Process for production of nanoparticles of solid lubricant and lubricant dispersions stable in oil and in water

Patent metadata

Field	Value
Publication number	US-9512377-B2
Application number	US-201214131582-A
Country	US
Kind code	B2
Filing date	Jul 12, 2012
Priority date	Jul 12, 2011
Publication date	Dec 6, 2016
Grant date	Dec 6, 2016

Abstract

The process basically comprises: dissolving a lamellar disulphide, as a source of the solid lubricant, in an aqueous solvent, forming a first aqueous solution; dissolving a reducing agent, as hydroxylamine, sodium hypophosphite or sodium borohydride, in an aqueous solvent, forming a second aqueous solution; mixing the first and second aqueous solutions, forming a third aqueous solution; neutralizing the pH of the third aqueous solution; dissolving a sulphur source, in an aqueous solvent, forming a fourth aqueous solution; mixing the third and fourth aqueous solutions, forming a fifth aqueous solution, which is contained and heated in an autoclave; cooling the fifth aqueous solution to the room temperature; and removing, from the autoclave, the nanoparticles in powder form.

First claim

The invention claimed is:

1. A process for production of solid lubricant nanoparticles, obtained from molybdenum or tungsten compounds to form lamellar metallic disulphides, characterized in that it comprises the steps of:
a—dissolving, under stirring, a source of the metallic element which defines the solid lubricant, in a solvent comprising water and heated between 50° C. and 90° C., forming a first aqueous solution;
b—dissolving, under stirring, a reducing agent selected from hydroxylamine, sodium hypophosphite and sodium borohydride, in a solvent comprising water and heated between 50° C. and 90° C., forming a second aqueous solution;
c—mixing the first and second aqueous solutions, forming a third aqueous solution, containing the metallic element which defines the solid lubricant and the reducing agent;
d—adjusting the pH of the third aqueous solution, to a neutral condition;
e—dissolving, under stirring, a sulphur source, in a solvent comprising water and heated between 50° C. and 90° C., forming a fourth aqueous solution;
f—mixing the third and fourth aqueous solutions, forming a fifth aqueous solution, containing the metallic element, the reducing agent and the sulphur;
g—containing the fifth aqueous solution in an autoclave and submitting it to heating for a period from 3 h to 150 h, and at a temperature from 100° C. to 350° C.;
h—cooling the fifth aqueous solution, still contained in the autoclave, to the room temperature, as a function of the morphological characteristics of the nanoparticles to be obtained; and
i—removing, from the autoclave, the nanoparticles obtained in the powder form, and submitting them to water-washing and drying operations.

2. The process, as set forth in claim 1 , characterized in that the solid lubricant is selected from molybdenum disulphide and tungsten disulphide.

3. The process, as set forth in claim 2 , characterized in that the source of the metallic element, which defines the solid lubricant, is selected from ammonium molybdate, metallic molybdenum, molybdenum dioxide and molybdenum trioxide, sodium tungstate, tungstic acid, tungstic anhydride and tungsten oxide IV, in concentrations ranging from 8.0 millimolar to 1.00 molar.

4. The process, as set forth in claim 1 , characterized in that the sulphur source is selected from thiourea and elemental sulphur, in concentrations ranging from 20 millimolar to 2.20 molar.

5. The process, as set forth in claim 1 , characterized in that the reducing agent is present in concentrations ranging from 20 millimolar to 2.20 molar.

6. The process, as set forth in claim 1 , characterized in that the sulphur source is defined by sodium dithionite, in concentrations ranging from 20 millimolar to 2.20 molar.

7. The process, as set forth in claim 1 , characterized in that the fifth aqueous solution is maintained under stirring for a period from 8 to 12 min and at a temperature from 50° C. to 90° C., for its homogenization before being conducted to the autoclave, in the interior of which the fifth solution is maintained at a temperature in the magnitude of 160° C. and during a period of 24 h, for the production of nanoparticles with nanoflower morphology.

8. The process, as set forth in claim 1 , characterized in that it further comprises the step of dissolving a morphology modifying agent in a solvent comprising water and heated between 50° C. and 90° C., forming a sixth aqueous solution, and adding the latter to the fifth aqueous solution, before being conducted to the autoclave, for the production of nanoparticles with nanosphere morphology.

9. The process, as set forth in claim 8 , characterized in that the morphology modifying agent is sodium saccharin in concentrations which can range from 1 millimolar to 150 millimolar.

10. The process, as set forth in claim 1 , characterized in that it further comprises the step of adding, under stirring and directly in the fifth aqueous solution, a morphology modifying agent selected from: PVP, PEG, pure ethylene diamine or mixed with water, sodium dodecyl sulfate, sodium dodecyl benzene, and cetyltrimethyl ammonium bromide in concentrations which can range from 1 millimolar to 150 millimolar, before said fifth aqueous solution is conducted to the autoclave, for the production of nanoparticles with nanosphere morphology.

11. The process, as set forth in claim 1 , characterized in that it includes the steps of:
dispersing the dry nanoparticles, obtained in step “i” of claim 1 , in a solvent selected from absolute ethanol and the like, acetone and the like, chloroform, methylene chloride and tetrachloromethane and the like, pure or in mutual combinations, said dispersion being formed in concentrations from 0.100 to 1.000 gram of nanoparticles for 100 ml of solvent; and
containing the dispersion in an autoclave and submitting it to a heating from 100° C. to 200° C. for a time period from 1 h to 12 h, making the nanoparticles become lipophilic.

12. The process, as set forth in claim 1 , characterized in that it includes the step of adding, to the fifth aqueous solution, defined in step “f” of claim 1 , a capping agent, in the concentration from 1.0 millimolar to 1.0 molar, selected from shellac or the like, PVP, a cationic surfactant as the cetyltrimethyl ammonium bromide (CTAB) and anyone from the family of the tertiary amines, so as to make the nanoparticles become hydrophilic.

13. The process, as set forth in claim 1 , characterized in that it includes the steps of:
redispersing, in water, the dry nanoparticles obtained in step “i” of claim 1 ;
adding, to the aqueous dispersion of dry nanoparticles, a capping agent, in the concentration from 1.0 millimolar to 1.0 molar, selected from shellac or the like, PVP, a cationic surfactant as the cetyltrimethyl ammonium bromide (CTAB), and anyone from the family of the tertiary amines;
submitting the aqueous dispersion of dry nanoparticles and the capping agent to a thermal treatment in their boiling temperature, in a reflux apparatus, for a time interval from 1.0 h to 4.0 h, so as to make the nanoparticles become hydrophilic; and
conducting the hydrophilic nanoparticles to any of the steps of: dispersing them directly in an aqueous base, to form an aqueous lubricant composition; and drying them to be stored for future use.

Assignees

• Binder Roberto
• Torres Fernando Withers
• Drago Valderes
• Bernardi Cristian
• Klein Aloisio Nelmo
• Binder Cristiano
• Teixeira Andre Messias
• Whirlpool Sa
• Univ Fed De Santa Catarina Ufsc

Inventors

• Binder Roberto
• Torres Fernando Withers
• Drago Valderes
• Bernardi Cristian
• Klein Aloisio Nelmo
• Binder Cristiano
• Teixeira Andre Messias

Classifications

• C10M2201/065

  Sulfides; Selenides; Tellurides · CPC title

• C01P2004/32

  Spheres · CPC title

• C10N2050/08

  Solids · CPC title

• C01P2004/62

  Submicrometer sized, i.e. from 0.1-1 micrometer · CPC title

• C10M103/06 Primary

  Metal compounds · CPC title