# US 2014/0193644 A1 · Polyelectrolyte multilayers having salt-controlled internal structures

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- Number: US 2014/0193644 A1
- Document ID: US20140193644A1
- Status: Published application
- Kind: A1
- Application number: 14/147,098
- Filed: 2014-01-03
- Published: 2014-07-10
- Earliest claimed: 2013-01-04
- Assignees: The Government of the United States of America, as represented by the Secretary of the Navy
- Inventors: Walter J. Dressick; Kathryn J. Wahl; Dmitri Y. Petrovykh; Nabil D. Bassim; Rhonda Michelle Stroud
- Web page: https://patentgrep.com/patent/US20140193644A1

## CPC

- C09D 125/18: Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
- C08K 3/30: Sulfur-, selenium- or tellurium-containing compounds
- C08K 3/32: Phosphorus-containing compounds
- C08K 5/098: Metal salts of carboxylic acids
- C08K 5/42: Sulfonic acids; Derivatives thereof
- Y10T 428/31612: As silicone, silane or siloxane
- Y10T 428/31663: As siloxane, silicone or silane
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

A method, and an article made therefrom, of: contacting a substrate with a first solution of first polyelectrolyte chains to form a layer of the first polyelectrolyte on the substrate; and contacting the layer of the first polyelectrolyte with a second solution of second polyelectrolyte chains to form a layer of the second polyelectrolyte. The first polyelectrolyte has a polyanion or polycation chain. The second polyelectrolyte has a polyanion or polycation chain of a charge opposite to that of the first polyelectrolyte. The first solution or the second solution is an aggregate-forming solution comprising an ionic species having at least two discrete sites of a charge opposite to that of the polyelectrolyte chains in the aggregate-forming solution. The ionic species forms, via bridging interactions, aggregates of the polyelectrolyte chains that remain intact in the aggregate-forming solution during the contact.

## Claims

### Claim 1

A method comprising:
contacting a substrate with a first solution comprising first polyelectrolyte chains to form a layer of the first polyelectrolyte on the substrate;
wherein the first polyelectrolyte comprises a polyanion or polycation chain; and
contacting the layer of the first polyelectrolyte with a second solution comprising second polyelectrolyte chains to form a layer of the second polyelectrolyte on the layer of the first polyelectrolyte;
wherein the second polyelectrolyte comprises a polyanion or polycation chain of a charge opposite to that of the first polyelectrolyte;
wherein the first solution or the second solution is an aggregate-forming solution comprising an ionic species having at least two discrete sites of a charge opposite to that of the polyelectrolyte chains in the aggregate-forming solution; and
wherein the ionic species forms, via bridging interactions, aggregates of the polyelectrolyte chains that remain intact in the aggregate-forming solution during the contact.

### Claim 2 (depends on 1)

The method of claim 1, further comprising:
depositing on the layer of the second polyelectrolyte one or more alternating layers of the first polyelectrolyte using the first solution and the second polyelectrolyte using the second solution.

### Claim 3 (depends on 1)

The method of claim 1;
wherein the aggregate-forming solution comprises the polycation chain; and
wherein the ionic species is an anion having two or more discrete fixed negatively-charged sites at an obtuse angle.

### Claim 4 (depends on 3)

The method of claim 3, wherein the method forms a multilayer structure having internal pores and comprised of layers of stacked polycation aggregates separated and held together by layers of polyanion.

### Claim 5 (depends on 3)

The method of claim 3, wherein the polycation chain is polyallylamine hydrochloride.

### Claim 6 (depends on 3)

The method of claim 3, wherein the polycation chain is polydiallyldimethylammonium chloride.

### Claim 7 (depends on 3)

The method of claim 3, wherein the ionic species is SO4−2, HPO4−2, or an organic dicarboxylate.

### Claim 8 (depends on 3)

The method of claim 3, wherein the polyanion chain is sodium polystyrene sulfonate.

### Claim 9 (depends on 3)

The method of claim 3, wherein the aggregate-forming solution is the second solution.

### Claim 10 (depends on 3)

The method of claim 3, wherein the substrate is a silicon or quartz substrate having a self-assembled monolayer of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

### Claim 11 (depends on 1)

The method of claim 1, further comprising:
rinsing the layer formed from the aggregate-forming solution with, in order:
1) a polyelectrolyte-free solution having the same salt composition as the aggregate-forming solution;
2) a 1.0 M NaCl solution; and
3) water.

### Claim 12 (depends on 1)

The method of claim 1, further comprising:
rinsing the layer formed from the aggregate-forming solution with water three times.

### Claim 13 (depends on 5)

The method of claim 5, further comprising:
depositing Na4Ru(BPS)3 on a layer of polyallylamine hydrochloride.

### Claim 14

An article made by a method comprising:
contacting a substrate with a first solution comprising first polyelectrolyte chains to form a layer of the first polyelectrolyte on the substrate;
wherein the first polyelectrolyte comprises a polyanion or polycation chain; and
contacting the layer of the first polyelectrolyte with a second solution comprising second polyelectrolyte chains to form a layer of the second polyelectrolyte on the layer of the first polyelectrolyte;
wherein the second polyelectrolyte comprises a polyanion or polycation chain of a charge opposite to that of the first polyelectrolyte;
wherein the first solution or the second solution is an aggregate-forming solution comprising an ionic species having at least two discrete sites of a charge opposite to that of the polyelectrolyte chains in the aggregate-forming solution; and
wherein the ionic species forms, via bridging interactions, aggregates of the polyelectrolyte chains that remain intact in the aggregate-forming solution during the contact.

### Claim 15 (depends on 14)

The article of claim 14, wherein the method further comprises:
depositing on the layer of the second polyelectrolyte one or more alternating layers of the first polyelectrolyte using the first solution and the second polyelectrolyte using the second solution.

### Claim 16 (depends on 14)

The article of claim 14;
wherein the aggregate-forming solution comprises the polycation chain; and
wherein the ionic species is an anion having two or more discrete spaced negatively-charged sites at an obtuse angle.

### Claim 17 (depends on 16)

The article of claim 16, wherein the method forms a multilayer structure having internal pores and comprised of layers of stacked polycation aggregates separated and held together by layers of polyanion.

### Claim 18 (depends on 16)

The article of claim 16, wherein the polycation chain is polyallylamine hydrochloride.

### Claim 19 (depends on 16)

The article of claim 16, wherein the polycation chain is polydiallyldimethylammonium chloride.

### Claim 20 (depends on 16)

The article of claim 16, wherein the ionic species is SO4−2, HPO4−2, or an organic dicarboxylate.

### Claim 21 (depends on 16)

The article of claim 16, wherein the polyanion chain is sodium polystyrene sulfonate.

### Claim 22 (depends on 16)

The article of claim 16, wherein the aggregate-forming solution is the second solution.

### Claim 23 (depends on 16)

The article of claim 16, wherein the substrate is a silicon or quartz substrate having a self-assembled monolayer of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

### Claim 24 (depends on 14)

The article of claim 14, wherein the method further comprises:
rinsing the layer formed from the aggregate-forming solution with, in order:
1) a polyelectrolyte-free solution having the same salt composition as the aggregate-forming solution;
2) a 1.0 M NaCl solution; and
3) water.

### Claim 25 (depends on 14)

The article of claim 14, further comprising:
rinsing the layer formed from the aggregate-forming solution with water three times.

### Claim 26 (depends on 18)

The article of claim 18, further comprising:
depositing Na4Ru(BPS)3 on a layer of polyallylamine hydrochloride.