Patent US5322559A successfully refreshed from Google Patents.
US5322559A
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Negative thermal expansion material
Assignee: Oregon State University
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Filing: 1993-05-11
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Granted: 1994-06-21
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Expires: 2013-05-11
Abstract
Abstract Compounds that satisfy the general formula A1-Y4+AY1+AY3+V2-XPXO7 exhibit isotropic NTE behavior in the range of normal ambient temperatures. Y is from about 0.0 to about 0.4, and more preferably is about 0.2. X is from about 0.6 to about 1.4, and is more preferably about 1. Particularly suitable NTE compounds have X about 1 and Y about 0. A4+ is selected from the group consisting of Hf, Zr, ZraMb, HfaMb and mixtures thereof wherein a plus b equals one and M is selected from the group consisting of Ti, Ce, Th, U, Mo, Pt, Pb, Sn, Ge and Si. More preferably, A4+ is selected from the group consisting of Hf and Zr. A1+ is selected from the group consisting of the alkali earth metals, and A3+ is selected from the group consisting of the rare earth metals. Such NTE materials exhibit isotropic negative linear expansion at a temperature below about 100 DEG C. The NTE materials also may be incorporated into compositions such as epoxy and ceramic compositions.
Inventors
- 👤 Arthur W. Sleight
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 14:51
CPC Classifications
C; C04; C04B; C04B35/00; C04B35/01; C04B35/447; C01; C01B; C01B25/00; C01B25/16; C01B25/26; C01B25/45
Claims Analysis
Total Claims: 41
Claim 1
Independent Claim
117 words
A compound according to the formula A 1-Y 4+ A Y 1+ A Y 3+ V 2-X P X O 7 , wherein X is from about 0 1 to about 1.9, Y is from about 0.0 to about 0.4, and wherein A 4+ selected from the group consisting of Hf, Zr, Zr a M b , Hf a M b and mixtures thereof wherein a plus b equals one and M is selected from the group consisting of Ti, Ce, Th, U, Mo, Pt, Pb, Sn, Ge and Si, A 1+ is selected from the group consisting of the alkali earth metals, and A 3+ is selected from the group consisting of the rare earth metals.
Claim 2
Dependent Claim
117 words
A compound according to the formula A 1-Y 4+ A Y 1+ A Y 3+ V 2-X P X O 7 , wherein X is from about 0 1 to about 1.9, Y is from about 0.0 to about 0.4, and wherein A 4+ selected from the group consisting of Hf, Zr, Zr a M b , Hf a M b and mixtures thereof wherein a plus b equals one and M is selected from the group consisting of Ti, Ce, Th, U, Mo, Pt, Pb, Sn, Ge and Si, A 1+ is selected from the group consisting of the alkali earth metals, and A 3+ is selected from the group consisting of the rare earth metals.
Claim 3
Dependent Claim
24 words
The compound according to claim 1 wherein X is from about 0.6 to about 1.4 and Y is from about 0.1 to about 0.2.
Claim 4
Dependent Claim
16 words
The compound according to claim 1 wherein X is about 1 and Y is about 0.2.
Claim 5
Dependent Claim
20 words
The compound according to claim 1 wherein the compound exhibits negative thermal expansion at a temperature below about 100° C.
Claim 6
Dependent Claim
25 words
The compound according to claim 4 wherein the compound exhibits negative linear expansion at a temperature of from about -25° C. to about 100° C.
Claim 7
Dependent Claim
17 words
The compound according to claim 1 wherein X is about 1 and wherein Y is about 0.
Claim 8
Dependent Claim
16 words
The compound according to claim 6 wherein the compound is ZrVPO 7 or HfVPO 7 .
Claim 9
Dependent Claim
20 words
The compound according to claim 1 wherein A 4+ is zirconium, A 1+ is lithium, and A 3+ is yttrium.
Claim 10
Dependent Claim
34 words
The compound according to claim 8 wherein the compound is Zr 0 .9 Li 0 .1 Y 0 .1 VPO 7 or Zr 0 .8 Li 0 .2 Y 0 .2 VPO 7 .
Claim 11
Dependent Claim
24 words
The compound according to claim 1 wherein A 4+ is zirconium, X is from about 0.1 to about 1.9 and Y is about 0.
Claim 12
Dependent Claim
107 words
The compound according to claim 10 wherein the compound is selected from the group consisting of ZrV 1 .9 P 0 .1 O 7 , ZrV 1 .8 P 0 .2 O 7 , ZrV 1 .7 P 0 .3 O 7 , ZrV 1 .6 P 0 .4 O 7 , ZrV 1 .4 P 0 .6 O 7 , ZrV 1 .2 P 0 .8 O 7 , ZrV 0 .8 P 1 .2 O 7 , ZrV 0 .6 P 1 .4 O 7 , ZrV 0 .4 P 1 .6 O 7 , and ZrV 0 .2 P 1 .8 O 7 .
Claim 13
Dependent Claim
191 words
The compound according to claim 1 wherein the compound is selected from the group consisting of ZrVPO 7 , HfVPO 7 , Zr 0 .9 Li 0 .1 Y 0 .1 VPO 7 , Zr 0 .8 Li 0 .2 Y 0 .2 VPO 7 , ZrV 1 .9 P 0 .1 O 7 , ZrV 1 .8 P 0 .2 O 7 , ZrV 1 .7 P 0 .3 O 7 , ZrV 1 .6 P 0 .4 O 7 , ZrV 1 .5 P 0 .5 O 7 , ZrV 1 .4 P 0 .6 O 7 , ZrV 1 .2 P 0 .8 O 7 , ZrV 0 .8 P 1 .2 O 7 , ZrV 0 .6 P 1 .4 O 7 , ZrV 0 .4 P 1 .6 O 7 , ZrV 0 .2 P 1 .8 O 7 , HfV 1 .9 P 0 .1 O 7 , HfV 1 .8 P 0 .2 O 7 , HfV 1 .7 P 0 .3 O 7 , HfV 1 .6 P 0 .4 O 7 , and Zr 0 .9 Ce 0 .1 VPO 7 .
Claim 14
Dependent Claim
81 words
A compound according to the formula A 1-Y 4+ A Y 1+ A Y 3+ V 2-X P X O 7 , wherein X is from about 0 5 to about 1.5, Y is from about 0.0 to about 0.4, and wherein A 4+ is selected from the group consisting of Hf and Zr, A.sup. 1+ is selected from the group consisting of the alkali earth metals, and A 3+ is selected from the group consisting of the rare earth metals.
Claim 15
Dependent Claim
81 words
A compound according to the formula A 1-Y 4+ A Y 1+ A Y 3+ V 2-X P X O 7 , wherein X is from about 0 5 to about 1.5, Y is from about 0.0 to about 0.4, and wherein A 4+ is selected from the group consisting of Hf and Zr, A.sup. 1+ is selected from the group consisting of the alkali earth metals, and A 3+ is selected from the group consisting of the rare earth metals.
Claim 16
Dependent Claim
24 words
The compound according to claim 13 wherein X is from about 0.6 to about 1.4 and Y is from about 0 to about 0.2.
Claim 17
Dependent Claim
19 words
The compound according to claim 14 wherein X is about 1 and Y is about 0.1 to about 0.2.
Claim 18
Dependent Claim
20 words
The compound according to claim 13 wherein the compound exhibits negative thermal expansion at a temperature below about 100° C.
Claim 19
Dependent Claim
16 words
The compound according to claim 13 wherein X is about 1 and Y is about 0.
Claim 20
Dependent Claim
16 words
The compound according to claim 17 wherein the compound is ZrVPO 7 or HfVPO 7 .
Claim 21
Dependent Claim
20 words
The compound according to claim 13 wherein A 4+ is zirconium, A 1+ is lithium, and A 3+ is yttrium.
Claim 22
Dependent Claim
34 words
The compound according to claim 19 wherein the compound is Zr 0 .9 Li 0 .1 Y 0 .1 VPO 7 or Zr 0 .8 Li 0 .2 Y 0 .2 VPO 7 .
Claim 23
Dependent Claim
24 words
The compound according to claim 13 wherein A 4+ is zirconium, X is from about 0.1 to about 2.0 and Y is about 0.
Claim 24
Dependent Claim
106 words
The compound according to claim 21 wherein the compound is selected from the group consisting of ZrV 1 .9 P 0 .1 O 7 , ZrV 1 .8 P 0 .2 O 7 , ZrV 1 .7 P 0 .3 O 7 , ZrV 1 .6 P 0 .4 O 7 , ZrV 1 .4 P 0 .6 O 7 , ZrV 1 .2 P 0 .8 O 7 , ZrV 0 .8 P 1 .2 O 7 , ZrV 0 .6 P 1 .4 O 7 , ZrV 0 .4 P 1 .6 O 7 and ZrV 0 .2 P 1 .8 O 7 .
Claim 25
Dependent Claim
172 words
The compound according to claim 13 wherein the compound is selected from the group consisting of ZrVPO 7 , HfVPO 7 , Zr 0 .9 Li 0 .1 Y 0 .1 VPO 7 , Zr 0 .8 Li 0 .2 Y 0 .2 VPO 7 , ZrV 1 .9 P 0 .1 O 7 , ZrV 1 .8 P 0 .2 O 7 , ZrV 1 .7 P 0 .3 O 7 , ZrV 1 .6 P 0 .4 O 7 , ZrV 1 .4 P 0 .6 O 7 , ZrV 1 .2 P 0 .8 O 7 , ZrV 0 .8 P 1 .2 O 7 , ZrV 0 .6 P 1 .4 O 7 , ZrV 0 .4 P 1 .6 O 7 , ZrV 0 .2 P 1 .8 O 7 , HfV 1 .9 P 0 .1 O 7 , HfV 1 .8 P 0 .2 O 7 , HfV 1 .7 P 0 .3 O 7 and HfV 1 .6 P 0 .4 O 7 .
Claim 26
Dependent Claim
17 words
A compound according to the formula A 4+ VPO 7 wherein A 4+ is zirconium or hafnium.
Claim 27
Dependent Claim
17 words
A compound according to the formula A 4+ VPO 7 wherein A 4+ is zirconium or hafnium.
Claim 28
Dependent Claim
21 words
The compound according to claim 23 wherein the compound exhibits negative thermal expansion from about -25° C. to about 100° C.
Claim 29
Dependent Claim
119 words
A composition comprising a compound of the formula A 1-Y 4+ A Y 1+ A Y 3+ V 2-X P X O 7 , wherein X is from about 0.1 to about 1.9, Y is from about 0.0 to about 0.4, and wherein A 4+ is selected from the group consisting of Hf, Zr, Zr a M b , Hf a M b and mixtures thereof wherein a plus b equals one and M is selected from the group consisting of Ti, Ce, Th, U, Mo, Pt, Pb, Sn, Ge and Si, A l+ is selected from the group consisting of the alkali earth metals, and A 3+ is selected from the group consisting of the rare earth metals.
Claim 30
Dependent Claim
119 words
A composition comprising a compound of the formula A 1-Y 4+ A Y 1+ A Y 3+ V 2-X P X O 7 , wherein X is from about 0.1 to about 1.9, Y is from about 0.0 to about 0.4, and wherein A 4+ is selected from the group consisting of Hf, Zr, Zr a M b , Hf a M b and mixtures thereof wherein a plus b equals one and M is selected from the group consisting of Ti, Ce, Th, U, Mo, Pt, Pb, Sn, Ge and Si, A l+ is selected from the group consisting of the alkali earth metals, and A 3+ is selected from the group consisting of the rare earth metals.
Claim 31
Dependent Claim
84 words
A composition comprising a compound of the formula A 1-Y 4+ A Y 1+ A Y 3+ V 2-X P X O 7 , wherein X is from about 0 i to about 1.9 and Y is from about 0.0 to about 0.4, and wherein A 4+ is selected from the group consisting of Hf and Zr, A 1+ is selected from the group consisting of the alkali earth metals, and A 3+ is selected from the group consisting of the rare earth metals.
Claim 32
Dependent Claim
84 words
A composition comprising a compound of the formula A 1-Y 4+ A Y 1+ A Y 3+ V 2-X P X O 7 , wherein X is from about 0 i to about 1.9 and Y is from about 0.0 to about 0.4, and wherein A 4+ is selected from the group consisting of Hf and Zr, A 1+ is selected from the group consisting of the alkali earth metals, and A 3+ is selected from the group consisting of the rare earth metals.
Claim 33
Dependent Claim
19 words
A composition comprising a compound of the formula A 4+ VPO 7 wherein A 4+ is zirconium or hafnium.
Claim 34
Dependent Claim
19 words
A composition comprising a compound of the formula A 4+ VPO 7 wherein A 4+ is zirconium or hafnium.
Claim 35
Independent Claim
250 words
A method for making a compound of the formula A 1-Y 4+ A Y 1+ A Y 3+ V 2-X P X O 7 , wherein X is from about 0.1 to about 1.9 and Y is from about 0.0 to about 0.4, and wherein A 4+ is selected from the group consisting of Hf, Zr, Zr a M b , Hf a M b and mixtures thereof wherein a plus b equals one and M is selected from the group consisting of Ti, Ce, Th, U, Mo, Pt, Pb, Sn, Ge and Si, A 1+ is selected from the group consisting of the alkali earth metals, and A 3+ is selected from the group consisting of the rare earth metals, the method comprising the steps of: providing a first aqueous mixture having a source of rare earth metals, a source of alkali metals, and a source of A 4+ ; providing a second aqueous mixture having a source of vanadium and a source of phosphorous; heating both the first mixture and the second mixture to a temperature of from about 80° C. to about 100° C.; adjusting the pH of the second mixture to be about 2 by adding a sufficient amount of an inorganic acid; combining the first aqueous mixture with the second aqueous mixture, thereby forming a precipitate; and heating the precipitate to a temperature of about 600° C. to about 800° C., for a period of time of from about 2 hours to about 6 hours.
Claim 36
Independent Claim
250 words
A method for making a compound of the formula A 1-Y 4+ A Y 1+ A Y 3+ V 2-X P X O 7 , wherein X is from about 0.1 to about 1.9 and Y is from about 0.0 to about 0.4, and wherein A 4+ is selected from the group consisting of Hf, Zr, Zr a M b , Hf a M b and mixtures thereof wherein a plus b equals one and M is selected from the group consisting of Ti, Ce, Th, U, Mo, Pt, Pb, Sn, Ge and Si, A 1+ is selected from the group consisting of the alkali earth metals, and A 3+ is selected from the group consisting of the rare earth metals, the method comprising the steps of: providing a first aqueous mixture having a source of rare earth metals, a source of alkali metals, and a source of A 4+ ; providing a second aqueous mixture having a source of vanadium and a source of phosphorous; heating both the first mixture and the second mixture to a temperature of from about 80° C. to about 100° C.; adjusting the pH of the second mixture to be about 2 by adding a sufficient amount of an inorganic acid; combining the first aqueous mixture with the second aqueous mixture, thereby forming a precipitate; and heating the precipitate to a temperature of about 600° C. to about 800° C., for a period of time of from about 2 hours to about 6 hours.
Claim 37
Dependent Claim
27 words
The method according to claim 28 wherein the first aqueous mixture comprises a source of hafnium, and the second mixture comprises a source of vanadium and phosphorous.
Claim 38
Dependent Claim
40 words
The method according to claim 29 wherein the source of hafnium is HfOCl 2 .8H 2 O, the source of vanadium is NH 4 VO 3 , and the source of phosphorous is (NH 4 ) 2 HPO 4 .
Claim 39
Dependent Claim
27 words
The method according to claim 28 wherein the first aqueous mixture comprises a source of zirconium and the second mixture comprises a source of vanadium and phosphorous.
Claim 40
Dependent Claim
38 words
The method according to claim 31 wherein source of zirconium is ZrOCl 2 .8H 2 O, the source of vanadium NH 4 VO 3 , and the source of phosphorous is (NH 4 ) 2 HPO 4 .
Claim 41
Dependent Claim
210 words
The method according to claim 28 wherein the compound according to the formula A 1-Y 4+ A Y 1+ A Y 3+ V 2-X P X O 7 is selected from the group consisting of ZrVPO 7 , HfVPO 7 , Zr 0 .9 Li 0 .1 Y 0 .1 VPO 7 , Zr 0 .8 Li 0 .2 Y 0 .2 VPO 7 , ZrV 1 .9 P 0 .1 O 7 , ZrV 1 .8 P 0 .2 O 7 , ZrV 1 .7 P 0 .3 O 7 , ZrV 1 .6 P 0 .4 O 7 , ZrV 1 .5 P 0 .5 O 7 , ZrV 1 .4 P 0 .6 O 7 , ZrV 1 .2 P 0 .8 O 7 , ZrV 0 .8 P 1 .2 O 7 , ZrV 0 .6 P 1 .4 O 7 , ZrV 0 .4 P 1 .6 O 7 , ZrV 0 .2 P 1 .8 O 7 , HfV 1 .9 P 0 .1 O 7 , HfV 1 .8 P 0 .2 O 7 , HfV 1 .7 P 0 .3 O 7 , HfV 1 .6 P 0 .4 O 7 , and Zr 0 .9 Ce 0 .1 VPO 7 .
References Cited (Backward Citations)
US3941715A
Cited
US4112194A
Cited
US4337173A
Cited
US4675302A
Cited
US4801566A
Cited
US5254510A
Cited
US5102836A
Cited
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