Method for producing a filter intended to filter nanoparticles, obtained filter and associated method for the collection and quantitative analysis of nanoparticles

Patent metadata

Field	Value
Publication number	US-9833750-B2
Application number	US-201314759339-A
Country	US
Kind code	B2
Filing date	Dec 24, 2013
Priority date	Jan 3, 2013
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

The present invention relates to a method for impregnating a filter having pores suitable for retaining particles within them that may be present in a flow of air suitable for passing through the filter, according to which the filter made up of a polymer membrane is impregnated with one or more organometallic salts by applying a treatment using supercritical CO 2 , the metal M of each salt being chosen from among the group of rare earths, yttrium, scandium, chromium, or a combination thereof. The invention also relates to the obtained filter and an associated method for the collection and quantitative analysis of nanoparticles.

First claim

The invention claimed is:

1. A process for the impregnation of a filter comprising pores which are capable of retaining, within them, particles liable to be present in an air stream intended to pass through the filter, according to which the filter composed of a polymer membrane is impregnated with one or more organometallic salts by applying a treatment with supercritical CO 2 , the metal M of each salt being selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, scandium, chromium, and a combination of these.

2. The process for the impregnation of a filter as claimed in claim 1 , according to which the treatment with supercritical CO 2 is carried out in an autoclave, the organometallic salt(s) being placed inside the autoclave at a distance from the filter comprising pores.

3. The process for the impregnation of a filter as claimed in claim 2 , according to which the treatment with supercritical CO 2 consists of the following stages:
a/ purging the inside of the autoclave with CO 2 at ambient pressure and temperature,
b/ pressurizing the inside of the autoclave to a pressure of between 73.8 and 350 bar, while maintaining the temperature at ambient temperature,
c/ raising the temperature of the autoclave to a temperature between 31° C. and 150° C. over a period of time of between 20 minutes and 5 h,
d/ maintaining at temperature and at pressure for a period of time of between 20 minutes and 5 hours,
e/ naturally cooling the autoclave until ambient temperature is reached,
f/ carrying out a calibrated escape of the CO 2 towards the outside of the autoclave until ambient pressure is reached.

4. The process for the impregnation of a filter as claimed in claim 1 , according to which a proportion by weight of the organometallic salt(s) with respect to the weight of the filter of less than or equal to 1% is selected.

5. A filter comprising pores which are capable of retaining, within them, nanoparticles liable to be present in an air stream intended to pass through the filter, the filter being composed of a polymer membrane impregnated with one or more organometallic salts, the metal M of each salt being selected from the group consisting of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, scandium, chromium, and a combination of these, the filter being liable to be obtained according to the process as claimed in claim 1 .

6. The filter comprising pores as claimed in claim 5 , the constituent polymer of the membrane being chosen from saturated polyesters.

7. The filter comprising pores as claimed in claim 6 , made of polycarbonate (PC).

8. The filter comprising pores as claimed in claim 5 , having a thickness of between 10 and 50 μm.

9. The filter comprising pores as claimed in claim 5 , the pores of the filter being holes with a calibrated diameter of between 0.05 and 2 μm.

10. The filter comprising pores as claimed in claim 5 , the density of the holes of the filter being between a number of 10 5 and 5×10 8 holes per cm 2 .

11. The filter comprising pores as claimed in claim 5 , the organometallic salt(s) being a complex of metallocene type, of formula M(Cp) n , in which n is an integer between 1 and 4 and Cp is a cyclopentadiene group.

12. The filter comprising pores as claimed in claim 5 , the organometallic salt(s) being a complex in which the metal has been subjected to chelation by groups carrying heteroelements chosen from amines and phosphines.

13. The filter comprising pores as claimed in claim 12 , the heteroelements being substituted by alkyl chains with at least four carbons.

14. The filter comprising pores as claimed in claim 5 , the organometallic salt(s) being a complex of formula M(PR) n , where n is an integer between 1 and 4 and R is a fluorinated, substituted, or branched aryl group or alkyl group.

15. The filter comprising pores as claimed in claim 5 , the organometallic salt(s) being a complex of amide type of formula M(NR 2 ) n , where n is an integer between 1 and 4 and R is a silyl-aliphatic group or an aromatic group.

16. The filter comprising pores as claimed in claim 5 , the organometallic salt(s) being a complex of phenanthroline or bathophenanthroline type of formula M(Phen) n , where n is an integer between 1 and 4 and Phen is phenanthroline.

17. The filter comprising pores as claimed in claim 5 , the organometallic salt(s) being a complex of carboxylate type of formula M(OOCR) n , where n is an integer between 1 and 4 and R is an alkyl chain with at least four carbons.

18. The filter comprising pores as claimed in claim 5 , the organometallic salt(s) being a complex of β-diketonate type of formula M(RCOCH 2 COR) n , where n is an integer between 1 and 4 and R is an alkyl chain with at least four carbons.

19. The filter comprising pores as claimed in claim 5 , the organometallic salt(s) being a complex of alkoxide type of formula M(OR) n , where n is an integer between 1 and 4 and R is an alkyl chain with at least four carbons.

20. The filter comprising pores as claimed in claim 5 , the organometallic salt(s) being a complex of β-ketocarboxylate type of formula M(OOCCH 2 COR) n , where n is an integer between 1 and 4 and R is an alkyl chain with at least four carbons.

21. The filter comprising pores as claimed in claim 5 , the organometallic salt(s) being a complex of phosphonate type of formula M(O 2 (O)PR) n , where n is an integer between 1 and 4 and R is an alkyl chain with at least four carbons.

22. The filter comprising pores as claimed in claim 5 , the organometallic salt(s) being a complex of sulfonate type of formula M(O 3 SR) n , where n is an integer between 1 and 4 and R is an alkyl chain with at least four carbons.

23. The filter comprising pores as claimed in claim 17 , the alkyl chain being fluorinated.

24. A process for the collection and analysis of nanoparticles according to which the following stages are carried out:
suction of an air stream liable to be laden with nanoparticles through the filter as claimed in claim 5 with an organometallic salt impregnated therein;
introduction of the filter into an X-ray fluorescence spectrometer;
quantitative analysis by X-ray fluorescence of the nanoparticles retained by the filter by division between the fluorescence signal emitted by a chemical element of the nanoparticles and the fluorescence signal emitted by the organometallic salt.

Assignees

• Commissariat Energie Atomique
• Commissariat à l'Energie Atomique et aux Energies Alternatives

Inventors

• Motellier Sylvie
• Clavaguera Simon
• Lhaute Korian
• Poncelet Olivier

Classifications

• G01N2015/0038

  Investigating nanoparticles · CPC title

• B01D63/087

  Single membrane modules · CPC title

• B01D2053/221

  Devices · CPC title

• G01N2223/635

  fluids, granulates · CPC title

• B01D69/148

  Organic/inorganic mixed matrix membranes · CPC title