Selective deposition of materials for composite structures via additive manufacturing

Patent metadata

Field	Value
Publication number	US-11999097-B2
Application number	US-201917057568-A
Country	US
Kind code	B2
Filing date	May 21, 2019
Priority date	May 21, 2018
Publication date	Jun 4, 2024
Grant date	Jun 4, 2024

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.

First claim

What is claimed is:

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.

2. 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.

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

4. 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.

5. 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.

6. 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.

7. 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.

8. 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.

9. 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.

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.

11. 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-ba

Assignees

• Virginia Polytechnic Institute And State Univ
• Virginia Tech Intellectual Properties Inc

Inventors

• HENSLEIGH Ryan
• Zheng Xiaoyu

Classifications

• B29C64/124 Primary

  using layers of liquid which are selectively solidified · CPC title

• B29C64/30

  Auxiliary operations or equipment · CPC title

• B33Y10/00 Primary

  Processes of additive manufacturing · CPC title

• B33Y40/20

  Post-treatment, e.g. curing, coating or polishing · CPC title

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title