Virginia Tech Intellectual Properties Inc

The Procter Gamble Company

Solvay Specialty Polymers Usa, LLC

Virginia Polytechnic Institute and State University

The Procter & Gamble Company

Christopher Bryant Williams

Timothy Edward Long

Viswanath Meenakshisundaram

Callie Elizabeth Zawaski

Travis Kyle Hodgdon

Corey James Kenneally

Douglas Michael Graham

Freddy Arthur Barnabas

Allison M Pekkanen

Nicholas Raymond Chartrain

Michael Sean Farrell

Joel Pollino

Kermit S Kwan

Philip J Scott

Jana Herzberger

Andre Stevenson

Abby Rebecca Whittington

Amelia M Elliott

Stéphane Jeol

Katherine V Heifferon

Maruti Hegde

Benjamin Tyler White

Justin Sirrine

Nicholas Alexander Meisel

Emily M Wilts

Da Ma

Viswanath Meenakshisundarm

David Lee McCarthy

Daniel Rau

Cody Weyhrich

Allison Pekkanen

The present invention relates to relates to a polymer formulation for three-dimensionally (3D) printing an article by stereolithography, the formulation comprising a functionalized polymer. The invention further relates to lithographic methods to form 3D objects that incorporate the aforementioned polymer formulation.

Photocurable polymer compositions

Binders and methods of binder jetting are provided based on the use of branched polymer binders. The applicants have found that, even more so than the molecular weight, the ability to achieve higher maximum printable concentrations leads to higher densities and improved structural properties of the manufactured articles. The methods can be used for a variety of articles from metal parts to structural ceramics, to tablets and other oral dosage forms. The branched chain polymers can include a short-chain branched polymer; a long-chained branched polymer; a hyper-branched polymer, a cyclic polymer; a comb-type polymer; a 3-arm star type polymer, a 4-arm star type polymer, a dendritic polymer, and a combination thereof. The branched-chain polymer can include various polymers such as polyvinylpyrrolidone, poly(vinyl alcohol), or poly(acrylic acid).

Binders and methods of binder jetting including branched polymer binders and articles made therefrom

In various aspects, top-down stereolithography apparatus and methods of use thereof are provided herein that allow for additive manufacturing of an article from a high-viscosity resin. The apparatus and methods can print resins having viscosities higher than conventional systems, e.g. viscosities up to about 100 Pa·s at the elevated temperature. The resin may have a room temperature viscosity of about 100 Pa·s, about 250 Pa·s, about 1000 Pa·s, or more. In some aspects, the resin is a solid at room temperature. The apparatus and methods do not rely upon solvents or other viscosity modifiers being added to the resin, and are capable of top-down additive manufacturing approaches which provide reduced stress on the printed article.

High-temperature stereolithography apparatus and methods of use thereof

In various aspects, a polymer resin is provided for vat or ultraviolet-assisted direct ink writing (UV-DIW) photopolymerization. The resin can include a polyamic acid salt formed from the addition of a photocrosslinkable amine to a polyamic acid. The resin can include a photoinitiator suitable for initiating crosslinking of the photocrosslinkable amine when exposed to a light source of a suitable wavelength and intensity. The polyamic acid can be formed, for instance, by the addition of a diamine to a suitable dianhydride. Methods of additive manufacturing using the resins are also provided.

Additive manufacturing of aromatic thermoplastics from photocurable precursor salts

Photocurable colloid binders are provided that overcome deficiencies associated with 3D printing of high molecular weight polymers via VAT photopolymerization. Methods of additive manufacturing are also provided using the binders. The approaches described herein effectively decouple the viscosity-molecular weight relationship by synthesizing and processing photo-reactive aqueous colloids that are sequestered within a photocrosslinkable scaffold. Sequestering polymers within discrete internal phases prevents inter-particle entanglement of the polymer chains, thus ensuring low viscosity. VP of polymer colloids results in a solid green body embedded with high molecular weight polymer particles. A post-processing heated drying step allows the polymers to coalesce and further entangle, forming a semi-interpenetrating network with mechanical performance of the high molecular weight material. The resins can further include inorganic particles such as silica and other ceramics, metal particles, and the like. The coalescence can result in the particles being encapsulated in polymer, yielding unique hybrid materials with tunable properties.

Synthesis and 3D printing of photocurable colloids

Photocurable polymers, photocurable polymer compositions and lithographic processes including the same

In various aspects, a polymer resin is provided for vat photopolymerization. The resin can include a polyamic acid salt formed from the addition of a photocrosslinkable amine to a polyamic acid. The resin can include a photoinitiator suitable for initiating crosslinking of the photocrosslinkable amine when exposed to a light source of a suitable wavelength and intensity. The polyamic acid can be formed, for instance, by the addition of a diamine to a suitable dianhydride. Methods of additive manufacturing using the resins are also provided.

A water-soluble polyurethane derived from: polyethylene glycol, polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol polymer, polypropylene glycol-block-polyethylene glycol-block-polypropylene and mixtures thereof, 1,1'-Carbonyldiimidazole, polyamine and mixtures thereof.

Polymeric materials and articles manufactured there from

Polymer resins for the vat photopolymerization of thermoplastics are provided, in particular for the vat photopolymerization of thermoplastics with exception thermal stability and mechanical properties. In some aspects, the polymer resins are prepared by ring opening of an aromatic dianhydride with an alcohol containing an acrylate or methacrylate to produce a photocrosslinkable diacid monomer; conversion of the photocrosslinkable diacid monomer to a photocrosslinkable diacyl chloride; and polymerization of the photocrosslinkable diacyl chloride with an aromatic diamine to produce a photocrosslinkable precursor polymer. Upon crosslinking and drying, a thermal imidization can yield aromatic polyimide polymers with high yield and with micron-scale structural resolution.

Compositions and methods of additive manufacturing of aromatic thermoplastics and articles made therefrom

Described herein are 3D printers capable of printing high-performance materials and uses thereof.

High temperature 3D printing via inverted heated build chamber

A method for manufacturing a three dimensional object includes steps of: providing a digital description of the object as a set of voxels; sequentially creating an actual set of voxels corresponding to the digital set of voxels. At least one voxel comprises a polymer derived from: polyol and an ionic monomer. The calculated charge density of the resulting polymer is 0.01 to 0.7 mEq/g. A three-dimensional object having at least one voxel. The at least one voxel including a polymer derived from: a polyol and an ionic monomer, and the calculated charge density of the resulting polymer is 0.01 to 0.7 mEq/g.

A water soluble container comprises a water soluble shell enclosing a volume. The water soluble shell comprises a set of voxels.

Water soluble containers and methods of making them

A method for manufacturing a three dimensional object includes steps of: providing a digital description of the object as a set of voxels; sequentially creating an actual set of voxels corresponding to the digital set of voxels. At least one voxel comprises a polymer derived from: polyol and an ionic monomer. The calculated charge density of the resulting polymer is 0.01 to 0.7 mEq/g.

Growing community of inventors

Blacksburg, VA, United States of America

Christopher Bryant Williams