Solution method for making molybdate and tungstate negative thermal expansion materials and compounds made by the method

• US 6,183,716 B1
• Filed: 07/30/1998
• Issued: 02/06/2001
• Est. Priority Date: 07/30/1997
• Status: Expired due to Fees

• Current Assignee: Oregon State University (Oregon University System)
• Original Assignee: Oregon State University (Oregon University System)
• Inventors: Sleight, Arthur W., Upadhyayula, Kameswari, Haygarth, John C., Closmann, Claire E.
• Primary Examiner(s): Dunn, Tom
• Assistant Examiner(s): Nguyen, Cam N.
• Application Number:
  US09/126,986
• Time in Patent Office: 922 Days
• Field of Search: 423/593, 423/606, 423/608, 502/300, 502/305, 502/308, 502/321
• US Class Current: 423/594.13
• CPC Class Codes: C01G 39/00 Compounds of molybdenum
• CPC Class Codes: C01G 39/006 Compounds containing, besides molybdenum, two or more other elements, with the exception of oxygen or hydrogen
• CPC Class Codes: C01G 41/00 Compounds of tungsten
• CPC Class Codes: C01G 41/006 Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/77 by unit-cell parameters, atom positions or structure diagrams
• CPC Class Codes: C01P 2006/10 Solid density
• CPC Class Codes: G01K 5/48 the material being a solid

Abstract

A method for making negative thermal expansion materials having the formula $A^{4+}M_2^{6+}O_8$

where A⁴⁺ is Zr⁴⁺, Hf⁴⁺, or mixtures thereof, and M⁶⁺ is Mo⁶⁺, W⁶⁺, or mixtures thereof, is described. The method comprises first forming an acidic, liquid mixture comprising stoichiometric amounts of (1) a soluble source of Zr⁴⁺, Hf⁴⁺, or mixtures thereof, and (2) a sodium-ion-free tungstate salt, a sodium-ion-free molybdate salt, or mixtures thereof. This liquid mixture is then heated, either at reflux temperature or in a closed system at pressures greater than ambient, to produce a solid fraction. The solid fraction is separated from the liquid mixture and heated a second time at a temperature and for a period of time sufficient to form compounds having the formula $A^{4+}M_2^{6+}O_8.$

The solid fraction generally is heated within the temperature range of from about 500° C. to less than about 700° C. An alternative embodiment of the method involves adding a fuel material to the materials listed above before the final heating step. A currently preferred fuel material is urea. The fuel material apparently undergoes an exothermic reaction that provides additional energy to help produce the desired compound. The use of the fuel has substantially reduced the reaction time, such as to less than an hour, and in certain embodiments the first heating cycle has been completed in about fifteen minutes. Novel negative thermal expansion materials made by the method also are described. Such novel negative thermal expansion materials have the formula $A_{1-x}^{4+}A_x^{\mathrm{\prime 4}+}M_{2-y}^{6+}M_y^{\mathrm{\prime 6}+}O_8$

where A⁴⁺ and A′⁴⁺ are Hf⁴⁺ or Zr⁴⁺, M⁶⁺ and M′⁶⁺ are W⁶⁺ or Mo⁶⁺, X is from 0 to 1, and Y is from about 0.05 to ≦2.

Claims

1. A method for making substantially single-phase, crystalline NTE compounds having the formula:

$A^{4+}<br><br>M_2^{6+}<br><br>O_8$

where A⁴⁺ is Zr⁴⁺, Hf⁴⁺, or mixtures thereof, and M⁶⁺ is Mo⁶⁺, W⁶⁺, or mixtures thereof, the method comprising;

forming a liquid mixture comprising stoichiometric amounts of (1) a soluble source of Zr⁴⁺, Hf⁴⁺, or mixtures thereof, and (2) a sodium-ion-free tungstate salt, a sodium-ion-free molybdate salt, or mixtures thereof;

adding an acid to the liquid mixture to acidify the liquid mixture;

refluxing the liquid mixture at ambient pressures for a period of about 48 hours or more, or at pressures greater than ambient for a period of from about 1 to about 24 hours;

separating a solid fraction from the mixture; and

heating the solid fraction to a temperature within the temperature range of from about 500°

C. to less than 700°

C. to form a compound having the formula $A^{4+}<br><br>M_2^{6+}<br><br>O_8.$

2. The method according to claim 1 wherein the liquid mixture is an aqueous solution.

3. The method according to claim 1 wherein the sodium-ion-free tungstate salt is ammonium tungstate.

4. The method according to claim 3 wherein the sodium-ion-free salt is ammonium metatungstate.

5. The method according to claim 1 wherein the sodium-ion-free molybdate salt is ammonium molybdate.

6. The method according to claim 1 wherein the mixture comprises ammonium metatungstate and ammonium molybdate.

7. The method according to claim 1 wherein the soluble source of Zr⁴⁺ or Hf⁴⁺ is an oxyhalide, oxynitrate, or mixtures thereof.

8. The method according to claim 1 wherein heating the solid fraction comprises heating to a temperature within the temperature range of from about 500°

C. to about 600°

C. for a period of less than about 48 hours.

9. The method according to claim 1 wherein heating the solid fraction comprises heating at pressures greater than ambient.

10. A method for making substantially single-phase, crystalline NTE compounds having the formula $A^{4+}$

M26+

O8

where A⁴⁺ is Zr⁴⁺, Hf⁴⁺, or mixtures thereof, and M⁶⁺ is Mo⁶⁺, W⁶⁺, or mixtures thereof, comprising;

forming a liquid mixture comprising stoichiometric amounts of (1) a soluble source of Zr⁴⁺, Hf⁴⁺, or mixtures thereof, and (2) a sodium-ion-free tungstate salt, a sodium-ion-free molybdate salt, or mixtures thereof;

adding a mineral acid to the liquid mixture;

refluxing the liquid mixture at ambient pressure for a period of about 48 hours or more, or at pressures greater than ambient for a period of from about 1 to about 24 hours;

separating a solid fraction from the mixture; and

heating the solid fraction to a temperature within the temperature range of from about 500°

C. to less than 700°

C. to form a compound having the formula $A^{4+}<br><br>M_2^{6+}<br><br>O_8.$

11. The method according to claim 10 wherein the sodium-ion-free tungstate salt is ammonium tungstate.

12. The method according to claim 11 wherein the sodium-ion-free salt is ammonium metatungstate.

13. The method according to claim 10 wherein the sodium-ion-free molybdate salt is ammonium molybdate.

14. The method according to claim 10 wherein the mixture comprises ammonium metatungstate and ammonium molybdate.

15. The method according to claim 10 wherein the soluble source of Zr⁴⁺ or Hf⁴⁺ is an oxyhalide, oxynitrate, or mixtures thereof.

16. The method according to claim 15 wherein the oxyhalide is selected from the group consisting of ZrOCl₂, ZrOBr₂, ZrOl₂, HfOCl₂, HfOBr₂, HfOI₂ and mixtures thereof.

17. The method according to claim 15 wherein the oxynitrate is ZrO(NO₃)₂ or HfO(NO₃)₂.

18. The method according to claim 10 wherein heating the solid fraction comprises heating to a temperature within the range of from about 500°

C. to about 600°

C. for a period of less than about 48 hours.

19. The method according to claim 10 wherein heating the liquid mixtures comprises refluxing the liquid mixture.

20. The method according to claim 10 wherein heating the liquid mixture comprises heating in a closed system.

21. The method according to claim 20 wherein heating in a closed system comprises heating the liquid mixture in a Parr bomb to a temperature within the range of from about 200°

C. to about 250°

C. and a pressure of from about 200 psi to about 300 psi.

22. The method according to claim 10 wherein the mineral acid is HCl or H₂SO₄.

23. A method for making substantially single-phase, crystalline NTE compounds having the formula:

$A^{4+}<br><br>M_2^{6+}<br><br>O_8$

where A⁴⁺ is Zr, Hf, or mixtures thereof, and M⁶⁺ is Mo, W, or mixtures thereof, comprising;

forming an aqueous mixture comprising stoichiometric amounts of (1) a zirconium oxyhalide, a zirconium oxynitrate, a hafnium oxyhalide, a hafnium oxynitrate, or mixtures thereof, and (2) sodium-ion-free ammonium tungstate, sodium-ion-free ammonium molybdate, or mixtures thereof;

acidifying the aqueous mixture using a mineral acid to obtain a pH of about 0 or less;

refluxing the aqueous liquid mixture at ambient pressures for a period of about 48 hours or more, or at pressures greater than ambient for a period of from about 1 to about 24 hours;

separating a solid fraction from the aqueous mixture; and

heating the solid fraction to a temperature of from about 500°

C. to less than about 700°

C. for a period of time sufficient to form a compound having the formula $A^{4+}<br><br>M_2^{6+}<br><br>O_8.$

24. The method according to claim 23 wherein the mixture comprises ammonium metatungstate and ammonium molybdate.

25. The method according to claim 23 wherein heating the solid fraction comprises heating to a temperature within the range of from about 500°

C. to about 600°

C. for a period of less than about 48 hours.

26. A method for making substantially single-phase crystalline NTE compounds having the formula:

$A^{4+}<br><br>M_2^{6+}<br><br>O_8$

where A⁴⁺ is Zr⁴⁺, Hf⁴⁺, or mixtures thereof, and M⁶⁺ is Mo⁶⁺, W⁶⁺, or mixtures thereof, the method comprising;

forming a liquid mixture comprising stoichiometric amounts of (1) a soluble source of Zr⁴⁺, Hf⁴⁺, or mixtures thereof, (2) a sodium-ion-free tungstate salt, a sodium-ion-free molybdate salt, or mixtures thereof, and (3) a fuel material;

adding an acid to the liquid mixture to acidify the liquid mixture; and

heating the mixture within the temperature range of from about 500°

C. to less than 700°

C. to form a compound having the formula $A^{4+}<br><br>M_2^{6+}<br><br>O_8.$

27. The method according to claim 26 wherein the fuel is carbohydrazide.

28. The method according to claim 26 wherein the fuel material is selected from the group consisting of carbohydrazide, oxalic acid, dihydrazide, maleichyrazides, 3-methyl-3-pyrazolin-5-one, and mixtures thereof.

29. The method according to claim 26 wherein the fuel material is urea.

30. The method according to claim 26 wherein heating the mixture comprises heating the mixture at a temperature of from about 500°

C. to about 600°

C. for a period of less than about one hour.

31. The method according to claim 26 and further including the step of sintering the compound at a temperature of greater than about 1200°

C.

32. A method for making substantially single-phase NTE compounds having the formula:

$A^{4+}<br><br>M_2^{6+}<br><br>O_8$

where A⁴⁺ is Zr⁴⁺, Hf⁴⁺, or mixtures thereof, and M⁶⁺ is Mo⁶⁺, W⁶⁺, or mixtures thereof, the method comprising;

forming an aqueous mixture comprising stoichiometric amounts of (1) a soluble source of Zr⁴⁺, Hf⁴⁺, or mixtures thereof, (2) a sodium-ion-free tungstate salt, a sodium-ion-free molybdate salt, or mixtures thereof, (3) a fuel material, and (4) HNO₃; and

heating the mixture at a temperature of from about 500°

C. to about 600°

C. for a period of time of less than about one hour, thereby forming a compound having the formula $A^{4+}<br><br>M_2^{6+}<br><br>O_8.$

33. A method for making fine particle, crystalline ZrW₂O₈, comprising:

forming 0.5M solutions of zirconium oxynitrate and ammonium metatungstate;

heating a first volume of the ammonium metatungstate solution to a temperature of about 60°

C.;

adding a second volume which is about half the first volume of the zirconium salt solution to the ammonium metatungstate;

adding 6M HCl to the mixture to form an acidified mixture;

heating the acidified mixture at 60°

C. until the mixture is concentrated at a slurry;

transferring the slurry to a Parr bomb and heating the slurry in the Parr bomb and was heated at 180°

C.;

filtering and washing material removed from the Parr bomb; and

sintering the material at a temperature of about 1200°

C. for a period of time less than about thirty minutes.

34. A negative thermal expansion material having the formula $A_{1-x}^{4+}$

AX′

4+

M2-y6+

My′

6+

O8

where A⁴⁺ and A′

⁴⁺ are Hf⁴⁺ or Zr⁴⁺, M<sup>6+ and M′

6+</sup> are W⁶⁺ or Mo⁶⁺, X is from 0 to 1, and Y is from about 0.05 to ≦

2.

35. The negative thermal expansion material according to claim 34 selected from the group consisting of ZrWMoO₈, ZrW_1.6Mo_0.4O₈ and ZrW_0.5Mo_1.5O₈.

36. A composition having a thermal expansion less than that of a material included in the composition, the composition comprising:

a first material having low or negative thermal expansion and a formula of $A_{1-x}^{4+}<br><br>A_x^{\mathrm{\prime <br><br>4}+}<br><br>M_{2-y}^{6+}<br><br>M_y^{\mathrm{\prime <br><br>6}+}<br><br>O_8$

where A⁴⁺ and A′

⁴⁺ are Hf⁴⁺ or Zr⁴⁺, M⁶⁺ and M′

⁶⁺ are W⁶⁺ or Mo⁶⁺, X is from 0 to 1, and Y is from about 0.05 to <

2; and

a second material, the second material exhibiting a positive thermal expansion.