# US 11,999,097 B2 · Selective deposition of materials for composite structures via additive manufacturing

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- Number: US 11,999,097 B2
- Document ID: US11999097B2
- Status: Granted
- Kind: B2
- Application number: 17/057,568
- Filed: 2019-05-21
- Published: 2021-07-01
- Granted: 2024-06-04
- Earliest claimed: 2018-05-21
- Assignees: Virginia Tech Intellectual Properties, Inc.
- Applicants: Virginia Polytechnic Institute and State University
- Inventors: Ryan Hensleigh; Xiaoyu Zheng
- Web page: https://patentgrep.com/patent/US11999097B2

## CPC

- B29C 64/124: using layers of liquid which are selectively solidified
- B29C 64/30: Auxiliary operations or equipment
- B33Y 10/00: Processes of additive manufacturing
- B33Y 40/20: Post-treatment, e.g. curing, coating or polishing
- B33Y 70/00: Materials specially adapted for additive manufacturing
- B29K 2105/0014: {Catalysts}
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS

## Abstract

Described herein are electroless material deposition methods and techniques that can be used to deposit one or more materials on a structure in a selective manner such that deposition can occur in predetermined areas. The methods and techniques of selective electroless material deposition methods described herein can be used to selectively deposit material(s) on 3D printed structures. In some aspects, the 3D structures can contain micro-features that can have one or more materials selectively deposited on their surface in one or more locations.

## Claims

### Claim 1

A method of electroless selective material deposition comprising:
a) forming a multi-material three-dimensional (3D) structure, wherein the multi-material 3D structure is formed with at least two polymers selected from the group consisting of: a negatively charged polymer, a positively charged polymer, and a neutral polymer, so as to form at least two differentially charged regions of the multi-material 3D structure selected from the group of: a negatively charged region, a positively charged region, and a neutral region;
b) bringing the multi-material 3D structure to a certain pH to activate or deactivate certain regions to be either neutral, positive, or negatively charged;
c) exposing the multi-material 3D structure to a deposition catalyst, wherein the deposition catalyst is positively charged or negatively charged,
wherein a positively charged deposition catalyst associates or attaches to negatively charged region(s), wherein a negatively charged deposition catalyst attaches to positively charged region(s), and wherein substantially no deposition catalyst attaches to neutral region(s) present in the multi-material 3D structure;
d) exposing the multi-material 3D structure from step c) to a first material to be deposited and allowing autocatalysis, attachment, and/or deposition of the first material on the 3D structure in regions where the deposition catalyst is present or if no catalyst is present to oppositely charged region(s), wherein if the deposition material is positively charged it associates or attaches to the negatively charged region(s), wherein a negatively charged material associates or attaches to positive charged region(s), and wherein substantially no material attaches to neutral region(s) present in the multi-material 3D structure;
e) optionally treating the multi-material 3D structure after step d) to remove the deposition catalyst present after step c);
f) optionally treating the multi-material 3D structure after step e) to activate regions with no deposition material to become positive, negative, or neutral wherein if this step does not occur there may still be positive, negative or neutrally charged regions in the multi-material 3D structure;
g) optionally treating the 3D structure after step f) to coat the previously deposited regions from step d) to become positive, negative or neutral;
h) optionally repeating step c);
i) optionally exposing the 3D structure from step h) to a second material to be deposited and allowing autocatalysis, attachment, and/or deposition of the second material on the 3D structure in regions where the deposition catalyst is present or if no catalyst is present to oppositely charged region(s), wherein if the deposition material is positively charged it associates or attaches to the negatively charged region(s), wherein a negatively charged material associates or attaches to positive charged region(s), and wherein substantially no material attaches to neutral region(s) present in the 3D structure;
j) optionally repeating steps e) through i) to build multiple layers upon previously deposited layers until a desired number of deposited layers is reached; and
k) optionally using direct or contactless electrochemical methods to deposit or remove materials on electrically independent areas.

### Claim 2 (depends on 1)

The method of claim 1, wherein the step of forming the multi-material 3D structure comprises forming the multi-material 3D structure using a multi-material additive manufacturing process, wherein the multi-material additive manufacturing process is optionally a light-based multi-material additive manufacturing process.

### Claim 3 (depends on 1)

The method of claim 1, wherein the multi-material 3D structure comprises micro-scale features.

### Claim 4 (depends on 1)

The method of claim 1, wherein the negatively charged polymer is selected from the group consisting of: polyacrylic acids (polyacrylates), polyacrylamides, siloxanes, polysulfonates, polyvinyls, polyphosphates, and combinations thereof.

### Claim 5 (depends on 4)

The method of claim 4, wherein the negatively charged polymer comprises one or more ionic groups, where each of the one or more anionic groups can each be individually selected from the group consisting of: a sulfonate, a carboxylate, a carboxylic acid, a hydroxide containing group, a group containing a halogen ion, an epoxide group, a phosphate group, a phosphinite group, a phosphonite group, a phosphinate group, a phosphonate group, a phosphide group, a nitrate group, a sulfide group, a thiolate group, and combinations thereof.

### Claim 6 (depends on 1)

The method of claim 1, wherein the positively charged polymer is selected from the group consisting of: positively charged polyacrylates, polyacrylamides, siloxanes, polyvinyls, polyamines, polyimines, polylysine, polymers having lysine functionalities, polyarginine, polymers having arginine functionalities, guanidine, polymers having guanidine functionalities, polymers having guanidinium functionalities, polymers having fully quaternized ammonium functionalities, cationic polymers that do not have primary or secondary ammonium functionalities, phosphonium, and combinations thereof.

### Claim 7 (depends on 6)

The method of claim 6, wherein the positively charged polymer comprises one or more cationic groups, wherein each of the one or more cationic groups can be individually selected from the group consisting of: an amide, an amine, an imine, an imide, an azide group, phosphonium group, and combinations thereof.

### Claim 8 (depends on 1)

The method of claim 1, wherein the neutral polymer is selected from the group consisting of: polyethylenes, polyacrylates, polyacrylamides, polyvinyls, polyethers, siloxanes, urethanes, and combinations thereof.

### Claim 9 (depends on 1)

The method of claim 1, wherein the deposition catalyst is a positively or negatively charged ion of a metal selected from the group consisting of: Pd, Pt, Ru, Ni, Co, Cu, Zn, Cr, Fe, Pb, Sn, Ag, Hg, Mn, and combinations thereof.

### Claim 10

A method of electroless selective material deposition comprising:
a) exposing a multi-material 3D structure to a deposition catalyst, wherein the deposition catalyst is positively charged or negatively charged,
wherein the multi-material 3D structure is formed with at least two polymers selected from the group consisting of: a negatively charged polymer, a positively charged polymer, and a neutral polymer, so as to form at least two differentially charged regions of the multi-material 3D structure selected from the group of: a negatively charged region, a positively charged region, and a neutral region
wherein a positively charged deposition catalyst associates or attaches to negatively charged region(s), wherein a negatively charged deposition catalyst attaches to positively charged region(s), and wherein substantially no deposition catalyst attaches to neutral region(s) present in the 3D structure;
b) exposing the multi-material 3D structure from step a) to a first material to be deposited and allowing autocatalysis, attachment, and/or deposition of the first material on the 3D structure in regions where the deposition catalyst is present
c) washing the 3D structure after step b) to remove the deposition catalyst present after step c);
d) optionally repeating step a) wherein the charge of the deposition catalyst is opposite from that of the catalyst used in step b); and
e) optionally exposing the 3D structure from step d) to a second material to be deposited and allowing autocatalysis, attachment, and/or deposition of the second material on the 3D structure in regions where the deposition catalyst is present.

### Claim 11 (depends on 10)

The method of claim 10, wherein the multi-material 3D structure is formed using a multi-material additive manufacturing process, wherein the multi-material additive manufacturing process is optionally a light-based multi-material additive manufacturing process.

### Claim 12 (depends on 10)

The method of claim 10, wherein the multi-material 3D structure comprises micro-scale features.

### Claim 13 (depends on 10)

The method of claim 10, wherein the negatively charged polymer comprises one or more ionic groups, where each of the one or more anionic groups can each be individually selected from the group consisting of: a sulfonate, a carboxylate, a carboxylic acid, a hydroxide containing group, a group containing a halogen ion, an epoxide group, a phosphate group, a phosphinite group, a phosphonite group, a phosphinate group, a phosphonate group, a phosphide group, a nitrate group, a sulfide group, a thiolate group, and combinations thereof.

### Claim 14 (depends on 13)

The method of claim 13, wherein the negatively charged polymer comprises one or more ionic groups, where each of the one or more anionic groups can each be individually selected from the group consisting of: a sulfonate, a carboxylate, a carboxylic acid, a hydroxide containing group, a group containing a halogen ion, an epoxide group, a phosphate group, a phosphinite group, a phosphonite group, a phosphinate group, a phosphonate group, a phosphide group, a nitrate group, a sulfide group, a thiolate group, and combinations thereof.

### Claim 15 (depends on 10)

The method of claim 10, wherein the positively charged polymer is selected from the group consisting of: positively charged polyacrylates, polyacrylamides, siloxanes, polyvinyls, polyamines, polyimines, polylysine, polymers having lysine functionalities, polyarginine, polymers having arginine functionalities, guanidine, polymers having guanidine functionalities, polymers having guanidinium functionalities, polymers having fully quaternized ammonium functionalities, cationic polymers that do not have primary or secondary ammonium functionalities, phosphonium, and combinations thereof.

### Claim 16 (depends on 15)

The method of claim 15, wherein the positively charged polymer comprises one or more cationic groups, wherein each of the one or more cationic groups can be individually selected from the group consisting of: an amide, an amine, an imine, an imide, an azide group, phosphonium group, and combinations thereof.

### Claim 17 (depends on 10)

The method of claim 10, wherein the neutral polymer is selected from the group consisting of: polyethylenes, polyacrylates, polyacrylamides, polyvinyls, polyethers, siloxanes, urethanes, and combinations thereof.

### Claim 18 (depends on 10)

The method of claim 10, wherein the deposition catalyst is a positively or negatively charged ion of a metal selected from the group consisting of: Pd, Pt, Ru, Ni, Co, Cu, Zn, Cr, Fe, Pb, Sn, Ag, Hg, Mn, and combinations thereof.

### Claim 19 (depends on 10)

The method of claim 10, further comprising the step of forming a multi-material three-dimensional (3D) structure, wherein the multi-material 3D structure is formed with at least two polymers selected from the group consisting of: a negatively charged polymer, a positively charged polymer, and a neutral polymer, so as to form at least two differentially charged regions of the multi-material 3D structure selected from the group of: a negatively charged region, a positively charged region, and a neutral region before step b).

### Claim 20 (depends on 1)

A 3D structure produced by the method of claim 1.