Method of manufacturing aqueous ceramic suspensions and the use of said suspensions

• US 5,362,472 A
• Filed: 09/04/1992
• Issued: 11/08/1994
• Est. Priority Date: 09/13/1991
• Status: Expired due to Fees

• Current Assignee: US Philips Corporation (Koninklijke Philips N.V.)
• Original Assignee: US Philips Corporation (Koninklijke Philips N.V.)
• Inventors: Romanowski, Gerd, Mayr, Walter, Opitz, Joachim, Lauter, Josef
• Primary Examiner(s): GREEN, ANTHONY J
• Application Number:
  US07/941,340
• Time in Patent Office: 795 Days
• Field of Search: 501/137, 423/598, 423/608, 423/593
• US Class Current: 423/598
• CPC Class Codes: C04B 35/4682 based on BaTiO3 perovskite phase
• CPC Class Codes: C04B 35/634 Polymers C04B35/636 takes precedence
• CPC Class Codes: C04B 35/63416 Polyvinylalcohols [PVA]; Polyvinylacetates
• CPC Class Codes: C04B 35/63424 Polyacrylates; Polymethacrylates

Abstract

A method describing the manufacture and use of aqueous suspensions comprising fine-powdered ceramic solid particles, dispersing agents and, if necessary, binders, in which method the manufacture of the suspensions includes the following process steps which are carried out separately or in combination:

washing the solid particles in water before preparing the suspension;

adding anionic compounds, in the form of sulphates, carbonates, iodates, chromates, oxalates, citrates and/or tartrates;

manufacturing the suspensions and/or storing the finished suspensions in a CO₂ -free gaseous atmosphere;

manufacturing the suspensions and storing the finished suspensions at a temperature below 20° C., preferably below 15° C.;

adding additional dispersing agents to the suspension at a time when reagglomeration of the solid particles in the suspension has not yet started or just started.

Claims

1. A method of manufacturing aqueous suspensions of deagglomerated finely powdered solid particles of barium titanate in a manner to prevent reagglomeration, said method comprising the steps of

(a) forming an aqueous suspension of solid particles of finely powdered barium titanate and dispersing agents, and

(b) carrying out at least one of the following sub-steps to prevent reagglomeration of said solid particles of finely powdered barium titanate for a given period of time:

(i) washing said solid particles at least once in water before carrying out step (a),

(ii) adding to said aqueous suspension anionic compounds of at least one of sulfates, carbonates, iodates, chromates, oxalates, citrates and tartrates,

(iii) providing said aqueous suspension in a gaseous atmosphere free of CO₂,

(iv) providing said aqueous suspension at a temperature of at most 20°

C. and

(v) adding additional dispersing agents to said aqueous suspension at least before reagglomeration of said solid particles begins.

2. A method according to claim 1, wherein all of said sub-steps (i)-(v) are carried out.

3. A method according to claim 1, wherein only said sub-step (i) is carried out.

4. A method according to claim 1, wherein only said sub-step (ii) is carried out by adding an oxalate.

5. A method according to claim 1, wherein only said sub-step (iii) is carried out.

6. A method according to claim 1, wherein sub-steps (ii), (iii) and (iv) are carried out, said sub-step (ii) being carried out by adding an oxalate.

7. A method according to claim 1, wherein only said sub-step (v) is carried out.

8. A method according to claim 1, wherein said solid particles of barium titanate have an average particle range less than about 0.5 μ

m.

9. A method according to claim 8, wherein said barium titanate solid particles have an average particle size ranging from about 0.1 to about 0.2 μ

m.

10. A method according to claim 1, wherein said additional dispersing agents in sub-step (v) comprise polyelectrolytes having a polymerization degree in the range from about 20 to about 100.

11. A method according to claim 10, wherein said additional dispersing agents are added in said sub-step (v) in an amount of about 0.3 to about 2.5 mg of polyelectrolyte/cm² of surface area of said solid particles.

12. A method according to claim 11, wherein said additional dispersing agents in said sub-step (v) comprise a polyacrylate.

13. A method according to claim 12, wherein said polyacrylate is ammonium polyacrylate.

14. A method according to claim 1, wherein said sub-step (v) is carried out by adding said additional dispersing agents in said sub-step (v) in an amount ranging from about 0.5 to 2 times the amount of said dispersing agents in said aqueous suspension in said step (a).

15. A method according to claim 14, wherein said additional dispersing agents in said sub-step (v) are added before reagglomeration of said solid particles.

16. A method according to claim 14, wherein said additional dispersing agents in said sub-step (v) are added upon beginning of reagglomeration of said solid particles.

17. A method according to claim 1, wherein said sub-step (ii) is carried out by adding at least one anionic compound as an ammonium salt.

18. A method according to claim 17, wherein said at least one anionic compound is added to said aqueous suspension before adding said dispersing agents in said step (a).

19. A method according to claim 17, wherein said at least one anionic compound is added in an amount of about 0.1 to 1.5 mol% of an amount of said solid particles in said aqueous suspension.

20. A method according to claim 1, wherein after adding said dispersing agents in said step (a), said aqueous suspension is subjected to an ultrasonic treatment in a frequency range of about 5 kHz to about 1 mHz, and thereafter a polymeric organic binder is added to said aqueous solution.

21. A method according to claim 20, wherein after addition of said binder, said aqueous suspension is subjected to another ultrasonic treatment in said frequency range of about 5 kHz to about 1 mHz.

22. A method according to claim 1, wherein a binder of polyvinyl alcohol is added to said aqueous suspension.

23. A method according to claim 1, wherein said gaseous atmosphere in sub-step (iii) is an inert gas atmosphere.

24. A method according to claim 23, wherein said inert gas atmosphere is one of an argon or a nitrogen atmosphere.

25. A method of manufacturing thin ceramic foils comprising the steps of forming slips of ceramic upon carrying out said method of claim 1 and forming thin ceramic foils having thicknesses ≦

25 μ

m from said slips.

26. A method according to claim 25 further comprising the step of stacking a plurality of said thin ceramic foils to form ceramic multilayer capacitors.