Fluoroalkylsilanated mesoporous metal oxide particles and methods of preparation thereof

• US 8,741,432 B1
• Filed: 08/10/2011
• Issued: 06/03/2014
• Est. Priority Date: 08/16/2010
• Status: Active Grant

• Current Assignee: United States Incorporated
• Original Assignee: United States Of America As Represented By The Secretary Of The Air Force
• Inventors: Campos, Raymond, Mabry, Joseph M., Guenthner, Andrew J., Haddad, Timothy
• Primary Examiner(s): Le, Hoa (Holly)
• Application Number:
  US13/206,994
• Time in Patent Office: 1,028 Days
• Field of Search: 428403-406, 427/215, 427/220, 427/372.2, 427/384, 427/397.7
• US Class Current: 428/403
• CPC Class Codes: C01P 2006/10 Solid density
• CPC Class Codes: C01P 2006/11 Powder tap density
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: C09C 3/12 Treatment with organosilicon compounds C09C3/006 takes precedence
• CPC Class Codes: Y10T 428/2991 Coated
• CPC Class Codes: Y10T 428/2995 Silane, siloxane or silicone coating

Abstract

Coated particles comprise a core of fumed or precipitated inorganic metal oxide having a surface area of about 50 to about 500 square meters per gram and a shell consisting of an array of fluoroalkyl molecular chains at a density of at least 1 chain per square nanometer, joined to the core by covalent chemical bonds and with a total organic content of at least 9.9 percent by weight. These particles are formed by the chemical attachment of fluoroalkyl-alkylsilanes after exposure to an alkylamine and followed by an extraction to remove any organic material not covalently bound. The dense packing of molecular chains in the fluoroalkyl shell combined with a mesoporous structure imparts a very low surface energy, a very high specific surface area, and surface texture over a wide range of length scales. Such features are highly desirable for the creation of, for example, superhydrophobic and superoleophobic surfaces, separation media, and release films.

Claims

1. A treated aggregate, comprising:

a) an inorganic oxide substrate having the formula SiO_x, wherein the inorganic oxide substrate possesses a specific surface area of at least 50 square meters per gram;

b) a molecular layer coating of —

CF₃ terminated molecular fragments, wherein the —

CF₃ terminated molecular fragments are covalently bonded to the inorganic oxide substrate such that at least 15 parts by weight of fluorine in the form of —

CF—

, —

CF₂—

, or —

CF₃ fragments is covalently bound to 100 parts by weight of the inorganic oxide substrate,

wherein the treated aggregate comprises a geometric shape that is determined by the inorganic oxide substrate and the molecular layer coating, the geometric shape being characterized by an occurrence of concave features of multiple sizes spanning a range from about 5 nm to about 0.001 mm.

2. The treated aggregate of claim 1, wherein the inorganic oxide substrate is fumed silica with an average particle diameter of about 7 nm, and wherein the molecular layer coating consists of —

Si(CH₃)₂CH₂CH₂—

(CF₂)₇CF₃.

3. The treated aggregate of claim 1, wherein the inorganic oxide substrate is precipitated silica, and wherein the molecular layer coating consists of —

Si(CH₃)_mCH₂CH₂—

(CF₂)_nCF₃, wherein m=1 or 2 and n=5 or 7.

4. The treated aggregate of claim 1, wherein the treated aggregate comprises a surface energy of less than 30 mJ per square meter.

5. A method of producing the treated aggregate of claim 1, comprising:

a) removing a plurality of physically adsorbed water from an inorganic silicon oxide with a specific surface area of at least 50 square meters per gram while leaving intact at least one surface hydroxyl group per square nanometer;

b) exposing the inorganic silicon oxide to an atmosphere containing a concentration of alkylamine vapor for a time to cause adsorption onto a plurality of the specific surface area;

c) dispersing the inorganic silicon oxide in a moisture-free carrier solvent having a neutral to acidic pH;

d) introducing at least a four-fold molar excess of a fluorinated chlorosilane coupling agent and stirring for 0.1-100 hours, whereby a portion of the fluorinated chlorosilane coupling agent is covalently bound to the inorganic silicon oxide;

e) removing the moisture-free carrier solvent and excess reagents by centrifugation;

f) removing substantially all non-covalently bound fluorinated chlorosilane coupling agent by continuous extraction in an extraction solvent with a neutral to acidic pH for 1-1000 hours to form a treated aggregate; and

g) drying the treated aggregate to remove the extraction solvent.

6. The method of claim 5, wherein the fluorinated chlorosilane coupling agent is selected from the group consisting of:

heptadecafluoro-1,1,2,2-tetrahydrodecyl)dimethylchlorosilane, tridecafluoro-1,2,2,2-tetrahydrooctyl)dimethylchlorosilane, heptadecafluoro-1,1,2,2-tetrahydrodecyl)methyl-dichlorosilane, and mixtures thereof.

7. The method of claim 5, wherein the alkylamine vapor is dimethylamine.