the amounts described above

Detailing Agents

In further examples, multi-fluid kits or three-dimensional printing kits can include a detailing agent. The detailing agent can include a detailing compound. The detailing compound can be capable of reducing the temperature of the powder bed material onto which the detailing agent is applied. In some examples, the detailing agent can be printed around the edges of the portion of the powder that is printed with the fusing agent. The detailing agent can increase selectivity between the fused and unfused portions of the powder bed by reducing the temperature of the powder around the edges of the portion to be fused.

In some examples, the detailing compound can be a solvent that evaporates at the temperature of the powder bed. In some cases the powder bed can be preheated to a preheat temperature within about 10° C. to about 70° C. of the fusing temperature of the polymer powder. Depending on the type of polymer powder used, the preheat temperature can be in the range of about 90° C. to about 200° C. or more. The detailing compound can be a solvent that evaporates when it comes into contact with the powder bed at the preheat temperature, thereby cooling the printed portion of the powder bed through evaporative cooling. In certain examples, the detailing agent can include water, co-solvents, or combinations thereof. Non-limiting examples of co-solvents for use in the detailing agent can include xylene, methyl isobutyl ketone, 3-methoxy-3-methyl-1-butyl acetate, ethyl acetate, butyl acetate, propylene glycol monomethyl ether, ethylene glycol mono tert-butyl ether, dipropylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol monobutyl ether, 3-Methoxy-3-Methyl-1-butanol, isobutyl alcohol, 1,4-butanediol, N,N-dimethyl acetamide, and combinations thereof. In some examples, the detailing agent can be mostly water. In a particular example, the detailing agent can be about 85 wt % water or more. In further examples, the detailing agent can be about 95 wt % water or more. In still further examples, the detailing agent can be substantially devoid of radiation absorbers. That is, in some examples, the detailing agent can be substantially devoid of ingredients that absorb enough radiation energy to cause the powder to fuse. In certain examples, the detailing agent can include colorants such as dyes or pigments, but in small enough amounts that the colorants do not cause the powder printed with the detailing agent to fuse when exposed to the radiation energy.

The detailing agent can also include ingredients to allow the detailing agent to be jetted by a fluid jet printhead. In some examples, the detailing agent can include jettability imparting ingredients such as those in the fusing agent described above. These ingredients can include a liquid vehicle, surfactant, dispersant, co-solvent, biocides, viscosity modifiers, materials for pH adjustment, sequestering agents, preservatives, and so on. These ingredients can be included in any of the amounts described above.

In some examples, the detailing agent can include a polar organic solvent having a boiling point from about 200° C. to about 320° C. in an amount from about 0.1 wt % to about 20 wt % with respect to the total weight of the detailing agent. In further examples, the detailing agent can include a dihydrazide antioxidant in an amount from about 0.1 wt % to about 10 wt %. In still further examples, the detailing agent can include both the polar organic solvent having a boiling point from about 200° C. to about 320° C. and the dihydrazide antioxidant.

Methods of Making 3D Printed Articles

The present disclosure also describes methods of making three-dimensional printed articles. FIG. 7 shows a flowchart illustrating one example method 700 of making a three-dimensional printed article. The method includes: iteratively applying individual build material layers of polymer particles to a powder bed 710; based on a three-dimensional object model, selectively jetting a fusing agent onto the individual build material layers, wherein the fusing agent includes water, a polar organic solvent having a boiling point from about 200° C. to about 320° C., and a radiation absorber 720; introducing a dihydrazide antioxidant to the polymer particles 730; and exposing the powder bed to energy to selectively fuse the polymer particles in contact with the radiation absorber to form a fused polymer matrix at individual build material layers 740.

In certain examples, the dihydrazide antioxidant can be introduced to the polymer particles by mixing the dihydrazide antioxidant into the polymer particles before applying the individual build material layers. In some examples, the amount of dihydrazide mixed into the powder bed material can be from about 0.05 wt % to about 5 wt % with respect to the total weight of the powder bed material. In other examples, the dihydrazide antioxidant can be introduced by including the dihydrazide antioxidant in the fusing agent and jetting the fusing agent onto the powder bed material. In still further examples, the dihydrazide antioxidant can be included in an additional fluid agent, such as an antioxidant agent or a detailing agent. The dihydrazide antioxidant can then be introduced to the powder bed material by jetting the additional fluid agent onto the powder bed.

In some examples, a detailing agent can also be jetted onto the powder bed. As described above, the detailing agent can be a fluid that reduces the maximum temperature of the polymer powder on which the detailing agent is printed. In particular, the maximum temperature reached by the powder during exposure to electromagnetic energy can be less in the areas where the detailing agent is applied. In certain examples, the detailing agent can include a solvent that evaporates from the polymer powder to evaporatively cool the polymer powder. The detailing agent can be printed in areas of the powder bed where fusing is not desired. In particular examples, the detailing agent can be printed along the edges of areas where the fusing agent is printed. This can give the fused layer a clean, defined edge where the fused polymer particles end and the adjacent polymer particles remain unfused. In other examples, the detailing agent can be printed in the same area where the fusing agent is printed to control the temperature of the area to be fused. In certain examples, some areas to be fused can tend to overheat, especially in central areas of large fused sections. To control the temperature and avoid overheating (which can lead to melting and slumping of the build material), the detailing agent can be applied to these areas

The fusing agent and detailing agent can be jetted onto the powder bed using fluid jet print heads. The amount of the fusing agent used can be calibrated based the concentration of radiation absorber in the fusing agent, the level of fusing desired for the polymer particles, and other factors. In some examples, the amount of fusing agent printed can be sufficient to contact the radiation absorber with the entire layer of polymer powder. For example, if individual layers of polymer powder are 100 microns thick, then the fusing agent can penetrate 100 microns into the polymer powder. Thus the fusing agent can heat the polymer powder throughout the entire layer so that the layer can coalesce and bond to the layer below. After forming a solid layer, a new layer of loose powder can be formed, either by lowering the powder bed or by raising the height of a powder roller and rolling a new layer of powder.

In some examples, the entire powder bed can be preheated to a temperature below the melting or softening point of the polymer powder. In one example, the preheat temperature can be from about 10° C. to about 30° C. below the melting or softening point. In another example, the preheat temperature can be within 50° C. of the melting of softening point. In a particular example, the preheat temperature can be from about 160° C. to about 170° C. and the polymer powder can be polyamide 12 powder. In another example, the preheat temperature can be about 90° C. to about 100° C. and the polymer powder can be thermoplastic polyurethane. Preheating can be accomplished with a lamp or lamps, an oven, a heated support bed, or other types of heaters. In some examples, the entire powder bed can be heated to a substantially uniform temperature.

The powder bed can be irradiated with a fusing lamp. Suitable fusing lamps for use in the methods described herein can include commercially available infrared lamps and halogen lamps. The fusing lamp 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 to coalesce printed layers. The fusing lamp can be configured to irradiate the entire powder bed with a substantially uniform amount of energy. This can selectively coalesce the printed portions with fusing agent leaving the unprinted portions of the polymer powder below the melting or softening point.

In one example, the fusing lamp can be matched with the radiation absorber in the fusing agent so that the fusing lamp emits wavelengths of light that match the peak absorption wavelengths of the radiation absorber. A radiation absorber with a narrow peak at a particular near-infrared wavelength can be used with a fusing lamp that emits a narrow range of wavelengths at approximately the peak wavelength of the radiation absorber. Similarly, a radiation absorber that absorbs a broad range of near-infrared wavelengths can be used with a fusing lamp that emits a broad range of wavelengths. Matching the radiation absorber and the fusing lamp in this way can increase the 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.

Depending on the amount of radiation absorber present in the polymer powder, the absorbance of the radiation absorber, 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 lamp can irradiate individual layers from about 0.5 to about 10 seconds per pass.

The 3D printed article can be formed by jetting a fusing agent onto layers of powder bed build material according to a 3D object model. 3D object models can in some examples be created using computer aided design (CAD) software. 3D object models can be stored in any suitable file format. In some examples, a 3D printed article as described herein can be based on a single 3D object model. The 3D object model can define the three-dimensional shape of the article. In some cases, an antioxidant agent can be added to portions of the 3D printed article, such as portions near the surface where yellowing would be visible. In further examples, the antioxidant agent can be added to portions of the powder bed that will remain as loose powder after printing, such as areas of the powder bed adjacent to the surface of the 3D printed article. In such examples, the 3D object model may include both the three-dimensional shape of the article and also the three-dimensional shape of the portion of the volume where the antioxidant agent is to be added. In other examples, the article can be defined by a first 3D object model and the antioxidant agent portions can be defined by a second 3D object model. Other information may also be included, such as structures to be formed of additional different materials or color data for printing the article with various colors at different locations on the article. The 3D object model may also include features or materials specifically related to jetting fluids on layers of powder bed material, such as the desired amount of fluid to be applied to a given area. This information may be in the form of a droplet saturation, for example, which can instruct a 3D printing system to jet a certain number of droplets of fluid into a specific area. This can allow the 3D printing system to finely control radiation absorption, cooling, color saturation, concentration of the dihydrazide antioxidant, and so on. All this information can be contained in a single 3D object file or a combination of multiple files. The 3D printed article can be made based on the 3D object model. As used herein, “based on the 3D object model” can refer to printing using a single 3D object model file or a combination of multiple 3D object models that together define the article. In certain examples, software can be used to convert a 3D object model to instructions for a 3D printer to form the article by building up individual layers of build material.

In an example of the 3D printing process, a thin layer of polymer powder can be spread on a bed to form a powder bed. At the beginning of the process, the powder bed can be empty because no polymer particles have been spread at that point. For the first layer, the polymer particles can be spread onto an empty build platform. The build platform can be a flat surface made of a material sufficient to withstand the heating conditions of the 3D printing process, such as a metal. Thus, “applying individual build material layers of polymer particles to a powder bed” includes spreading polymer particles onto the empty build platform for the first layer. In other examples, a number of initial layers of polymer powder can be spread before the printing begins. These “blank” layers of powder bed material can in some examples number from about 10 to about 500, from about 10 to about 200, or from about 10 to about 100. In some cases, spreading multiple layers of powder before beginning the print can increase temperature uniformity of the 3D printed article. A fluid jet printing head, such as an inkjet print head, can then be used to print a fusing agent including a radiation absorber over portions of the powder bed corresponding to a thin layer of the 3D article to be formed. Then the bed can be exposed to electromagnetic energy, e.g., typically the entire bed. The electromagnetic energy can include light, infrared radiation, and so on. The radiation absorber can absorb more energy from the electromagnetic energy than the unprinted powder. The absorbed light energy can be converted to thermal energy, causing the printed portions of the powder to soften and fuse together into a formed layer. After the first layer is formed, a new thin layer of polymer powder can be spread over the powder bed and the process can be repeated to form additional layers until a complete 3D article is printed. Thus, “applying individual build material layers of polymer particles to a powder bed” also includes spreading layers of polymer particles over the loose particles and fused layers beneath the new layer of polymer particles.

Definitions

It 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.

As used herein, “colorant” can include dyes and/or pigments.

As used herein, “dye” refers to compounds or molecules that absorb electromagnetic radiation or certain wavelengths thereof. Dyes can impart a visible color to an ink if the dyes absorb wavelengths in the visible spectrum.

As used herein, “pigment” generally includes pigment colorants, magnetic particles, aluminas, silicas, and/or other ceramics, organo-metallics or other opaque particles, whether or not such particulates impart color. Thus, though the present description primarily exemplifies the use of pigment colorants, the term “pigment” can be used more generally to describe pigment colorants and other pigments such as organometallics, ferrites, ceramics, etc. In one specific aspect, however, the pigment is a pigment colorant.

As used herein, “ink jetting” or “jetting” refers to compositions that are ejected from jetting architecture, such as ink-jet architecture. Ink-jet architecture can include thermal or piezo architecture. Additionally, such architecture can be configured to print varying drop sizes such as less than 10 picoliters, less than 20 picoliters, less than 30 picoliters, less than 40 picoliters, less than 50 picoliters, etc.

As used herein, “average particle size” refers to a number average of the diameter of the particles for spherical particles, or a number average of the volume equivalent sphere diameter for non-spherical particles. The volume equivalent sphere diameter is the diameter of a sphere having the same volume as the particle. Average particle size can be measured using a particle analyzer such as the Mastersizer™ 3000 available from Malvern Panalytical. The particle analyzer can measure particle size using laser diffraction. A laser beam can pass through a sample of particles and the angular variation in intensity of light scattered by the particles can be measured. Larger particles scatter light at smaller angles, while small particles scatter light at larger angles. The particle analyzer can then analyze the angular scattering data to calculate the size of the particles using the Mie theory of light scattering. The particle size can be reported as a volume equivalent sphere diameter.

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. When using the term “substantial” or “substantially” in the negative, e.g., substantially devoid of a material, what is meant is from none of that material is present, or at most, trace amounts could be present at a concentration that would not impact the function or properties of the composition as a whole.

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 little below” the endpoint. The degree of flexibility of this term can be dictated by the particular variable and determined based on the associated description herein.

As used herein, a plurality of items, structural elements, compositional elements, and/or materials may be presented in a common list for convenience. However, these lists should be construed as though individual members of the list are individually identified as a separate and unique member. Thus, no individual 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.

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 the numerical values explicitly recited as the limits of the range, and also to include individual numerical values or sub-ranges encompassed within that range as if individual numerical values and sub-ranges are explicitly recited. As an illustration, a numerical range of “about 1 wt % to about 5 wt %” should be interpreted to include the explicitly recited values of about 1 wt % to about 5 wt %, and also include individual values and sub-ranges within the indicated range. Thus, included in 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 a single numerical value. Furthermore, such an interpretation should apply regardless of the breadth of the range or the characteristics being described.

Examples

The following illustrates examples of the present disclosure. However, it is to be understood that the following are merely illustrative of the application of the principles of the present disclosure. Numerous modifications and alternative devices, 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.

Adipic dihydrazide was mixed with a sample of polyamide 12 powder in an amount of 1 wt % adipic dihydrazide based on the total weight of the polyamide 12 powder and the adipic dihydrazide together. Triethylene glycol (a polar organic solvent having a boiling point of about 287° C.) was then added to the mixture in an amount of 10.18 wt % based on the total weight of the mixture. For comparison, a control sample of polyamide 12 powder without adipic dihydrazide was also mixed with triethylene glycol in the same amount. The first sample and the control sample were aged for 20 hours at 175° C. The control sample had a light brown color after the aging, whereas the sample that included the adipic dihydrazide remained white.

The samples were dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol. The sample that included the adipic dihydrazide dissolved well. This sample had a milky appearance due to insoluble fillers in the polymer powder, but the polymer itself appeared to dissolve completely. The polymer of the control sample did not dissolve, indicating that the polyamide 12 was altered by an interaction with the triethylene glycol. Without being bound to a specific mechanism, the polyamide 12 powder may have been crosslinked by the triethylene glycol.

In another test, a sample of polyamide 12 powder was mixed with a detailing agent that included triethylene glycol and 4 wt % adipic dihydrazide, based on the total weight of the detailing agent. A control sample of polyamide 12 powder was mixed with detailing agent containing triethylene glycol, but without adipic dihydrazide. These samples were also aged for 20 hours at 175° C. The sample without the adipic dihydrazide had a dark brown color after aging, while the sample with the adipic dihydrazide had a slightly yellow color. These results indicate that the adipic dihydrazide can be added to the powder or to the fluid agent. In either case, the adipic dihydrazide can effectively reduce the interactions between the triethylene glycol and the polyamide 12 powder.

THREE-DIMENSIONAL PRINTING WITH DIHYDRAZIDE ANTIOXIDANTS

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