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

Patent metadata

Field	Value
Publication number	US-2022088855-A1
Application number	US-202017442811-A
Country	US
Kind code	A1
Filing date	Mar 25, 2020
Priority date	Mar 25, 2019
Publication date	Mar 24, 2022
Grant date	—

Abstract

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).

First claim

1 . (canceled)

2 . A method of binder jetting of a 3D-printed article in a layer-by-layer fashion, the method comprising:
a) providing a first layer of powder; b) ink-jet depositing a binder onto the first layer of the powder in a pattern that corresponds to a first layer of the article, wherein the binder comprises a branched-chain polymer and a solvent; c) providing a subsequent layer of powder onto either the first layer of powder or a previous layer of powder; d) ink-jet depositing the binder onto the subsequent layer of powder in a pattern that corresponds to a subsequent layer of the article; e) repeating steps (c) and (d) to form the article layer-by-layer by forming each subsequent layer of the article on a previous layer of the article;
wherein the concentration of the branched-chain polymer in the binder is above a maximum printable concentration of the otherwise same binder and under the otherwise same conditions except replacing the branched-chain polymer with a linear-chain polymer of the same repeat units and having the same M n .

3 . The method according to claim 2 , wherein the branched-chain polymer has a M n of about 5 kg mol −1 to about 75 kg mol −1 .

4 . The method according to claim 2 , wherein the branched-chain polymer has a polydispersity index (PDI) of about 1.0 to about 30.0.

5 . The method according to claim 2 , wherein the branched-chain polymer has a glass transition temperature (T g ) of about 40° C. to about 250° C.

6 . The method according to claim 2 , wherein the branched-chain polymer is selected from the group consisting of 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.

7 . (canceled)

8 . (canceled)

9 . The method according to claim 2 , wherein the branched-chain polymer is selected from the group consisting of polycarbonates, polyolefins, polymethacrylates, polystyrenes, polyamides, polyurethanes, poly(ethylene terephthalate), poly(lactic acid), poly(glycolic acid), polyhydroxbutyrate, polydioxanones (e.g., 1,4-dioxanone), δ-valerolactone, 1-dioxepanones (e.g., 1,4-dioxepan-2-one and 1,5-dioxepan-2-one), polyesters, poly(ethylene glycol), poly(ethylene oxides), polyacrylamides, cellulose esters, fluoropolymers, vinyl polymers, silk, collagen, alginate, chitin, chitosan, hyaluronic acid, chondroitin sulfate, glycosaminoglycans, poly(hydroxyethyl methacrylate), polyvinylpyrrolidone, poly(vinyl alcohol), poly(acrylic acid), polyacetate, polycaprolactone, poly(propylene, glycol)s, poly(amino acids), copoly (ether-esters), poly(alkylene oxalates), polyamides, poly(iminocarbonates), polyoxaesters, polyorthoesters, polyphosphazenes, polypeptides and copolymers, block copolymers, homopolymers, blends and combinations thereof.

10 . (canceled)

11 . The method according to claim 2 , wherein the binder further comprises a surfactant.

12 . (canceled)

13 . The method according to claim 2 , wherein the solvent comprises water or other aqueous solvents, organic solvents, and a mixture thereof.

14 . (canceled)

15 . The method according to claim 2 , wherein the branched-chain polymer is made via a living radical polymerization of a monomer selected from the group consisting of styrene, vinyl benzyl chloride, 2-vinyl pyridine, 4-vinyl pyridine, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, butyl acrylate, acrylic acid, methacrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, acrylamide, methacrylamide, dimethyl acrylamide, dimethyl(meth)acrylamide, allyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminoethyl acrylate, divinyl benzene, ethyleneglycol dimethacrylate, ethyleneglycol diacrylate, triethylene glycol dimethacrylate, tetraethyleneglycol dimethacrylate, triethyleneglycol diacrylate, tetraethyleneglycol diacrylate, 1,3,5-triallyl-1,3,5-triazine-2,4,6(1 H,3H,5H)-trione, dodecane thiol, hexane thiol, 2-mercaptoethanol and fragments arising from azobis isobutyronitrile, di-f-butyl peroxide, and f-butyl peroxybenzoate.

16 . The method according to claim 2 , wherein powder is selected from the group consisting of a ceramic powder, a polymer powder, a carbon powder, a metal powder, a drug or other bioactive compound.

17 . (canceled)

18 . (canceled)

19 . (canceled)

20 . (canceled)

21 . A printable binder capable of being printed through an ink-jet nozzle, the binder comprising a branched-chain polymer and a solvent,
wherein the concentration of the branched-chain polymer in the binder is above a maximum printable concentration of the otherwise same binder and under the otherwise same conditions except replacing the branched-chain polymer with a linear-chain polymer of the same repeat units and having the same M n .

22 . The printable binder according to claim 21 , wherein the branched-chain polymer has a M n of about 5 kg mol −1 to about 50 kg mol −1 .

23 . The printable binder according to claim 21 , wherein the branched-chain polymer has a polydispersity index (PDI) of about 1.0 to about 10.0.

24 . The printable binder according to claim 21 , wherein the branched-chain polymer has a glass transition temperature (TO of about 40° C. to about 100° C.

25 . The printable binder according to claim 21 , wherein the branched-chain polymer is selected from the group consisting of 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.

26 . (canceled)

27 . The printable binder according to claim 21 , wherein the branched-chain polymer is selected from the group consisting of polycarbonates, polyolefins, polymethacrylates, polystyrenes, polyamides, polyurethanes, poly(ethylene terephthalate), poly(lactic acid), poly(glycolic acid), polyhydroxbutyrate, polydioxanones (e.g., 1,4-dioxanone), δ-valerolactone, 1-dioxepanones (e.g., 1,4-dioxepan-2-one and 1,5-dioxepan-2-one), polyesters, poly(ethylene glycol), poly(ethylene oxides), polyacrylamides, cellulose esters, fluoropolymers, vinyl polymers, silk, collagen, alginate, chitin, chitosan, hyaluronic acid, chondroitin sulfate, glycosaminoglycans, poly(hydroxyethyl methacrylate), polyvinylpyrrolidone, poly(vinyl alcohol), poly(acrylic acid), polyacetate, polycaprolactone, poly(propylene, glycol)s, poly(amino acids), copoly (ether-esters), poly(alkylene oxalates), polyamides, poly(iminocarbonates), polyoxaesters, polyorthoesters, polyphosphazenes, polypeptides and copolymers, block copolymers, homopolymers, blends and combinations thereof.

28 . The printable binder according to claim 21 , wherein the branched-chain polymer is present at a concentration from about 3% to about 30%, about 3% to about 20%, about 3% to about 15%, or about 5% to about 15% by weight based upon a total weight of the binder.

29 . (canceled)

30 . (canceled)

31 . The printable binder according to claim 21 , wherein the solvent comprises water or other aqueous solvents, organic solvents, and a mi

Assignees

• Virginia Tech Intellectual Properties Inc

Inventors

• Williams Christopher B
• Wilts Emily M
• Long Timothy E
• Ma Da

Classifications

• B29C64/165 Primary

  using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber · CPC title

• B29C64/153 Primary

  using layers of powder being selectively joined, e.g. by selective laser sintering or melting · CPC title

• B22F1/052

  characterised by a mixture of particles of different sizes or by the particle size distribution · CPC title

• B22F2999/00

  Aspects linked to processes or compositions used in powder metallurgy · CPC title

• B22F10/14

  by jetting of binder onto a bed of metal powder · CPC title