J/V-wy

NBSIR 81-2217/e

Feasibility Study: Compilation and

Evaluation of Properties Data for

Basalt, Granite, Tuff, and Shale

L. H. Gevantman

Office of Standard Reference Data

National Measurement Laboratory

U.S. Department of Commerce

National Bureau of Standards

Washington, DC 20234

January 1 981

Final

Prepared for Office of Nuclear Waste Isolation

Battelle Memorial Institute

505 King Avenue

Columbus, OH 43201

t'

NBSIR 81-2217

FEASIBILITY STUDY: COMPILATION AND

EVALUATION OF PROPERTIES DATA FOR

BASALT, GRANITE, TUFF, AND SHALE

L. H. Gevantman

Office of Standard Reference Data

National Measurement Laboratory

U.S. Department of Commerce

National Bureau of Standards

Washington, DC 20234

January 1981

Final

Prepared for Office of Nuclear Waste Isolation

Battelle Memorial Institute

505 King Avenue

Columbus, OH 43201

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

FEASIBILITY STUDY: COMPILATION AND EVALUATION

OF PROPERTIES DATA FOR BASALT, GRANITE, TUFF, AND SHALE

Lewis H. Gevantman

A study on the feasibility of compiling and evaluating selected physical

property data on basalt, granite, shale, and tuff has been completed. The

data are to be used to design geological waste repositories for radioactive

nuclear waste. Sufficient data on the thermodynamic, mechanical, thermophysical,

and electrical properties have been identified to exist in the literature to

warrant further data evaluative effort. A bibliography of the selected data

is given.

Key Words: Basalt; bibliography; electrical properties; granite; mechanical

properties; nuclear waste isolation; shale; thermodynamic properties;

thermophysical properties; tuff.

Table of Contents

Purpose

Approach

Results

Conclusions

Appendix I

1

1

2

4

Appendix II

Purpose

This effort was initiated to determine the feasibility of assembling an evaluated numerical generic data base on the properties of selected geological

materials. The selection of such materials is predicated on their utility as

a medium in which to store highly radioactive nuclear waste. The materials of

interest have been identified by the Office of Nuclear Waste Isolation (ONWI)

and are salt, granite, basalt, tuff, and shale. A data base has been compiled

on the properties of domed and bedded salt, and is contained in a monograph

which will be issued soon [1]. Another compilation on salt, shale, basalt,

and granite covering their geological, hydrological, and seismological properties

was published recently [2]. However, the thermophysical, electrical and other

properties for the latter three materials are not treated in sufficient depth

to permit decisions to be made on the design of repositories in these media.

Consequently a more detailed survey of the literature has been made to establish

the extent and depth of coverage of data for these materials. The outcome of

this effort will be used to judge the value of proceeding with the evaluation

of the data to form a data base for use in waste repository design.

Approach

The National Bureau of Standards ' Office of Standard Reference Data

(NBS-OSRD) was given the task of assembling a body of experts to perform this

task. It turned to two data centers: the National Center for the Thermodynamic

Data of Minerals, under the direction of Dr. John L. Haas, Jr., and the Center

for Information and Numerical Data Analysis and Synthesis (CINDAS) under the

direction of Professor Y. S. Touloukian. The former is located at the U. S.

Geological Survey, Reston, Virginia, and the latter at Purdue University, West

Lafayette, Indiana. The material property data were assembled under the

general headings of thermodynamic, mechanical, thermophysical, and electrical

data. These in turn were further categorized into the chemical composition,

mineralogy, heat capacity, enthalpy, entropy, Gibbs free energy, molar volume

changes with pressure and temperature; elastic, dynamic, and static properties;

compressive, tensile, and shear strength; creep; permeability, porosity, and
2

hardness; thermal conductivity, expansion, capacity, and diffusivity;

electrical conductivity as a function of selected parameters.

A complete bibliography was assembled and examined for data content. In

addition, some review was given to the validity of the data, both in terms of

the proper application of the experimental measurement and the subsequent

theoretical treatment to arrive at the desired value. A recommendation on whether to proceed with further effort could then be based upon a positive

assessment of the existing data base.

Results

The results are detailed in two appendices. Each appendix represents the

contribution of each data center in its area of expertise. Each appendix

presents a bibliography, a sample of the data surveyed, the degree of reliance

to be placed on the data, a review of the experimental techniques employed,

and a recommendation on how to proceed beyond the present effort.

The results are summarized here to give an overall view of the degree of

% success achieved. Thus* in the area of thermodynamic property data it was established that sufficient data exist in the literature to characterize

approximately 66 mineral phases common to granite, tuff, shale, and basalt.

Where experimental data are lacking or insufficient, the properties will be

estimated to an acceptable accuracy (< 5%) . Difficulties in data evaluation

are foreseen for mineral phases having variable water content and composition.

As an example, Table 2 of Appendix 1 displays the available epxerimental data

on the thermodynamic properties of minerals and is reproduced below. A more

detailed reading of the available data is given in Table 3 of that appendix.

For mechanical property data it has been possible to identify over 200

out of 1100 papers surveyed which contain useful information. A series of

tables has been constructed in Appendix 2 showing the density and elastic

property data for the four materials of interest. In addition, graphs are plotted for selected material specimens to show the broad variation in reported

value as a function of temperature or pressure. The data for permeability.
3

porosity, and hardness are treated in similar fashion. Few data on hardness

exist other than for granite.

Thermophysical and electrical property data have been culled and compiled

from the literature. Ninety useful papers for thermophysical properties and

31 references for electrical properties have been assembled in Appendix 2.

In addition, brief discussions on the applicability of selected experimental

techniques are given.

Some examples for four thermophysical properties are presented for the

four materials as a function of temperature. The data are presented graphically and show disparity in the reported values. Consequently many of the

graphs are represented as a band of values rather than a single line.

The electrical properties discussed pertain mainly to conductivity and

resistivity. Again the experimental techniques are discussed briefly, and

then a few graphs and one table are included to demonstrate the type of data

encountered. It is demonstrated that the electrical behavior of basalt and

granite is dependent largely on water content. Little information exists on

the electrical properties of shale and tuff.
4

Conclus ions

As a result of the review of the literature and the preliminary examination

of the data it is possible to conclude:

1. An adequate body of data exists for attempting an evaluative effort.

2. The data for thermodynamic properties either exist or can be

estimated to provide a reliable data base.

3. The number of data values for mechanical, thermophysical, and

electrical properties reported are adequate to narrow the choices

required in the design criteria for nuclear waste repositories, but

cannot be said to be of sufficient quality to permit recommended values.

The utility of the evaluative process will be twofold: first, to

narrow the spread between values, and second, to indicate where useful

measurements can be made to improve data accuracy.

4. The electrical properties of shale and tuff are not well reported in

the literature. Considerably more experimental data are required.

5. Site-specific data on all the properties seem lacking in varying

degrees

6. The generation of a generic data base for the properties and materials

cited is timely because it provides a useful data base for present design

criteria and points the direction for future data collection effort

required to characterize a nuclear waste repository.
References

1. Gevantman, L. H. , Editor, Physical Properties Data for Rock Salt,

NBS Monograph 167, Washington, DC 1981.

2. Isherwood, Dana, Geoscience Data Base Handbook for Modeling a Nuclear

Waste Repository, Vols. 1 and 2, prepared for U. S. Nuclear Regulatory

Commission, NUREG/CR-0912 , UCRL-52719, NRC FIN No. A0277, Washington,

DC, 1980.

APPENDIX I

Feasibility Study

Data for Nuclear Waste Disposal, Thermodynamic Properties

of Basalt, Granite, Shale, and Tuff

Gilpin R. Robinson, Jr., Constance M. Schafer, John L. Haas, Jr.

U.S. Geological Survey, 959 National Center

Reston, VA 22D92

Feasibility Study

Data for Nuclear Waste Disposal, Thermodynamic Properties

of Basalt, Granite, Shale, and Tuff

Gilpin R. Robinson, Jr., Constance M. Schafer, and John L. Haas, Jr.

U.S. Geological Survey, 959 National Center

Reston, VA 22092

A compilation is presented of the available experimental data on the

thermodynamic properties of 66 mineral phases which are commonly present in

some of the rock types proposed as nuclear waste storage candidates:

1) granite, 2) tuff, 3) shale, and 4) basalt. A summary of the chemistry and

mineralogy of each rock type is given. A procedure to evaluate an internally

consistent set of thermodynamic properties for minerals from the compiled

experimental data is presented.

It is concluded that sufficient data of quality exist to evaluate the

thermodynamic properties of most of these mineral phases. These data are

summarized in Table 2 and cited in detail in Table 3. Efforts will be

focused on deriving the properties of the end-member components of mineral

phases which possess solid solution. Where experimental data are lacking or

insufficient, the properties of heat capacity, volume thermal expansion, and

volume compressibility can be estimated with an accuracy of a few percent.

The greatest uncertainties and evaluation difficulties are fogseen for mineral

phases having variable water content (zeolites, some mineral hydrates, some

clays).

Key words: Thermodynamics; minerals; nuclear waste; data evaluation.

1
Contents Page

1. Introduction . 3

2. Summary of rock-type chemistry and mineralogy 5

2.1. Granite and other crystalline igneous rocks 5

2.1.

a. Major mineral constituents . 5

2 . 1

.

b. Minor mineral constituents 6

2.1.

c. Alteration phases 7

2.2. Tuff 8

2.

2.

a. Phenocrysts 9

2.2.

b. Accessory phenocrysts 9

2.2.

C. Matrix 10

2.2.

d. Alteration products 11

2.3. Flood basalt ..... 13

2.

3.

a. Major constituents 13

2.3.

b. Alteration products 14

2.4. Shale 17

2.

4.

a. Major constituents 17

2.4.

b. Typical minor constituents 18

3. Summary of available experimental data on the thermodynamic

properties of minerals 22

Table 1 - Representative rock compositions 19

Table 2 - Summary of available experimental data on thermodynamic

properties of minerals 24

Table 3 - All experimental data surveyed on the thermodynamic

properties of selected minerals/phases 29

Table 4 - Mineral phases, formulas, and codes used in tables

1, 2, and 3 116

Table 5 - List of abbreviations used for journals 123

2
1.

Introduction

The thermal and chemical environment of a potential nuclear waste

repository must be known and understood before an intelligent decision can

be made regarding radioactive waste storage. A properly evaluated set of

thermodynamic data can provide some of the needed information. This report

presents a procedure to evaluate an internally consistent set of thermodynamic data for minerals and contains a tabulation of experimental data

which may be used in this evaluation. Experimental data pertinent to

mineral phases in 1) granitic, 2) tuffaceous, 3) shale, and 4) basaltic

rock types are presented.

The report is divided into two sections. The first section briefly

summarizes the chemical and physical character of the proposed repository

rock types and identifies for each rock type:

1. a generalized chemical system describing the rock type,

2. the major mineral constituents,

3. the minor mineral constituents, and

4. the common alteration phases.

The second section is in essence a tabular summary of all available

experimental data on heat capacity, relative enthalpy, entropy, enthalpy

of formation, enthalpy of reaction, Gibbs energy of reaction, chemical

potential, molar volume, volume expansivity, and volume compressibility

for the mineral phases of interest.

3
The data are to be used to generate an evaluated set of thermodynamic

data for minerals. The evaluation will involve additional information for

phases not tabulated here to provide an extensive, internally consistent,

and hopefully reliable data base. An important feature of the evaluation

procedure is the identification of inconsistent and erroneous data in the

set of experimental data under consideration.

4
2. Summary of rock-type chemistry and mineraloqy

2.1. Granite and other crystalline igneous rocks

Granitic crystalline igneous rocks occur as large, relatively homogeneous

bodies which consist primarily of a qranular aggregate of feldspar minerals

and quartz. Grain size typically ranges between 1 mm to a few cm. The

model chemical system is Na20-l<20-Ca0-(Fe0)-(Fe2G3 )-Al 203 -Si02-H2G. Oxide

components in parenthesis are of lesser importance. The minerals and their

chemical formulas are given below. A typical analysis, including the norm

and mode, is given on Table 1.

a. Major mineral constituents

The major minerals, as cited above are quartz and the feldspars. They

generally account for up to 95 percent of the mineral volume. The formulas

are as follows:

Ouartz - Si 02

1 Plagioclase feldspar

Albite

Anorthite

K-feldspar (mi crocline)

approximately Ano 20:Alb 80

NaAlSi 3 0R

CaAl 2-Si 2^R

KA1 Si 3 08

Ano 20:Alb 80 signifies a composition of 20 percent anorthite and 80

percent albite of GFW (molar) units in the feldspar. The three-character

abbreviations for end-member mineral components are defined in Table A, p.

116. This notation style is used throughout the description of rock types.

5
b. Minor mineral constituents

The minor constituents of granites

of the rock and include the following:

Muscovite

Biotite

Annite

Phlogophite

Garnet

Almandine

Magnetite

Amphibole

account for less than 5 volume percent

KAl 3Si 3O10 (OH )2

commonly annite

KFe3Al ^1*30 jo (OH)

2

KMg3

Al Si 30 10 (0H)2

commonly almandine

Fe3 A1 2 si 3°12

Fe3°4

commonly hornblende - Na xCa2(Mg,Fe)5_2y

A1 x+4ySl'8-x-2y°22(°H )2

x « 0-1, y

« 0.5

6
c. Alteration phases

Alteration generally occurs near fractures at depth or near the weathering

surface during erosion. Rock bodies which have experienced thermal metamorphism

may show pervasive alteration. Alteration phases, besides quartz and the

feldspars, include the following minerals:

Epidote - Zoisite Ca2FeAl 2Si 30 12 ( 0H) - CaAl 3Si 30 12 (OH)

Clays

Kaolinite Al 2

Si 205(0H)4

Smectite commonly montmoril Ionite - beidellite

Alkali-free

Montmoril Ionite - A^Si 4O

j g

(OH

) ^

* nH 20

Montmoril Ionite (l/2Ca,Na)o.33

(Al 1> 67 ,(Mg,Fe)o >33

Si 4

0

10 (0H)2*nH20

Beidellite (l/2Ca,Na)o.33(Al 2 ) (A1 0.33, Si 3. 57)

O10 (OH) 2

* nH 20

Nontronite (l/2Ca,Na) 0> 33 (Fe+3

)(Al 0# 3 3 ,Si 3>67 )

Calcite

O10 (OH) 2

* nH 20

n < 2

CaC03

7
2.2'. Tuff

Tuff is an indurated (hardened by temperature, pressure, and/or chemical

reaction) volcanic deposit, predominantly composed of volcanic ash (fraqmental

volcanic material with a grain size diameter less than 4mm). The fragmental

material may consist of:

1. quenched magma in the form of glass particles,

2. phenocrysts (crystals grown in the magma chamber), and

3. rock fragments.

Tuff occurs as sheetlike bodies surrounding volcanic centers, and

deposits range from less than a meter to more than 1000 meters thick.

Large tuff units commonly are formed from volcanic air-fall or avalanche

deposits. The avalanche deposits may be welded from the heat present

during deposition.

The bulk composition of large tuff sheets typically ranges between

quartz 1 atite-dacite and rhyolite. A representative analysis, norm, and

mode are given in Table 1. The typical range of silica content and

phenocrysts in large tuff sheets is as follows:

Rhyolite «— Quartz Latite-Dacite

75 wt. % S i

0

2 «—

+

62 wt. % Si02

0% phenocrysts «—-* 50?, phenocrysts

(volume percent)

Tuffs can be categorized into several types, which occur as zones in

large deposits (Smith, 1961, USGS Prof. Paper 354-F, 149-159, plate 20-0):

1. unwelded to partially welded zone

2. partially to completely welded zone

8
3. devitrified zone

4. altered zone

The model chemical system is Na20-K20-CaO-(MgO)-(FeO)-(Fe203 )-Al203 -Si02-

H2O. Mineral constituents of tuffs consist of phenocryst and matrix phases.

a. Phenocrysts

The phenocrysts which typically vary between 0 and 50 volume percent could

be any one or more of the following:

Plagioclase feldspar - typically Ano 20: Alb 80 - Ano 50: Alb 50

Albite NaAl Si 3O3

Anorthite CaAl 2$i 2^8

K-feldspar (sanidine) - KAlSi 308

Quartz Si02

Biotite typically annite

Annite KFe3AlSi 30 in (0H) 2

Phlogophite- KMg3

A1 Si 3O10 C0H )

b. Accessory phenocrysts

The accessory phenocrysts, which are typically less than 2 volume percent,

may be one or more of the following:

Cl i nopyroxene typically Ferroaugite - approximately

Hed 41 :Dio 27:Cts 19:Cen 13

Hedenbergite CaFe(Si0 3 )2

Diopside CaMg(Si0 3 )2

Ca-Al Cl inopyroxene- CaAl 2

S i O5

C1 inoenstatite MgSi0 3

9
Cl inoferrosil ite

Orthopyroxene

Enstatite

Ferros il ite

Wol 1 astonite

Amphibole

- ' FeSi03

MgSi03

FeSi 03

CaSi 03

commonly hornblende - Na xCa2(Mg,Fe)5_2y

Al x+4ySi8-x-2yn 22( 0H )2

Fayal ite

Magnetite

1 1 men ite

x * 0-1, y

» 0.5

- Fe2 $i 04

Fe304

FeTi 03

c. Matrix

Typically the matrix varies from ab-out 50 to 100 volume percent. It

varies by zone:

1. In the unwelded-to-parti ally-welded zone and the parti ally-weldedto-completely-welded zone , the typical matrix is glass or glass plus

alteration products. Glass tends to hydrate with time. IJnhydrated fresh

glass typically has a water content of < 1 wt. percent H2O, while

hydrated glass typically has a water content of 2-4 percent. Porosity

may range up to 50 percent in the unwelded-to-partially-welded zone.

2. In the devitrified zone the typical matrix is a microcrystal 1 ine

intergrowth of alkali feldspar (Na-K feldspar) and Cristobal ite ( Si O2 )

3. In the altered zone the matrix is typically clay (montmoril Ionite)

and/or zeolite minerals replacing glass and sometimes phenocrysts.

10
Alteration occurs more rapidly in hydrated glass than unhydrated glass and

hydration may be necessary to achieve alteration.

d. Alteration products

Typical alteration products are:

1. Clays

a. Smectite - commonly montmorillonite - beidellite

Alkali-free montmorillonite - A^Si^OigCOH^'n^f)

Montmorillonite - (l/2Ca,Na) 0 .33( A h;67 »

Mg» F e)o.33) si 4°10

(0H) 2 *nH 20

Beidellite - (l/2Ca,Na)g

> 23(Al2)(AlQ> 33,Si2^g7)n|Q(0H)2*nH2n

Nontronite - (l/2Ca,Na) 0> 33 (Fe 2

+3

)

A1 o.33 ,Sl'3.67) 0 lo( nH )2* nH 2 n

n < 2

b. Kaol inite/Halloysite/Dickite - A^-Si^sCOH^

2. Zeolites

a. Clinoptolite - (Na,K,Ca) 2 _ 3

Al 3 (Al ,Si )2^13^36*^H2^

(generally an impure heulandite)

b. Heulandite - CaAl2Siy0^g*6H20

c. Anal cite - NaAlSi^Og *H 20

3. Miscellaneous

a. Calcite - CaC03

b. Illlte - (K,H30) x+y

(Al 2 . x (Mg,Fe)

x)(Si 4 .y(

Al

y

)0 10 (0H) 2

-

l-x-y-zH20 x+y+z < 1

11
Observed alteration sequences are :

glass hydrated glass rr—montmoril Ionite ill ites/mica

heul andite/cl i noptol ite

spherulites 'residual" glass

-

'* (microcrystal 1 ine alkali feldspar plus

Cristobal ite/quartz)

2

Barrows, 1980, GSA Bull., 91, 199-210.

12
2.3. Flood basalt

Flood basalt occurs as sheets of rapigidly cooled basaltic lava erupted

from a volcanic center in continental basement. Individual sheets typically

have great areal extent and range between less than 1 meter to 100 meters in

thickness.

The model chemical system is Ca0-(Na20)-Fe0-(Fe203)-Mg0-Al203-Si02-(H20,C02)

A typical analysis, norm, and mode is given on Table 1.

a. Major constituents

The major constituents consist of phenocrysts and matrix phases. Phenocrysts typically account for 0 to 10 percent of the rock- volume with matrix

comprising the remainder. Gas bubbles (vesicles) occur in some basalt units,

usually near the top surface of the flow.

1. Phenocrysts usually are:

01 ivine

Forsterite

Faya! ite

Plagioclase

Anorthite

Albite

typically For 90:Fay 10

Mg2Si 04

Fe2

Si 04

typically Ano 60 : A1 b 40

CaAl 2S i 2^8

NaAl S i 3O3

2. Matrix, which typically is a microcrystall ine intergrowth of:

Cl inopyroxene - typically pigeonite - approximately

Cen 46:Cfs 38:0io 9:Hed 7

Diopside - CaMg(Si 03)2

Hedenbergite - CaFe(Si 03)2

13
Cl inoenstatite

Hypersthene

Clinoferrosil ite

MgSi03

FeSi03

approximately Ens 60 :Fes 40

Enstatite MgSi'03

Ferros il ite FeSi 03

Plagioclase

Anorthite CaA^Si^Og

Albite NaAl Si 3O3

b. Alteration products

Alteration products typically occur in vesicles or along fractures and

flow-unit contacts in basalts. . The low- and intermediate-temperature

alterations are temperature-induced responses to heated fluids moving

through the rock, and most of the alteration phases require the addition

of either water or carbon dioxide to the rock. The intermediate- and

high-temperature alterations are a result of thermal metamorphism of the

rock body. Rasalts which have experienced thermal metamorphism may show

pervasive alteration.

1 . Low temperature (T < 250 °C) reactions typically produce the

following minerals:

Calcite CaC03

CaMg(C03)2

Ca2FeAl2Si 30 12 (0H) - Ca^Al 3^i 30 1 2( nH)

Ca2Al 2$i 3O10 (OH)

2

CaA^Si^Oy (OH);? *HpO

Dolomite

Epidote - Zoisite

Prehnite

Lawsonite

14
Zeol ites

Laumontite - CaA^Si^O^ *AH 20

Heulandite - CaA^SiyO^g * 6 HpO

Anal cite - NaAl Si^Og *HpO

Wairakite - CaA^Si^O^ *2HpO

2. Intermediate temperature (T < 375°C) reactions typically produce

the following minerals:

Calcite CaCOg

Dolomite - CaMg(C03 ) 2

Albite NaAlSi 3 0g

Zoisite Ca2

Al 3-Si 30 12 (°H

Chlorite (Clinochlore) M g5 A l 2 Sl* 3°10 (0H)4

Amphibole

Tremolite Ca2 Mg5 Sig0 22 ( 0H ) 2

Acti nol ite Ca2 Fe 5 Sig0 22 ( 0H ) 2

Anthophyl 1 ite Mg7 Sig0 22 ( 0 H ) 2

3. High temperature (T > 350°C) reactions typically produce the

following minerals:

Amphibole commonly Hornblende - Na x Ca 2 ( Nig,Fe )5

A 1 x+4y si 8-x-2y°22( nH )2

x * 0-1, y

* 0.5

Garnet typically Almandine or Grossul ar

Grossul ar Ca3Al 2 Si 30^2

15
Almandi ne Fe3 A1 2

Si 30^2

Pyrope - Mg3Al2Si’30^2

Cl i nopyroxene

Hedenbergite CaFe(Si 03)2

Diopside CaMg(Si0 3 )2

Ca-Al Clinopyroxene CaAl 2

^ i 06

Wollastonite CaSi 03

Orthopyroxene

Enstatite MgSi 03

Ferros il ite FeSi 03

01 i vine

Forsterite Mg2

Si 04

Fayal ite Fe2Si 04

Spi nel

Magnetite Fe304

16 -
2.4. Shale

Shale is a rock composed of detrital particles with an average grainsize diameter less than 1/16 mm in which the clay fraction (grainsize <

' 1/256 mm) predominates over the silt fraction (grainsize 1/16 - 1/256

mm). Detrital particles are fragmental material produced by the disintegration and weathering of rocks. Shales are an abundant rock type

deposited in sedimentary basins and typically occur as tabular bodies

with great areal extent.

The model chemical system is K2n-Mg0-(Fe0)-(Fe2f)3)-(Na20)-Al2f)3-Si02-H20.

A typical analysis and mode are given in Table 1.

a. Major constituents

The major constituents are as follows:

1 . Cl ays

a. Smectite - commonly montmoril Ionite - beidellite

Alkali-free montmorillonite - Al

2

Si 40jQ(0H) 2 *nH 2

D

Montmoril Ionite - (l/2Ca,Na)Q #33 (Al 1 >6 7 > ( Mg , Fe) 0 . 33si 4°10

(0H) 2 *nH 20

Beidellite - (l/2Ca,Na)g 33(A12)(A1

q 33 9 Si 3 gy )0jg (0H)

2 *nH 2 0

Nontronite - (l/2Ca,Na)g 33 (Fe2

^ )

( A

1 q 33*^3 gy)D^Q(0H) 2 *nH 20

n < 2

b. Kaolinite/Halloysite/Dickite - Al2Si2D5(0M)4

c. Illite - (K,H3 0) x+y(Al 2 . x ,(Mg,Fe)

x )(Si 4 .y

,Al

y

)0 10 (0H) 2

*

l-x-y-zH2D x+y+z < 1

d. Mixed- layer clay - inter! ayered mixture of illite - smectite

17
2. Muscovite - KA1 3

-Si 3O 10 (OH )2

3. Chlorite

Clinochlore - MgsAl 2

-^i 3O 10 (^ H )4

4. Quartz - Si02

b. Typical minor constituents

Typical minor constituents are as follows:

1. Plagioclase - typically Ano 0:Alb 100 - Ano 5:Alb 95

Albite NaAl Si 30 8

Anorthite CaAl 2 ^ 1

* 2O 8

2. K-feldspar (Microcl ine)- KA1 S

i

30q

3. Carbonates

Calcite CaC03

Dolomite CaMg(C03)2

Ankerite CaFe(C03)2

4. Oxides

Magnetite Fe304

Hematite ^ e2^3

5. Organic matter

Carbon C

6. Pyrite FeS2

18
Table 1. Representative rock compositions

Oxide wt. % Granite9 Tuffb Basalt0 Shale^

Chemical composition

Si02 73.60 66.0 53.8 58.10

Ti02 0.18 0.55 2.0 0.65

AT 2°3 13.84 15.4 13.9 15.40

Fe203 0.63 2.6 2.6 4.02

FeO 1.43 2.0 9.3 2.45

MnO 0.04 0.1 0.2

MgO 0.29 1.3 4.1 2.44

CaO 1.34. 3.2 7.9 3.11

Na20 3.74 3.5 3.0 1.30

K2 0 4.27 4.3 1.5 3.24

h2 o 0.17 0.88 1.2 5.00

P2O5 0-02 0.22 0.4 0.17

Mi sc. 0 .13 e 4.07 f

TOTAL 99.68 99.96 99.9 99.95

Norm (wt. %) (calculated from chemical composition)

Quartz 31.20 20.1 3.9

K-feldspar 25.38 25.7 8.9

Albite 31.44 30.8 25.2

Anorthite 6.95 13.4 20.0

19

i
Table 1. Continued

Granite3 Tuffb Basalt0 Shale^

Diopside 13.9

Wol 1 astonite 0.6

Enstatite 3.2

Ferrosil ite 0.8

Hypersthene 2.55 15.3

Enstatite

*

Ferrosil ite

Ilmenite 0.30 1.0 3.8

Magnetite 0.93 3.9 3.7

Apatite 0.5 0.9

TOTAL 98.75 100.00 98.6

Mode (measured) (volume %)

Quartz 33.0 2.2 Quartz 30.8

K-feldspar 32 1.3

Feldspar 4.5

Plagiocl ase 34 35

Biot ite 2 5.4 Fe-oxides <0.5

Amphibole

(hornblende)

Magnetite

Orthopyroxene

Cl i nopyroxene

01 ivine

<1

1.8

</> 4->

(/> o

o

c

<u

0.5

1.5

<5

<5

<5

Carbonates 3.6

Organic

matter 1

Clays 59.9

20 _
Table 1 . Continued

Granite3 Tuffb Rasal

c Shale^

Matrix 52 h >90 i

An content of

Plagioclase

(mole %)

21 36 63

102.5 100.2 100.0 100.39

TOTAL

aRubidoux Granite, California, sample El-167, Larsen, 1948, GSA Mem. 29.

b Snowshoe Mtn. Quartz Latite, Colorado, sample S-56A, Ratte and Steven, 1967,

(JSGS Prof. Paper 524-H.

cAverage Yakima basalt (analysis b, p. 593), Columbia River Plateau,

Washington-Oregon, Waters, 1961, AJS, 259 , 583-611.

^Average shale, Shaw and Weaver, 1965, J. Sed. Pet., 35. » 813-222.

eco

2

fco2 +so 3+c

9Clays include: illite and mixed-layer clays, kaolinite, and chlorite

(listed in order of decreasing abundance).

^Matrix comprises: 1) glass + alteration products in welded tuff, 2) microcrystalline intergrowth of plagioclase and Cristobal ite in devitrified tuffs,

and 3) clays + zeolite minerals in altered tuffs.

1 Matrix comprises: intergrown microcrystall ine cl i nopyroxene (pigeonite),

orthopyproxene, and plagioclase with minor Cristobal ite (listed in order of

decreasing abundance).

21 '
3. Summary of available experimental data on the thermodynamic

properties of minerals

Table 2 summarizes the experimental data on heat capacity (Cp), relative

enthalpy (Hj-H 298)» entropy (S), enthalpy of formation (H), enthalpy of

reaction (H), Gibbs energy of reaction (G), molar volume (V), volume thermal

expansion (dV/dT), and volume compressibility (dV/dP) available for the mineral

phases of interest. The symbols in the above parentheses identify the type

of data in Table 2. An X in the column under a data-type symbol indicates

experimental information is available on that thermodynamic property for the

phase. If heat capacity or relative enthalpy data are available, the

temperature range (above 298 K) of the measured data is given.

Indirect constraints on thermodynamic properties caused by the functional

relationships among thermodynamic properties are not shown in the table.

Measurement of Gibbs energy at different temperatures for a phase constrains

the properties of enthalpy and entropy for the phase if the heat capacity is

known. For example, no experimental calorimetic data on entropy or enthalpy

exist for anthophyl 1 ite; however, data on a series of phase equilibrium

studies (Gibbs energy of reaction) and heat capacity are available and cover

a sufficiently broad temperature range to constrain the properties of

entropy and enthalpy.

22
V/here data are lacking or insufficient, estimates of the thermodynamic

properties are needed to evaluate the properties of the phase. In most cases

only heat capacity, volume thermal expansion, and volume compressibility need

to be estimated, and these properties may be estimated with an accuracy of a

few percent. For example, the heat capacity of hedenberqite will need to be

estimated to evaluate the available phase equilibria data and derive

entropy, enthalpy, and Gibbs energy properties. Phases lacking data on

heat capacity, entropy, and enthalpy and having only one measured value

of Gibbs energy (epistilbite, heulandite, Ma-montmori 1 1 onite, and stilhite

in this compilation) need estimated values for heat capacity and entropy.

Molar entropy also may be estimated using the techniques developed by Helgeson

and others (1978, AJS, 278-A , 229 p.) and Cantor (1977, Science, 198 , 2D6-207).

The information summarized on Table 2 indicate that it should be possible

to derive internally consistent thermodynamic Droperties for most of the

tabulated phases. The symbols in the left-hand column of Table 2 identify

the repository rock type commonly containing the mineral as a component.

Table 3 contains all the available experimental data listed by

reference citation for each mineral phase in Table 2. These citations have

been through a preliminary evaluation in that 1) we reviewed each citation to

insure there were no obvious errors in experimental technique and 2) we determined that there was no obvious ambiguity in the identification of the phases.

We are aware of conflicts in the cited experimental data, but these cannot be resolved at this time. To resolve them, one must compare the conflicting data with theory and with other properties measured on the phase (or phases)

in the data sets. This can be done best during the correlation procedure!

23
Table

l.

Summary

of

available

experimental

data

on

thermodynamic

properties

of

minerals

Chrysotile

Mg?

Si?

0r

(OH)
CpJ

Cp

range

Rock

type

Mineral/phase

Formula (H

T“ H

298^

^T

-H

298^

(T/K) SHGV

dV/dT

dV/dP

25

Graphite CX

298-

6000
Cp

Cp

range

Rock

type

Mineral/phase

Formula (h

t' H

?qr)

(T/K) SH6V

dV/dT

dV/dP

26

S,G,T

Microcline

KAlSK0oX

298-

1400

Table

2

.

Continued

28
Table 3.

All experimental data surveyed on the thermodynamic

properties of selected minerals/phases

29
All available experimental data surveyed on the thermodynamic

properties of selected minerals/phases

This table of experimental data is arranged alphabetically by mineral

name. The table includes mineral name, formula, mineral group, solid solution

variability, and a summary of experimental data on the thermodynamic

properties of minerals. The summary of experimental data includes literature

citation, data type, temperature/pressure range of measurement, and the

phases involved in the study. The legend for the phase codes (shown under

the "Phases studied" heading) is given in Table 4.

The notation for data type is as follows:

Cp - heat capacity. Heat capacity typically is measured using

low-temperature calorimetry or differential scanning

calorimetry.

Hj-Hr - relative enthalpy. Relative enthalpy typically is measured

by drop calorimetry.

S - entropy. Third-law entropy is calculated by integration of

heat capacity from low-temperature calorimetry. Configurational or magnetic contributions to entropy may need to be

added to the third-law entropy value.

H - enthalpy. Data on enthalpy of formation and enthalpy of

reaction are included in this category. These properties

typically are measured using solution calorimetry or combustion calorimetry. The reaction studied is given under

the "Phases studied" heading for each citation.

30
G - Gibbs energy. Data on Gibbs energy of reaction are included

in this category and are measured by phase equilibria studies,

electromotive force measurements (emf), or determination of

equilibrium constants. The reaction studied is given under

the "Phases studied" heading for each citation.

V - molar volume and changes in response to changes in temperature or pressure. The volume properties are typically

measured by x-ray diffraction techniques or physical measurements of size or density.

dH/dX - partial molar enthalpy. Partial molar enthalpy is determined

by solution calorimetry measurements on a mineral series with

variable composition. The composition range of the study is

shown in the parenthesis given under the "Phases studied"

heading for each citation.

a - chemical potential (activity). Chemical potential is determined by phase equilibria studies among phases of variable,

but known, composition. The composition range of the study

is shown in the parenthesis given under the "Phases studied"

heading for each citation.

dV/dX - partial molar volume. Partial molar volume typically is

measured by x-ray diffraction techniques on a mineral series

with variable composition. The composition range of the

study is shown in the parenthesis given under the "Phases

studied" heading for each citation.

31
A?

.SI

ordered

In

tetrahedral

sites

32
Manghanf,

1970,

Phys.

Earth

Planet.

Int.,

3,

456-461

G

550-625°C/2500-4500

bars

Anl=Alb*Nep+M

?0

33
Important

solid

solution

34
A1,S1

disordered

In

tetrahedral

sites c<

<T3

fSI O’< oCNJ <+<II Kl O’£T5 a. oc\j

t-oo+

<T3 c

II

<T3 Q-

<v

fOc<

OOC < *T_ o

Q.E

35

Important

solid

solution

C<

37

Yoder

«

Weir,

1960,

AJS,

258-A

,

420-433

V

25°C/1000-10000

bars
Andaluslte

Al,SiO

K

-

trfmorph

with

Kyanlte,

Sllllmanlte

And

38
(.Fe

,A1

J)

Andradite

-

Grossular

Join

L. •o<

*

39
Annlte

KFe,AlS1

10

m

(0H),

-

Mica

group,

BJotlte

series

Ann

40
(CaAl.NaSI)

Anorthlte-Alblte,

low/Analblte

join

(Plagloclase

series)

o

c<

41
Hoschek,

1974,

Cont.

Min.

Pet.,

47,

245-254

G

725-825°C/1000

bars

Ano+Ccl-Geh*Gro+CO
43
Reference

Data

Range

Phases

studied

5

44
cn

*-> <

45
Aragonite

CaCO,

-

dlmorph

with

Calclte

Ara
Boehmlte

A10(0H)

-

dlmorph

with

Dlaspore

47
Reference

Data

Range

Phases

studied

3

U

CO

48
49

Hoschek,

1973,

Cont.

Min.

Pet.,

39,

231-237

G

495-635°C/4000-6000

bars

Phl+Ccl+Qza=Tre+San+C0

?

+H,,0
47,

245-254 6

715-825°C/1000-4000

bars

Gro+Cor+Ccl-Geh+CO

50

Valdya 4

others,

1973,

JGR,

NS.

6893-6898 V

25°C/20000-45000

bars

Cc2
(Al,,FeS1)

Ca-Al

CHnopyroxene

-

Kedenbergtte

Join

5-1
Reference

Data

Range

Phases

studied

type (

Teinperature/pressure)

52
Reference

Data

Range

Phases

studied

type

(Temperature/pressure)

King

S

others,

1967,

US

Bur.

Hines

Rpt.

Inv.

6962,

19p

Cp

53-296

K/l

atm

Chr

53
Important

solid

solution

Co

o o o C3 O o

54
CUnoenstatHe

MgSIO,

-

Pyroxene

group;

trlmorph

with

Enstatlte,

Protoenstatlte

Cen

55
Cl

Inofcrrosl

1

Ite

FeSIO,

-

Pyroxene

group;

trlmorph

with

Ferroslllte,

Protoferrosl

1

Ite

Cfs

"56
'57

Essene

S

others.

1972,

EOS,

53,

544

G

800-1200°C/18500-29000

bars

Jad+Kya=Ana+Cor
58

Olaspore

AIO(OH)

-

dlmorph

with

Boehmlte

Ola

O C£ CS O O

a.

v£>

60
Clay

group;

trlinorph

with

Kaollnlte,

Halloyslte

Us

CL

61
Dlopslde

CaMgS1 9

0,-

Pyroxene

group

Dio

62

Warner S

Luth,

1974,

Am.

Min.,

59,

98-109 a

900-1

300

°C72000-

10000

bars

D1o+Ens(MgS10 3

-CaMyS1 206

join)

Newton &

others,

1977,

Geochlm.

Cosmo.

Acta,

41^.

369-377

dV/dX

25°C/1

atm

01ofCts(CaMySi ?0

fi

-CaAl?

Si06

join)
Reference

Data

Range

Phases

studied

type

(Temperature/pressure)

63
Enstatlte

MgSIO,

-

Pyroxene

group;

trlinorph

with

Cl

Inoenstatlte,

Protoenstatlte
65
Epldote

Ca2

FeA12

S130

12

(0ll) -

Epldote

group

i66
0J _ CD 0> c i-

<D 0) 4-> CJ

10 >3 o >> O -Ml

o.3O

o

<u

mPO

i LTJ CNJ

•u

o

CO

a> o_c

coo

CD

s

o

'67
Important

solid

solution

68
if

o»c4; Xo

tQ.so

L.cn

o>c

Q)X0

L. Cl1co 0

co

01

<DOc4> U0) L—0J q:

O1 omc

L.•V o

in

10

cr»

69
Important

solid

solution

L.O

«/> L.

(/) i- -Oo

o

ootr>

C-) otolOoto

ooo

CM

I o

ooO'

ootooo

o

•o oil ^cc Q

«3 *> f TH- t0ZSCSOC5OCDOOOC3t3C3C5C3OO OO

70
71
Reference

Data

Range

Phases

studied

no

72
t- o

73
Important

solid

solution

O

fc. . o

74
75
Hal

loyslte

Al?

Sl?

0c(0H). -

Clay

group;

trlmorph

with

Kaollnlte,

Dlcklte

76
(Fe,Mg)

Hedenberglte

-

Olopslde

Join

77
Reference

Data

Range

Phases

studied

type

(Teinperature/pressure)
79
Generalized

end-member

components

80
81
Kyanlte

Al?

S10r

-

trlmorph

with

Andaluslte,

Sllllmanlte

>>
Reference

Data

Range

Phases

studied

type

(Temperature/

pressure)

83
Reference

Data

Range

Phases

studied

t

84
Data

Range

Phases

studied

type

(

Temper

a

ture/pres

sure)

C

Q)

85
(Mg,Ca)

Magnesite

-

Dolomite

Join

C7>

'TJ

O O C5 O O CS CJO O 55 O >

£6

Swanson

S

others,

1957,

US

NBS

Clrc.

539,

7,

70p

V

25°C/1

atm
87
Reference

Data

Range

Phases

studied

type

(Temperature/pressure)

88
89
A1,S1

ordered

In

tetrahedral

sites

90
Generalized

end-member

components

91
(K.Na)

Muscovite

-

Paiayonlte

join
(Na,K)

Paragonlte

-

Muscovite

join

03
Important

solid

solution

Q.

!
95
Reference

Data

Range

Phases

studied

type

(Temperature/pressure)

>»

Cl
Reference

Data

Range

Phases

studied

type

(Temperature/pressure)

37
Reference

Data

Range

Phases

studied

type

(Temperature

/p

ressure)

98
o

Q.

"59
Quartz -

alpha,

beta

StO--

polymorph

with

Trldymlte,

Cristobal

Ite,

Coeslte,

Stlshovlte

Qza.Qzb

100

Kracek 4

Neuvonen,

1952,

AJS,

Bowen

Vo!.,

293-318 H

347.

85

K/l

atm

Ano+ll„0*Line+G1b+Qza

102
103
104

Valdya

A

others,

1973,

JGR

,

78,

6893-6898

V

25°C/5000-45000

bars
A1.S1

disordered

In

tetrahedral

sites

oo

105

Hewitt,

D.,

1975,

Ajn.

Min.,

60,

391-397

G

460-681

°C/2000-8000

bars

Phl+Ccl+Qza=Tre+SanrC0

?

+H?0
106
107
CaAl,S1

7

0.o*7H ?

0

-

Zeolite

group

108
109
CM ©

O

NJ croo

HO
Important

solid

solution

m
Important

solid

solution

n-2
(Ca.Fe)

Wollastonite

- C5

Inoferrosi

1

1

te

join

113
Haselton

5

others,

1978,

Geophys.

Res.

Lett.,

5,

753-756

G

1000-1325°C/10000-19000

bars

Cc2+Qzb=Wol+C0

114
Reference

Data

Range

Phases

studied

type

(Temperature/pressure)

O

115
Table 4.

Mineral phases, formulas, and codes used in tables 1, 2, and 3

-116
Table 4 . Mineral phases, formulas, codes used in tables 1 , 2 , Ft 3

Code Phases Formul

Akt Akermanite Ca2 MgSi 2 07

Alb Albite, low NaAl Si 30^

Aim Almandine Fe3

Al 2Si 30 i 2

Ana Analbite NaAl Si 3O8

Anl Analcite NaAl S

2*^6 *^2^

And Andal usite A 1 2

S

0 5 Adr Andradite Ca3Fe2 Si30 12

Ann Annite KFe3AlSi30 10 (0H) 2

Ano Anorthite CaAl 2 Si 2 0 g

Ant Anthophyl 1 ite Mg7Si80 22 (0H) 2

Atg Anti gorite Mg4sSi 34035 (OH

62

Ara Aragonite CaC03

Roe Boehmite A 10 ( 0H)

Bru Brucite Mg( 0H) 2

Run Bunsenite NiO

Cts Ca-Al Cl i nopyroxene CaAl 2 SiOg

Cel Calcite-I CaC03

Cc2 Cal cite-II CaC03

Cal Calcium Ca

C 0 2 Carbon dioxide co 2

Cga Carnegieite, alpha NaAl S

04

Cgb Carnegieite, beta NaAlSi 0 4

-117
Table 4. Continued

Code Phases Formul

a

Ctd Chi orotoid FeAl 2

Si 05 ( 0H ) 2

Chr Chrysotile Mg3 Si 2O 5 ( 0 H )4

Cln Cl inochlore Mg5Al 2 Si30io(OH)8

Cen Cl i noenstatite MgSi 03

Cfs Cl inoferrosil ite FeSi 03

Czo Clinozoisite Ca2

Al 3 Si 30 i 2 ( 0 H)

Crd Cordierite Mg2 A 1

S

50 ^ 3

*H 2 0

Cor Corundum A1 2°3

Cra Cristobal ite, alpha Si 0 2

Crb Cristobal ite, beta Sin 2

Cwo Cyclowoll astonite CaSi 03

Dia Diaspore A10(0H)

Die Dickite A1 2

Si 20s (OH )

H 20 Di hydrogen oxide h 2 o

Dio Diopside CaMcj(Si03 ) 2

Dol Dolomite CaMg(C03) 2

Ens Enstatite MgSi 03

Ept Epidote Ca2 FeAl 2 Si 30 i 2 ( 0 H)

Epi Epi st i 1 bite CaAl 2 Si 60 16

‘5H;>n

Fay Fayal ite Fe2Si 04

Fee Fe-Cordierite Fe2

A VSi 5°18‘ H

2

0

Fgh Ferrigehlenite Ca 2 Fe2Si 07

-118
Table 4 . Continued

Code Phases Formul

Fes Ferros

1 ite FeSiOg

For Forsterite Mg2-Si04

Geh Gehl enite Ca2Al 2^1*07

Gib Gibbs ite A1 ( 0H) 3

Gra Graphite c

Gro Grossul a

Ca3 A1 2si 3°12

Hal Hal 1 oysite A 1 2 S i 2O5 (OH )4

Hed Hedenbergite CaFe(Si03)2

Hem Hematite Fe2 03

Hey Hercynite FeAl 2^3

Heu Heul andite C a

A

2 S i yC^g) ’SHgG

111 111 ite (K,H3

0 ) x+y (Mg,Fe) x

A 1

-x+y^ 1

* 4 -y^l 0 ^

(_x-y-z)H20

x+y+z < 1

Ilm Ilmenite FeTi03

Irn Iron Fe

Jad Jadeite NaAl ( S

0 3 )

Kip Kal iophil ite KA1 S

0 4

Kal Kal si 1 ite KA 1 S

0 4

Kao Kao! inite A 1 2^i 2^5 ) 4

Kya Kyanite A 1 2^ i G5

.119
Tab-1 e 4. Continued

Code Phases Formul

a

Lar Larnite Ca2Si04

Lau Laumontite CaA^^i^Oi^ * 4 HpO

Law Lawsonite C aAl 2 Si 2^7 ) 2 *^2^

Leo Leonhardite Ca2 Al^ Si 3O 24 *7H 2 0

Leu Leucite KA1 Si 206

Lme Lime CaO

Mag Magnesite MgC0 3

Mcc Magnesiocalcite (Ca,Mg)C 03

Mgt Magnetite Fe3°4

Mar Margarite CaAl4Si 2^10

Mei Meionite Ca4

Al 6Si 60

2 5

*C 02

Mer Merwinite Ca3 Mg(Si04)2

Mic Mi croc! ine KAlSi 3 0 8

Mai Monalbite NaAlSi 30g

Mtc Monticellite CaMgSi04

Mus Muscovite KAl 3 Si 3Oio(OH)2

Nmt Na-Reidel 1 ite Na .33 A1 2CAl .33 Si 3 .67H°10 (° H )2

Nat Natrol ite Na2Al2Si 30in '2H 20

Nep- Nephel ine NaAl Si 04

Nic Nickel Ni

Ofs Orthoferrosil ite FeSi 0 3

Par Paragonite NaAl 3 Si 3O10 (OH)

120
Table 4 . Continued

Code Phases Formul

Per Pericl ase MgO

Phi Phi ogophite KMg3

Al Si 30 10 (OH )

K 20 Potassium oxide k 2o

Pre Prehnite Ca2 Al 2 Si30io(OH) 2

Pen Protoenstatite MgSi 0 3

Pfs Protoferrosi 1 ite FeSi 0 3

Pyt Pyrite FeS2

Pyp Pyrope Mg3Al2Si 3°i2

pyr Pyrophyl 1 ite A1 2^i 40 10 ( OH )

Pyo • Pyrrhotite Fe l-x s

Qza Quartz, alpha Si 0 2

Qzb Quartz, beta Si 0 2

Ran Ranki nite Ca3 Si 2 07

Rut Rutile Ti 0 2

San Sanidi ne KAlSi 30 8

Sid Si derite FeC0 3

Hsi "Silicic acid" b^SifU

Sil Si 1

imanite A 1 2 S i 0 5

N20 Sodium oxide Na2 0

Spl Spi nel MgAl 2 04

St a Staurol ite Fe2 AlgSi40 23 (0H)

h 2o Steam h 2°
t

Table 4. Continued

Code Phases Formul

a

Stl Stilbite C a A

2

^

i 2^18 * ^2^

Tic Talc ^93Si 4O in ( OH

)

2

Tre Tremol ite Ca2Mg5Sig022( nH )2

Wai Wairakite CaA^Si^O^ *2^0

h 2o Water h 2o

Wol Wol 1 astonite CaSi 03

Wus Wustite Fe l-x°

Zoi Zoi site Ca 2 Al 3 Si 3O 1

(

)

122
Table 5.

List of abbreviations used for journals

123 .
Table

5.

List

of

abbreviations

used

for

journals

124

GSA

Mem.

Geological

Society

of

America

Memoirs
Geophys.

Res.

Lett.

Geophysical

Research

Letters

U5

JGR

Journal

of

Geophysical

Research
Abbreviated

reference

Full

reference

126

Proceedings

of

the

National

Academy

of

Sciences

(U.S.)
Abbreviated

reference

Full

reference

127

Elek.

Angew.

Phys.

Them.

Zeltsclirlft

fur E1

eklr

ochemle

und

Angewandte

Physikal

Ische

Chemle
Abbreviated

reference

Full

reference

128
APPENDIX II

SECTION 1.

FEASIBILITY STUDY

DATA FOR NUCLEAR WASTE DISPOSAL

THE MECHANICAL PROPERTIES OF

BASALT, GRANITE, SHALE, AND TUFF

H . R . Hume

Center for Information and

Numerical Data Analysis and Synthesis (CINDAS)

Purdue University

2595 Yeager Road

West Lafayette i Indiana 49707

This is a report covering the data on the mechanical properties of basalt,

granite, shale, and tuff. The properties covered are briefly defined and their

respective peculiarities are discussed. Some statistics are presented for

each rock system and property describing the data known to exist in the literature. Typical examples of the data in both tabular and graphical form are also

presented. The report provides a most exhaustive bibliography on the subject

of the report.

This report reviews the feasibility for proceeding with a more comprehensive

study and evaluation of the mechanical properties of the four rock systems. A

companion report treats the thermal and electrical properties of these same

rocks.

1

TABLE OF CONTENTS

INTRODUCTION 1

GENERAL SYMBOLS 2

DATA TABLE SYMBOLS .

‘ 2

GENERAL INTRODUCTION ..... 3

PROPERTIES 4

Density 4

Elastic Properties 5

Dynamic Constants ....... 6

Static Constants ... ......... 6

Discussion of Elastic Properties Data (Part A) 9

Discussion of Elastic Properties Data (Part B) 15

Discussion of Elastic Properties Data (Part C) 20

Strength 26

Compressive Strength 26

Tensile Strength 26

Shear Strength 27

Discussion of Strength Data . 28

Creep 34

Creep of Rock In-Situ 37

Time Dependent "Strength” 37

Discussion of Creep Data . . i . 38

Permeability 40

Porosity 41

Hardness 46

Discussion of Hardness Data 46

CONCLUSION 46

BIBLIOGRAPHY 49

1
GENERAL SYMBOLS

e strain

•e strain rate

a normal stress

major principal stress

a 3 minor principal stress

T shear stress

P mean stress

m

y Poisson's ratio

K bulk modulus

1/K compressibility

G shear modulus; modulus of rigidity

E Young's modulus; modulus of elasticity

Vp longitudinal wave velocity; P wave velocity

V

g

shear wave velocity; S wave velocity

k permeability

p porosity

p density

H hardness

DATA TABLE SYMBOLS

P pressure, MPa

p porosity, %

R test in bending, MPa

T tangent modulus at 50% fracture strength

w water, %

J_ right angle to

// parallel to

* dynamic test values

** saturated or wet

- location not known

D differential stress, MPa

S stress, MPa

2
GENERAL INTRODUCTION

This report surveys the data available in the literature on the mechanical

properties of four major rock types with a view to their potential use as nuclear waste disposal depositories.

Specific guidelines as to the nature of the properties required have been

supplied by the National Bureau of Standards and as far as possible these guidelines have been adhered to.

A total of about 1100 possible abstracts were retrieved from computer

search files and were visually screened. Of these, a total of approximately

230 documents were selected and were further examined in detail. In this report the number of references is presented property by property and, therefore,

the number of references per property varies. In addition, at this time the

number of salient documents is presented rather than the number of data sets.

This can be misleading since, though a property may have only a few references,

the amount of data presented may be extensive.

It is the nature of data surveys that much, if not all, of the information

collected is the work of others. This report and its final form are no exception and in many cases certain works are heavily drawn upon. In particular,

attention is drawn to the work of Lama et al. cited in reference [115].

. At present, in this report property data for four rock types is presented

as well as a general indication of the state-of-the-art and the number of references that will be utilized,. The format of the data

presentation is both graphical and tabular, with more

emphasis being placed on the latter format since it is the most common form

in the published literature.

Four rock types, namely: basalt, granite, shale, and tuff, have been

considered and in extracting data, petrological definitions of these rocks

have been strictly adhered to as far as possible. These definitions are given

below as obtained from reference [107j

.

Basalt : an extrusive, fine-grained rock composed primarily of calcic plagioclase

with or without olivine.

Granite : a plutonic rock consisting essentially of alkali feldspar and quartz.

3
Shale: a laminated sediment in which the constituent particles are of predominantly clay grade. This includes indurated, laminated, or fissile claystones and siltstones.

Tuff : a rock composed of compacted volcanic fragments less than 4 mm in diameter.

For the purposes of this report, partial data has been provided

as an example for the four rock types. Geologically more common rocks such as granite and basalt are much more fully represented in the literature and con- sequently the amount and type of data is far more extensive than for less common

types. Relevant data accompanies each property and appears after the discussion

provided for that property or group of properties. Unless otherwise indicated,

all data are laboratory values.

PROPERTIES

Density

This property is defined as the mass per unit volume. The volume, however,

varied depending on what phase of the naturally occurring rock is considered.

The solid phase obviously has a different volume than the solid phase + gas

phase, for example. If one takes into account the three possible phases that

coexist in natural rock, i.e., solid, liquid, and gas, it becomes apparent that

several definitions of density are possible and, in fact, do exist. These are

divided into "true," "apparent, M and "bulk" determinations.

"True" determinations take into account the volume of only the solid phase

of the rock with respect to the mass of the rock.

"Apparent" determinations use the dry (solid + gas) mass of a unit volume

of solids.

"Bulk" determinations use the prevailing conditions (solid + liquid + gas)

of the rock to determine the mass of a unit volume of rock.

"Specific gravity" is, for practical purposes, a relative density with

respect to water.

"Grain density," as the name implies, is a density determination in which

the mass of the grains of the rock and the volume of these grains are utilized.

4
A problem with published literature at present is that most often the type

of density is not stated - the value is merely quoted. Generally, it appears

wise to presume that densities given ere "apparent" values. The same applies

to specific gravities.

The various densities can be obtained using the "pycnometric , " "buoyancy,"

or "direct measurement" techniques. In the case of the first two, both use

pycnometers and are applications of Archemedes principle. Of these methods,

the "buoyancy" method is the most accurate.

TABLE 1.

DENSITY DATA STATISTICS

Rock Type No. of Documents

Granite 52

Basalt 39

Tuff 17

Shale 16

Elastic Properties

The elastic properties considered here are:

.Young's modulus (secant and/or tangent)

Bulk modulus

Shear modulus

Poisson's ratio

Compressibility (the reciprocal of the bulk modulus)

Wave velocities

The determination of the above properties can be static (with exception of

wave velocities) or dynamic, and either laboratory or in-situ. Overall, in

both in-situ and laboratory tests it is important to be able to measure load

stresses and deformation accurately and be able to minimize or remove factors

which lead to erroneous or distorted values.

Dynamically obtained elastic constants tend to be higher than those

obtained statically; however, they are of importance when one needs to know

the behavior of rock subjected to shock loading.

5
Basically, elastic constants achieved by static methods are indicative

of large strains, e.g., 10-3

, which occur in mining. Dynamic methods investigate lower strains of 10” 5

. Static methods give rise to larger scatter of

results, while dynamic methods give rise to less.

Dynamic Constants

These constants are calculated from elastic wave velocities and density.

In-situ seismic reflection or refraction can be used with refraction being

the more popular. Laboratory values are determined using either the ultrasonic

or resonance techniques.

For the purposes of this work, two kinds of waves are considered; namely:

P or compression and S or shear waves. Both of these are body waves, i.e.,

transmitted through (rather than along the surface) the body. Compressional

waves cause longitudinal particle oscillation, while shear waves cause transverse oscillation.

In the case of the laboratory methods mentioned, the basic difference

between the two is the frequency at which the velocities are determined. The

excitation frequency, however, has been shown to have no effect on the wave

velocities, but a significant effect on the calculation of Poisson’s ratio.

Wave velocities, like other properties, are affected by various factors.

Briefly, these factors are:

1) Rock type

2) Texture (grain size is important)

3) Density (density and average atomic weight dictate velocity of longitudinal waves)

A) Porosity (velocity decreases with increasing porosity)

5) Anisotropy (velocity parallel to layers greater than velocity perpendicular to layers)

6) Water content (generally water saturation increases velocity in hard

rocks)

7) Temperature (velocity of longitudinal waves decreases with increase

in temperature)

Static Constants

In-situ values are generally obtained by one of the following methods:

6
Plate bearing tests

Pressure tunnel tests

Borehole tests

These are all large scale tests and are expensive to perform. The specifics

of such tests vary depending on the conditions encountered.

Laboratory values are obtained by several methods. Some of the commonly

used methods are:

Simple Direct Compression or Tension Test : In these tests prismatic specimens

are loaded in compression or tension.

Bending Tests : Young’s modulus can be determined using 3 or 4 point loading

of a beam.

Brazilian Test : Poisson's ratio and Young’s modulus can be obtained by measur

ing the strains at the center of a loaded disk in both vertical and horizontal directions.

Triaxial Test : Solid and hollow specimens can be loaded triaxially and deformations can be measured. These stresses and deformations can then be

utilized to find Young's modulus.

All the elastic constants are related to one another provided one assumes

a perfectly elastic, isotropic, homogeneous material. Rock seldom fulfills

these conditions; however, in certain instances, it may be close enough to

allow approximate fulfillment of these assumptions.

Moduli in tension and compression are not the same and may vary from 1

to 10 times or more. Variations of moduli with stress are due to changes occurring in the structure of rocks during loading and unloading. Comparison

of in-situ and laboratory values indciate a good deal of difference in many

cases and this discrepancy is a function of discontinuities present in the insitu condition.

7
TABLE 2

ELASTIC PROPERTIES DATA STATISTICS

Property

No. of Documents

Granite Basalt Tuff Shale

Static Properties

Young's modulus 51 28 18 24

Bulk modulus 9 9 1 0

Shear modulus 9 7 2 0

Poisson's ratio 30 21 14 14

Compressibility 9 9 1 0

Dynamic Properties

Young's modulus 17 8 6 10

Bulk modulus 6 1 0 0

Shear modulus 8 3 3 4

Poisson's ratio 8 4 2 3

Compressibility 6 1 0 0

Wave velocities 9 10 5 1

8
Discussion of Elastic Properties Data (Part A)

A sample of the tabular data for all the rock types are presented in the

following pages.

Figure 1 is reproduced as an example of the curve data. The curve of

Young's Modulus versus confining pressure (Fig. 1) was determiend on samples

from Units 3 and 4a of Diamond Dust Tuff. Samples were obtained from various

depths in boreholes. Dynamically obtained modulus values at confining pressures

below 0.3 MPa can be expected to be higher than in-situ field or static measurements by as much as several hundred percent. This discrepancy is due to

fractures and grain boundary effects.

There is no consistent value for Young's Modulus for all samples; however,

above confining pressures of 0.4 MPa the modulus values obtained are in reasonable agreement with statically obtained values.

4 •

9
DENSITY AND ELASTIC PROPERTIES

PART A

Density p

Modulus of Elasticity E

Modulus of Rigidity G

Poisson's Ratio V

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[10]
Discussion of Elastic Properties Data (Part B)

Granite and basalt are represented in the sample tabular data. No such

data have been retrieved on shale or tuff.

Sample curve data for shale are presented in Figure 2. Cylindrical drill

samples 3.81 cm in diameter and 2.54 cm long were tested after being oven dried

for 48 hours at 366 K. Specimens were enclosed with neoprene jacket and transducers attached to each end, the system then sealed in a pressure cell and confining pressures achieved by the system were of the order of 70 MPa.

As can be seen from the curve, initially dry Green River shale has a higher

compressibility than its water saturated counterpart. The trend for both wet

and dry samples not unexpectedly shows decreasing compressibility with increasing

confining pressure.

15
DENSITY AND ELASTIC PROPERTIES

PART B

Density

Bulk Modulus

Compressibility

P

16
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(PART

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Discussion of Elastic Properties Data (Part C)

Sample tabular data are presented for all four rock types in the following

pages.

Figure 3 represents a sample of the curve data. Specimens of Westerly

and Troy Granite, 1.3 cm in diameter and 2.5 cm long, were used to measure shear

and compressional wave velocities for confining pressures of 0.1 MPa and AO MPa

for temperatures ranging from about 245 to 275 K.

Samples were saturated with water near the melting point of ice after being

oven dried. Temperatures during the tests were accurate to ±0.5 K whilst pressures were accurate to ±1 MPa.

20
DENSITY AND ELASTIC PROPERTIES

PART C

Density p

Longitudinal Wave Velocity V^

Shear Wave Velocity V

g

21
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(PART

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22
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25

Figure

3.

Variation

of

Wave

Velocity

with

Temperature

for

Granite

[6].
Strength

The true relation between stress and strain for rock undergoing loading

can often only be described using a curve. Many factors can affect this relationship and so there is no one unique curve. Some of these factors include

temperature, moisture content, confining pressure, stress path loading rate,

and strain rate.

In this section the term "strength" has the conventional implication; that

is, it is time independent, i.e., time dependent effects are disregarded. Time

dependent "strength" is treated in the section dealing with creep. There are

three basic strength parameters to be considered; namely: compressive strength

(o j — G 3 ) , tensile strength (a 1 -G 3 ), and shear strength (x) . These terms are generally defined for tests of short duration where neither temperatures nor

pressures are so extreme as to make the rock behave other than in a brittle

fashion.

Compressive Strength

This is defined as the force applied at failure divided by the initial

cross sectional area perpendicular to the direction of loading. Usually this

is obtained from a uniaxial test, but it can also be obtained from triaxial

results though the added sophistication is hardly necessary.

There are several factors which influence the values obtained over and

above purely petrological factors such as mineralogy. These factors include:

1) End-effects due to friction between specimen and load platens

2) Specimen geometry

3) Rate of loading

A) Testing environment, e.g., moisture, temperature, etc.

Tensile Strength

Tensile strength of rock is considerably less than the compressive strength.

However, since the propagation of tensile cracking leading to tensile failure

in rock is not uncommon, it is necessary to assess the tensile strength.

There are basically two methods of determining tensile strength. One is

the direct method which implies a direct tensile l oad on a rock specimen, and

the other is the indirect method in which a tensile stress is induced in a specimen rather than directly applied to it.

26
The direct method is self-explanatory; however, indirect techniques bear

some examination. Bending tests and diametral compression of disks give rise

to induced tensile stress. In both of these types of test, no direct tensile

load is applied. In the case of binding, a certain amount of inaccuracy occurs

due to creep which takes place just prior to failure. Disk compression tests

(e.g., Brazilian) are somewhat controversial and conflicting results have been

reported. Overall it seems some combination of tensile failure and shear failure

occurs making the results questionable unless precautions are taken to prevent

the feasibility of shear failure.

Shear Strength

Shear strength lacks an exact definition, but here it will be defined as

the shearing force necessary to cause failure divided by the cross sectional

area along which the failure occurs.

Again, there are several tests for determining shear strength. The basic

methods are:

The zero normal stress method

The torsion method

The oblique shear method

The triaxial test

The best agreement and best results are given by the torsion and triaxial

methods. Shear tests with compression are considerably better than zero normal

stress tests since they do not produce bending, plus the usual tensile stress

associated with the latter tests.

TABLE 6

.

STRENGTH DATA STATISTICS

Property

No. of Documents

Granite Basalt Tuff Shale

Compressive strength 55 15 19 28

Tensile strength 30 7 8 9

Shear strength* 2 0 2 3

*Since there is no unique value for shear strength, the

cohesion C and the angle of internal resistance (J> are given which enables quick assessment of the shear strength

over a continuous range of confining pressures.

27
Discussion of Strength Data

A sample of the tabulated data is presented in the following tables. Data

for all four rock types are presented; however, it will be noted that shear

strength is poorly represented. This is purely a function of the data available

The sample curve in Figure 4 was obtained from triaxial compression tests

on specially prepared samples of Westerly granite. Normal cylindrical samples

have larger diameter steel discs epoxed to each end of the sample with a thick

layer of steel reinforced epoxy.

The purpose of this technique was to prevent radial stresses developing

at the end of each specimen due to the mismatch in elastic properties between

rock and machine platen. This method prevented end effects from extending into

the central region of the specimen where failure occurs.

To achieve this, specimens have to be longer and care has to be taken so that binding stresses are not introduced during loading. A feature of this

curve is that it is nonlinear, which is what has increasingly come to be

expected.

28
STRENGTH

Shear Strength T

Ultimate Strength O

ULX

Compressive Strength a

Tensile Strength

29
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30
STRENGTH

(Continued)

44 o

oo 00 00 o CTv CTV CTV CTv 00 vO vO CO vO vO 00 rs n* o o o CM CM CM CM CM CM m m CTV CTv CTv s3- m m

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31
STRENGTH

(Continued)

•w o

rH m o o rH rH VO vO co <r CTi CT\ m

3 z CNJ ct\ rH rH O o CO St sf CTV Pi ^ rH rH rH rH rH

COM

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• o

rH o

Shear

trength (MPa)

-©-

o

CO

3

O u #k •H to •k O rH

4-1 3 rH o * CO 3

to 4-1 <u CT» 3 3 o £3 #k CO 3 3 o (0 3 «•* 3 3 S-4 T3 3

hJ TO 3 (U rH 4-1 «k 3 3 H

to H rH tO 44 tH 3 •H TJ > tO u •H to #* 3 3 3 3

c a) 3 .3 cO Pi to P O 3 3

cO 523 to co 60 a 60 V4 3 <3 a:

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Japan Shale;

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33

CONFINING

PRESSURE

, P,

MPo
Creep

Three general approaches are usually adopted to study creep. They are the

micromechanistic, phenomonological, and empirical methods. Of the three, the

latter is the most popular. In this technique, experiments are conducted to

obtain a continuous stress-strain history in terms of parameters like time,

stress, and temperature. This information is then used to derive empirical

creep equations that describe a particular material's creep behavior. A general equation which defines the performance of a material over its entire range

of behavior is the following:

e(t) = £

0 + £

p

(t) + A(t ) + eT

(t) (Emery et al. 141])

where

e(t) = total strain (i.e., elastic + creep)

e 0 = instantaneous strain (elastic)

£p(t) = primary creep

A(t) = steady state creep

e^t) = tertiary creep (See Figure 5)

Since rock is not an ideally elastic material, its behavior is usually

complex and often a function of the mineral composition. This complexity gives

rise to the problem that it is often difficult to characterize a rock quantitatively without first obtaining stress-strain relationships over the entire

range of the conditions anticipated. Theoretical modeling of the stress-strain

or time-strain behavior is greatly hindered by the variations in environment

possible, e.g., temperature, pressure, etc.

Definitions of characteristics of time-dependent properties are far from

universal and controversy still exists. For this reason nomenclature will be

defined here and hereafter all references to a particular characteristic will

assume these definitions.

Creep : plastic deformation under constant load showing an obvious decreasing

strain rate.

Yield Point : some materials show a sudden inhomogeneous extension at constant

load in their stress-strain curves as soon as the elastic limit is exceeded.

Yield Strength : to circumvent the problems associated with determining the

elastic limit accurately for materials not showing a yield point, one nor- mally chooses an arbitrary plastic strain, usually 0.2%, and quotes the

related stress as the yield strength.

34
Plasticity : behavior of a solid material once the elastic limit has been exceeded

and implies permanent non-recoverable strain.

Creep Strength : the stress in a constant stress, constant temperature test that

will produce a specified strain in a specified time.

Plastic Creep Limit : implies below a certain stress all creep is anelastic

(= fully recoverable with time once load is removed), whilst above it creep

is partly anelastic and partly plastic.

Anelastic Creep : creep fully recoverable with time once load is removed.

Ultimate Strength : the maximum stress immediately prior to failure.

Creep Stress : conventional stress in a creep test.

Creep Strain : the gradual strain observed in creep.

Creep Rate : the slope of the stress-strain curve in the creep stage.

Creep is determined from so-called creep tests which are constant stress

. tests. These tests can be accomplished in several modes; namely: in bending,

torsion, compression, or tension. Two approaches are used in these tests.

One is to load the specimen and subject it to this load for a long period while

measuring deformation with time. The other is to load the specimen incrementally

and measure the deformation with time for each increment. In all these cases,

steady state creep is what is required.

An idealized curve for rock at constant stress is shown in the figure on

the following page.

Primary (transient) and secondary (steady state) creep represent the bulk

of the creep work done on rock. Generally, empirical equations have been deI veloped by researchers to fit the time-strain behavior recorded by their exper-

! iments. Numerical methods have more recently been used to achieve fits for

experimental data.

Several factors influence creep. At this stage it is not our intent to delve

into them in any detail other than just to mention them. They are:

1) Nature of the stress, i.e., tensional or compressional, etc.

2) Level of stress (relationship between creep-stress is not necessarily

linear.

3) Confining pressure (increase in confining pressure decreases creep rate)

A) Temperature (generally an increase in temperature causes an increase

in creep rate.

5) Moisture and humidity (creep seems to increase with wetting)

6) Structural effects (variation in grain size, crystal orientation produce

effects)

35
tnrBjqs

36

Figure

5.

Ideal

Creep

Curve.
Creep of Rock In-Situ

Most research has been accomplished on rock salt. Several creep relationships have been developed, generally for underground openings or pillars in

rock salt mines. The diversity of relationships developed tends to lead to

the conclusion that, as has been indicated earlier, the mechanism of creep is

not at all well characterized and so it would seem prototype modeling in the

in-situ case is still the best way to go if creep parameters are required.

Time Dependent "Strength"

This, arguably, could be presented under the section entitled "Strength."

However, as it will be seen later, strength will be defined as time independent

for the purposes of this report, although there is a grey area where time effects

overlap. For this reason it is probably better to present data as stress-strain

or time-strain data and allow the user to select so-called "strength" values

for his particular purpose. Obviously, neither of these two forms are totally

independent of time in the former instance and stress in the latter instance,

but at least these two parameters have been "de-emphasized" to some extent due

to the nature of the testing being used.

Using the terminology of Price [71], this section deals with "long term

strength." This "strength" can be assessed using either direct or indirect

methods. The direct metho d is iterative in nature and is essentially a "trial

and error" method. It required that several creep tests be done at differing

loads and the highest load at which no failure takes place enables an assessment of the "long term strength." This method is conservative and generally

only approximate.

TABLE 8.

CREEP DATA STATISTICS

Rock Type No. of Documents

Granite 4

Basalt 0

Tuff 0

Shale 2

37
Discussion of Creep Data

It will be noted that no tabular data are presented because the

literature presents such data as either curves or equations derived from those

curves.

A sample of such time dependent deformation data is produced in Figure 6.

Specimens for the test were cored from a block of Westerly granite. Confining

pressures of up to 1 GPa were achieved using an argon pumping system.

Creep readings were measured up to the melting point of the granite (993 K)

under confining pressures of 400 to 500 MPa and water pressures of 100 MPa.

A series of runs at different temperatures, but at a single load of 64 MPa,

are plotted against the log of time in Figure 6. In this figure anelastic

strain has been normalized against the initial elastic strain. As is expected,

creep is greater at higher temperatures.

38
‘ nivhis ousvnHNV aasnvwyoN

39

Figure

6.

Normalized

Anelastic

Creep

Curves

of

Westerly

Granite

at

Various

Temperatures

for

a

Stress

of

64

MPa

(32]
Permeability

Permeability is a function of the porosity of rock. Fluid is transmitted

throughout a rock by interconnecting pores. The fact that a rock is porous

does not imply that it is permeable since closed pores (not interconnected with

the external surface) do not allow the passage of fluids.

Permeability can be a highly anisotropic property; for instance, radial

permeability may vary greatly from longitudinal permeability within a rock.

Another point to consider is the permeating medium. Permeability is obviously

going to vary with fluid viscosity. Generally speaking, laboratory tests are

of two basic kinds; namely, either gas permeability tests or liquid permeability

tests. Each of these, in turn, can usually be broken down into radial or longitudinal tests.

In-situ tests are generally much better indications of rock mass permeability since they take into account the effects of fractures within the mass.

Two conditions exist in-situ, one being the fully saturated case and the other

the unsaturated case.

Water is pumped from the ground via a borehole in the former case. The

reverse is true in the latter since water has to be pumped into the ground.

More recent methods use radioactive isotope tracer techniques. These are introduced into water at one location and their arrival time at another point

is noted. Isotopes with very short half lives are chosen so as not to contaminate ground water.

TABLE 9.

PERMEABILITY DATA STATISTICS

Rock Type No. of Documents

Granite A

Basalt 2

Tuff A

Shale 2

Data for both permeability and the following porosity are presented together

since permeability is a function of porosity in many cases. Only tabular data are presented.

AO
Porosity

Porosity is defined as the ratio of the volume of internal open spaces

(pores or voids) to the bulk volume of the rock. It can also be expressed in

terms of grain density and the dry density of the rock.

Factors which generally influence the porosity of rocks are:

1) Size distribution of grains

2) Shape of grains

3) Solidity of grains

4) Orientation of grains

5) Degree of compaction

6) Amount of nongranular material in pores or coating of grains

Pores are either interconnected and open to the exterior or closed (isolated)

and not connected to the exterior. Different terminology applies to these two cases. When only interconnected open pores are considered, the porosity is

known as apparent porosity. When both open and closed pores are considered,

the value obtained is termed total porosity.

If at least two of the three forms of volumes (for example, grain volume,

pore volume, and bulk volume) are known, one can calculate porosity. Methods

of obtaining these volumes are cited in several sources and will not be discussed here. Porosity has the effect on the mechanical properties of rocks

that all strength properties decrease with increase in porosity because:

1) Stress concentration caused on the boundary of the pores reduces the

strength.

2) Decrease in the bearing area of the rock causes decrease in strength.

3) Pores may be filled with water or some other liquid which may help in

crack propagation by reaction at the points of stress concentration

by reducing its surface energy.

TABLE 10.

POROSITY DATA STATISTICS

Rock Type No. of Documents

Granite 29

Basalt 10

Tuff 18

Shale 13

.41
PERMEABILITY AND POROSITY

Permeability k

Porosity p

42
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543

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Pd CO M CO M CO OO 5H CO M CO CO M CO M CO M H

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PERMEABILITY

AND

POROSITY

(Continued) o

COG i—1 G Jo G G CX G 4J 13 0 t—1

4-1 J> •H

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G

G

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Jo

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Basalt;

Mussa

Quarry, -

5.7---

108

Brazil
PERMEABILITY

AND

POROSITY

(Continued)

o

55

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fO0

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vO

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G G

cp CP O rO 0 0

Pi Pi M o o O Q Q CJ u

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g Jo CO o Pi Pi CO •H Pi CO 50 G

p td CO P

td d O * #* *H o O' • r. cd 0 G

o p •H G O

l-J JO td i—

l

00 Q CQ

Pi td p

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G JO a) td a) tH P

td •—

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0 CQ e> CP P i—

1

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tu <3 <u •H rq N

CP p G G

>> • » •H G • #> • l\ P H p 1—

1

p to •H p T—

1

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<—

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1

•H rH

td N td p d G N G a o to td CO no CO G to 0 o td p td G G G P G G

Pd w PO PQ 3 po CP PO CQ Q

45
Discussion of Hardness Data

Several measures of hardness exist, many of them being developed for

metallurgical purposes. Certain scales have been utilized to describe the hardness of rock. The most famous of these is the Mohr's scale; however Vickers

microhardness and Shore scleroscopic hardness are also commonly used. Some

difficulty has been encountered in isolating hardness data for some of the

rock types. This is probably due to the character of the rock, e.g., friability,

which makes testing difficult.

TABLE 12.

HARDNESS DATA STATISTICS

Rock Type No. of Documents

Granite 2

Basalt 1

Tuff 0

Shale 0

HARDNESS

Mohs Hardness

Vickers Hardness

Shore Hardness

CONCLUSION

This report is a summary of the various properties investigated and also

an indication of the state of the art, both with respect to the amount of data

available and the testing techniques existent. Additionally, partial data for

all four rock types have been provided.

46
In certain cases data are sparse ^nd this is largely a function of either

lack of published data or difficulty in isolating and retrieving data which

is either unpublished or obscure. In data collection of this type, heavy dependence is placed on existing abstracting and indexing services available

nationally and internationally. Unfortunately, experience often indicates that

these services are not quite as complete as they might seem and so it is possible to miss valuable contributions. In the present work, all reasonable

attempts have been made to obtain as much salient data as possible. An added

difficulty is that research on certain rock types may still be fairly rare and

so, in actuality, there is very little in the way of data available.

TABLE 13.

HARDNESS

Hardness

Rock Type and Location Mohs

(2)

Avg.

Vickers

kg/mm 3 (3)

Shore

(4)

Remarks Ref,

No.

Granite; Inada, India 6.1 860 - 17

Granite; Mannar i, India 6.5 860 - 17

Granite; Barre, VT 6.1 860 - 17

Granite; Stone Mt., GA 6.3 860 - 17

Granite; Westerly, RI 6.3 860 - 17

Barre Granite — — 90.3 23

- - 87.3 23

- - 88.8 23

Westerly Granite - - 93.8 23

- - 92.4 23

- - 94.2 23

Dresser Basalt — - 95.0 23

- - 93.2 23
Properties which at present have limited data will be supplemented wherever

possible through personal contacts with specialists in the field. Presentation

of the final report will be in the same format as the present report in that

it will contain some figures and a large number of data tables in addition to

a complete bibliography.

48
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49
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50
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219. Anderson, R.E., "A Study of the Structure Between Pahute Mesa and the

Toryabe Range, Nevada," U.S. Geological Survey Tech. Lett. NTS-182,

38 pp . , 1967

.

220. Kitsunezaki, C., "In-Situ Determination of Variation of Poisson's

Ratio in Granite Accompanied by Weathering Effect and Its Significance

in Engineering Projects," Disaster Prev. Res. Inst., Kyoto Univ., Bull.,

15(92), Pt. 2, 1965.

221. Japanese National Committee on Large Dams, "Present Status of Measurements of Structural Behaviour of Dams in Japan," Trans. 6th Cong. Large

Dams, New York, Vol. 2, R. 25, Q. 21, 301-57, 1958.

222. Bacon, L.O. , "A Method of Determining Dynamic Tensile Strength of Rock

at Minimum Loading," Bureau of Mines Rept. BM-RI-6067, 22 pp., 1962.

223. Mellor, M. and Rainey, R. , "Tensile Strength of Rocks at Low Temperatures,

Preliminary Data Report," U.S. Army Terrestrial Sciences Center, Unofficial Memorandum, 34 pp., 1968.

224. Iida, R.,0kamoto, R., and Yasue, T., "Geological Rock Classification

of Dam Foundation," Rock Mech. Jpn. , I_, 161-3, 1970.

226 . Cogan, J., "The Creep of Weak Rocks in the Burgin Mine," Stanford Univ.,

Ph.D. Thesis, 315 pp., 1975.

226. Cording, E. J. , Hendron, A.J., and Deere, D.U., "Rock Engineering for

Underground Caverns," Proc. Symp. Underground Rock Chambers, Phoenix,

Arizona, 567-600, 1971.

63
227. Dvorak, A., "Tests of Anisotropic Shales for Foundation of Large Bridge,"

Proc. 1st Cong. Int. Soc. Rock Mech., Lisbon, Vol. II, 537-41, 1966.

228. Fernandes, L.H.G. and De Sousa, A.A.C., "Le Comportement du Barrage de

Salamonde Dans les Premiers 15 Mois du Remplissage de sa Retenue,"

Trans. 5th Cong. Large Dams, Paris, Vol. Ill, Q. 16, R. 18, 261-72,

1955.

229. Gimm, W.A.R., Richter, E., and Rosietz, G.P., "Uber das Verformungsund Festigkeitsverhalten des Gebirges bei Grossversuchen im

Eisenerzbergbau, " Proc. 1st Cong. Int. Soc. Rock Mech., Lisbon, Vol. I,

457-63, 1966.

230. GTCNF (Groupe de Travail du Comite National Francais, France), "La

Deformabilite des Massifs Rocheux Analyse et Comparaison des Resultats,"

Trans. 8th Cong. Large Dams, Edinburgh, Vol. II, R. 15, Q. 28, 287-312,

1964a.

231. Habetha, E., "Large Scale Shear Tests for the Waldeck-II Pump Fed

Storage Station Construction Project," Proc. 2nd Int. Cong. Int.

Assoc. Eng. Geol. Sao Paulo, Vol. I, Paper IV-35, 1974.

232. Hayashi, M. , Fuziwara, Y. , and Komoda, H., "Dynamic Deformability and

Viscosity of Rock Mass and Rock Fill Material Under Repeated Loadings

In-Situ and Triaxial Test," Rock Mech. Jpn., Vol. II,- 84-6, 1974.

233. Chong, K.P., Smith, W.J., and Khaliki, B.A., "Creep and Relaxation of

Oil Shale," Proc. 19th U.S. Symposium on Rock Mechanics, Vol. I,

414-8, 1978.

64
APPENDIX II

SECTION 2.

FEASIBILITY STUDY

DATA FOR NUCLEAR WASTE DISPOSAL

THE THERMOPHYSICAL AND ELECTRICAL PROPERTIES OF

BASALT, GRANITE, SHALE, AND TUFF

Y. S. Touloukian

Center for Information and

Numerical Data Analysis and Synthesis (CINDAS)

Purdue University

2595 Yeager Road

West Lafayette, Indiana 47907

TABLE OF CONTENTS

Page

PART I. THERMOPHYSICAL PROPERTIES 1

NOMENCLATURE 1

INTRODUCTION 2

DEFINITIONS AND THEORETICAL CONSIDERATIONS 3

Thp-rmal Conductivity

Coefficient of Linear Thermal Expansion

Thermal Capacity

Thermal Diffusivity

MEASUREMENT METHODS FOR THERMAL CONDUCTIVITY

Divided 3ar Technique

Stacked Disks Method

Cylindrical Heat Flow Technique

Discussion of Sources of Error in Thermal Conductivity

Measurements

Sampling errors

Contact resistance error

MEASUREMENT METHODS FOR THERMAL EXPANSION

Push-Rod Dilatometars

Interferometer Technique

X-Ray Methods

REFERENCES TO TEXT 15

EXAMPLES OF NUMERICAL DATA 17

INDEX TO BIBLIOGRAPHY TO DATA ON THERMOPHYSICAL PR0PERTI5S OF

BASALT, GRANITE, AND TUFF 21

REFERENCES TO DATA 25

PART II. ELECTRICAL PROPERTIES

DEFINITIONS

ELECTRICAL CONDUCTIVITY AND ITS VARIATIONS

MEASUREMENT OF ELECTRICAL PROPERTIES AND SOURCES OF ERRORS

DISCUSSION OF DATA

Electrical Properties of Basalt

Electrical Properties of Granite

Electrical Properties of Shale and

IE IAInOLD

m

vovovo

cooooo

cr>

o

n

<p

J

PART I. THERMOPHYSICAL PROPERTIES OF BASALT, GRANITE, SHALE, AND TUFF

A

Aoaa,b,c

3

c

c 0 » c 1

D

d

d

P

f

h

b,k,2

L

“2 3 3 LL/L

l

2a

N

n

pQ

NOMENCLATURE

a constant: A =* [ (Q/4irX) iln D] + . . . lattice constant

probe radius (in eq. 7)

lattice spacings

ratio of heat capacities of medium and probe material

thermal conductance per unit length

calibration constants in eq. 10

specific heat at constant pressure

specific heat at constant volume

defined as: D = 4a/ 1.7811 a

2 (in eq. 7); also diameter of specimen

bar

separation of the lattice planes (in eq. 24)

diameter of the p1 th fringe

focal length of lens in interferometer

defined as: h = X/ac

Miller indices for the planes

length of specimen bar; also distance between surfaces

length at 293 K

coefficient of linear expansion (incremental)

thickness of specimen

logarithm to the base e number of fringes

refractive index

pressure

volume proportion of constituents in a two component material

heat flux

radius of bar specimen; also ratio of thermal conductivities of a two component material: r - X,/Xdistance between fringes

absolute temperature

sound velocinv
w perpendicular distance between the specimen and the line that joins

the separators in a Fizeau interferometer

x distance along specimen

Greek

Symbols

aa,e>Y

yG

A

£

8

X

X

X

b

c

X f X Z

XR

V

IT

Pa

i

thermal diffusivity

angles between lattice axis (in eq. 24)

coefficient of thermal linear expansion

coefficient of thermal volumetric expansion

Griineisen parameter

a finite change in a quantity

coefficient of extinction

angle between the direction of incident or reflected ray and the

direction normal to the surface

thermal conductivity

thermal conductivity of brass bar

thermal conductivity of continuous phase (matrix) of a two component

material

thermal conductivity of the fluid phase

lattice, or phonon, conduction coefficient

thermal conductivity of rock

wavelength of. -light in vacuum

a finite change in a quantity

mathematical constant: it = 3.1416

density

Stefan-Boltzmann constant: a = 1.38054 x 10 2

3

J k

1

defined as: x = at/a 2

INTRODUCTION

The thermophysical properties of interest are the thermal conductivity,

the expansion coefficient, and thermal capacity (the product of specific heat

and density) . Thermal diffusivity is not an independent property since it is

the ratio of thermal conductivity to thermal capacity. The various factors

involved in the measurement and accuracy of these properties are discussed,

together with illustrative examples.
DEFINITIONS AND THEORETICAL CONSIDERATIONS

THERMAL CONDUCTIVITY

The lattice, or phonon, transfer coefficient, X^, which is usually

referred to as the thermal conductivity of the material, is defined as the

ratio of heat flow per unit area to temperature gradient and is connected to

other physical properties, including seismic velocities, by means of the

Gruneisen parameter yq. The relationship is shown in eq. ( 1 ) where is the

specific heat at a constant volume, V is the mean sound velocity, Ag is the

lattice constant, 3Vis the volumetric thermal expansion coefficient, and

T the absolute temperature.

. 1

CvVA

0 1

1 " 3 8v

yg

T

( 1 )

The Gruneisen parameter is essentially a measure of the fractional change of

pressure on heating a material at constant volume, so that seismic velocity

and thermal conductivity are related by means of the effect of pressure cn the lattice constant.

Strictly speaking, eq. (1) applies only at temperatures well above the

Debye temperature and refers only to very simple isotropic single crystals

.

Thera is some debate as to whether the temperature dependence is as T

‘

(three phonon mode) or T (four phonon mode) . The argument is largely

academic in our context since by the time the temperature is high enough to

worry about the difference, we are in a region where X,. is dominant.

Since the range of thermal conductivities of minerals spans only cr.e or

two orders of magnitude, and the range from gases to pure metals is only five

of six orders of magnitude, compared with more than 20 orders of magnitude to

electrical conductivities, the influence of compositional and structural vari

tions is far lass than in the case of electrical properties.

COEFFICIENT OF LINEAR THERMAL EXPANSION

The linear thermal expansion coefficient, £,: , is defined as the fraction

change in length per deg X temperature change. The volume expansion coeffici

£„, is similarly defined as the fractional volume change per deg X. The rela

between the two is obvious.
THERMAL CAPACITY

Thermal capacity is defined as the amount of heat per unit volume required

to heat the material one degree K and is the product of the specific heat at

constant pressure, Cp, and density, p. The value of accepting this as a thermal

property, rather than just the specific heat, is that the product pep has a built-in, self-compensating factor. The great majority of minerals and impervious rocks, pep lies within 20% of 2.3 W s cm

3 K

1

. For porous rocks, the

thermal capacity can be found by weighting the thermal capacity of the pore

fluid and the matrix material according to their volume proportions.

THERMAL DIFFUSIVITY

Thermal diffusivity, a, is defined as the ratio of thermal conductivity

to thermal capacity, eq. (2). Because of the above-mentioned relative con- stancy of pep, it is usually simpler and more accurate to obtain a by measuring

the conductivity by an established method and determining a from eq. (2).

( 2 )

Measurement of diffusivity can be made directly by the "flash" method.

In this technique, an instantaneous energy source is applied to a specimen

in the form of a thin disk and the temperature rise as a function of time is

measured in the back face of the specimen. The instantaneous source can be

a high energy pulse or laser applied to the surface of a disk shaped specimen,

this latter now being a popular technique [17,19,25].

In actual practice, a heat source, such as flash tube or laser, supplies

a flash of energy to the front face of a thin disk specimen and the temperature as a function of time at the rear face is automatically recorded. The

thermal diffusivity is obtained from the thickness of the specimen, £, and a specific time, t at which the back face temperature reaches half its

maximum value by the expression

a = 1.37 £

2

/7T 2

t-|_/2 • (3)

The thermal conductivity of the specimen is then calculated by the relation

A = pac

p

( 4 )
where X is the thermal conductivity, p is the density, and Cp is the specific

heat at constant pressure.

In all cases, the basic assumption is that a very high pulse of energy

lasts for an infinitesimally short time. Recent developments concern the

corrections required for finite pulse time effects [2,12,23].

Results from the "flash1 * technique appear to be reasonably consistent

with different workers reporting values within about 10% of each other on apparently identical materials. However, there does not appear to have been

any systematic comparison of diffusivity values obtained using the "flash"

technique with those obtained using a standard temperature- time curve technique on the same material. This omission may not have serious implications for

measurements made at ordinary temperatures and pressures, but may have considerable significance for the increasing number of experiments being made at

high pressures and high temperatures.

MEASUREMENT METHODS FOR THERMAL CONDUCTIVITY

It is convenient to divide the experimental methods into two broad groups:

(a) one dimensional steady state, comparator types, and (b) two dimensional

(cylindrical), absolute type. Although it is possible to use one dimensional

transient techniques, none are used, or have been used, to a significant

extent

.

3y far, the great majority of steady state techniques (one dimensional)

are comparative methods, the comparison being made in one of two ways. In both

cases negligible lateral heat loss is assumed and the unknown disk is usually

placed at the center of a geometrically symmetrical arrangement with a constant

temperature difference maintained across the system [3,4]. Toe thermal contact

resistance is either kept small enough to be ignored or else determined and

eliminated by measurements on samples of different thicknesses, or by measurements on one sample but using different conductivity fluids in the interface

region. In the following discussion, negligible contact resistance is assumed

except in the section specifically discussing the errors which night arise if

there are unsuspected contact affects.
DIVIDED BAR TECHNIQUE

Two bars are used, each several centimeters long, and a typical experiment

consists of measuring the temperature gradient, dT/dx, along the reference bar,

usually brass, of known conductivity, [7]. The amount of heat per unit

area per unit time flowing down the bar is determined from

Q - (5)

The temperature drop across the unknown specimen is measured, and since its

thickness and the heat flowing through it are known, the conductivity of the

unknown can be determined by using eq. (5) with a suitable change in subscript.

STACKED DISKS METHOD

The unknown sample is usually sandwiched between two reference disks of

known conductivity [8], and the temperature differences across each of the

disks are determined. That is, the temperature gradient through each of the

disks is found, and once again, since the conductivity of the standards are

known, the conductivity of the unknown sample can be determined. The reference

material may be an artificial material with a conductivity, calibrated against

a standard such as quartz, in the middle of the range of rock conductivities,

or it could be a standard material itself.

In both cases the calibration materials used by the great majority of

researchers are fused quartz and crystalline quartz cut so that the heat flow

is perpendicular to the optic axis.

CYLINDRICAL HEAT FLOW TECHNIQUE

There are again two basic approaches - the transient and the steady state

cases. In both cases a long heating probe supplies energy at the rate of Q

per unit time per unit length, the length, L, being considerably greater than

the diameter (D)

;

usually L > 50D.

In the steady state case temperature sensors are located at known radii,

r ; and r 2 , and from the temperature difference, (T,-T 2

)

,

between them the

conductivity can be determined from eq. (6) once the steady state has been

reached.

rO
X

Zn(r2 /r 1 )

( 6 ) ,-91.

2ir T L -T2

Frequently, a true steady state is not reached in which case the same equation

may be used for the quasi-steady state case as can readily be shown by manipulation of eq. (19) in Chapter 13, Section 5 of ref. [11].

In the transient case the rise of temperature with time is monitored

and the conductivity determined from eq. (7)

.

IT = t^t- [2h + Zn(Dt) - (4h - 3) (2B7)" 1 + (3 - 2) (2B7)" 1 Zn(Dt) ] (7)

47TA

where D =» 4a/1.7811 a

2

, 7 = at/a 2

, h ** X/ac, 3 is twice the ratio of thermal

capacities of the medium and probe material, a is the probe radius, t is time,

and c is the thermal conductance per unit length of the contact layer.

"A Equation (7) is for a probe of finite radius. Such probes are used for

the in-situ determination of thermal conductivity [6], with or without the

presence of a thermal contact resistance at the boundary. In this case a log-log plot is made from which both X and 7 (and, therefore, thermal capacity)

may be determined from the 'displacement of the origin [20].

If the radius of the probe is very small, so that 7 is always large, even for relatively small times, then the above equation reduces to the

familiar line source form, eq. (3).

T ‘ MX c + A (3)

where the constant A = [ (Q/ 4rr A ) In D] + . . . . It can readily be seen that

a plot of temperature rise versus xn t should be a straight line in the early

part of the experiment from the slope of which the conductivity may be determined, eq. (9).

n

in(t./t.)

; -

~ mx " "

4ttL (T 2 -T-)

This is the standard technique used for ocean sediments [29] but has been used

only occasionally for measurement on continental materials [31]. Care has co be exercised since there are some "false' 7 asymototes and the best method of

reduction is to record the temperature- time data continuously and calculate

•trees usens ec . _na most rettao_e rasu_:

r*. £ it — c n s

/ C \

V " /

•
Since the constant contains the diffusivity, once X has been determined

then t (and hence pCp) can be found from the intercept of the best straight

line.

DISCUSSION OF SOURCES OF ERROR IN THERMAL CONDUCTIVITY MEASUREMENTS

Sampling Errors

Because of the small scale heterogeneity of most rocks, particularly

those that are coarse grained or bedded, an important source of error in

establishing a conductivity of rock in bulk is the age-old one of finding

representative samples. In some cases, conductivities measured on contiguous

samples, of approximately 10 cm

3 volume, can give conductivities that differ

by 50% even though each sample value has a precision of 1%.

For this reason, few rock conductivity apparatuses are designed to give

high accuracy, say better than 1%. Rather they are designed to give results

rapidly to within 5% and the average of many samples taken to give a unit

conductivity.

Contact Resistance Error

One frequently overlooked but sometimes important source of error which

is always present and cannot be removed is the contact resistance at the

sample-equipment interfaces [5]. If a relatively high conductivity is used

in the interface, its thermal resistance can be made quite small relative to

the thermal resistance of the sample and the effect ignored. Water is a good

fluid to use since its conductivity is relatively high and in many cases the

requirement is for the conductivity of water saturated rocks. However, if air

or oil are used, then large errors can result, especially if the rock is coarse grained and porous. It may be necessary to use these fluids if the conductivity

of oil saturated rocks is required or if the material is so metastable that it

disintegrates when soaked in water.

If enough material is available the contact resistance can be found from

measurements on samples of significantly different thicknesses, the basic as- sumption being that the surface finish and conductivity of each sample is the same

If there is only sufficient material for one sample, it is possible to

determine a contact resistance correction from measurements using saturation

(nondisintegrating) fluids of different conductivities.

8
MEASUREMENT METHODS FOR THERMAL EXPANSION

PUSH-ROD DILATOMETERS

The push-rod dilatometer method for measuring thermal expansion is

experimentally simple, reliable, and easy to automate [13]. With this method,

the expansion of the specimen is transferred out of the heated zone to an extensometer by means of rods (or tubes) of some stable material. The expansion of the specimen is given by

AL

L29 3

<AL)

a

c ° T +

3 3

( 10 )

where (AL) ais the apparent change in length as calculated from the difference

between the extensometer readings at two different temperatures, and c 0 and

c : are calibration constants for the system. If the reference rod is made the

same length as the push rod and a second specimen placed on the base plate,

the dilatometar will measure the difference between the specimens [27]. The

difference, or differential expansion, is given by

(AL) (AL) (AL)

r s ^ a

T T 0 T

J-‘2 9 3

-*-‘2 9 3 —2 9 3 (ID

When used this way the dilatometer can have a very high sensitivity. This

technique is also very useful for quality control measurements and for studying

phase transitions. _ _ _

One of the most common sources of error in using dilatometers is the

measurement of temperature. All coo often the temperature that is measured

is not the temperature of the specimen. This is especially true in measurements made while the temperature is changing. If a thermocouple is used, care

must be taken to ensure that its junction and specimen are at the same temperature. They can be at different temperatures even if in contact with each

other. Another common source of error, especially for flexible materials or materials near their softening temperatures, is deformation under the load of

the push rod. Special techniques such as increasing sample diameter, reducing

push rod pressure, and using horizontal mounts must be used for these soft

natarca-S

.
The uncertainty of this method depends on the quality of the push rod

used and precision of construction. Results of two or three percent uncertainty may be achieved routinely.

INTERFEROMETER TECHNIQUE

These methods are based on the interference of monochromic light

reflected from two surfaces [21] that are separated by a specimen or by the

combination of a specimen and a reference material. The general condition

for interference is

2nL cos 9 = NX^ (12)

where n is the index of refraction of the atmosphere between the surfaces,

L the distance between the two surfaces, 9 the angle between the direction

of the incident rays and the direction normal to the surfaces, N the order

of interference, and \v

the wavelength of the light in vacuum. Monochromatic

light sources that may be used include cadmium, helium, mercury, and sodium

low-pressure discharge lamp [10] and a stabilized He-Ne laser [26].

If slightly inclined surfaces are illuminated with collimated light and

viewed at normal incidence (9=0 for all rays)

,

fringes of equal inclination

are observed. When the surfaces are flat the fringes will be straight; otherwise, they are determined by the contour of the surfaces. This type of interference is used in the Fizeau interferometer [1], If plane-parallel

surfaces are illuminated with an extended source (9 will vary)

,

fringes of

equal inclincation are observed. This type of interference (concentric rings)

is used in the Fabry-Perot interferometer [16],

When an interferometer is used to measure thermal expansion, the expansion

of the specimen is given by

AL = AN _ An

L 2nL cos 9 n

( 13 )

where AN is the number of the fringes that pass a fiducial mark and An is the

change of refractive index. A useful approximation for the refractive index

is

T„P n « 1 + (nr -l)

r

(14)
where Oj. is the index at the reference temperature T

r and the reference

pressure P . In vacuum or in a sufficiently low-pressure atmosphere

AL ^ AN

L 2L cos 9

( 15 )

In a Fizeau interferometer (straight fringes) the fractional part of

AN is easily determined from measurements of the position of the fiducial

mark between two fringes. In the Fabry-Perot interferometer (circular

fringes) the fractional part, v , is given by

nLdp 2 v » 1 — p

+ (16)

where dp is the diameter of the pth fringe (counted from the center of the

concentric pattern) and f is the focal length of the lens that forms the

pattern. If measurements are made on the second and fourth fringes, the

fractional part is

3d 2 - d

2 v = — (17)

j 2 j 2 c 4 - d 2

The number of fringes that move past a reference point during the expansion

of a specimen can be counted by eye or automatically by photographic [30] or photoelectric [15] techniques. Another way of determining AN is by

finding the value of N at each temperature. This can be done by using at

least three different wavelengths [10]. From eq. (12) it can be seen that

(N. + VjH! = (N 2 + v 2 )X 2 = (N, + 'J 3 )X 3 (13)

where N, , N2 , and N 3 are the fringe integers and 'J

,

, v 2 , and v , are the fringe

fractions for each of the three wavelengths. In the method of exact fractions

a value is guessed for N, (^ZnL/X , ) and using the measured value of the

values of (N 2 + v 2

) and (N 3 + v - ) are calculated. This procedure is repeated

with different values of N 1 until the calculated values of v- and v- agree

with their measured values. If N is known, then
The Fizeau interferometer can be used to measure either the absolute or relative expansion of a specimen. In the relative method a pedestal of one material fills most of the space within a ring or cylinder of a second material.

The pedestal is preferably made of a reference material. While the ring supports the optical flat, the interference is formed by reflections from the

optical flat and the top surface of the pedestal. Since the reflecting

surfaces are close together this method has three advantages: (1) the fringes

are bright and well defined; (2) the change of the refractive index of the gas

within the small space does not affect the measurements; and (3) longer speci- mens can be used with a corresponding increase in sensitivity. The thermal

expansion is given by

AL

Lr <14

UJ s 2nL

s

' L

s UJ ( 20 )

where the subscripts s and R refer to the specimen and reference materials.

When the last term can be ignored.

If one or all three of the separators in a Fizeau interferometer expand

differently, the difference will cause a rotation and/or change in the spacing

of the fringes. In the first case where the two similar separators made from

a reference material are exactly the same length the difference in expansion

of the other material is given by

AL 'al^

WA^j

1 1 | UJ s UJ R

" 2Ls n 2 S 2 n 1 S

1

( 21 )

where W is the perpendicular distance between the specimen and the line that

joins the separators and S is the distance between fringes.

When the optical flats of a Fabry-Perot interferometer are made highly

reflecting the multiple reflected beams cause a great increase in sharpness

of the fringes. This sharpness results in a higher sensitivity in the mea- surement of fringe fractions and, hence, in the expansion measurements. The

sensitivity of a polarizing interferometer [14] is also higher because the

measurement of the polarization angle is a more sensitive way of determining

a fringe fraction. The laser is an extremely efficient source of radiation

for this type of interferometer because it can be constructed to emit a polarized beam. This method is inherently capable of producing results of

very high accuracy if the samples are properly prepared.

12
X-RAY METHODS

These methods are based on the diffraction of a collimated beam of

monochromatic x-rays that is scattered by atoms in a crystal lattice. The

Bragg law

X » 2d(hk£)sin 9 (22)

gives the condition for constructive reflection of the incident radiation.

Here d is the separation of the lattice planes, h, k, and l are the Miller

indices for the planes, and 9 is the angle measured between the direction cf

the incident or reflected beam and the planes. Except for a small correction

due to refraction, the measurement of expansion is independent of wavelength

such that

Ad(hkl)

d(hki)

= -cos 9 A9

sin 9j - sin 9

2 sin 9 2 (23)

where 9

X and 32 are the angles of incidence of the beam with the crystal

plane at temperatures T 1 and T2 , respectively.

The relationship between the separation of lattice planes and the

symmetry of the crystal lattice is given by

d

2 = [1 - cos2 a - cos

2 3 - cos2 y + 2 cos ct cos 3 cos y] / [ (h/a) 2 sin 2 t

+ (k/b) 2 sin2 3 + (1/c) 2 sin2 y + x (cos ct cos 3 - cos y)

3.0

2hi 2kZ + —— (cos a cos y - cos 3) - -r~ (cos 3 cos y - cos z) ] ac dc

(24)

where a, b, and c are lattice spacings and a, 3, and v are the angles between

lattice axis b-c, c-a, and a-b , respectively. Using this equation, it can be shewn that for a cubic crystal (where a=b=c and u=-£=y=90 a ) such as NaCl,

the expansion can be obtained from any set cf lattice planes (hki) , e.g.,

la id(hki)

a (hkl)

= -cot 9 IS

The thermal expansion of crystalline materials can be accurately measured

with x-ray cameras and diffractometers under conditions that preclude the use

of any other method, as when the specimens are very small, weak, and/or irregular in shape. These methods are also unique in that they tan easily be used
to determine the principal coefficients of thermal expansion of anisotropic

crystals and permit direct observation of phase changes. There is a further

advantage in that measurements with x-rays do not include effects that are observed in measurements on bulk specimens. The problems associated with

heating the specimen and accurately measuring its temperature in both x-ray

cameras and diffractometers are discussed in several articles [9,22,24].

Unique x-ray techniques exist for special situations. In particular,

the use of the Bond technique for single crystals [23] has resulted in a sensitivity of 10 7 in measurements of La./ a. [1]. In this technique the specimen is rotated between equivalent diffracting orientations on either side of

the incident beam. The value of 9 thus obtained is unaffected by any specimen

eccentricity, absorption, and zero errors, and errors due to specimen title

and beam axial divergence are minimized.

The inherent accuracy of this technique is extremely high for well

characterized and stable materials.
REFERENCES TO TEST

1 .

2 .

3.

4.

5.

6 .

7.

3 .

9.

10 .

11 .

12 . 13.

14.

L5 . 16.

17.

IS.

19

.

20 .

22 .

ASTM, ASTM Standards, Part 41, 1974.

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1965; English translation: High Temp., 3_(1) , 47-52, 1965.

Schroder, J., Rev. Sci. Instrum., 34 , 615-21, 1963.

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Beck, A.E., Geophysics, 41 , 9-16, 1977.

Beck, A.E., Anglin, F.M. , and Sass, J.H., Can. J. Earth Sci., S_, 1-19,

1971.

Benfield, A.E., Proc. Roy. Soc. London, A173 , 428-50, 1939.

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Brand, J.A. and Goldschmidt, H.J., J. Sci. Instrum., _33_, 41-5, 1956.

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502 pp., 1951.

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,

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American Institute of Physics, New York, 147-8, 1974.

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EXAMPLES OF NUMERICAL DATA

In this part of the report, illustrative data are given for four thermophysical

properties of basalt, granite, shale, and tuff as a function of temperature.

In a number of cases, specific comments pertaining to the applicability of

the data are made on the figures or in the captions to each figure but, in

general, the following points should be borne in mind when interpreting the

data and putting them to a particular use.

Rocks are classified broadly in terms of their mineralogical and structural

characteristics. Within a particular rock type there may be a sufficient variation of these characteristics to give very different thermal properties; for

example, in granite the thermal conductivity value depends quite strongly upon

the quartz content but, nevertheless, other factors may have a strong influence,

producing much scatter about a linear trend when quartz content is plotted

against conductivity.

For porous rocks, the thermal conductivity may be strongly dependent

upon the conductivity of the pore fluid; as indicated in an earlier section,

it may sometimes be necessary to calculate thermal conductivity from a knowledge of the rock matrix, porosity, and nature of the pore fluid. However,

it is most important that the thermal conductivity of the matrite material be

accurately known. Among the various parameters influencing the thermal properties of rocks, porosity is perhaps the most important. Because of this,

much of the original literature data has been rejected because the data on conductivity values are given with no reference to the porosity of the rocks.

In trying to estimate the probable variation of a thermal property with

temperature (or pressure) , the room temperature value in the appropriate

figure should first be located and an interpolated curve drawn roughly parallel

to the ones shewn for a specific case with a possibly different starting rocn

temperature value.

In reviewing the vast amount of data in the literature, one finds that

many of the frequently quoted sources are, in fact, secondary sources which,

upon investigation, sometimes differ from the original source both in magnitude

of the property values as well as interpretation. Wherever ocssible, the

original sources have been consulted. Except for a limited number of specific

cases, it has not been possible to recommend temperature deoendent prooerty
values due to the extreme scatter in the data and the lack of adequate

specimen characterization. Hence, it was decided to report a band, or a range of probable values, a property can assume based on the various parameters discussed above. An extensive bibliography is presented with the data

figures for those interested in recreating the topography of the original

data for a given property.

Upon careful examination of the literature data on the thermophysical

properties covered in this Section, it became clear that the literature, while

reasonably abundant in data, is most inadequate for the proper selection and

recommendation of reliable design data. Hence, it became necessary to discard

large numbers of data references and to be satisfied by the simple indications

of upper and lower bounds within which the data may fall based on rock composition, structure, porosity, water content, etc. These factors often influence

the variation of the property more than such variables as temperature and

pressure. Whenever adequate data were available, histograms were constructed

for the room temperature thermal conductivity of certain rock systems.

Sight-specific data are nearly non-existent for well characterized rocks

for either in-situ or laboratory measurements. The need for new data, in

nearly all areas, cannot be stressed strongly enough for well characterized

specimens

.

On pages 19 through 23 illustrative examples of data are given in Figures

1 through 10.

IS
THERMAL

CONDUCTIVITY,

W

nf

FIGURE 1. THERMAL CONDUCTIVITY OF BASALT.

FIGURE 2. THERMAL DIFFUSIVITY OF BASALT.
SPECIFIC

HEAT

, J

kg"'

K

-'

,

THERMAL

LINEAR

EXPANSION

FIGURE 3. THERMAL LINEAR EXPANSION OF BASALT [63].

TEMPERATURE , K

FIGURE 4. SPECIFIC HEAT OF BASALT.

20
THERMAL

Dlf

FUSIVITY

, 10

m

•

1

THERMAL

CONDUCTIVITY,

W

nf

FIGURE 5. THERMAL CONDUCTIVITY CF GRANITE ROCKS.
FIGURE 7. THERMAL LINEAR EXPANSION OF GRANITIC ROCKS [45].

FIGURE 8. SPECIFIC HEAT OF GRANITIC ROCK [59].
THERMAL

LINEAR

EXPANSION,

%

THERMAL

CONDUCTIVITY

, W

m

FIGURE 9. THERMAL CONDUCTIVITY OF TUFF [15].

FIGURE 10. THERMAL LINEAR EXPANSION OF
INDEX TO BIBLIOGRAPHY TO DATA ON THERMOPHYSICAL PROPERTIES OF

BASALT, GRANITE, AND TUFF

References cited here contain data which were used as the

basis for the figures presented in this report, While the presentation of

the data is generally from room temperature to 1500 K, the listed references

cite data below and above these temperature limits. Refer to the Bibliography

for the reference citations.

Basalt

Thermal conductivity: 8,12,15,17,18,19,21,22,23,24,27,29,30,36,33,39,

40,42,46,53,60,61,64,68,70,74,75,80,82,85,87,90

Thermal diffusivity: 8,11,18,44,48,54,67,68,69,80,81,83,84,85,89

Thermal expansion: 26,32,34,55,56,63,72,73,79,85

Specific heat: 8,11,14,18,19,30,38,49,52,59,68,71,79,35,86

Granite

Thermal conductivity: 2,5,7,8,13,16,19,20,22,28,33,35,43,50,51,62,64,

65,76,77,78,88

Thermal diffusivity: 1,8,13,62,89

Thermal expansion: 25,32,45,55,56,58,66,72,73

Specific heat: 4,8,9,10,13,14,19,31,37,52,57,59,71,77

Tuff

Thermal conductivity: 3,8,15,35,38,41,62,78,87

Thermal diffusivity: 8,41,62

Thermal expansion: 47

Specific heat: 6,8,38,62
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U.S. Geological Survey Open File Rept. 75-567, 1975.

89. "The Thermal Diffusivity of Eight Well-Characterized Rocks for the Temperature Range 300-1000 K," Hanley, E.J., DeWitt, D.P., and Roy, R.F.,

Eng. Geol. , 12, 31-47, 1978.

90. "Thermal Conductivity of Vesicular Basalr from Hawaii," Robertson, ‘ E.C

.

and Peck, D.L., J. Geophys. Res., _79_(32) , 4875-88, 1974.
31

PART II. ELECTRICAL CONDUCTIVITY OF BASALT, GRANITE, SHALE, AND TUFF

DEFINITIONS

Rocks are generally electrical nonconductors. However, under this category

it may be useful to define three classes of materials; namely:

Nonconductor : A material in which there are energy barriers between the

atoms and where electrons are tightly trapped near atoms. Electrical conductivity increases with increasing temperature as thermal activity overcomes the energy barriers. This broad group of materials can be further

sub-classified as:

a) Insulators : Materials with very large energy barriers between atoms

such that electrons generally are not the charge transport carriers.

At elevated temperatures charge is carried by ionic conduction through

the movement of entire atoms within the material. At lower temperatures,

charge transport is by tunnelling or defect diffusion.

b) Semiconductors : Materials with energy barriers that are slightly higher

than the available energy from thermal activation at room temperature.

At higher temperatures, electrons may be sufficiently activated to overcome the barriers. At lower temperatures, charge transport is by electrons or holes moving across barriers that are lowered by impurities

within the material. (A hole is the positive charge associated with

the absence of an electron or vacancy moving through the material.)

c) Electrolytes : Materials which split (dissociate) into oppositely charged

particles when dissolved in appropriate solutions. The motion or the

charged particles is hindered by the viscosity of the solution and

interparticle interactions. Electrical conductivity of these materials

in solution generally increases with increasing temperature until near

the critical point of the solution where it decreases with further temperature increase.

ELECTRICAL CONDUCTIVITY AND ITS VARIATIONS

E inure II illustrates the great range ot elsctraca_ concuctavat” - common materials. As already discussed in the general introduction, ncs terials have electrical conductivities that are extremely dependent upc

state and content of water in the material. The most important aspects

in materials involve the void morphology in the total amount of void so able for water and the connectivity of the voids. Secondary aspects cr the surface area of the voids and the chemical interactions between ths

m tne

water

a. — — •- g ’

so -Lucz.cn ana . .1 -
Electrical

Conductivity,

Mho/m

FIGURE 11. THE ROOM TEMPERATURE DC ELECTRICAL CONDUCTIVITY

OF A VARIETY OF MATERIALS*

10 8• • • copper

10 s

• • • iron

10 4

10 2

10°

• • •

• • •

tellurium

germanium

• • •

aa

<u T3

•H

UJ ...

10“ 2

rH3

CO

10- 4

• • • silicon • • •

10“ 6 selenium (cryst.) ..._ • • •

1 to

'o

1

-H

10” 10 iodine

polyethylene _i— m 10" 12 selenium (amorph.) ..

03

CJ •H 10“ 14 paraffin/ teflon

• • • •H

10" 15 diamond

10" 13 beryllium oxide

cn

0) -oX

o

. . . ocean water

. . . wet basalt

. . . water (ice)

. . . dry basalt

. . . single crystal olivine

. . . powdered dry basalt

. . . alumina

*As the basalt example shows, most materials can have greatly increased conductivities by the addition of water or greatly reduced conductivities by powdering

(Reduction of grain-grain contacts).

A number of complications arise in materials that do not obey the linear

relationship between current density and electric field, known as Ohm's Law.

Olhoeft [14] has discussed some of the implications of such nonlinear behavior,

with many examples existing in the literature [1,5,3,9,10,17,18, and others].

In materials which exhibit nonlinear electrical behavior, it is the water-rock

chemical interaction, through oxidation-reduction chemistry or cation exchange

processes, that cause and determine the observed nonlinearities. Thus, the

chemistry of water-rock interactions is very important in determining electrical

properties of wet rocks through surface conduction, interracial polarization,

and charge transport by chemical reaction at or across the water-rock boundary.

It is because of this last feature that the measurement of the electrical properties of wet rocks is particularly prone to error.

32
MEASUREMENT OF ELECTRICAL PROPERTIES AND SOURCES OF ERRORS

Before giving examples of electrical properties, let us consider the

sources of error in typical measurements . In dry rock measurements, the Largest

errors are caused by current leakage around the sample (through the sample

holder assembly), by cable coupling, by capacitance fringing effects, and by

systematic instrument biases. Of these errors, adequate sample measurement

system design can eliminate or reduce these effects to a very small fraction

of one percent (±0.4% spread worldwide among all standard laboratories) in

absolute terms or less than ±0.005% relative. The principle method of accomplishing this is by the use of 3-terminal or 3-electrode sample holders [13,20].

In wet rocks, additional errors occur due to current leakage around the

sample via wet surface conduction paths, faradaic charge transfer impedances

between the electrodes and the sample, and chemical reaction between sample

and sample holder. These error sources can be reduced to a fraction of one

percent by using inert materials (platinum and teflon as examples) in a fourterminal shielded sample holder [15] . As these errors are not known as well

as the dry system errors, they will be discussed in detail.

Figure 12 illustrates a typical four-terminal call arrangement. The

significant sorucas of error are listed and shown in the circuit diagram of

Figure 13. Leakage and surface conduction are eliminated by proper sample jacketing (potting or confining pressure sleeve) and sample holder construction.

The charge transfer impedance at the current electrodes is not important, as

it lies outside the region where potential drop is measured (though it nay

prove troublesome to the source) . The charge transfer impedance at the potential electrodes is minimized by using a very high input impedance measurement

circuit so no significant currant (picoamperes or less) is drawn through that

circuit. The potential electrodes are also not allowed to touch the sample

to prevent contact polarizations and related phenomena [13]. Either the potential electrodes are separated from the sample by a thin porous teflon membrane,

or by a small distance in the solution, or by a paste of fumed silica gel, all

of which add a small error typically less than 0.3% in magnitude and a few nilli

radians in phase. The capacitative and inductive cable couoling affects are eliminated by using driven shield circuitry and adequate low noise shield
FIGURE 12. TYPICAL FOUR-TERMINAL ARRANGEMENT FOR THE

MEASUREMENT OF ELECTRICAL PROPERTIES OF

ROCK SAMPLES.

SOURCE

FIGURE 13. ELECTRICAL CIRCUIT DIAGRAM OF THE FOUR-TERMINAL C

ARRANGEMENT (FIGURE 12) INDICATING THE PRESENCE 0

MAJOR SOURCES OF ERROR.

'>1 M
construction techniques. Thus, Figure 14 summarizes the typical 4-electrode

sample holder.

Instrumentation and noise errors are still possible (such as source harmonic

distortion, receiver Hilbert distortion, etc.), but these errors may be handled

by standard statistical techniques and good laboratory practice.

DISCUSSION OF DATA

ELECTRICAL PROPERTIES OF BASALT

Figure 15 [12] illustrates the extreme sensitivity of electrical properties

to small amounts of water in silicates such as basalt. The DC electrical conductivity does not begin to change until there is sufficient water in the sample to create a connected path from one electrode to the other in the measurement system (in this case about 0.002 wt.% water or about 20% of a monolayer).

The dielectric permittivity and loss tangent, however, do not begin to change

significantly until more than a monolayer (about 0.01 wt.%) of water has

T

- -uilRi U— . SCHEMATIC OF

(SEE FIGURES

> T AND *5 ^ \

-—' J •
entered the sample, by which time the

DC electrical conductivity has increased

by an order of magnitude (see detailed

discussions in [12]. The dielectric

properties do not change in the first

monolayer as the strongly bound water

molecules are strongly hindered from

rotating, hence the orientational polarization is reduced, with the result

that the dielectric permittivity of

water in the first adsorbed layer is

reduced to about 6 from the free water

value of 80. By the time a few weight

percent water has entered the sample,

the dielectric permittivity has increased (typically ) by several tens of

percent at low frequencies and not at

all at high frequencies, while the DC

electrical conductivity has increased

by as many as 9 orders of magnitude.

The frequency dependence of wet

and dry rocks is generally well understood, but not widely measured on many

rock types. The pore structure and

water-rock chemical interactions are

the dominant causes of frequency

MONOLAYERS OF WATER

FIGURE 15 . VARIATION OF ELECTRICAL

PROPERTIES OF 3ASALT

,

PARTIALLY SATURATED

WITH WATER.

dependence. The nonlinear (current/voltage) dependence of electrical properties

are only minimally understood for iron sulfide systems, and little measured or understood for others. The pressure dependence of electrical properties is

generally unimportant except in wet rocks as pressure causes porosity changes,

as it affects the liquid-gas phase of water, and above the critical temperature

of water. Pressure has very little effect on the electrical properties of dry

rocks

.

6

DIELECTRIC

PERMITTIVITY,
ELECTRICAL PROPERTIES OF GRANITE

Figure 16 illustrates a summary of the available data for the electrical

properties of granite as a function of temperature, water content, and, pressure

(a similar figure holds for basalt; see [16]). Lebedev and Khitarov [11] and

Hyndman and Eyndman [7] have previously discussed the importance of water on

electrical properties deep within the earth (see also [2, 3, 4, 6]). To incorporate recent results, the next few figures quickly review the effects of pressure,

temperature, and salt concentration upon water in rocks (see also [16,19]).

First, water has two striking effects as shewn in Figure 6. The amplitude

of the resistivity changes by many orders of magnitude as water is added to

granite, and the temperature dependence changes nearly as dramatically. Near

room temperature the activation energy of the electrical resistivity of dry

granite is around 0.5 eV, increasing to about 1.5 eV near a few hundred degrees

Celsius. The activation energies in wet granite are near 0.1 eV and very constant with increasing temperature (until the melting temperature of the granite

or the critical temperature of the solution is reached.

At 1000° C, in order to produce a one order of magnitude change in electrics

resistivity of a dry granite, either the oxygen fugacity must be changed by

more than 6 orders of magnitude, or the dry hydrostatic pressure by 13C0 MPa,

or che temperature by 55°C, or the water content by 0.3 weight percent. At

lower temperatures, the effects of water are even more pronounced and dominant.

From room temperature to melting, the electrical resistivity of granite is ncstl

controlled by water content and temperature, relatively independent of either

lithostatic or hydrostatic pressure.

ELECTRICAL PROPERTIES CF SHALE AND TUFF

A preliminary search of the literature provided little information on the

electrical properties of shale and tuff other than some room temperature DC

conductivity as well as relative dielectric permittivity and loss tangent which

are reported here in Tables 1 and 2. New measurements on tuff will be forthcoming scon, however.
TEMPERATURE ( x 100 °C)

1000/ T (K)

FIGURE 16 . SUMMARY OF THE AVAILABLE DATA ON ELECTRICAL RESISTIVITY VERSUS

TEMPERATURE FOR WET AND DRY GRANITE.

Open circles are vacuum dry (10_li MPa) Westerly Granite (using

the experimental techniques described in [21-23]). Closed circles

are 0.4 molar NaCla q solution-saturated Westerly Granite (using

the experimental techniques described in [19]). Solid lined

(with water pressure indicated in MPa) are water-saturated

El'dzurta Granite from the Northern Caucasus [11].

38

TABLE

1.

DENSITY

,

DC

ELECTRICAL

CONDUCTIVITY

,

RELATIVE

DIELECTRIC

PERMITTIVITY

AND

LOSS

TANGENT

OF

BASALT,

GRANITE,

SHALE,

AND

TUFF

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42
REFERENCES

1. Biegler, T. , Rand, D.A.J., and Woods, R- , "Oxygen Reduction on Sulfide Minerals," in Trends in Electrochemistry (Bockris , J.O.M. , Editor),

Plenum Publishing Corp., New York, NY, 291-302, 1977.

2. Brace, W.F., "Resistivity of Saturated Crustal Rocks to 40 km Based

Upon Laboratory Measurements", The Structure and Physical Properties

o f th e Earth’s Crust, (Heacock, J.G., Editor), AGU Mono. 14, Washington, DC, 243-55, 1971.

3. Brace, W.F. and Orange, A.S., "Further Studies of the Effects of Pressure on Electrical Resistivity of Rocks”, J. Geophys . Res., 73 , 5407-20,

1968.

4. Burnham, C.W., '’Water and Magmas : A Mixing Model", Geochim. Cosmochim.

Acta, 39, 1077-84, 1975.

5. Hall, S.H., "A Method of Measuring Rock Electrode Kinetics," J. Electroanal. Chem. , 59, 323-33, 1975.

6. Hermance, J.F., "An Electrical Model for the Sub-Icelandic Crust",

Geophysics, 3 8., 3-13, 1973.

7. Hyndman, R.D. and Hyndman, D.W., "Water Saturation and High Electrical

Conductivity in the Lower Continental Crust”, Earth Planet. Sci. Lttrs.,

4, 427-32, 1968.

8. Katsube, T.J., Ahrens, R.H., and Collett, L. , "Electrical Nonlinear

Phenomena in Rocks," Geophys., 318., 106-24, 1973.

9. Klein, J.D. and Shuey, R.T., "Nonlinear Impedance of Mineral- Electrolyte

Interface. Part I: Pyrite," Geophysics, 13, 1222-34, 1973.

10. Klein, J.D. and Shuey, R.T., "Nonlinear Impedance of Mineral- Electrolyte

Interface. Part II: Galena, Chalcooyrite, and Graohite,” Gecchysics,

43., 1235-49, 1973.

11. Lebedev, E.3. and Khitarov, N.I., "Dependence of the Beginning of

Melting of Granite and the Electrical Conductivity of its Melt on High

Water Vapor Pressure", Geochemistry Int., 1., 193-7, 1964.

12. Olhoeft, G.R., "The Electrical Properties of Permafrost," Univ. of

Toronto, Toronto, Canada, Ph.D. Thesis, 172 pp., 1975.

13. Olhoeft, G.R.., "Electrical Properties," in Initial Report of the Petrophysics Laboratory, U.S. Geological Survev Circular 739, Reston, 7A,

1-24, 1979.

14. Olhoeft, G.R., "Nonlinear Electrical Properties," in Nonlinear Behavior

of Molecules. Atoms and Ions in Electric. Magnetic or Electromagnetic

Pi elds (Neel, L. , Editor) , Elsevier Publishing Co., Amsterdam, 395-410,

19 79.

15. Olhoeft, G.R., "Initial Report of the Petrophysics Laboratory: 13

7 ~— 1979 Addendum," U.S. Geological Survev Oren Pile Reoort 30-522. 12 or.,

1980.

16. Olhoeft, G.R.., "Electrical Properties of Rucks". Physical Prooerrles of

Rocks ar.d Minerals . Cnapt. 9, (Touloukian, W.R., Judd. J.R., and Roy.

P..P., Editors), McGraw-Hill Book Co., New York, NY, 19 30.
17 . Peter, E. , "Electrochemistry of Sulfide Minerals," in Trends in Electrochemistry (Bockris , J.O.M., Rand, D.A.J., and Welch, B.J., Editors),

Plenum Publishing Corp. , New York, NY, 267- 90 , 1977 . 18 . Scott, P.D. and Nichol, M.J., "The Kinetics and Mechanisms of the NonOxidative Dissolution of Metal Sulfides," in Trends in Electrochemistry , Plenum Publishing Corp., New York, NY, 291- 302 , 1977 . 19 . Ucok, H. , "Temperature Dependence of the Electrical Resistivity of

Aqueous Salt Solutions and Solution-Saturated Rocks", Univ. of Southern

California, Ph.D. Thesis, 154 pp., 1979 . 20. Von Hippel, A.R., Dielectric Materials and Applications , MIT Press,

Cambridge, MA, 438 pp., 1954.

21. Olhoeft, G.R., "Electrical Properties," Initial Report of the Petrophysics Laboratory, USGS Circular 789, 1-25, 1979.

22. Olhoeft, G.R. , "Nonlinear Electrical Properties," Nonlinear Behavior of

Molecules, Atoms and Ions in Electric, Magnetic or Electromagnetic

Fields , (Neel, L. , Editor), Elsevier Publishing Co., Amsterdam, 395-

410, 1979.

23. Olhoeft, G.R., "Initial Report of the Petrophysics Laboratory: 1977-1979

Addendum," USGS Open File Report 80-522, 9 pp., 4f . , 1980.

24. Duba, A., "Are Laboratory Electrical Conductivity Data Relevant to the

Earth?" Acta. Geodaet. , Geophys . et Montanist. Acad. Sci. Hung., 11,

485-96, 1976.

25. Fyfe, W.S., Price, N.J., and Thompson, A.B., Fluids in the Earth's

Crust , Elsevier Publishing Co., Amsterdam, 383 pp., 1978.

26. Lebedev, E.B., "Physical Properties of Magmatic Melts," Phv s i ca1- ch em- istry Problems in Hydrothermal and Magmatic Processes ," (Tushkin, A. A.

,

Editor), Nauka Press, Moscow, 33-47, 1975.

27. Robertson, J.K. and Wyllie, P.J., "Rock-water systems, With Special

Reference to the Water-deficient Region," Am. J. Sci., 271 , 252-77,

1971.

28. Shaw, H.R., "Diffusion of H 2 0 in Granitic Liquids: Part I. Experimental data; Part II. Mass Transfer in Magma Chambers," Geochemical Transport and Kinetics , Hofman, A.W., Giletti, 3.J., Yoder, H.S., Jr., and

Yund, R.A., Editors), Carnegie Inst, of Wash., Pub. 634, 139-70,

19 74.

29. Olhoeft, G.R., Elliot, C. , Fuller, B.D., Keller, G.V., Scott, W.J., and

Strangway, D.W., "Proposed Standards for the Presentation of Zlectrxcai

and Electromagnetic Data," (Report of the Subcommittee on Electrical'

Standards), Soc. Explor. Geophys., Tulsa, OK, 13 pp., 1978.

30. Ucok, H. , Olhoeft, G.R., and Ershaghi, I., "Electrical Resistivity of

Geothermal 3rines," in Symposium on Oilfield Chemistry and Geothermal

Brines , Society of Petroleum Engineers, Dallas, TX, SPE 7878, 163-71,

1979.

31. Drury, M.J. and Hynaman, R.D., "The Electrical Resistivity of Oceanic

3asalts," J. Geophys. Res., _84_, 4537-46, 1979.
Parkhomenko , E.I. and 3ondarenko, A.T., Electroconductivity of Rocks at

High Pressures and Temperatures, Nauka Press, Moscow, Russia, 276 pt> .

,

1972.

Robertson, E.C. and Peck, D.L., "Thermal Conductivity of Vesicular 3asalt

from Hawaii," J. Geophys. Res., 79 , 4375-4388, 1974.

Hunt, G.R. and Salisbury, J.W., "Visible and Near Infrared Spectra of

Minerals and Rocks: XII. Metamorphic Rocks", Modern Geology, 5_, 219-228,

1976.

NBS-1 14A irev. 2-80

U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET (See instructions)

1. PUBLICATION OR

REPORT NO.

NBSIR 81-2217 yf

2. Performing Organ. Report No, 3. Publication Date

February 1981

4. TITLE AND SUBTITLE

Feasibility Study: Compilation and Evaluation of Properties Data for Basalt,

Granite, Tuff, and Shale

5. AUTHOR(S)

Lewis H. Gevantman

6. PERFORMING ORGANIZATION (If joint or other than NBS. see instructions)

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

7. Contract/Grant No.

8. Type of Report & Period Covered

9. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street. City. State. ZIP)

Office of Nuclear Waste Isolation

Battelle Memorial Institute

505 King Avenue

Columbus, OH 43201

10. SUPPLEMENTARY NOTES

| | Document describes a computer program; SF-185, FIPS Software Summary, is attached.

11. ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a significant

bi bl iography or literature survey, mention it here)

A study. on the feasibility of compiling and evaluating selected physical

property data on basalt, granite, shale, and tuff has been completed. The data are

to be used to design geological waste repositories for radioactive nuclear waste.

Sufficient data on the thermodynamic, mechanical, thermophysical, and electrical

properties have been identified to exist in the literature to warrant further data

evaluative effort. A bibliography of the selected data is given.

12. KEY WORDS (Six to twelve entries; alphabetical order; capitalize only proper names; and separate key words by semicolon s) Basalt; bibliography; electrical properties; granite; mechanical properties; nuclear

waste isolation; shale; thermodynamic properties; thermophysical properties; tuff.

13. AVAILABILITY

j | Uni imited

ixsj For Official Distribution. Do Not Release to NTIS

1

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