. (j <, .

-.

.%. ,

J. Am. Cerom. Soc., 72 [71 1268-70 (1989)

Precise Nondestructive Determination of the Density of Porous Ceramics

Erik C. M. Pennings* and Wolfgang Grellner
Elek-troschmelzwerkKempten GmbH, 8960 Kempten, Federal Republic of Germany
A f a s t , accurate, inexpensive, and

nondestructive method to determine the density of very porous ceramics has been found. This method is an extension of the water-displacement technique with three weighings and the use of glycerol instead of water. For small ( 1 .I3 g ) , 29% porosity B,C pellets, the precision is 0.002 glcm and the accuracy is b e t t e r than 0.006 g/cm compared with the geometric density. [Key words: density, nondestructive testing, porous materials, porosity, glycerol .]
apparent bulk porosity of sintered ceramic materials is an important physical property which is used for process control and evaluation. The determination of the density must therefore be accurate, easy to perform, and nondestructive, because sintered products constitute a large economic value. The geometric determination of the volume is not generally applicable because sintered products may have complicated forms. Most techniques to determine the density therefore involve
T H E P. S. Nicholson- contributingeditor Manuscript No. 198864. Received October 4, 1988; approved November 20, 1988. *Present address: Depattment of Electrical Engineering, Delft University of Technology, P.O. Box 5031, 2600 GA Delft. the Netherlands.

in some way the submersion of the sample in a liquid. The volume of the sample may be estimated either directly, by reading the displacement of liquid, or indirectly, by measuring the weight of the submerged sample and using the Archimedes law. For high-porosity materials, problems arise because of the impregnation of the sample by the liquid. The measured volume will consequently be too small and the estimated density too large. The methods that obviate this problem depend either on complete impregnation before submersion or on prevention of impregnation. Complete impregnation before submersion is used in the water-displacement technique with two or three* weighings and their extension^.^'^ These methods, however, are cumbersome and inaccurate for high-porosity ceramics. Impregnation may be prevented by coatin the sample before submersion in water, or by using mercury6 or sand7 instead of water. The coating technique changes the density and is destructive because of difficulties in removing the coating. Mercury displacement is usually considered the most reliable and accurate method, but it poses the problem of environmental pollution, is a possible health hazard and is, therefore, expensive and destructive. Inaccuracies are caused by the irreproducible meniscus around the sample holder at the mercury-air interface and by the fact that mercury fills all macropores

larger than 7.5 pm. We now propose a different method that prevents these problems.

EXPERIMENTAL PROCEDURE
Most methods are based on two measof the dry urements. First the weight, M I , sample is measured to find the true mass, m, of the sample (Fig. ](A)). The sample is then submerged in a liquid with density pliq,and the true volume, V, of the sample is estimated from the weight Mz(Fig. 1 ( B ) ) . A third weighing of the wet sample, however, can correct for the amount of liquid, Viq, that has impregnated the pore volume, V p (Fig. l(C)). The sample is taken out of the liquid, and adhering drops must be removed from the surface by blotting it with a damp cloth, which makes the method slightly operator biased. The real problem, in fact, with porous materials is to define the volume unambiguously. The result of the three weighings including the correction for the density of air pb, may be written as

M I =m -pmr(V -Vp)
M*=m -p,(V-Vliq)+p&p M3=m +pliqVIiq-pairO-Vp
-Vfq)
+V,iq)

(1)

(2)
(3)

Equations (1) to (3) lead to the density, p , of the sample.

(4)

Since the density of air is small compared with the other densities, Eq. (4) may be simplified to

The p value will be smaller than its approximation po and the relative correction is

Fig. 1. Extended liquid-displacement method. (A) The weight of the dry sample is determined. (B) Submerged in liquid, the lift of the displaced liquid is measured. (C) Since the liquid impregnates the sample we will find an incorrect volume for the sample, which can be corrected by weighing the sample a third time.

In this equation we introduce p,,,,,, as the mineralogical density of the material with zero porosity, which in most cases is accurately known. The last step is justified if only the first-order correction with respect to p& is retained.
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Communications of the American Ceramic Society

Table I. Relevant Properties of Water, Mercury, and Glycerol at 2OoC*
Water Mercury Glycerol

1269

The geometric density, pgeo =m/Vgeo, and its approximation, p;eo==MI/VReo, differ by the amount
Pgco -ppm-

GlyceroVwater**

Pau(1 -Vp/V)

PRO

P-Pau(l -Vp/V)

-2 ! ! L Pllr x + Pmln-PPLT

PIN"

(7)

Surface tension* (mN[m) Viscosity ((mN.s)/m ) Vapor pressure (Pa) Heat capacity <J/(kg-K)) Density (g/cm ) Thermal-expansion coefficient ( x IO-~/K)

72.75 1.0025 2335.5 4181.6 0.99823 0.21

475 1.589 0.1627 139.5 13.546 0.18

62.5t.t 1499 53$.! 2322'** I .260 0.49

65.7'.t 112.9 1067' 2552'.' 1.223

(80%) (85%) (83%) (80%) (86%)

The two corrections have opposite signs and will both be smaller than 1 x lo-' if the density of air is taken to be paa= I .OOx I O - ~g/cm3. Three weighings in combination with Eqs. ( 5 ) and (6) allow us to calculate the density of the sample, and this method does not depend on the porosity or on the amount of liquid that has impregnated the sample.
CHOICE OF LIQUID

*Datafrom Ref. 8 . 'Data from Ref. 9. 'At 25T. q o air. '98 wt% glycerol. **Number in parentheses is wt& C,H,O,.

Our method depends o n the constancy of V,q during the second and thud weighings. This requirement may be achieved by choosing an appropriate liquid with a very high viscosity in combination with bad wetting properties. The time needed by the liquid to fill a pore depends linearly on the viscosity. A high viscosity, therefore, ensures that the impregnation process is so slow that the liquid does not have enough time to leave the sample when is is taken out. We found that for this reason water is not the appropriate liquid and that a glycerol (CH20HCHOHCH20H)-water mixture with 86 wt% glycerol met most of our demands. Table I gives a survey of the relevant parameters for glycerol, water, and mercury, revealing the following advantages of glycerol: (1) The low surface tension of glycerol reduces the irreproducible forces associated with the meniscus formed around the suspension wire at the glycerol-air interface. The low vapor pressure of glycerol prevents the formation of bubbles at the sample-glycerol interface. (2) Glycerol is chemically inert and may be easily removed from the sample by means of water or acetone. (3) The high viscosity of glycerol ensures that the impregnation process is very slow, and it also cuts down convection currents in the liquid. (4) Glycerol has a higher density than water which increases the difference M3-ki2 and consequently the precision. ( 5 ) A low thermal-expansion coefficient and a large heat capacity of glycerol reduce the influence of thermal and mechanical disturbances on the density of the liquid. In this respect glycerol has no advantages over water or mercury.

Fig. 2. Scanning electron micrograph of a boron carbide (B,C)pellet with 29% porosity (bar= 10 pm).

comparing the results with the geometrically calculated density. The B4C pellets had an average open porosity of V p / V = 2 7 . 9 % , a s d e t e r m i n e d by m e r c u r y porosimetry (Fig. 2). After submersion of the sample in glycerol, equilibrium was established within a few minutes, and it was found that only 26% of the open pore volume was filled with glycerol. We measured the density for 9 different samples of B4C and repeated each measurement 10 times. The measurements were done by

two experimenters to minimize operator bias. The results are given in Table 11. The mineralogical density for B4C, p,,,,,,=2.516 g/cm3, leads to a correction (pRco - ~ : ~ ~ ) / p ;+4.0x ~,= according to Eq. (7), and to a correction ( p - p o ) / po= -4.2X according to Eq. (6). These corrections are slightly smaller than the standard deviation. For this reason, we corrected only the sample averages. After correction, the difference between the two sample-averaged densities is 0.006 g/cm3.

Table 11. Densities for B4C Samples Determined Geometrically and by Means of the New Method
Sample No. Geometric density* (glcm') Density according to F!q. (5)' (g/cm') Relative difference
(P

- P,.,)/P

EXPERIMENTAL RESULTS
We measured the densities of boron carbide (B4C) pellets, with a well-defined cylindrical geometry, which resulted in a volume of 0.632 cm3. The precise volume allowed us to estimate the accuracy or absolute correctness of the new method by

2 3 4 5 6 7 8 9 Sample average Sample average corrected for air 1.7726(30)

~I

1.776(9) 1.733(9) 1.770(9) 1.773(9) 1.788(9) 1.772(9) 1.769(9) 1.787(9) 1.779(9) 1.7719(30)

1.797(3) 1.743(2) 1.783(3) 1.783(2) 1.794(2) 1.776(1) 1.775(3) 1.788(2) 1.778(1) 1.7797(5) 1.7790(5)
\ ,

1.1% 0.6% 0.7% 0.5% 0.6% 0.3% 0.3% 0.1% - 0.1% 0.44% 0.36%

*The maximum error is indicated within parentheses. 'Ten measurements have been done for each sample. The densities are averages and the value within parentheses is the standard deviation.

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Communications of the American Ceramic Society

be removed. The new method is therefore easy, fast, inexpensive, nondestructive, and precise, even for ceramics with very high porosity.

Vol. 72, No. 7

We consider this value a pessimistic estimate for the accuracy, since the geometric density is usually too small (a micrometer will determine the maximum dimension for an uneven surface). The mean density, p= I .779 g/cm3. gives an average porosity of Vp/V=29.3%, which compares well with the average open porosity of 27.9%. determined using mercury porosimetry. After the density was measured, the samples were carefully cleaned by submersion in acetone and water. The weight of the dried samples indicated that all glycerol had been removed.

ACKNOWLEDGMENTS
The authors thank Miss S. Kampermann for her help with the measurements and the Elektroschmelzwerk Kempten GmbH for the opportunity to do this work and their permission to publish it.

CONCLUSIONS
From Table 11, it is concluded that the precision or reproducibility of the new method is better than 0.003 g/cm3, which is at least a factor of 3 better than the geometric method. The accuracy is better than 0.006g/cm' by comparison with the geometric density. The determination is nondestructive because all the glycerol could

REFERENCES '"Standard Test Method for Bulk Density of Granular Refractory Materials,'' ASTM Designation (2-357-85. 1987 Book of ASTM S t a n d a r d s , Vol. 15.01; pp. 124-26. American Society for Testing and Materials, Philadelphia, PA. %andard Test Methods for Apparent Porosity, Water Absorption, Apparent Specific Gravity, and Bulk Density of Burned Refractory Brick and Shapes by Boiling Water," ASTM Designation C-20-83. 1987 Book of ASTM Standards, Vol. 15.01; pp. 7-10.

American Society for Testing and Materials. Philadelphia. PA. 'H. D. Leigh 111 and G. H. Lufcy. "Bulk Density Determination of Periclase Aggregates by a New Water Method." Am. Ceram. Soc. Bull.. 60 [71 719-23. 29 ( 198I ). 'D. S. Perera, "Errors Associated with the Determination of Bulk Density of Granular Refractory Materials," Am. Ceram. Soc. B u l l . . 60 171 693-94 (1981). 'K. H. Moyer, "Measuring Density of P/M Materials with Improved Precision," I n t . J . Powder Merall. Powder Techno/.. 15 [ I ] 33-35. 37-42 (1979). b"Standard Test Method for Bulk Density and Porosity of Granular Refractory Materials by Mercury Displacement," ASTM Designation C-493-86. 1987 Book of ASTM Standards, Vol. 15.01; pp. 159-62. American Society for Testing and Materials, Philadelphia, PA. 'P. Anelt and U. Schierloh. "Rapid Determination of the Unfired Density of Granular Materials by Means of a Sand Addition Method" (in Ger.). Keram. Z . . 34 [51 266-68 (1982). 8Landolt-Bornstein,Zahlenwene and Funktionen, 6th ed., (Vol. I1 Pt. I 1971). (Vol. I1 Pt. 2a 1960). (Vol. II Pt. 3 1956). (Vol. 11 Pt. 4 1961). (Vol. I1 PI.5a 1969). Springer-Verlag. Berlin, FRG. 'R.C. Emst, C. H. Watkins. and H. H. Ruwe. "The Physical Properties of the Ternary System Ethyl Alcohol-Glycerin-Water," 1. Phys. Chem.. 40 151 627-35 (1936). 0

_,

> , \ * .

J. Am. Cerum. Soc., 72 171 1270-73 (1989)

Effect of Silicon Carbide Additions on the Crystallization Behavior of a Magnesia-Lithia-Alumina-Silica Glass

Dennis N. Coon*,+
Idaho National Engineering Laboratory, EG&G Idaho, Inc., Idaho Falls, Idaho 83415

Glass in the MgO-Li20-A1203-Si02 system was observed to crystallize readily at temperatures from 700" to 900C. The primary crystalline phase evolved was Li,Si,O,, and the secondary phase evolved was Li,Si03. The glass was amorphous after heating in air at 1050C for 30 min. The addition of 0.5 wt% Sic powder resulted in the crystallization of Li,Si03 during heating in air at 1050C for 30 min. It was suggested that the difference in crystallization behavior with S i c ad-

dition was due to dissolution of Sic into the oxide glass. [Key words: glass, crystallization, magnesia, silicon carbide, alumina.]
system are candidates for matrix materials in Sic-fiber-reinforced composite materials' and as brazing materials to join S i c ceramics.' A major advantage of these glasses is the ability to prepare low thermal expansion glass-ceramics containing phases based on spodumene or eucryp tite solid solution^.^ The potential to dissolve SIC into a magnesium aluminosilicate oxynitride glass to form oxycarbide glasses has been r e p ~ r t e d Both . ~ the hardness and glasstransition temperature of that glass were reported to increase with increasing carbon content. It was suggested that the property changes were a result of an anionic substitution of tetravalent carbon for divalent oxygen in the glass structure. An increase in glass-transition temperature indicates a change in the thermal

GLASSES in the Mg0-Li20-AI2O3-SiO2

characteristics of the glass as a result of SIC dissolution. A change in the thermal characteristics would be expected to alter the temperature range in which crystallization is observed. Crystallization of a glass occurs by the process of nucleation and growth.' A detailed discussion of crystallization is beyond the scope of this paper, and the reader is referred to one of the excellent review articles available.5*6 The crystal growth rate ( u ) is modeled according to the following equation: u=Adexp( -AGlkT)]
x [ 1 - exp( -AG * / k T ) ] (1)

T. J. Clark--contributing

editor

Manuscript No. 199278. Received March 3. 1988; approved November I , 1988. Supported by the U.S. Department of Energy, Office of Fossil Energy, under Contract No. DEAC07-761Wl570. 'Member. American Ceramic Society. 'Now with the Department of Mechanical Engineering, University of Wyoming, Laramie, WY 8207I .

where A,, is a constant, k is the Boltzmann constant, and T is the temperature. AG is the activation energy for ion diffusion across the crystalline particle-glass interface. The free energy associated with the conversion of 1 mol of atoms from the metastable state (glass) to the stable state (crystal) is given as A G * . The energy term AG * is dependent on the temperature