Patent Application
20200367477
The field of the invention is artificial coral.
Coral provide food, shelter, protection, and spawning areas for hundreds of species of fish and other marine organisms. However, natural coral once damaged may take a long time to recover. Thus, there is a need for providing artificial coral articles to be inhabited by coral reef ecosystems.
One aspect of the disclosed embodiments related to a method for introducing an artificial coral article to coral reef polyps and fragments.
Another aspect of the disclosed embodiments related to methods for preparing artificial coral articles using a three-dimensional (3D) printer, a powder composition, a binder composition, and optionally one or more post-processing agents.
Another aspect of the disclosed embodiments related to artificial coral articles and intermediate articles thereof prepared by the methods disclosed herein.
Another aspect of the disclosed embodiments related to the powder compositions and/or the binder composition used for preparing artificial coral articles as disclosed herein.
Another aspect of the disclosed embodiments related to a method for screening a powder composition and/or a binder composition for uses in preparing an artificial coral article as disclosed herein.
One aspect of the disclosed embodiments related to a method for introducing an artificial coral article to coral reef polyps and/or fragments. In certain embodiments, the introducing step is through means of asexual reproduction, budding, cloning, and/or fragmentation.
In certain embodiments, the introduction of the artificial coral article to coral reef polyps and/or fragments comprises I) introducing the artificial coral article to the coral reef polyps and/or fragments in a first wild environment (e.g., the field) to provide a first artificial coral article combination; and II) introducing the first artificial coral article combination to coral reef polyps and/or fragments in a second wild environment, wherein the first and the second wild environments may be the same or different.
In certain embodiments, the introduction of the artificial coral article to coral reef polyps and/or fragments comprises I) introducing the artificial coral article to the coral reef polyps and/or fragments in a controlled condition (e.g., a lab condition) to provide a first artificial coral article combination; and II) introducing the first artificial coral article combination to coral reef polyps and/or fragments in a second wild environment.
Another aspect of the disclosed embodiments related to an artificial coral article and/or intermediate article prepared by a method disclosed herein. Pictures of example artificial coral articles are shown in
As used herein the term “intermediate article” means an article prepared by a method disclosed herein that are not post-processed.
Another aspect of the disclosed embodiments related to a method for preparing an artificial coral article comprising:
In certain embodiments, the post-processing step would not alter the 3D configuration of the first intermediate article, and therefore, the first intermediate article and the artificial coral article have an identical 3D design. In certain embodiments, the post-processing step may alter the 3D configuration of the first intermediate article, and therefore, the first intermediate article and the artificial coral article may have different 3D designs.
Optionally, the preparation method further comprises excavating the greenware of step B). Optionally, the preparation method further comprises collecting the powder composition that is not incorporated in the artificial coral article or intermediate article (i.e., the unused powder composition). Optionally, the preparation method further comprising using the collected unused powder composition in the printing step.
In certain embodiments, the printing step comprises:
In certain embodiments, the mixture layer is provided by:
In certain embodiments, the layer of mixture of step a) is provided by:
In certain embodiments, the pressure is applied by a roller bar, wiper, or hopper. In certain embodiments, steps ia) and/or iia) comprise depositing or rolling over the layer of the powder composition using a roller bar, wiper, or hopper.
In certain embodiments, each layer (e.g., the powder composition layer and the mixture layer) may have a thickness of about 0.0762 mm, about 0.1016 mm, about 0.127 mm, about 0.2032 mm, about 0.254 mm, about 1 mm to about 8 mm, or about 2 mm to about 7 mm.
Unless otherwise specified, “pre-curing” a mixture layer as used herein means hardening or toughening the mixture layer so that another layer of a powder composition or a mixture of a powder composition and a binder composition may be applied to the cured mixture layer with a desired configuration.
The greenware prepared as disclosed herein may be post-processed to provide the artificial coral article with enhanced mechanical strength, durability, and/or waterproof suitable for use as a safe and lasting home for coral reef ecosystems. The post-processing step may include applying one or more post processing agents to the greenware. The one or more post processing agents may be applied by the same or different methods selected from the group consisting of brushing, spraying, dipping, and submersion.
Examples of the post-processing agents include, without limitation, polymers (e.g., resins). In certain embodiments, polymers used for post-processing may infiltrate the porous structure of the greenware through capillary action before the polymers set or cure. Polymers with low viscosity are preferred for effective infiltration to the greenware. Since the artificial coral articles may be a new home for coral reef ecosystems, polymers used for pos-processing should also be safe to aquatic and crustaceous lives and should not leach harmful chemicals.
Examples of suitable polymers include, without limitation, epoxy resins, and polyeurothane resins.
In certain embodiments of the preparation methods disclosed herein, using a 3D printer (e.g., Zcorp 310) comprises Steps 1 to 4 as disclosed below.
Step 1: Configuring the 3D Printer with the 3D Model of an Intermediate Article to be Printed
A 3D model is provided for the intermediate article with a desired 3D design and “sliced” into layers for printing, e.g., using a typical 3D slicer tool. Configurations and parameters of each “sliced” layer are provided for the 3D printer to determine a space (area, thickness, location) in which to deposit a powder composition disclosed herein, a binder composition disclosed herein, and/or a mixture thereof. A “sliced” layer may be a Boolean code, meaning a closed (watertight) area is consider “inside” the print area and an open area that is NOT the closed area is considered the “outside” print area.
Step 2: Printing the Intermediate Article Using the 3D Printer
In certain embodiments, a base (e.g., a build plate, a build bed) is provided for the intermediate article to be built on layer by layer. The base may be a flat rigid object that the powder may be deposited on as desired so that when excess powder is removed during excavation, the flat rigid object can be picked up and carry the 3D printed object (which may be too fragile to be picked up by itself). The base may also be referred to as a build plate. The base may also be referred to as a build bed when the base already includes some powder.
Subsequent layer of the powder composition is deposited on a pre-cured mixture layer, and the binder composition is deposited to provide another mixture layer with desired shape. The binding composition activates the powder composition for pre-curing to provide another pre-cured mixture layer before another layer of the powder composition is deposited thereon.
In one example, a thin layer of the powder composition may be rolled flat in a base (e.g., a build plate, a build bed). Depending on the mechanics of the 3D powder printer, the initial layers, in addition to all subsequent layers, may be added and/or evened by a roller bar, wiper, or hopper. For example, a new layer of the powder composition may be deposited or rolled over with a specified layer height. Once the layer of powder is provided, a print head uses and X axis and Y axis to “print” the specified layer as fed to the machine by the “slicer” program in Step 1. The print head may deposit the binder composition to the specified area of each “slice” of the desired intermediate article similar to how a conventional printer prints ink on a piece of paper. After a “sliced” layer is “printed” and pre-cured, a new layer of the powder composition is added and prepared using means previously described. Each layer of the thickness of the layer of the powder composition, as well as saturation or quantity of the binder composition deposited, may be parametrized before the printing begins and/or adjusted accordingly during the printing. Layers of the powder composition deposition in the printing process can range from about 1 mm to about 8 mm in thickness. Thickness of each layer may be chosen by the user based upon the configuration and properties of the powder composition and binder composition (e.g., how the chosen powder composition receives the binder composition). A balance may be struck between layer thickness. For example, when a new layer of powder is deposited, the layers adhere to each other and are not dragged away or damaged in the mechanics of the printing process. This process of layer deposition, preparation, and printing are repeated until the desired intermediate article is built up, layer by layer.
Step 3: Excavating the Intermediate Article, and Recycling of the Powder Composition
Once the 3D printer completes the printing process, the 3D printed intermediate article may sit in the base of powder for a time sufficient to dry (e.g., about 3-48 hours, or more, e.g., until sufficient liquid has dried/evaporated from the intermediate article). After the 3D printed intermediate article is excavated from the base of powder. In certain embodiments, the excavating may be accomplished by using brushes and/or air compressed guns to remove uncured powder composition (i.e., the unused powder composition). This unused powder composition may be recycled and used again. The excavated intermediate article is now considered a “greenware,” which means that it is strong enough to hold its shape independently but can still be broken and has not been post-processed. This may be similar to ceramics wherein a clay article is called “greenware” after it is dried but before it is fired and turned into its final hard ceramic form.
Step 4: Post-Processing
The greenware prepared as disclosed herein may be further post-processed to provide the artificial coral article with enhanced mechanical strength, durability, and waterproof suitable for use as a safe and lasting home for coral reef ecosystems. The post-processing step may include applying one or more post processing agents to the greenware. The one or more post processing agents may be applied by brushing, spraying, dipping, and/or submersion. Examples of the post-processing agents include, without limitation, polymers as described herein.
In certain embodiments, the printing method further comprises steps α and step β as described below.
Step α: Loading the Powder Composition into the 3D Printer
A thoroughly mixed powder composition is added into the base (e.g., a build plate, a build bed) of the 3D printer. The powder composition may be “fluffed” due to the mixing process. A pressure may be applied (e.g., by compression of a flat plate) to the powder composition as loaded to provide a compact load of the powder composition. The compact load of the powder composition may provide a better mechanical spreading during printing.
Step β: Loading the Binder Composition into the 3D Printer
A binder composition is loaded into the 3D printer. In certain embodiments, the binder composition is a liquid that travels well through the hoses and print head mesh of the 3D printer, as well as is received well by the powder composition for desired pre-cure results.
Another aspect of the disclosed embodiments related to a powder composition comprising a base composition, and an adhesive composition. In certain embodiments, the powder composition further comprises one or more wicking agents, one or more hygroscopic agents, one or more absorbent agents, one or more deflocculants, or a mixture thereof.
The powder composition disclosed herein can be used for preparation of the artificial coral articles as disclosed herein.
The powder composition has particle sizes of between 200-60 mesh size, about 37-250 microns; or about 60 microns or about 230 mesh size; and has a desired spreadability.
In certain embodiments, a powder composition comprises about 2 to about 5 parts of a base composition, about 1 to about 3 parts of an adhesive composition, and about 0 to about 3 parts of other additives, and all parts are by weight.
A) Base Composition
The base composition should be insoluble or hardly soluble in water, and is preferred to has a neutral pH and desired mechanical and structural property for the intermediate article and/or the final artificial coral article.
Examples of the base composition include without limitation, a calcium salt with a low water solubility (e.g., calcium carbonate, calcium sulfate, etc.), geopolymers such as a ceramic composition (e.g., a phosphate ceramic such as magnesium phosphate ceramic); a plaster; and mixtures thereof. A base composition may stick or bind when activated by the binder composition.
In certain embodiments, the magnesium phosphate ceramic may be prepared by reacting magnesium oxide in an aqueous solution of a phosphate. Examples of phosphates include, without limitation, ammonium phosphate, monoammonium phosphate, potassium phosphate, and monopotassium phosphate.
The magnesium phosphate ceramic has a desired hard cementitious like quality and is largely pH neutral. It is advantageous compared to a concrete because concrete is basic and leaching. Examples of magnesium phosphate ceramic includes, without limitation, Ceramicrete, Grancrete, Gigacrete, AirKrete, and mixtures thereof.
Similarly, a plaster also has the desired neutral pH and cementitious like property, thus may be used as a filler to augment mass and quantity of the mixture.
B) Adhesive Composition
An adhesive composition comprises one or more adhesive agents.
A suitable adhesive agent sticks or binds when activated by the binder composition. The adhesive agent helps to create overall strength of the intermediate article and the artificial coral article, as well as helps in layer adhesion for subsequent layers during the preparation process. Examples of adhesive agents include, without limitation, sugar (e.g., powdered sugar), cellulose and derivatives thereof (e.g., methyl cellulose, carboxy celluloses such as carboxy methyl cellulose (CMC), salts of carboxy cellulose (e.g., sodium carboxy methyl cellulose (Na CMC)), hydroxyethyl cellulose), modified starch (e.g., modified starch ether), wheat paste, polymer (e.g., polyvinal alcohol (PVA) powder), gum Arabic, and mixtures thereof.
For example, sugar may be used as an adhesive agent for its binding characteristics. Sugar may provide strong structural characteristics after wetted with the binder composition and dried. Sugar may also act as a hygroscopic agent.
In certain embodiments, one or more adhesive agents may be a mixture of a powdered sugar can and a starch additive to further improve the wicking ability and flow rate when spreaded.
Cellulose derivatives may be used as a glue binder and/or a thickening agent. For example, methyl cellulose, CMC and Na CMC may be used as a glue binder. In certain embodiments, the adhesive agents are CMC and/or Na CMC. In certain embodiments, hydroxyethyl cellulose may be used as a thickening agent and bonding material that help shaping of the intermediate article during excavation. In certain embodiments, the amount of CMC used is about 33% (wt.) or less.
Modified starch ether is a polysaccharide that may be used as a thickening agent to improve shaping.
In certain embodiments, one or more adhesive agents are a mixture of one or more modified starch ethers and one or more cellulose derivatives (e.g., methyl cellulose, carboxymethyl cellulose).
A wheat paste may be used as a glue binder.
A polymer suitable as an adhesive agent may be a water soluble polymer such as PVA powder.
C. Other Additives
The powder composition may further include one or more other additives selected from the group consisting of wicking agents, absorbent agents, hygroscopic agents, deflocculants. Examples of additives include, without limitation, agents provided in Table 1.
Wicking agents and hygroscopic agents are optional and may help the mechanical and structural property of the intermediate articles and the artificial coral articles disclosed herein.
One or more wicking agents may lower the surface tension on top of a powder composition layer to improve absorbance of the liquid binder composition into a layer of powder composition. A wicking agent may also help to increase the strength of the intermediate articles.
One or more hygroscopic agents may prevent the liquid binder composition from spreading into unprinted areas.
Deflocculants may improve the flowability and/or spreadability of the powder composition. Powder flowability may be influenced by particle size. The lower the particle size the higher the flowability. Also, deflocculants with small particle size may increase the flowability of the powder composition.
Another aspect of the disclosed embodiments related to a binder composition comprising one or more solvents. Optionally, the binder composition further comprises one or more glycols (e.g., sugar), one or more humectants and/or one or more surfactants.
The binder composition is a solution having a viscosity of about 10 to about 12 cps, about 1 to about 10 cps, or about 1.35 cps, and a surface tension of about 45 dynes/cm to about 75 dynes/cm. The viscosity of the binder composition should be sufficiently low to avoid clogging the print head, and sufficiently high to avoid leaching.
In certain embodiments, the one or more solvents are selected from the group consisting of water, alcohols, and mixtures thereof. Alcohols may help shorten the time required to pre-cure a mixture layer because alcohols are more volatile than water and may help the solvents to dry and/or evaporate more quickly.
Water helps hydrate and activate the powder composition for pre-curing, especially the adhesive composition of the powder composition. Optionally, the water used is distilled/filtered. However, water that is not distilled or filtered may damage the 3D printer's feed lines and print head with build-up of minerals and residues in the undistilled/unfiltered.
Alcohols help significantly to prevent oversaturation of water and accelerate evaporation of the binder composition in the mixture layer. An alcohol content should be sufficiently low to allow the powder composition to be saturated by water for proper activation and pre-curing of the mixture layer. However, it the alcohol content is too low, the time to pre-cure/dry may become excessive.
Examples of alcohols include, without limitation, ethanol, isopropyl alcohol, sake, and 100+ proof vodka. In certain embodiments, the binder composition comprises 1:1 water and sake.
A small amount of glycols (e.g., sugar) in the binder composition may be beneficial to adhere the mixture layers together. This component of the binder composition especially helps increase layer adhesion between a mixture layer and a powder composition layer. The “stickiness” allows the next powder composition layer to properly adhere to the last pre-cured mixture layer such that all layers are bound into a final object. However, too much glycols (e.g., sugar) content in the binder composition may clog the 3D printer and/or stick part of the mixture layer or powder composition layer to a tool used to even the mixture layer (e.g., roller bar, wiper, or hopper). Too much glycols (e.g., sugar) that is not properly dissolved in the binder composition may become too viscose and clog the 3D printer's hoses and the fine mesh used to dispense the binder composition. An excessive amount of glycols (e.g., sugar) may increase friction as well. Increase in friction or clogging of the 3D printer's print head may cause errors in the printing and overheat of the print head.
One or more humectants may be used to hydrate the powder composition and helps to draw the one or more solvents into the powder composition layer to form a relatively even mixture layer of the powder composition and the binder composition.
One or more surfactants are used to lower the liquids surface tension of the binder composition to improve the mixing of the powder composition and the binder composition. The one or more surfactants may also help the liquid binder travel through the print head's mesh to reduce friction in the print head. Otherwise, the print head may be overheated or clogged by the residues of the binder composition. Additionally, surfactants may decrease the surface tension between a component of a 3d printer (e.g., a roller bar, e.g., a spinning bar) that pulls the powder composition to create a smooth and even layer of powder composition on top of the previous pre-cured mixture layer.
Examples of surfactants include, without limitation, surfynol (acetylene glycol), sodium laurel sulfate, and polysorbate.
Examples of binder compositions are provided in Examples 3 and 4.
Another aspect of the disclosed embodiments related to testing various powder composition. In certain embodiments, the method includes steps 1 to 2.
Before powder selection begins, one can test various mixtures to which powder composition works best.
In certain embodiments, the tests can be conducted by mixing a small batch of a powder composition (between 1 Teaspoon and 1 Cup) and then laying each composition on a flat, non pourus surface (Plastics, Acrylic, glass, etc.). Each composition is then spread or compress to be thin (˜ 1/16″-½″) and flat. The tested composition is then sprayed with a mist, to simulate that of a print head used in the 3D printer, in order to visibly examine who the tested composition both receives powder and dries to harden. An ideal composition is one which receives powder and hydrates well, but does not bead or let the liquid pool on top. An ideal composition also creates a thick/hard film or layer on top. An ideal composition dries within less than 24 hours and is hard/strong enough to pick up and hold itself against gravity.
Once an optimal powder composition is selected, the powder must be mixed in their appropriate mixtures with ratios by weight. The powder is to be mixed thoroughly. This means that all powder must be sifted to remove clumps. All clumps that are do not sift out are removed to avoid adding hard cemented material or moisture brought in from mixed powders. Powders are then thoroughly mixed well together to create a homogenous looking mixture. Mixture is best done by mechanical means (mixing apparatus, drill with mixing bit, etc.). Once the powder is thoroughly sifted and mixed, it is ready for printing.
Powder compositions disclosed in Example 2 were tested with a binder composition consisting of 3 parts (v.) of water, 6 parts (v.) of sake, 0.85 parts (v.) of propylene glycol and 0.15 parts (v.) of surfynol, (i.e., Binder composition No. 3 as shown in Table 4C of Example 3)
Powder composition No. B prepared a greenware with strength less than that prepared using a powder composition of No. C.
Powder composition No. C provided the best greenware among the compositions tested in this example.
PVA powder worked well in place of CMC as adhesive, and in combination of sugar. PVA showed as a better adhesive (in powder composition No. E) than sugar (powder composition NO. D). However, PVA is more expensive than sugar.
Magnesium ceramic prepared by MgO and phosphate was used as a base composition and an adhesive agent (Powder composition G), and provided greenware more durable and water resistant than those prepared by powder compositions without magnesium ceramic component (e.g., powder compositions A, G, and C). However, magnesium ceramic was more costly and more complicated to make.
Uses of plaster as a filler for the base composition (e.g., powder composition No. A) brought the cost down but was not as desired for polyps growth.
Powder composition No. B had weaker strength, as use of wheat paste did not produce very good strength for the intermediate article.
The most preferred powder composition in this example was powder composition No. C.
Four binder compositions were prepared and tested with a powder composition consisting of 3 parts (wt.) calcium carbonate, 2 parts (wt.) plaster, 2 parts (wt.) sugar, 2 parts (wt.) maltodextring, and 1 part (wt.) carboxymethyl cellulose (Powder composition No. C). Binder compositions comprising sake (Nos. 1 and 3) showed more reliable results than a binder composition comprising vodka (NO. 2). A binder composition comprising propylene glycol, surfynol and sake (No. 3) worked better than a binder composition comprising propylene glycol and sake (No. 1). Surfynol helped reducing the viscosity of the binder composition, which in turn reduced friction, heat generation, and damage to the print head. A binder composition comprising an alcohol (No. 3) worked better than a binder composition without an alcohol (No. 4), although both binder compositions had propylene glycol and surfynol. Alcohol may help reduce drag on the print and drying time needed. However, a higher ratio of alcohol and water may result in less strength overall in the greenware. Sake worked well as alcohol content as it allowed quicker drying time and better layer adhesion overall.
Binder composition Nos. provided in Table 4E below were tested with a powder composition consisting of 3 parts (wt.) calcium carbonate, 2 parts (wt.) plaster, 2 parts (wt.) sugar, 2 parts (wt.) maltodextrin, and 1 part (wt.) CMC.
Various powder compositions were prepared and tested with binder composition No. 3 as shown in Table 4C of Example 3. Each composition was evaluated based on the following parameters:
1) Spread, characterized by 0-100%, which indicates how well a powder composition layer was spread by a roller bar. Poor spreading was shown when one or more pre-cured mixture layers was dragged or disrupted by the roller bar when the roller bar spread a powder composition layer. Lower value (0%) indicated higher level of layer drag which could be caused by poor adhesion of layers and/or too much surface tension of roller bar.
2) Strength, characterized by 0-5, which indicated the strength of the greenware (i.e., the intermediate article). A lower strength would result in a weaker part of the greenware that was likely to break in handling and processing. The intermediate article might immediately crumble upon excavation if the strength was too low.
3) Acceptable, characterized by yes or no, which indicated whether or not the intermediate article prepared was acceptable for post-processing and subsequent use. “Yes” might include minor defects in form but still acceptable for post-processing and subsequent use. “No” means the mixture did not reliably produce an intermediate article suitable for post-processing and subsequent use.
Additional powder compositions were tested with binder composition No. 1 disclosed in Example 3, which consists of 30 parts (v.) of water, 60 parts (v.) of sake and 10 parts (v.) of propylene glycol.
Addition of plaster worked well and did not impact outcome very much as long as plaster was no more than calcium carbonate. In some embodiments plaster helped strengthen or stabilize the intermediate article.
PVA worked well and acted as a strong binder for this application. However, it could be very expensive with relation to the cost of other adhesive materials.
The foregoing description of embodiments has been presented for purposes of illustration and description. The foregoing description is not intended to be exhaustive or to limit embodiments of the present invention to the precise form disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of various embodiments. The embodiments discussed herein were chosen and described in order to explain the principles and the nature of various embodiments and its practical application to enable one skilled in the art to utilize the present invention in various embodiments and with various modifications as are suited to the particular use contemplated. While operations are depicted in the drawings in a particular order, this should not be understood as requiring that such operations be performed in the particular order shown or in sequential order, or that all illustrated operations be performed, to achieve desirable results. The features of the embodiments described herein may be combined in all possible combinations of methods, modules, systems and compositions.
