Negative Thermal Expansion Materials

Literature Review
By C A HALL
November 7, 2009

Introduction

Most materials expand significantly when heated, and successful engineering design must

take this phenomenon into consideration. Mechanical assemblies that operate over a temperature

range will experience differing expansions between components, due to local temperature

variations and differences in material properties. The different expansion behaviors will induce

internal stresses that can lead to premature failure if not properly considered. Methods to protect

against this can be seen most readily in large structures, such as expansion joints within bridged

roadways and multi-story buildings. Magnitudes of thermal stresses can be predicted and

minimized through systematic engineering design1,2; however, the cyclical nature of stress

common in engineering applications cannot be avoided. This type of loading can be more fatal to

designs than excessive magnitudes, due to the catastrophic nature of fracture and cracking

common in fatigue failures3. Many practical engineering designs experience temperatures

cycling through large ranges (e.g. aircraft, turbine engines, and electronics), and methods to

extend life and reliability are sought.

Some materials do not exhibit positive thermal expansion, and instead contract upon heating.

A number of common materials display this Negative Thermal Expansion (NTE); however, the

contractions are small relative to the positive thermal expansions of common materials near

room temperature. The temperature ranges that this phenomenon occurs over are also usually

relatively short and far below room temperature4. Examples of two common materials are

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silicon5 and ice water6, for which NTE occurs only below 120 K and 73 K, respectively. A

number of novel inorganic compounds have been discovered within the past 25 years that display

significant NTE over extended temperature ranges7,8. These materials have applications in

reduction and possible elimination of thermal expansion in composites, as well as customization

of thermal expansion behavior.

Mechanism

Thermal expansion is broadly defined as the change in a unit volume of material due to an

increase in temperature. Two different definitions exist, one based on the „extrinsic‟ physical

volume of the material, and the second based on the „intrinsic‟ unit cell of the crystal structure.

The ability to experimentally determine NTE with accuracy and repeatability is greater for the

intrinsic mechanism, as the variability of density and from hysteresis can cause the extrinsic

characteristic to vary significantly from sample to sample4. Extrinsic NTE does not necessarily

correlate with intrinsic, due to the difference in mechanisms than govern the contraction. The

two mechanisms are anisotropic and isotropic, which describe the nature of NTE through

changes in the unit cell dimensions.

Anisotropic Mechanism. Most materials that exhibit negative thermal expansion do so with

this mechanism, where one or two unit cell axes expand while the other(s) contract. Large

amounts of material strain are generated from the unequal contraction, and microcracks are

formed within material when cooled. Microcracks close when the body is heated and reform

when cooled, which achieves NTE. The extrinsic NTE is greater than the intrinsic due to this

phenomenon. In some cases the intrinsic thermal expansion is positive, but the anisotropy causes

overall NTE.4

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 Due to the presence of microcracks the thermal conductivity of materials exhibiting this type

of behavior is very low, making them suitable in specific applications. While cracks are good for

thermal resistance, they significantly degrade the mechanical properties; materials composed of

cracks by definition have low mechanical strength and low resistance to fatigue3. Also, due to the

unpredictable nature of microcrack growth and termination, there is significant hysteresis during

thermal cycling of materials exhibiting anisotropic NTE.4

Isotropic Mechanism. The bulk of research towards understanding and designing materials

with NTE has focused on the isotropic mechanism. An experimental advantage to isotropic

contraction is uniformity in measured properties despite preparation procedures. The uniform

contraction does not lead to microcracking, which greatly increases mechanical properties

relative to anisotropic contraction. Symmetry must be present within the crystal structure in all

three axes directions; therefore, the geometry must be cubic or amorphous. The general

mechanism is reported to be due to motion of atoms perpendicular to bonds4 as shown in figure

1. Increasing the thermal energy within a bond will increase vibration; however, the mode of

vibration impacts the apparent bond length differently. When heat is added to a material, the

increased thermal energy excites the atoms to a higher vibration state, which intuitively

lengthens the chemical bonds and causes positive thermal expansion. When the motion is

transverse to the bond, the average bond distance may decrease and cause NTE.

Figure 1. Schematic of how increased thermal energy can lead to apparent bond length reduction9

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 The specific mechanism of NTE in the ceramic structures reviewed4,8,9 is based on the

“libration”, or tilting of the polyhedra composing the crystal structure. The polyhedra are

composed of a metallic cation surrounded by oxygen anions, and tilting is caused through the

thermal motion illustrated in figure 1. Rigidity of the bonds composing the individual polyhedra

is greater than for the corner sharing bonds, and tilting is more energetically favorable than

expansion of the polyhedra. The crystal structure has been modeled as rigid units4,8,9 which

corner share at flexible angles. Increasing thermal energy causes tilting, which can cause

negative thermal expansion in specific crystal geometries, as shown in figure 2.

History

Research in NTE materials is evident as early as the 1950‟s, within the ceramic community10.

No single discoverer of novel compounds was found; however, the existence of near-zero and

negative expansion materials is reported as commercially available, e.g. ceramic coatings for gas

turbine blades11 and additives to control expansion behavior of electrical resistors12. One

example of a NTE material is reported as Lithium Alumina Silicate12, which was available under

Figure 2. Schematic illustrating NTE through tilting of rigid polyhedra8

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the trade name Stupalith by Stupakoff Ceramic and Manufacture Company. Starting in the late

1970‟s and early 1980‟s research increased drastically on NTE materials7. Much research has

been conducted by Sleight4,9,13 towards characterization of different NTE materials. Much

research has been focused on the novel ceramic compound zirconium tungstate.

Discussion of Zirconium Tungstate

This inorganic ceramic compound has been intensely researched within the last two decades,

due to its large magnitude of contraction and large temperature interval for which NTE is

displayed. The magnitude of negative expansion for the material is on the same order as “high-

expansion” ceramics9. Zirconium tungstate shows this strong NTE over practically all of

temperatures that it is stable and meta-stable4,9, 0.3-1050 K.

Synthesis. Zirconium tungstate is synthesized by sintering a homogenized mixture of

zirconium and tungstate ions. The specific precursors vary according to the procedure, and are

usually a mixture of different salts containing the required ions. The precursors are finely milled

and combined, such that the diameters are reduced below one micron. The common method for

mixing involves suspending the precursors in a fluid, and spray-drying the slurry to obtain a

homogenous powder. The resulting powder is pressed into molds and sintered up to temperatures

of around 1180 C. Zirconium tungstate is thermodynamically stable only in the temperature

range 1380-1530 K, therefore the sintered material must be quenched to retain the product. In

order to retain as much product as possible, the ceramic is quenched in liquid nitrogen.14,15

The specific precursors vary according to the published method. One commonly referenced

method14 uses ammonium metatungstate, zirconium oxychloride, and zirconium oxynitrate,

reportedly due to solubility levels in the solvent (water). Another method15, which focuses

mainly on creation of custom mixtures of zirconium oxide and zirconium tungstate, involves

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suspending zirconium and tungsten oxides in a solvent with a polymer lubricant. The lubricant

reportedly improved the density of the compound after pressing and sintering.

Difficulty in the synthesis is related to the temperature range of kinetic stability for zirconium

tungstate, for both sintering and quenching. For zirconium oxide and tungstate mixtures, the

sintering temperature of the oxide is above the stability range for the tungstate; difficulties can

arise where the tungstate is sintered around solid particulate oxide, which greatly impacts

homogeneity and mechanical strength15. Also, quenching from 1200 C to -60 C is an extreme

thermal shock to the material, which may affect the practical geometry of the ceramics

achievable.

Current State of the Art. Currently researched topics are concerned with identifying more

efficient methods for manufacture of NTE compounds, as well as compositions of ceramic

mixtures for tailored thermal expansions properties. The advantages of matching thermal

behaviors of ceramic coatings to engineering materials have been found reported11 as early as the

1950‟s. Customized NTE ceramics with near-zero thermal expansion have been synthesized15,

where the behavior is observed from 0-450°C. More complex methods for the synthesis of pure

NTE compounds are also current topics of research, e.g. the precursors can be suspended in an

ionic gel state to maintain homogeneity during sintering16.

Conclusion

Negative thermal expansion materials are a class of compounds that will be a current topic of

research for many years to come. The eventual application of NTE materials as additives to

engineering composites is expected by the author to improve the thermal fatigue resistance of

current designs, as well as change design processes involved with highly optimized mechanical

assemblies (e.g. aircraft, turbine engines, or spacecraft).

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(1) Bai, J; Maute, K; Sandeep, R. S; Raj R. Mechanical Design for Accommodating Thermal Expansion Mismatch
in Multilayer Coatings for Environmental Protection at Ultrahigh Temperatures. J. Am. Ceram. Soc. 2007, 90,
170-176.
(2) Padture, N. P; Gell, M; Jordan, E. H. Thermal Barrier Coatings for Gas-Turbine Engine Applications. Science.
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(3) Juvinall, R. C; Marshek, K. M. Fundamentals of Machine Component Design, 4th ed.; Wiley: New York, 2006.
(4) Sleight, A. W. Isotropic Negative Thermal Expansion. Annu. Rev. Mater. Sci. 1998, 28, 29-43.
(5) Lyon, K. G; Salinger, G. L; Swenson, C. A. Linear Thermal Expansion Measurements on Silicon From 6 to 340
K, J. Appl. Phys. 1977, 48, 865-868.
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and 265 K. Acta. Cryst. 1994, B50, 644-648.
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ZrW2O8 and HfW2O8. Chem. Mater. 1996, 8, 2809-2823.
(10) Singer, F. Ceramics. Indust. Eng. Chem. 1952, 44, 2296-2308.
(11) Manson, S. S. Behavior of Materials Under Conditions of Thermal Stress. N.A.C.A. 1953, TN 2933, 317-350.
(12) Rudner M. A. Electrical Resistors and Other Bodies with Negligible Temperature Coefficient of Expansion.
U.S. Patent 2,883,502, Jan. 28, 1955.
(13) Sleight, A. W. Negative Thermal Expansion Material. U.S. Patent 5,322,559, May 11, 1993.
(14) Meyer, C. D; Driessche, I. V; Hoste, S. Synthesis of the Negative Thermal Expansion Compound ZrW2O8 by
the Spray Drying Technique. Key Eng. Mat. 2002, 206, 11-14.
(15) Buysser, K. D; Lommens, P; Meyer, C. D; Bruneel, E; Hoste, S; Driessche, I. V. ZrO 2-ZrW2O8 Composites
with Tailor-Made Thermal Expansion. Ceram. Silikaty. 2004, 48, 139-144.
(16) Buysser, K. D; Driessche, I. V; Schaubroeck, J. EDTA Assisted Sol-Gel Synthesis of ZrW2O8, J. Sol-Gel Sci.
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