Isotropic negative thermal expansion ceramics and process for making

Abstract

Ceramic monoliths are described which exhibit tunable coefficients of thermal expansion from about −5 to −11×10−6° C.−1 near ambient temperatures. These two-phase ceramics, which are fabricated, for example, by reactive sintering of WO3 and ZrO2, consists of a matrix of ZrW2O8 with inclusions of ZrO2 having diameters less than 10 &mgr;m. Additives may increase the density of the monoliths to greater than 98% of the calculated density. Green body densities, pre-sintered particle size distribution, sintering atmosphere, microstructure, and mechanical properties are discussed. These ceramics may be used as substrates for thermally compensating fiber Bragg gratings.

Description

FIELD OF THE INVENTION

[0001] This invention pertains to isotropic, negative thermal expansion ceramics, and to a process for preparing isotropic, negative thermal expansion ceramics which may, for instance, be used in temperature compensating grating packages.

TECHNOLOGY REVIEW

[0002] As described in U.S. Pat. No. 5,694,503, incorporated herein by reference, it is possible to package a fiber grating on or in a negative expansion material so that the package and grating dimensions decrease with an increase in temperature, resulting in minimal variation of the reflection wavelength with temperature.

[0003] In order for this approach to be practical the value for the thermal expansion of the package/substrate material must lie within an acceptable range. The ideal expansion coefficient is given by the expression 1 α ideal = α fiber + - A ( 1 - P e ) ⁢   ⁢ λ nom

[0004] where &agr;fiber is the thermal expansion of the fiber grating (for instance, 0.55×10−6° C.−1), A is the temperature sensitivity of the unpackaged grating (e.g., 0.0115 nm °C.−1 for a particular 1550 nm grating), Pe is the photoelastic constant (typically 0.22) and &lgr;nom is the nominal grating wavelength (˜1550 nm in many cases). For a particular 1550 nm grating an “ideal” package material would have a thermal expansion coefficient (CTE) of −8.96×10−6° C.−1. A package material will still be beneficial even if its thermal expansion is not exactly equal to the ideal value. For the above assumptions a factor of about 20 improvement in temperature sensitivity would be achieved if the package material's thermal expansion coefficient were within 0.47×10−6° C.−1 of the ideal value. Such improvement in thermal stability of a fiber grating would be of commercial importance.

[0005] It is known that ZrW2O8 is metastable at room temperature, with the lower limit of stability being at 1105±3° C., below which ZrW2O8 decomposes into ZrO2 and WO3. See, for instance, J. Graham et al., J. American Ceramics Society, Volume 42, page 570 (1959), and L. L. Y. Chang et al., J. American Ceramics Society, Volume 50, page 211 (1967). It is also known that ZrW2O8 has a relatively high and isotropic negative coefficient of thermal expansion (CTE) over an extensive range of temperatures that includes room temperature. See, for instance, C. Martinek et al., J. American Ceramics Society, Volume 51, page 227 (1968) and T. A. Mary et al., Science, Volume 272, page 90 (1996). Specifically, the CTE is substantially constant from near absolute zero temperature to 150° C., with a value near −10×10−6° C.−1. The material exhibits an order-disorder transition at 150° C., after which the CTE drops to −5×10−6° C.−1. This value of the CTE is maintained until the decomposition of ZrW2O8 which occurs at a relatively high rate near 800° C.

[0006] In view of this complex behavior of ZrW2O8, it is not surprising that earlier attempts to produce mechanically strong monolithic bodies of ZrW2O8, that have a predetermined negative CTE, did not yield fully satisfactory results. For instance, C. Verdon et al., Scripta Materialia, Volume 36, page 1075 (1997) report that their attempts to form electrically conducting bodies from ZrW2O8 and Cu with a low CTE resulted in decomposition of the ZrW2O8 and formation of Cu2O along with other compounds. Such decomposition is generally undesirable and hinders the production of suitable bodies.

[0007] To the best of our knowledge, prior art efforts to make ZrW2O8 ceramic bodies used the conventional technique of sintering ZrW2O8 powder. Thus produced bodies have densities less than 90% of the theoretical density and exhibit relatively poor mechanical properties, specifically, a low modulus of rupture. Additional prior art describes the preparation of ZrW2O8 powder from oxide precursors to be an incomplete reaction.

[0008] In view of the importance, for instance, a reduction of the temperature dependence of the reflection wavelength of optical fiber gratings, it would be highly desirable to be able to reproducibly make mechanically strong ceramic bodies having tunable negative CTE values, the ceramic bodies being useful, for example, for packaging of fiber gratings. This application discloses a method for making such bodies.

SUMMARY OF THE INVENTION

[0009] We have made the surprising discovery that reactive sintering of appropriate percursor powders (e.g., ZrO2 and WO3) can result in (negative CTE) bodies (e.g., ZrW2O8) with substantially improved properties, as compared to analogous bodies produced by the prior art sintering techniques.

[0010] To the best of our knowledge, the prior art does not provide any suggestion that the use of reactive sintering could provide the observed improved results. By “reactive sintering” we mean herein compacting the unsintered body of the precursor oxides, rather than the powder of the desired final phase, and then forming the desired phase and densifying the body in a single heat treatment step.

[0011] In a broad aspect of the invention is embodied in a method of making negative CTE ceramic bodies, and in bodies produced by the method.

[0012] More specifically, the invention is embodied in a method of making a ceramic body having isotropic negative thermal expansion, the body having a major constituent selected from the group consisting of ZrW2O8, HfW2O8, ZrV2O7 and HfV2O7. The method comprises the steps of providing a powder mixture, forming a “green” body that comprises the powder mixture, and heat treating the green body. The powder mixture comprises a first and a second oxide precursor powder, selected respectively from the group consisting of ZrO2 powder and HfO2 powder, and the group consisting of WO3 powder and V2O5 powder. The heat treatment of the green body includes heating the body to a temperature below the melting temperature of the selected constituent, such that the selected major constituent is formed from the green body by reactive sintering.

[0013] By a “green” body we mean herein the compacted precursor powders as a monolithic body prior to sintering.

[0014] In a preferred embodiment the powder mixture has a non-stoichiometric composition (e.g., excess ZrO2), and the heat treatment results in formation of a 2-phase material, e.g., ZrW2O8 majority phase, with ZrO2 inclusions dispersed in the majority phase. This embodiment allows tailoring of the CTE of the body.

[0015] In a further preferred embodiment the powder mixture comprises a minor amount of a sintering aid (e.g., Y2O3, Bi2O3, Al2O3, ZnO, TiO2, SnO2), whereby the density of the sintered body is substantially increased.

[0016] Important note for processing

[0017] Due to the unusually narrow stability region of ZrW2O8, standard techniques for synthesizing and densifying composite ceramics containing ZrW2O8 produce monoliths with inadequate physical properties. High purity ZrW2O8 is thermally stable between 1105 and 1260° C. Above 1260° C. ZrW2O8 peritectically decomposes into a Liquid phase, and below 1105° C. it decomposes into ZrO2 and WO3. Additives significantly alter the stability region of ZrW2O8; this study demonstrates a working temperature range of 1140 to 1180° C. for Y2O3 doped ZrW2O8.

BRIEF DESCRIPTION OF THE DRAWING

[0018] FIG. 1. Percent densities of ZrW2O8.xZrO2 monoliths with Y2O3 additive plotted with respect to weight percent of additional ZrO2.

[0019] FIG. 2. SEM micrograph of a ZrW2O8.18 wt. % ZrO2 monolith viewed with secondary electron imaging. ZrO2 inclusions with various particle sizes having a maximum diameter of approximately 10 &mgr;m appear with darker contrast.

[0020] FIG. 3. Relative thermal expansion of a ZrW2O8.9.5 wt. % ZrO2 monolith taken over an extensive temperature range. The coefficient of thermal expansion (CTE) for the range −100 to 100° C. and 200 to 300° C. is −10×10−6 and 3×10−6° C.−1, respectively. A reversible order-disorder transition takes place near 140° C. which does not compromise the mechanical strength of the monolith.

[0021] FIG. 4. Relative thermal expansion over ambient working temperatures for several ZrW2O8.xZrO2 monoliths. The following compositions are presented (label, wt. % excess ZrO2, volume fraction ZrO2): a, 37.0%, 0.337; b, 19.5%, 0.174; c, 9.5%, 0.084, d, 0%, 0. Nonlinearity of the thermal expansion is enhanced as the zirconia content increases.

[0022] FIG. 5 illustrates the dependence of the Coefficient of Thermal Expansion (CTE) between 0 and 100° C. of two-phase ZrW2O8.xZrO2 ceramics as weight percent of additional ZrO2. The change in CTE demonstrates a linear relationship to the relative amount of ZrO2 inclusions.

[0023] FIG. 6. Reflection wavelength of a fiber Bragg grating as a function of temperature is compensated by a ZrW2O8 9.5 wt. % ZrO2 substrate throughout ambient temperature range.

DETAILED DESCRIPTION OF THE INVENTION

[0024] The synthesis of ZrW2O8 has been described as challenging due its metastability. However, the fabrication of monoliths via reactive sintering is straightforward and reproducible upon consideration of the following points: additives (including impurities), particle size, and sintering atmosphere. Similarly, reactive sintering may be used to prepare HfW2O8, ZrV2O7, and HfV2O7.

[0025] Additives

[0026] In phase equilibria, additives which form a eutectic may be utilized as a liquid phase sintering aid, thereby significantly increasing the density of a ceramic. Liquid phases accelerate material transport during sintering by serving as a solvent for the solid phase with subsequent precipitation to yield dense ceramics. Monoliths of ZrW2O8.xZrO2 prepared with a Y2O3 additive have achieved, densities greater than 99% the calculated theoretical density (FIG. 1). The density of a high purity ZrW2O8 monolith is only 92%. Several oxides typically used as sintering aids including refractory oxides were investigated (Table 1). Increased densities were observed without decomposition of ZrW2O8 for small amounts (0.1 wt. %) of additives. In order to easily observe enhanced differences in density, the samples were milled for only two hours (vide infra). Of the additives which were surveyed, all increased the density of the monoliths with exception of SiO2. The following series illustrates the relative effectiveness of the additives: Y2O3>Bi2O3>Al2O3˜ZnO>TiO2.

[0027] Densification via liquid phase sintering has been demonstrated in several ceramic systems and is extensively employed in the ceramic industry in order to decrease sintering times and temperatures. For effective liquid phase sintering, only 1 vol. % of liquid within grain boundaries is necessary to aid densification. Increasing the concentration of Al2O3, TiO2, or Y2O3, to a few weight percent leads to complete decomposition of ZrW2O8 and melting of the monolith at the sintering temperature. This suggests that a liquid phase is present at 1180° C. even at low concentrations of additives. Similar equilibria have been observed in the alkali metal-WO3—ZrO2 systems with eutectic temperatures below 600° C. Consequently, liquid phase sintering is a preferred mechanism for enhanced densification.

[0028] Due to the impact of additives on the sintered density, it is important to characterize the impurities in the starting materials and grinding media. An important consideration is the selection of appropriate grinding media based on composition in order to prevent undesired impurities, such as Al2O3 and calcium stabilized ZrO2, from incorporation into the monoliths.

[0029] Pre-sintering Particle Size

[0030] The particle size, particle size distribution, and uniformity of particle packing are important factors in the densification process. In this study of the preparation of ZrW2O8.xZrO2 monoliths, these factors have the greatest impact on sintered density. In general, smaller particles are more reactive and tend to densify at lower temperatures. Coarse particles have less surface energy which diminishes the driving force for consolidation. For conventional powder processing, the optimum particle diameter is approximately 1 &mgr;m. Particles significantly smaller than this are difficult to pack uniformly and densely due to agglomeration and undergo excessive shrinkage with entrapped porosity during firing. In addition, a range of particle sizes is advantageous towards achieving maximum packing density in the green body. However, non-uniformities in particle packing may result in voids which are difficult to eliminate during the densification process. Variations in green body densities produced during the forming process can also result in warpage during sintering.

[0031] The dependence of sintered density on green body density was accomplished by dry-pressing samples at applied pressures of 1000 psi to 20,000 psi. All the samples were pressed in the same ¼ in. cylindrical die and therefore had the same green diameter. Information in Table 2 expounds the effects of green body density on linear shrinkage and the aspect ratio of the pellets after sintering. Samples pressed at lower pressures had lower green densities and underwent greater linear shrinkage during firing. All samples consolidated to a similar density of approximately 4.45 g/cm3, independent of their initial green densities. The initial particle size or surface area, rather than initial green density of the compact had a greater impact on the final sintered density. These data suggest that the primary driving force for densification of ZrW2O8 is the reduction of surface free energy. However, complexities due to reactive sintering with the aid of additives obscure the sole effect of surface energy minimization.

[0032] The as-received mixture of powders had a bimodal particle size distribution around 600 &mgr;m and 50 &mgr;m. Monoliths fabricated from this coarse, unreactive material actually decreased in density after sintering. It was necessary to comminute the starting materials by vibratory milling. As the milling time increased the particle size initially decreased significantly to approximately 1 &mgr;m diameter. Milling times were limited to 16 h due to concerns of contamination from the grinding media.

[0033] Sintering Atmosphere

[0034] Loss of oxygen in ZrW2O8 has been observed at temperatures as low as 500° C. in vacuum, while retaining the crystal structure. Another study found that oxygen scavengers (e.g. Cu) promote decomposition of ZrW2O8 at low temperatures (600° C.) through the formation of Cu2O. It has been found that monoliths sintered in air at 1180° C. partially decompose on the surface, followed by volatilization of WO3. Heating ZrW2O8 in a N2 atmosphere at the sintering temperature leads to complete decomposition into ZrO2 and WO3, whereas sintering in pure oxygen produced single phase ZrW2O8 with minimal surface decomposition. In addition, monoliths sintered in oxygen demonstrated reproducible physical properties.

[0035] Microstructure

[0036] The microstructure of a nearly stoichiometric ZrW2O8 monolith reveals large grains of ZrW2O8 having approximately a 20 &mgr;m diameter which form the matrix of the ceramic. The uniform distribution of pores and grain sizes is indicative of a homogeneously sintered material. A SEM micrograph of a ZrW2O8.18 wt. % ZrO2 monolith is presented in FIG. 2 in which excess zirconia is observed as nearly spherical inclusions having various diameters. Individual ZrW2O8 grains cannot be distinguished in the SEM image.

[0037] For the ZrW2O8.xZrO2 compositions surveyed, the ZrO2 volume fraction was below the percolation limit such that a 0-3 connectivity (isolated inclusions of ZrO2 in a matrix of ZrW2O8) was preserved. The percolation limit for a second phase with monodisperse diameters has been calculated to exist at a critical volume fraction of 0.183. Although we have prepared samples with a greater volume fraction of zirconia, all evidence indicates isolated inclusions. Thus significantly higher volume fractions are necessary to reach the percolation limit which is due to the distribution of diameters of the inclusions. Beyond the percolation limit the properties of a monolith with two interpenetrating 3-dimensional matrices (3-3 connectivity) may demonstrate anomalies. In addition, it is possible that the stress placed on a 3-3 ceramic due to the tetragonal to monoclinic phase transformation of the ZrO2 matrix would lead to catastrophic failure of the monoliths.

[0038] Powder X-ray diffraction indicates the presence of only the &agr;—ZrW2O8 phase (Powder Diffraction File, Joint Committee on Powder Diffraction Standards, JCPDS, Swarthmore, Pa., card number 13-557) and monoclinic Baddeleyite ZrO2 phase (JCPDS card number 37-1484). However, small amounts of additional phases may be present. The lower detectable limit of other phases by X-ray diffraction is estimated to be 1%.

[0039] Thermal Expansivity

[0040] ZrW2O8 has demonstrated a negative thermal expansion from 0.3 to 1050 K. The temperature dependence of the thermal expansion of a monolith of ZrW2O8 with 9.5 wt. % excess ZrO2 is shown in FIG. 3. The order-disorder phase transition at 150° C. is reversible and does not compromise the mechanical strength of the monoliths. In addition, cracking due to the large difference in thermal expansion of ZrW2O8 and ZrO2 was not observed over the temperature range of −100° to 300° C. The linear negative thermal expansion of the composite facilitates its utilization in applications.

[0041] The coefficient of thermal expansion of diphasic ceramic monoliths can be tuned by compensating the large negative thermal expansion of ZrW2O8 with a material having a positive CTE such as ZrO2. Zirconia was chosen as the second phase for its thermodynamic stability in the presence of ZrW2O8 and for the ease of processing via the reactive sintering technique. Several other refractories react with ZrW2O8 at the sintering temperature and therefore lead to irreproducible results due to decomposition. In addition to stability, the thermal expansion of ZrO2 is roughly linear from 20 to 100° C. with a CTE of 8×10−6° C.−1. This is advantageous since the compensation of the thermal expansion leads to an averaged CTE which is also linear over ambient temperatures (FIG. 4). These diphasic ceramics can be tuned from −5 to −11×10−6° C.−1 for dense monoliths. A linear correlation between the CTE and the volume fraction of ZrO2 occurs over a broad range of compositions (FIG. 5). A simple model, based on an additive relationship of thermal expansions for a monolith without zirconia with a CTE of −11×10−6° C.−1 and pure ZrO2 with a CTE of 8×10−6° C.−1, would have a slope of 19. The linear fit to our data has a slope of 17.6 which is in close agreement for the compositions surveyed. This approach, which neglects any anomalies at the percolation limit, suggests that a monolith with a volume fraction of ZrO2 of 0.58 would have a zero CTE.

[0042] The thermal expansion was measured along three directions normal to the faces of the ceramic bars. Although ZrW2O8 crystallizes in a cubic space group, the monoliths are prepared by uniaxially compressing the pre-sintered powder mixture. This processing could introduce anisotropic macroscopic properties. However, the thermal expansion of the bars demonstrates isotropic behavior. Heating rates up to 20° C./min to temperatures of 400° C. with a TMA analyzer did not reveal any decomposition or cracking which would be distinguished as irreproducibility or discontinuities in the CTE, respectively. Degradation of the ceramics was not observed through several heating and cooling cycles.

[0043] Compensating the CTE with excess WO3 has been accomplished, but the monoliths have extremely high porosity at the surface to a depth of approximately 120 &mgr;m. In order to fabricate mechanically robust monoliths, extensive machining is necessary to remove the porous layer.

[0044] Fiber Grating Package

[0045] The Bragg wavelength (&lgr;) in a vacuum is given by

&lgr;=2neff&Lgr;

[0046] where neff is the effective refractive index for the guided mode in the fiber, and &Lgr; is the period of the index modulations of the fiber (˜0.5 &mgr;m for a particular 1550 nm grating). The Bragg wavelength of a fiber Bragg grating is temperature dependent primarily due to the temperature dependence of the refractive index of the silica based glass. In addition, the Bragg wavelength is strain dependent by altering the fringe spacing. As the temperature increases the refractive index of glass increases and vice versa. Also, due to the positive thermal expansion of silica (CTE˜0.5×10−6° C.−1), the fringe spacing increases slightly with temperature. The wavelength shift that corresponds to refractive index (n) changes due to temperature (T) variations and thermal expansion of silica glass (&agr;thermal) can be calculated as follows: 2 λ = 2 ⁢ n ⁢   ⁢ Λ ⅆ λ ⅆ T = 2 ⁢ Λ ⁢   ⁢ ⅆ n ⅆ T + 2 ⁢ n ⁢   ⁢ ⅆ Λ ⅆ T Δλ = 2 ⁢ Λ ⁢   ⁢ n n ⁢ ⅆ n ⅆ T ⁢ Δ ⁢   ⁢ T + 2 ⁢ n ⁢ Λ Λ ⁢ ⅆ Λ ⅆ T ⁢ Δ ⁢   ⁢ T Δλ = λ ⁡ ( 1 n ⁢   ⁢ ⅆ n ⅆ T + α thermal ) ⁢ Δ ⁢   ⁢ T where ⁢   ⁢ CTE = α thermal = 1 Λ ⁢ ⅆ Λ ⅆ T

[0047] For a 100° C. temperature change the shift in wavelength for a particular 1550 nm grating is measured to be about 1.15 nm. The portion of this shift due to the CTE of the silica fiber (&agr;thermal) is ˜0.08 nm, which is less than 8% of the total shift.

[0048] As mentioned before, the grating wavelength is also sensitive to strain. If a grating is stretched, then the grating wavelength will increase. The strain and wavelength relationship can be presented as follows: 3 Δ ⁢   ⁢ λ λ = Δ ⁢   ⁢ l l ⁢ ( 1 - P e )

[0049] where &Dgr;l/l=&egr;, the strain, and Pe is the effective photo-elastic constant (˜0.22) Due to this effect, it is possible to package a fiber grating on or in a negative expansion material so that package and grating dimensions decrease with an increase in temperature, resulting in a value of &Lgr; that falls as the temperature increases. By choosing the appropriate negative expansion coefficient (˜−9×10−6° C.−1) that maintains a constant neff&Lgr; product, a grating whose reflecting wavelength shows minimal variation with temperature can be achieved.

[0050] The dependence of the reflection wavelength of both a compensated and an uncompensated fiber Bragg grating as a function of temperature is shown in FIG. 6. The grating that is compensated by a ZrW2O8.9.5 wt. % ZrO2 monolith demonstrates a 0.05 nm deviation from −40 to 80° C., which is nearly ideal. This substrate can be utilized to fabricate a thermally compensated package suitable for WDM (wavelength division multiplex) applications.

[0051] Mechanical Strength

[0052] Four-point bending tests were performed on bars of ZrW2O8. Preliminary tests revealed a low modulus of elasticity (0.5×106 psi) for the ZrW2O8.xZrO2 monoliths. The modulus of rupture was determined to be 3000 psi. With regards to the grating package, an applied force of 89 N is required to break the monolith which is much greater than the maximum tensile force which is exerted by the fiber (2 N).

[0053] The monoliths demonstrate brittle failure having an approximate conchoidal fracture surface. The mechanism proceeds via intergranular fracture around ZrO2 inclusions and intragranular throughout the ZrW2O8 matrix. Therefore shearing at boundaries between ZrW2O8 grains does not occur at room temperature.

[0054] Conclusion

[0055] Reactive sintering of WO3 and ZrO2 powders produces dense monoliths with adequate strengths. The reactive sintering technique circumvents the inherent metastability of ZrW2O8 in the early stages of densification, thereby yielding reproducible fabrication conditions. Monoliths containing zirconia inclusions demonstrate a range of thermal expansion coefficients linearly related to the volume fraction of ZrO2. A monolith of ZrW2O8.xZrO2, which exhibits a negative thermal expansion in the desired range, has been successfully prepared and shown to thermally compensate a fiber Bragg grating. 1 TABLE 1 Effect of Sintering Aids on the Density of Monoliths Additive (0.1 wt. %) Density (g/cm3) None 3.25 SiO2 3.10 TiO2 3.82 ZnO 3.94 Al2O3 3.95 Bi2O3 4.05 Y2O3 4.21

[0056] 2 TABLE 2 Effect of Green Body Density on Shrinkage Applied Sintered Linear Pressure Diameter Shrinkage Aspect Density (psi) (mm) (%)a Ratiob (g/cm3)  1000 5.94 6.45 1.13 4.49  5000 6.02 5.20 1.17 4.42 10000 6.03 4.25 1.24 4.51 20000 6.20 2.36 1.32 4.41 aLinear shrinkage determined along diameter. bAspect ratio defined as diameter/height of cylindrical monolith after sintering.

EXAMPLES

[0057] The following examples are presented to assist those skilled in this technology to understand and practice the invention, without in any way intending to limit the invention to the exemplified embodiments.

Example 1

[0058] Preparation of ZrW2O8 composite ceramics via reactive sintering technique utilizing methyl ethyl ketone (MEK) as the milling solvent.

[0059] Milling of ZrO2 and WO3 mixture in methyl ethyl ketone (MEK) for 10-20 hours utilizing stabilized ZrO2 grinding media.

[0060] Addition of approximately 2 wt. % of an organic binder (QPAC-40, PAC Polymers Inc.) which is soluble in MEK to above mixture,

[0061] Evaporation of MEK during continuous stirring of mixture,

[0062] Sieving of dried mixture through 30-100 mesh screen,

[0063] Pressing of powder mixtures to form green body,

[0064] Firing in an oxygen atmosphere on a bed of coarse ZrW2O8 grains on Pt foil,

[0065] Slowly heating said green body around 50° C. per hour to around 250° C.,

[0066] Subsequent heating of said green body around 500° C. per hour to around 1150 to 1200° C. with an optimal sintering temperature of 1180° C.,

[0067] Holding said green body at 1180° C. for around 5 hours,

[0068] Cooling quickly to room temperature by withdrawing the sintered monolith from the furnace.

Example 2

[0069] Preparation of ZrW2O8 composite ceramics via reactive sintering technique utilizing water as the milling solvent.

[0070] Milling of ZrO2 and WO3 mixutre in water for 10-20 hours utilizing stabilized ZrO2 grinding media,

[0071] Addition of approximately 5-10 wt. % of an organic binder (polyvinyl alcohol) which is soluble in water to mixture,

[0072] Evaporation of water during continuous stirring of mixture,

[0073] Sieving of dried mixture through 30-100 mesh screen,

[0074] Pressing of powder mixture to form green body,

[0075] Firing in an oxygen atmosphere on a bed of coarse ZrW2O8 grains on Pt foil,

[0076] Slowly heating said green body around 50° C. per hour to around 250° C.,

[0077] Subsequent heating of said green body around 500° C. per hour to around 1150 to 1200° C. with an optimal sintering temperature of 1180° C.,

[0078] Holding said green body at 1180° C. for around 5 hours,

[0079] Cooling quicly to room temperature by withdrawing the sintered monolith from the furnace.

Example 3

[0080] Extrusion of pre-reacted powders.

[0081] Milling of ZrO2 and WO3 mixture in methyl ethyl ketone (MEK) for 10-20 hours utilizing stabilized ZrO2 grinding media,

[0082] Evaporation of MEK,

[0083] Sieving of dried mixture through 30-100 mesh screen,

[0084] Addition of approximately 0.3 wt. % plasticizer and lubricant (Union Carbide, PEG-400) to powder mixture.

[0085] Addition of approximately 1.0 wt. % dispersant (Angus Chemical Co., AMP-95) to powder mixture,

[0086] Addition of approximately 4.5 wt. % binder (Rohm and Haas, B-1051) to powder mixture,

[0087] Addition of approximately 2.4 wt. % binder (Rohm and Haas, B-1052) to powder mixture,

[0088] Addition of approximately 6.1 wt. % water to powder mixture.

[0089] Blended under low shear conditions,

[0090] Extruded through die at room temperature.

Example 4

[0091] Preparation of ZrV2O7 composite ceramics via reactive sintering technique utilizing water as the milling solvent.

[0092] Milling of ZrO2 and V2O5 mixture in water for 10-20 hours utilizing stabilized ZrO2 grinding media,

[0093] Addition of approximately 5-10 wt. % of an organic binder (polyvinyl alcohol) which is soluble in water to mixture,

[0094] Evaporation of water during continuous stirring of mixture,

[0095] Sieving of dried mixture through 30-100 mesh screen,

[0096] Pressing of powder mixture to form green body,

[0097] Firing in an oxygen atmosphere on a bed of coarse ZrV2O7 grains on Pt foil,

[0098] Slowly heating said green body around 50° C. per hour to around 250° C.,

[0099] Holding said green body at 850-900° C. for around 5 hours,

[0100] Cooling quickly to room temperature by withdrawing the sintered monolith from the furnace.

[0101] It is understood that various other modifications will be apparent to and can readily be made by those skilled in the art without departing from the scope and spirit of this invention. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the description as set forth herein, but rather that the claims be construed as encompassing all the features of patentable novelty that reside in the present invention, including all features that would be treated as equivalents thereof by those skilled in the art to which this invention pertains.

Claims

1. A method of making a ceramic body having an isotropic negative coefficient of thermal expansion, the body having a major constituent selected from the group consisting of ZrW2O8, HfW2O8, ZrV2O7 and HfV2O7, comprising the steps of,

a) preparing a powder mixture comprising a first and a second oxide precursor powder, the first oxide precursor powder selected from the group consisting of ZrO2 powder and HfO2 powder, and the second oxide precursor powder selected from the group consisting of WO3 powder and V2O5 powder;

b) forming a green body comprising said powder mixture; and

c) heat treating the green body at a temperature below the melting temperature of the selected major constituent, and forming the selected major constituent from the heat treated green body by reactive sintering.

2. The method according to

claim 1, wherein the powder mixture contains a non-stoichiometric amount of one of the first and second precursor powders, such that said ceramic body further comprises a second constituent, the non-stoichiometric amount selected to provide the ceramic body with a predetermined value of the negative coefficient of thermal expansion.

3. The method according to

claim 1, wherein the powder mixture further comprises a sintering aid selected to yield an increased density of the ceramic body.

4. The method according to

claim 3, wherein the sintering aid is selected from the group consisting of Y2O3, Bi2O3, Al2O3, ZnO, TiO2, SnO2 and combinations thereof.

5. The method according to

claim 1, wherein said powder mixture is prepared by vibrational milling of said first and second oxide precursor powders in a milling solvent to form a slurry, adding a binder to said slurry, and evaporating said milling solvent to form a powder mixture.

6. The method according to

claim 1, wherein said green body is formed by sieving said powder mixture to form a sieved powder, and pressing said sieved powder to form a green powder.

7. The method according to

claim 1, wherein said heat treatment comprises firing said green body in an oxygen atmosphere, slow heating said fired body to about 250° C., subsequently heating to about 1150° to 1200° and soaking said body for about 5 hours, and quenching said heated body to room temperature to form said ceramic body having an isotropic negative coefficient of thermal expansion.

8. A composition consisting essentially of the ceramic body produced by the process of

claim 1.

9. A two-phase composition comprising a first phase consisting essentially of the ceramic body produced by the process of

claim 2, and a second phase comprising at least one oxide selected from the group consisting of WO3, V2O5, ZrO2 and HfO2.

10. The two-phase composition according to

claim 9, wherein said second phase consists essentially of WO3.

11. The two-phase composition according to

claim 9, wherein said second phase consists essentially of ZrO2.

12. The two-phase composition according to

claim 9, wherein said second phase consists essentially of HfO2.

13. The two-phase composition according to

claim 9, wherein said second phase consists essentially of V2O5.

14. The two-phase composition according to

claim 10, containing up to about 35 weight % WO3, compared to the weight of the first phase.

15. The two-phase composition according to

claim 11, containing up to about 35 weight % ZrO2, compared to the weight of the first phase.

16. The two-phase composition according to

claim 12, containing up to about 35 weight % HfO2, compared to the weight of the first phase.

17. The two-phase composition according to

claim 13, containing up to about 35 weight % V2O5, compared to the weight of the first phase.

18. The two-phase composition according to

claim 9 having a thermal expansion coefficient of about −9±2.5×10−6° C.−1.

19. The two-phase composition according to

claim 9 having a thermal expansion coefficient of about −9±1×10−6° C.−1.

20. The two-phase composition according to

claim 9 having a thermal expansion coefficient of about −9±0.25×10−6° C.−1.

21. An article comprising an optical fiber attached to a support, said support comprising a two-phase composition according to

claim 9.

22. An article comprising an optical fiber attached to a support, said support comprising a two-phase composition according to

claim 11.

23. An article comprising an optical fiber attached to a support, said support comprising a two-phase composition according to

claim 15.

24. An article comprising an optical fiber attached to a support, said support comprising a two-phase composition according to

claim 18.