EPA-650/2-75-043
February 1975
Environmental Protection Technology Series
                        INVEST
                    PARTICULATE MATTER

                        MONITORING USING
               CONTACT ELECTRIFICATION
                                        «*

                    53SZ
                                          LU
                                          o
                                     PRO

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                                   EPA-650/2-75-043
            INVESTIGATION OF
PARTICULATE MATTER MONITORING
 USING CONTACT ELECTRIFICATION
                      by

                 Dr. Walter John

           California State College, Stanislaus
              Turlock, California 95380
                 Grant No. 802726
                ROAP No. 26AAM-65
             Program Element No. 1AA010
          EPA Project Officer: Mr. John Nader

           Chemistry and Physics Laboratory
         National Environmental Research Center
       Research Triangle Park, North Carolina 27711
                  Prepared for

       U.S. ENVIRONMENTAL PROTECTION AGENCY
        OFFICE OF RESEARCH AND DEVELOPMENT
             WASHINGTON, D. C. 20460

                 February 1975

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                        EPA REVIEW NOTICE

This report has been reviewed by the National Environmental Research
Center - Research Triangle Park, Office of Research and Development.
EPA, and approved for publication.  Approval does not signify that the
contents necessarily reflect the views and policies of the Environmental
Protection Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
                    RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environ-
mental Protection Agency, have been grouped into series. These broad
categories were established to facilitate further development and applica-
tion of environmental technology.  Elimination of traditional grouping was
consciously planned to foster technology transfer and maximum interface
in related fields.  These series are:

          1. ENVIRONMENTAL HEALTH EFFECTS RESEARCH

          2. ENVIRONMENTAL PROTECTION TECHNOLOGY

          3. ECOLOGICAL RESEARCH

          4. ENVIRONMENTAL MONITORING

          5. SOCIOECONOMIC ENVIRONMENTAL STUDIES

          6. SCIENTIFIC AND TECHNICAL ASSESSMENT REPORTS

          9. MISCELLANEOUS

This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series.  This series describes research performed to
develop and demonstrate instrumentation, equipment and methodology
to repair or prevent environmental degradation  from point and non-
point sources of pollution.  This work provides  the new or improved
technology required for the control and treatment of pollution sources
to meet environmental quality standards.
This document is available to the public for sale through the National
Technical Information Service, Springfield, Virginia 22161.

                 Publication No. EPA-650/2-75-043
                                 11

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                              ABSTRACT






The theory of the charging of aerosol particles by contact electricity




is reviewed, as well as the development of monitors for particulate




matter based on this principle.  Data on the performance of these




monitors is scarce and sometimes contradictory.  In the present work,




laboratory tests were carried out with a variety of test dusts.  The




results show that the dynamic response of the contact electricity




monitor tracks well with that of an optical detector.  The total charge




correlates well with the gravimetric mass.  Humidity has little effect




on the response, but droplets cause failure of the instrument.  Pre-




charge on the particles did not influence the detector.  Some evidence




was obtained showing that particle size does not have an important




effect on the response, although there is a cutoff for very small




particles.  Results for the sensitivity of the instrument can be grouped




according to the electrical resistivity of the material.  It is found




that the condition of the surface of the Inconel probe has a major




effect on the sensitivity.  Additional work is necessary on this aspect




of the detector.  The theory of Cheng and Soo for the charging of metal




particles is discussed.  There is at present no theory applicable to




insulators.
                                 iii

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                              CONTENTS
List of Figures                                      vi




List of Tables                                       vi




Acknowledgements                                    vii








SECTIONS
   I    Conclusions                                   1



  II    Introduction                                  2



 III    Theory of Charging of Aerosol Particles




        by Contact Electricity                        4



  IV    Contact Electricity Monitors for




        Particulate Matter                            9



   V    Experimental Measurements                    15




  VI    References                                   36




 VII    Bibliography                                 38



VIII    Appendix - Theory of Contact Charging of



        Aerosol Particles                            41

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                    LIST OF FIGURES








                                                    Page




No.




 1   Experimental Layout                             16




 2   Dust Generator                                  19




 3   Dynamic Response                                23




 4   Charge vs. Mass for Aluminum Oxide              25




 5   Charge vs. Mass for Aluminum                    27




 6   Sensitivity vs. Date                            33
                     LIST OF TABLES
No.




 1   Sample  Characteristics                          21




 2   Sensitivity Measurements                        34
                                vi

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                          ACKNOWLEDGEMENTS









This project was supported by the U.S. Environmental Protection Agency




under Grant No. R-802726-01.  The project officer was Mr. John Nader,




National Environmental Research Center, Research Triangle Park, N.C.




I thank Mr. Nader for his encouragement of this work and for helpful




suggestions.  I express my appreciation also to Dr. Carl Gatlin,




President, California State College, Stanislaus, and to the College




Foundation for their sponsorship of this project.









Mr. Joseph Zurlinden assisted with all phases of the experimental work.









Thanks are also due to Mr. Arnold H. Gruber and 1KOR, Inc. for supplying




valuable information on the IKOR AQM.
                                    vii

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                             SECTION I




                            CONCLUSIONS








The pnisent experimental results confirm the promising findings reported




by others concerning the dynamic response of the contact electricity




monitor, as well as the good correlation of total charge to mass deter-




mined gravimetrically.  No evidence was found for disturbing effects of




humidity (below the dew point) or precharge.  Particle size was found




not tc have an important influence on the response, although a cutoff




at very small particle size exists.








The sensitivities for various substances can be grouped according to




electrical resistivity.  This is predicted by the theory of Cheng and




Soo for metals and good semiconductors.  There is no  applicable theory




for insulators.  Sensitivities  ranged over a factor of 60, so  that




some  constituents of  a mixture  will be  difficult to detect.








It was  found  that the condition of  the  surface of  the stainless steel




probe had  a major influence  on  the  sensitivity.  Additional work  is




necessary  before this surface effect can be understood,  or at  least




controlled.
                                  -1-

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                               SECTION  n

                             INTRODUCTION



When aerosol  particles  come into  momentary  contact with a surface, they

                                                1 2
may acquire an  electrostatic charge as a  result. '     This phenomenon

                                                               3 8
has been  used as  the basis  of a monitor for particulate matter. '     An

aerosol stream  can  be drawn past  an insulated  probe.  Particles colliding

with the  probe  then transfer or carry  away  charge from the probe.  The

electrical current  from such a probe has  been  found to correlate

surprisingly  well with  the  mass concentration  of the aerosol. '



The contact electricity type of monitor offers some important advantages

by making possible  in-situ  measurements in  real time.  The monitor can

respond fairly  rapidly  to changes in mass concentration and is  sensitive

over a wide range,  particularly to high concentrations.  The electrical

signal is convenient  for data collection  and the device is comparatively

simple in construction.  The history of these  instruments goes  back more

than a decade,  and  at  least two models have been available commercially.
     •H/.  R.  Harper,  "Contact and Frictional Electrification", Oxford U.
Press, Oxford,  (1967).
     2L.B.  Loeb,  "Static Electrification", Springer-Verlag.  Berlin,
(1958).
     ,A.  Schutz,  Staub 24_, 359 (1964).
     *A.  Schutz,  Staub J26, 18 (1966).
     5A.  Schutz,  Staub-Reinhalt der Luft, Band 26 (1966)  No. 5,  Seite
198/201,  1-4.
     6R.  Prochazka,  Staub 24_, 353 (1964).
     7R.  Prochazka,  Staub 26_, 22 (1966).
     8L.  Cheng  and S.L.  Soo, J, Appl.  Phys.  41, 585  (1970).
     ^H.  Schnitzler, SchrReihe Ver. Wass.-Boden Lufthyg,  Berlin-Dahlem,
V.  33, Stuttgart (1970).
    ^IKOR,  Inc., unpublished reports, and private comm.  from A.H.
Gruber.

                                   -2-

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In spite of this, the contact electricity monitor has not come  into

general use.  This may be partially due to a feeling on the  part  of

potential users of the need for better understanding of the  physical

principles involved in this type of monitor. *    The present investi-

gation was undertaken to assess the current state of knowledge  of these

principles.  In addition, laboratory experiments vere devised to  determine

the important parameters involved in the operation of these  instruments.
    •^G.J.  Sem,  et  al,  "Instrumentation  for Measurement  of Particulate
 Emissions  from  Combustion  Sources", Vol.  I:  Particulate Mass, Therrao-
 Systems, Inc. APTD-0733,  (1971).

                                   -3-

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                             SECTION III



   THEORY OF CHARGING OF AEROSOL PARTICLES BY CONTACT ELECTRICITY







General Theory







It is necessary to discuss first the terminology used.  "Contact" elec-



tricity refers to charge transferred as a result of pure contact with



no sliding or rubbing.  On the other hand, "triboelectricity" involves


                                         1 2
rubbing (tribo is Greek meaning rubbing).  '     The latter may include



the transfer of material and local heating.  In the case of the



charging of aerosol particles, it is not clear which type of inter-



action takes place.  Probably all types are involved to some degree.



In the present work, we shall use the  term "contact" in discussing



the charging of particles, recognizing that other kinds of interactions



may well be present.







Pure contact is difficult  to achieve in practice.  Harper1   has succeeded



in some careful experiments with  large metal spheres.  His results agree



with the theory for  contact between metals.  When two metals touch, the



difference in the  contact  potentials of the two materials will cause a



flow of electrons  to  take  place.  The  buildup  of charge will continue



until the resulting  electric potential equals  the difference in  the two



contact potentials.
                                  -4-

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This charging of metals can also be described in terms of the quantum

mechanical energy band theory.1'12'13    In a metal, the energy levels

are filled up to a certain maximum energy, the Fermi level.  The

additional energy from the Fermi energy up to zero energy is called the

work function.  When two metals are brought into contact, the Fermi

levels will initially be at different heights (energies).  Electrons

will then flow  from the higher  to  the lower until  the two Fermi levels

are equalized.  At that time, the  difference  in work  functions gives  the

difference  in potential of the  two metals.



 In the case of  metals,  some charge can  flow even when there is  a  small

 gap between the surfaces  by the quantum mechanical tunnel effect.

 A serious complication arises during the separation of the metals.

 The air breaks down and an appreciable  back-flow of charge takes  place.

 The net charge transferred as a result  of the contact then depends on

 the magnitude of the backflow.



 The theory for metal-metal contact can be generalized to include semi-

 conductors.1'12    Whereas for metals  the charges reside on the  surface,

 for semiconductors there  are fewer electrons available  at  the surface

 and there will be a flow  of  charge from the  interior.   Since there  is

 now an appreciable resistivity, there  will be  an  associated time delay
     12"Static Electrification,  1971",  Proc.  of the Third Conf. on
  Static electrification organized by the Static Electrification Group
  of the Institute of Physics held in London, May 1971.  Conf. Series,
  No. 11, The Institute of Phys., London and Bristol.
     13"Electrostatics and Its Applications", A.D. Moore, Ed., John
  Wiley & Sons, N.Y., (1973).
                                    -5-

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with a time constant  in seconds given by 8.85-10   Kp, where K is the



dielectric constant and P  the  resistivity in ohm-cm.  This implies




that the amount of charge  transferred will depend on the duration of



contact.  Even for large spheres,  the time constant becomes too large



for appreciable flow  of charge in  the case of semiconductors having




high resistivity.








Insulators have an even higher resistivity so that there is no flow of



charge from the bulk  material. Surface states become the important



source of charge  for  transfer. Such surface states are complicated,




depending on  the  detailed  physical and chemical condition of the



surface.  Adsorbed ions giving rise to electric double layers play



an important  role.  Harper    states that the charge transferred



consists of ions  rather than electrons.  It may be mentioned also



that there is a class of insulators designated electrophobic which




apparently have no surface levels  available for contact charging, if




the surfaces  are  clean.  These materials include  some common plastics



such as nylon, lucite and  teflon.








In the case of insulators  particularly,  there are other charging mech-




anisms besides contact charging which may have to be considered, such




as electrolytic effects for moist  surfaces and  frictional sffects


                                   1 2
resulting in  transfer of material. '








The foregoing has been a brief review of  the  status  of knowledge of



contact charging.  The reader  is  referred  to  the  bibliography  for



further information.   He  can sumarize by saying  that our knowledge
                                  -6-

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 is  good  or  quantitative for metals but becomes progressively worse

 as  we make  the  transition to insulators.  This applies to ideal

 surfaces; in  real  cases, the charging mechanism may be drastically

 altered  by  contamination of the surfaces or by the physical condition.



 Charging of Aerosol Particles



 When the theory of contact charging is applied to aerosol particles,

 there are some  additional considerations.  We are concerned with the

 impact of the particle with a solid surface, a metal in the practical

 case of  a probe.  The charging is a dynamic process;**   the duration

 of  contact  is short, of the order of 10~9 to 10~10 seconds for our

 present  purposes.  Therefore, there will be no time for flow of charge

 from the bulk material for substances having resistivities greater

 than about  ID-*  ohm-cm.



 The surfaces  of metal particles will invariably be oxidized.  According

 to Harper,t1' such oxide layers behave as a metal with a work function

 of about 5.5eV. Most oxides are semiconductors; when the layer is

 thick, it behaves as a semiconductor.  If the layer is not too thick

 then, charge  can be transported either by conduction or by tunnelling.



A serious attempt to calculate the contact charging of metal particles

has been made by Soo and his collaborators.3'1^    Cheng and
   •^S.L. Soo, "Dynamics of Charged Suspensions", Topics in Current
Aerosol Research, Vol. 2, International Reviews in Aerosol Physics and
Chemistry, Pergamon Press Ltd., Oxford, (1971).
                                 -7-

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consider the impact of spherical particles in some detail.  This




theory greatly overestimates the magnitude of the charging.  Cheng




and Soo point out that the theory applies to clean surfaces; surface




contamination could have an important influence on the charge transfer.




In Appendix I, this theory is discussed in terms of the present




application.








In conclusion, some progress has been made in understanding the contact




charging of particles, but theoretical predictions are not yet quanti-




tative, and there is no theory available for insulators.
                                   -8-

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                             SECTION IV


         CONTACT ELECTRICITY MONITORS FOR PARTICULATE MATTER





Review of Instrument Development





An early version of an instrument employing a spherical metal probe was

                    o
described by Schiitz.     A later version of his instrument utilized a


probe-in-nozzle technique.     Prochazka  »    has described the develop-


ment of the Konitest, an instrument which was produced commercially for


a time.  In the Konitest, the electrode is a tube of a semiconductor,


steatite (magnesium hydrosilicate).  The gas is introduced radially


and the resulting helical path causes the particles to impinge on  the


walls of the tube.  In a second version, the tube is shaped as a Venturi

                                   g
nozzle.  Soo and his collaborators    constructed instruments using a


spherical metal electrode and also  a tubular electrode.  In the USSR,


Kisler     has described some contact electricity instruments including


a monitor using a wire probe.  The  IKOR Air Quality Monitor was apparently


independently developed and  is now  commercially  available.      It utilizes


a bullet-shaped Inconel probe in  a pipe.





In  all  of  the instruments mentioned above,  the  transfer  of  charge  to  the


probe by particles  colliding with it  results  in  a  current which  is con-


 tinuously monitored with  an  electrometer.   Some  other types  of  instruments


have been developed to  observe  the electrical pulses produced by  individual
    15S.  YA.  Kisler,  Mekh.  Avtomat.  Proizvod.,  2£ (9):  27-28, (1972)
                                 -9-

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 particles.   Min, et al.     described such a device whereby  particles

 charged by  wall collisions induce a voltage on an electrode.   Detectors

 for individual particles, however, appear to be applicable only  to

 large  particles carrying substantial charges.  Other types of  monitors

 have been developed which utilize electrostatic charging  of  particles

 but not contact charging.  Grindell 17  described a dust  monitor which

 charged the particles in a high voltage corona.  The particles were

 then precipitated on a collector electrode and the current determined.

                                        18
 In  the instrument developed by Coenen,     the particles  acquired charge

 by  repeated collisions with the plates of a high-voltage  capacitor.



 Characteristics of the Contact Electricity Monitor



 Some experimental investigations have been made of the  characteristics of

 the contact electricity monitor.  These investigations  are few in number;

 most are  under field rather than laboratory conditions.   On  some of the

 most important characteristics, there are contradictory reports.  The

 status is summarized below by topic.



 (1)  Electrical current vs. mass concentration.  In most  cases the instru-

 ments  are to be used as an indirect measurement of the  particulate mass

 concentration  in the gas monitored.  It is most important to establish

 the  correlation between the electrical current  from the probe  and the

mass concentration measured gravimetrically.   Schfltz   reported the
   16K. Min, B. T.  Chao,  and M.E. Wyman,  Rev.  Sci.   Instr. 34, 529 (1963)
   17D.H. Grindell,  Proc.  Inst.  Elec.  Engrs.  (London) 107A;  353-365,
(Jan. 1960).
   18W. Coenen, Staub  27.,  32  (1967).

                                 -10-

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following relationship for quartz dust:



                                I = akb



where I is the electrical current in amperes, k is the mass concentration



in mg/nr*, the exponent b ranges between 1.26 and 1.30, and a is inversely



proportional to the particle diameter.







On the other hand, Prochazka *>  found the Konitest to give an accurately



linear indication for concentrations from 0 to 3g/m^.  The dusts were



sampled at various industrial sites.  Ito, et al. ^  also reported a



linear relationship for a Konitest monitoring cement kiln exhaust at



the exit of an electrostatic precipitator for concentrations up to



10g/m3.  Schnitzler, et al. 9  found a correlation coefficient of 0.92



between the gravimetric mass and the Konitest reading for effluent from



a coal-fired plant.  The performance of the Konitest compared very



favorably to the best response obtained from transmissometers and beta



radiation attenuation monitors at the same location.





              Q

Cheng and Soo °  obtained plots of mass flow vs. probe current using coal



dust.  The plots show small deviations from linearity, being concave



upward.







Field tests of the IKOR Air Quality Monitor show that the integrated



current  (total charge) has a reproducible ratio to the gravimetric mass



for aluminum oxide.      Good agreement was also obtained between the
   19
    *T. Ito, H. Saito, and N. Furuya, Proc. Japan  Soc. of Air Poll.,

13th,  (1972), p.  247.




                                 -11-

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total charge and the mass concentration obtained with an EPA sampling



train.  These tests did not span a wide range of concentrations.



(2)  Dependence of the current on particle size.  As pointed out above,



Schiltz    found the constant a to be inversely proportional to particle



diameter.  Thus, higher sensitivity is predicted for small particles.


                                 o

On the other hand, Cheng and Soo    predict a current independent of



particle size for one experimental configuration.  They report that



this was verified by Min.  Ito, et al. 19  report the Konitest to be



little affected by particle size when sampling cement dust.
(3)  The effect  of humidity.  Water  layers on surfaces usually contain



dissolved  impurities.   Some  authors  believe electrolytic ions are


                                2                   1
important  for  contact  charging.      However, Harper    does not, and



tried unsuccessfully to obtain  an experimental correlation between



humidity and charging.








Schiitz ^   reported no  effect on his  instruments' performance  for relative



humidity up  to 99%.   He did  warn that droplets of water cause erroneous



indications.   Cheng  and Soo ®   point out that the conductivity of


                                                                    19
mineral particles increases  with the relative humidity.  Ito, et al.



state that humidity  caused no problems in their  tests of the  Konitest.



Kisler 15  states that the humidity  of the gas should be below the  dew



point.








(4)  Temperature effects.  Schiitz4   stated that the contact  electricity



monitor  should not be operated  above 70°C due  to the presence of thermal



emf 's.   However, a modified  IKOR AQM has been  operated  at  593°C.
                                  -12-

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(5)  Probe material.  With the exception of the Konitest, most instruments



have used metal probes.  According to Schfltz,    the use of metal for the



probe ensures that the charging will always be positive.  It seems clear



that this is a dubious assumption; in fact in field tests of the IKOR the



sign of the current has been found to vary with material and the standard



IKOR AQM is equipped with an automatic polarity-reversing circuit to



maintain positive indication on the recorder.







(6)  Composition of dust sampled.  Although  field tests have been conducted



with a variety of dusts, there has been no reported correlation of the



response according  to  some characteristic  of  the dust sampled.  Schtltz



concluded  that the  influence of the properties  of the material was far


                                                  19
less decisive than  the particle size.   Ito,  et  al.      stated that the



current obtained  for  a given mass concentration depended on the material,



but  that  for cement dust the electrical  resistance had  little effect  on



the  output.  Most users of the  contact  electricity monitors have  simply



empirically calibrated the monitor for  each  type of dust sampled.





                                         o

According t«j  the  theory  of Cheng  and  Soo,     the amount of charging



depends on the  electrical  conductivity, the  density,  and the  elastic



properties of  the materials  of  both particles and  probe.  (See  Appendix I)







 (7)   Discussion.  The above  review indicates that  the mass correlation



 observed by several experimenters is surprisingly  good.  However, there



 is need for additional work to clarify some of the conflicting reports
                                  -13-

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in order to identify the real problems associated with this type of




instrument.  There is also a need for tetter understanding of the




charging mechanism.
                                  -14-

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                             SECTION  V




                      EXPERIMENTAL MEASUREMENTS








Experimental Arrangement








Because of the Incomplete state of the theory of the contact electricity




type of monitor and because experimental information is sparse and




sometimes contradictory, a series of controlled laboratory tests were




devised to investigate the response of such a detector under various




conditions.  The goal was to determine the important parameters affecting




the operation and to try to understand these in terms of the theory.









The general arrangement is shown schematically in Fig. 1.  Room air is




drawn into a metal manifold 70 cm long x 3.2 cm inside diameter.  Inlets




were provided for adding humidified air and aerosol generated from test




dusts.  The manifold ended in the inlet of the IKOR Air Quality Monitor.*




Another inlet nearby led to an optical analyzer.  The main aerosol stream




passed the IKOR probe, through the filter  (or blank) and then was impelled




by the IKOR blower to the exhaust.








The airflow rate through the IKOR AQM was between 8 and  14 £/s  (17-30 CFM) .




The room air temperature was maintained at 23°C by  the laboratory air




conditioning and the relative humidity was stable over long periods of




time, being typically at about 50%.  Even on the most sensitive scale,




no room dust could be detected by the IKOR AQM.
*IKOR, Inc. Burlington, Mass.




                                 -15-

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                         Exhaust
                              t
                                         Figure 1.  Experimental Layout

               Double lines  denote pipes  for aerosol,  single lines  denote electrical cable.

                                         Hygrometer
                                                                     n
  Humidity
  Generator
       t
                                                              L
                                        IKOR
                                        Sensor-
                                        Probe
Gravimetric
   Filter
    Dust
  Generator
 Source of
Compressed
    Air
                                                    CLIMET
                                                    Optical
                                                    Analyzer
  Air Filter
and Regulator
                                                    Chart
                                                   Recorder
                                                                              IKOR
                                                                            Integrator
                                                                              IKOR
                                                                            Control
                                                                              Unit
                           Single
                          Channel
                          Analyzer
                           Multi-
                         Channel
                         Spectrum
                         Analyzer
                                                                                                                       Chart
                                                                                                                      Recorder
Counter

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The IKOR Air Quality Monitor








A Model 206 IKOR AQM was used for this work.  This unit consists of a




stainless steel sampling pipe, 2.4 cm inside diameter x 135 cm long,




connected to a flexible Teflon-lined hose 318 cm long.  The hose




conducts the aerosol  stream to the sensor unit where it passes




through a stainless steel pipe 2.4 cm i.d. containing an Inconel 625




probe shaped like a bullet and centered in the pipe.  At the widest




part the probe is 2.0 cm in diameter.  The probe is insulated and




connected to an electrometer circuit which is of a modern operational




amplifier (integrated circuit) design.  The electrical current is




read out on a panel meter and on a Rustrak recorder.  The readout is




linear with a switch for 5 decades of sensitivity.  During the present




work, the absolute current was determined with a Keithley 610 C




Electrometer; full scale on the IKOR meter ranges from 10~^ to 10~^ amp.




The IKOR unit was also equipped with a current integrator so that the




total charge accumulated over a period of time could be determined.  The




IKOR electronics was very stable, maintaining its zero setting and




calibration over two months of operation.









The airflow rate of the IKOR AQM is determined by difference in pressure




sensed by pitot tubes.  Thermocouples are provided for measurement of



gas temperature.
                                -17-

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The Optical Analyzer








A Climet CI-201 Optical Analyzer* was used to obtain an independent



measure of aerosol concentration.  In this instrument, forward-scattered



light is sensed by a photomultiplier.  The output of a count-rate meter




is displayed on a chart recorder with a  logarithmic scale.  The analog




pulses from individual particles were passed through a single channel



analyzer and then to a counter.  The analog pulses were also processed



by a 1024 channel pulse-height  analyzer  to obtain particle size spectra.



The system was calibrated with  monodisperse  latex spheres.  It was




determined that the spectrum analyzer operated between 1.0 and 5.5 microns.



The counter had a threshold set at  3.7 microns in order to reduce the




counting rate  to -manageable levels.








Dust Generator








The dust generator  devised for  this work is  shown in  Fig. 2.  Compressed



air is  filtered,  regulated, and passed  through copper tubing to a



hypodermic needle (hole dia. 4-10" cm)  positioned near the dust sample



in the bottom of  the  test tube.  The  jet stirs up the dust; the air



stream  containing entrained particles then rises past the washers




 (intended  to  intercept large particles)  and leaves  via the side arm.



The aerosol  stream then emerges as a jet which Impinges on the bottom




of the  second test tube.   This was designed to break  up aggregates and




to further disperse the dust.
 *Climet Instruments Company, Redlands, California






                                 -18-

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     Figure 2


  Dust Generator
                      Compressed Air
Hypodermic-
  Needles
   -19-

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The generator effectively discriminated against large particles or aggre-

gates.  For example, very little output could be obtained with stainless


steel particles with diameter 24-48ynu  Also, no appreciable output could


be obtained from a sample of carbon black particles 0.47ym diameter which


agglomerated strongly.  For all samples used, the peak of the size dis-


tribution as obtained  from  the optical analyzer was below one micron.

This was irrespective  of the size information provided by the supplier


of the sized samples.   In the case of stainless steel samples, a bimodal


distribution was obtained;  however, the preponderance of the particles


were in the less-than-one micron size group.




Samples used included  polydisperse aluminum oxide and polydlsperse aluminum.


These materials were replaced often in order to avoid depletion of the


smaller particles.  The remaining samples were sized in varying degrees.


Table 1 lists the characteristics of  the samples.




A maximum flow rate of 11 £/min was achieved by the generator, with dust

                                    •»
concentrations ranging up to 0.1 g/m  .  The maximum dust concentration

which could be generated depended on  the type of sample.  Also, the


stability of the concentration  level  depended on the sample characteristics.


For some samples, the  concentration was stable for extended periods,

for others frequent adjustments were  necessary.  With this generator,


tests could be run for about  one hour with  1 g of sample.
                                   -20-

-------
 Sample

 Titanium Dioxide


 Red Iron Oxide


 Silicon Dioxide

 Fly Ash


 Aluminum Oxide


 Glass Beads


 Glass Beads


 Molybdenum



 Tungsten



 Carbon Black



 Stainless  Steel


 Silver


 Copper


 Aluminum


 Aluminum
       TABLE 1

SAMPLE CHARACTERISTICS



   Origin

   P.I.S.* No.  2-12


   P.I.S, No. 25-4


   P.I.S. No. 10-6

   P.I.S. No. 14-1


   Ma theson, Coleman
   & Bell

   P.I.S. No. 8-7


   P.I.S. »o. 8-1


   P.I.S. No.' 19-6



   P.I.S. No. 19-1



   P.I.S. No. 2-6



   P.I.S. No. 27-1B


   P.I.S. No. 27-7


   P.I.S. No. 27-6


   P.I.S. No. 27-2A


   Unknown  origin
Remarks

0.45pm av. dia.**
10.3m2/g surface area

0.3-0.Sum dia.,
spheroidal oxide

1-4.Sum dia.

Hum av. dia., 82wt.%
less than 44um

Reagent grade powder,
polydisperse

3-8um dia.,
soda-lime glass

0.5-3um dia.,
soda-lime glass

4.4um dia.,  100% between
0 and lOum,  nonspherical
metal

l.OSum av.  dia., 100%
between 0 and Sum,
nonspherical metal

O.Olum av.  dia., 97%
between 0.005 and 0.017,
surface area 1000m2/g

6-12um dia., spherical
metal

6-9ym dia.,
spherical metal

5-150um dia.,
spherical metal

spherical metal,
0.5-6um

polydisperse
 *Particle Information Service, Grants Pass,  Oregon.
**Size information from P.I.S., however,  see  discussion in Sec.  IV concerning the
  observed particle size spectra.

                                      -21-

-------
Experimental Tests








Tests were performed  to Investigate the dynamic response of the monitor,



the correlation of the total charge to the sampled mass, the effect of




humidity, precharge effects, particle size effects, the importance of the



surface condition of  the probe, and the sensitivity for various substances.



These tests are described below.








(1)  Dynamic response.  The time  constant  (1/e) of the IKOR AQM is approxi-



mately 10 sec.  Since the Climet  optical analyzer is orders of magnitude




faster, an R-C network was added  to increase the Climet time constant to



4 sec.  Fig. 3 shows  the superimposed chart recordings of the two instruments




for polydisperse aluminum oxide dust.  Since the original IKOR record was



linear, it was necessary to transform it for the log plot.  It has been



pointed out before that a logarithmic display is advantageous for a



contact electricity monitor.








Some of the differences in the records, particularly the more extreme highs



and lows of the Climet t:ace, can be attributed to the 2.5 times shorter




time constant of the  Climet.  Of  course, there can be some real differences




in the instantaneous  concentrations at the sampling inlets.  Also, the



Climet sampled only the large end of the size distribution.








On the basis of many  such runs, it is concluded that the correlation of




the current records is satisfactory.  There is one difference which should




be mentioned.  Sometimes at the very beginning of a run, the IKOR AQM is
                                  -22-

-------
                 i'lgure
                               -.jsponse
                 Comparison of detector signals
               for polydisperse aluminum oxide dust
                                              IKOR AQM
                                              OPTICAL ANALYZER
0
100
200
300       400

Time, Seconds
500
600
700
                                   -23-

-------
much  less  sensitive.   The sensitivity may increase by  an order of magnitude




in the  first  minute or so.  This may happen even  if  the instrument has




been  previously running on the same dust, sometimes  even within the




hour.   This sensitizing effect will be discussed  further below in Sec. (6).








(2)   Correlation of total charge to sampled mass.  A series of runs were




•nade  with  polydisperse aluminum oxide to compare  the integrated current




from  the IKOR AQM to  the mass  determined gravimetrically.  Gelman type A,




142mm dia. fiberglass filters  were weighed to  0.1 rag.  Since the room




humidity was  very stable, the  filters were simply kept open to the room




throughout the operation.  Reproducibility of  the weights was found to




be within  0.1 mg in most cases.  Runs were about  20  minutes in duration,



with  the average concentration varied from run to run.








The results are plotted in Fig. 4.   The line is drawn  with a 45° slope




corresponding to true proportionality.   The line was located by eye.




It is concluded tliat  the proportionality is satisfactory over a factor



20 in concentration.








It is reasonable to expect a strictly proportional response.  If each




particle independently transfers charge to the probe,  that charge will




eventually be returned to ground through the electrometer.  Since the




probe is maintained very near  to ground potential by the circuit, there




should be no  charging effects.   One could imagine a  buildup of particles




on the probe  which would then  alter the response for subsequent particles.*




This, however,  would  shift the entire response curve.  This was not




observed during the aluminum oxide runs.   However, a shift was seen during
                                  -24-

-------
Figure
                        Charge vs. Mass for Aluminum Oxide
        Plot of total  charge from the IKOR AQM vs gravimetric

        mass of aluminum  oxide sample.  The line is drawn at

        45° (exact proportionality).
   100 r
01
-M
•H

§
0)   in
hd   10
6
                                                              o
                                               o   o
               o
       10
                                      100
                                Mass,  Mg.


                                -25-

-------
 the  succeeding aluminum measurements.   Mass correlations were also run


 for  the aluminum dust.   The results are graphed in Fig. 5.  The numbers



 are  in  sequential order of the runs.   There was a very close propor-



 tionality for a while,  then the sensitivity apparently decreased to the



 dashed  line.   Further discussion of this decreasing sensitivity will


 follow  in Sec.  (6).   It is concluded,  however,  that the response of



 the  IKOR is proportional to mass for both aluminum oxide and aluminum,


 i.e., an insulator and  a metal.






 (3)  Effect of humidity.  Moisture was added to the air by passing com-



 pressed air through warm, moist filter paper.   The relative humidity was


 measured by the wet bulb-dry bulb technique.  Using aluminum oxide dust,



 the  relative  humidity was varied from  45% to 69%.   No effect on the IKOR



 response was  observed.   The upper limii: to such an effect is estimated



 at 20%.   Incidentally,  the IKOR AQM cannot tolerate the introduction of



wet  steam.  This evidently causes electrode leakage and complete instrument


 failure until the probe structure is dry.   Problems from droplets have



been mentioned  by other authors.  *       The lack of humidity-produced



 effect  is an  indication that the charge transfer process does not involve


 surface electrolytic effects or that such effects  are not important.



The present tests did not investigate  possible  effects from very low


humidity.






 (4)  Precharge  effects.   From published work, it is evident that the



separation  of dust particles as in our dust generator results in electrical

                           20
charging  of the particles.       If the particles are charged before
          Kunkel, J. Appl. Phys. 21, 820  (1950)



                                  -26-

-------
   1000 r-
M
•4->
•H

£
100
Q>
bfl
ft
     10
                          Figure 5.   Charge  vs. Mass for Aluminum


                      Plot of total  charge from the IKOR AQM vs gravimetric

                      mass of aluminum  sample.  The lines are drawn at 45°.

                      Data points  are numbered sequentially.
                                                                                 I    I
                                     10
                                                             100
500
                                           Mass,  Mg,
                                          -27-

-------
encountering  the  IKSOR probe,  this  might  affect  the response.  We investi-



gated this possible  effect  by using a radioactive source to irradiate the



aerosol stream emerging from the dust generator.  This should reduce the



charge through the interaction between charged  gaseous ions and the


          21
particles.      A 1.2mCi Cd-109 source was  placed within a centimeter



of the 6 mm air tube,  which had a  thin Al foil  window to pass the



radiation.  It is estimated that 2-5R/hr was  incident on the aerosol



stream.  The  ratio of  the IKOR current for  aluminum oxide dust with



and without radiation  was 0.97 ± 0.28.   It  is concluded that no effect



was produced.







This finding  is reinforced  by the  observed  lack of effect of humidity.



If significant precharging  effects were  present, one would expect humidity



to have an appreciable influence on it.







(5)  Particle size effects.  Direct observation of particle size effects



would require the measurement of the complete particle size distributions



of the aerosols actually sampled.   Since only the > lym portion of the



distribution  was  measured in the present experiments, the information on



particle size effects  is more indirect.  However, there are several kinds



of evidence which are  persuasive as to a surprising lack of dependence of



the IKOR AQM  response  to particle  size.  Our  experimental evidence against



dependence on particle size includes:
   21D. Keefe, P.J.  Nolan,  and T.  Rich,  Proc.  R.  Irish Acad. 60, 27 (1959)
                                   -28-

-------
(a)  Many samples of materials were  used with  various quoted particle




    sizes.   There were obvious variations as  judged by eye.  The




    polydisperse Al and a sized (0.5-6 micron)  Al  sample gave closely




    similar results for the sensitivity in yC/g.   One glass bead  sample



    quoted  as 0.5-3 micron diameter and another 3-8 micron diameter




    yielded sensitivities of 0.46 ± 0.01  and  0.41  ± 0.03 yC/g.








(b)  The IKOR AQM flow rate was varied to  investigate the effect on




    sensitivity.  A variation of flow rate would affect the probability




    of impaction on the probe.  Also, the charging process could  itself




    be velocity dependent.  Both of these effects  involve particle size.



    Over a  variation of a factor of 1.7 in flow rate, the sensitivity




    measured gravimetrically changed by less  than  25% (standard deviation)



    for Al203, and by less than 18% for Al.








(c)  A crude test for response to very small particles was made with




    cigarette smoke from filter cigarettes.  The IKOR AQM barely




    responded to levels which were  off scale  for the optical analyzer.




    This shows there is an effective cutoff in the response to very small




    particles, no doubt due to the  fact  that  they  tend to follow  the




    stream  lines and hence fail to  impact on  the probe.  This test shows




    that the present instrument does not  respond inordinately to  very




    small particles; in fact, for sufficiently small particles it does



    not respond at all.
                                  -29-

-------
 In  summary,  these tests are not sufficient to rule out  a dependence on




 particle size, but they do show that such a dependence  is not pronounced




 above  the cutoff.  In Appendix I, it is shown that the  theory of Cheng




 and Soo predicts the charging to be dependent on particle size.  The




 overall response also depends on the probability of impaction on the




 probe.   This depends on the details of the instrument design.  Evidently




 the IKOR AQM is well designed in this respect.








 (6)  Surface condition of the probe.  Direct evidence was obtained that




 the condition of the surface of the probe of the IKOR instrument has a




very important effect on the sensitivity.  It was mentioned above that




 there  is sometimes a sensitizing effect at the beginning of a run.  It




was  also mentioned that the sensitivity changed during  the measurements




with Al dust.   On July 2, 1974, a series of sensitivity runs was commenced




with various substances, beginning with A^C^.   On July 30, upon returning




 to  A1203,  it was found that the sensitivity had increased by a factor of 5.




The  sensitivity for Al increased by almost a factor of  10 from July 10 to



August  1.








Between runs with different substances, the apparatus was thoroughly




cleaned.   The  probe was wiped clean with a dry cloth and replaced without




touching with  hands.   The probe has a polished  surface  with less than a




mirror  finish.   Some deep scratches can be seen.   After a run, no dust




could be seen  on the forward surface of the probe even  under close




scrutiny.  A light coating could be seen on the tail surface where the
                                  -30-

-------
diameter Is reduced, probably owing to the slower stream velocity there.




The reassembled apparatus was then run with clean air until no indication




could be seen on the most sensitive scale.









Following the last measurement with Al dust which indicated increased




sensitivity, the probe was cleaned following the instructions suggested




by the manufacturer.  This consisted of scrubbing the probe with an




abrasive cleaner (Ajax) and a nylon brush.  This was followed by a




washing with detergent and a thorough rinse.  Surprisingly, the result




was a lower sensitivity for Al, almost to the first value obtained on




July 10.









There would seem to be two possible explanations of the surface sensitizing




effect.  One would be a cleaning effect or exposure of fresh surface




produced by the bombardment by particles, analogous to sand-blasting.




The other possibility is that a coating of particles builds up on the




surface, altering the charging conditions, since particles would then




encounter other particles rather than the surface itself.  At present




the evidence is insufficient to allow one to decide between these two




possible explanations.  The author leans slightly towards the sand-




blasting hypothesis.









(7)  Sensitivity for various substances.  A variety of materials were




sampled to investigate the sensitivity of the IKOR instrument.  The




samples were chosen to cover a range of electrical resistivity, particle




size, particle shape, and chemical composition.  Many of the materials




are found in stack effluent.
                                  -31-

-------
In Fig. 6,  the measured  sensitivities have been graphed versus the date




of the measurement.   Because of  the  change of sensitivity discussed above




in (6) , the first measurements of Al^Os and Al have been arbitrarily




excluded, i.e.,  the  data from July 13-August 1 is used.  When these




data are arranged in the order of increasing sensitivity, it is found




that they are naturally  grouped  according to electrical resistivity




(see Table  2).








The value for fly ash is consistent  with its principal constituents,




Si02, Al203> and iron oxide. The resistivity of the glass beads was
10  ohm- cm, many  orders  of  magnitude less  than  the other insulators.




Molybdenum and  tungsten  have about  3.3  times higher resistivity than




copper.  Both were  described as  nonspherical particle samples and




both are brittle  metals.  Thus,  the area of contact for these particles




may be smaller, thus  reducing the charging.  The other metals were




described as spherical particle  samples.
                                   -32-

-------
Figure 6.   Sensitivity vs Date

Plot of sensitivity measurements for various substances
vs the date of the measurement.
3.0




2.0
CO
M
>>
•r-l
- rf
U
*fH
(A
c 1.0
(11
W
C/l








	


*

-
•
-

Ej
c
"E

^^

0)
0)

-U
en
0)
(0 M
0) Ol
1-1 p-l p.
C* W fii
•H > 0
« r-< O
4J -H y^
00 CO \£J
0 ©



o
•-I
PQ
C CO CU
o -o ••-•
,O CO Q)
t-i fl) CO
10 (0 C
U Ol 01 3
to T3 T3 H
/VJ » -H -H ^\
V«/ C9 X X V/
rH O O
O -H -r-t
_^ O Q 01
"w & C 3

< O 3 0 "x
•H U O
^s C2 4
3 ^^^
C
O) 
-------
                                 TABLE 2




                        SENSITIVITY MEASUREMENTS








  I.  Insulators                                      vC/g




          Titanium dioxide                        0.051  ± 0.004*




          Red iron oxide                          0.06  ±0.01




          Silicon dioxide                         0.09  ±0.02




          Fly ash                                 0.148  ± 0.005




          Aluminum oxide                          0.20  ± 0.01




          Glass beads 3-8y                        0.41  ± 0.03




          Glass beads 0.5-3y                      0.46  ± 0.01









 II.  Intermediate conductors, semiconductors




          Molybdenum**                            0.51  ±0.04




          Tungsten**                              0.67  ± 0.13




          Carbon black                            0.68  ±0.09









III.  Metallic conductors




          Stainless steel                         2.0  ±0.5




          Silver                                  2.0  ±0.2




          Copper                                  2.1  ±0.2




          Aluminum                                2.9  ±0.4









  *standard deviation




 **nonspherical metal particles
                                    -34-

-------
Carbon black is a semiconductor with a resistivity intermediate to




insulators and metals.








The ranking according to electrical resistivity can be understood in




terms of the characteristic time for charge transport.  For good in-




sulators, this time is large so that only the area in the vicinity of




the contact is involved in charge transfer.  The area is larger for




semiconductors.  For metallic conductors the charge can probably be




transported from the entire particle.  The oxide layers on the metal




particles are presumably thin enough so that they can be penetrated




either by electron tunnelling or by conduction with a small time




constant.  The dependence on electrical resistivity is further discussed




from a theoretical viewpoint in Appendix I.








These data provide a basis for predicting  the sensitivity  for other




substances, at least  for dry dusts.  It is likely that they will  fall




within the range spanned by the table.  The wide range in  the sensi-




tivities  (factor of 60) has some implications for the detection of




components of a mixture.  A small amount of an insulator would be




difficult to detect in the presence of metals or even semiconductors.




The charges per particle implied by the data of Table 2 are not




unreasonable.  However, we must regard the sensitivities listed as




lower limits until the question of the probe surface  is cleared up.
                                   -35-

-------
                             SECTION  VI

                              REFERENCES
 1.  W.  R.  Harper,  "Contact and Frictional Electrification", Oxford U.
     Press,  Oxford,  (1967).

 2.  L.  B.  Loeb,  "Static Electrification", Springer-Verlag, Berlin,
      (1958).

 3.  A.  Schutz,  Staub 24. 359 (1964).

 4.  A.  Schutz,  Staub £6, 18 (1966).

 5.  A.  Schutz,  Staub-Reinhalt der Luft,  Band  26  (1966) No. 5, Seite
     198/201,  1-4.

 6.  R.  Prochazka,  Staub 24, 353 (1964).

 7.  R.  Prochazka,  Staub 26, 22 (1966).

 8.  L.  Cheng  and S.  L.  Soo, J.  Appl.  Phys. 41, 585  (1970).

 9.  H.  Schnitzler,  SchrReihe Ver.  Wass.-Boden Lufthyg, Berlin-Dahlem,
     V.  33,  Stuttgart (1970).

10.  IKOR,  Inc., unpublished reports,  and private comm. from A. H.
     Gruber.

11.  G.  J.  Sem, et  al,  "Instrumentation for Measurement of Particulate
     Emissions from  Combustion Sources",  Vol. I:  Particulate Mass,
     Thermo-Systems,  Inc.  APTD-0733,  (1971).

12.  "Static Electrification,  1971", Proc. of the Third Conf. on static
     electrification  organized by  the  Static Electrification Group of
     the Institute  of Physics  held  in  London, May 1971.  Conf. Series,
     No. 11, The Institute  of  Phys., London and Bristol.

13.  "Electrostatics  and Its Applications", A. D. Moore, Ed., John Wiley
     & Sons, N.Y.,  (1973).

14.  S. L. Soo, "Dynamics  of Charged Suspensions", Topics in Current
     Aerosol Research, Vol.  2,  International Reviews in Aerosol Physics
     and Chemistry, Pergamon Press  Ltd.,  Oxford, (1971).

15.  S. YA. Kisler, Mekh. Avtomat.  Proizvod., 2£ (9):  27-28, (1972).

16.  K. Min, B. T. Chao, and M.E. Wyman,  Rev. Sci. Instr. 34_, 529 (1963).
                                  -36-

-------
17.  D. H. Grindell, Proc.  Inst.  Elec. Engrs. (London)  107A;   353-365,
     (Jan. 1960).

18.  W. Coenen, Staub 2T_y 32 (1967).

19.  T. Ito, H. Saito, and N.  Furuya, Proc. Japan Soc.  of Air Poll.,
     13th, (1972), p. 247.

20.  W. B. Kunkel, J. Appl. Phys. 2^, 820 (1950).

21.  D. Keefe, P. J. Nolan, and T. Rich, Proc. R. Irish Acad. 60, 27
     (1959).                                                  ~~
                                  -37-

-------
                            SECTION VII

                            BIBLIOGRAPHY
I.  Static and Contact Electricity

        W.R. Harper, Proc. R. Soc. A205, 83 (1951).  The Volta effect
        as a cause of static electrification.

        F.A. Vick, Suppl. No. 2, Brit. J. Appl. Phys. (London) (1952).
        Theory of contact electrification.

       "Static Electrification", L.B. Loeb, Springer-Verlag, Berlin,
        1958.  A classical reference, somewhat dated.

       "The Electrical Behavior of Aerosols", K.T. Whitby and B.Y.H.
        Lui, Chap. 3, "Aerosol Science", C.N. Davies, Ed., Acad. Press,
        N.Y., (1966).

       "Contact and Frictional Electrification", W.R. Harper, Oxford,
        1967.  The best  single source of information on static electri-
        city.

       "Static Electrification", Proceedings of the Conference organ-
        ized by the Institute of Physics and the Physical Society,
        Static Electrification Group, London, May 1967.  Inst. of Phys.
        and Phys. Soc. Conference Series Number 4.

        A. Schutz, Staub 27_,  (12) 24  (1967).  Electrical charging of
        aerosols.

       "Fluid Dynamics of Multiphase  Systems", S.L. Soo, Blaisdell
        Publ. Co., Waltham, Mass. (1967).

       "Electrostatics", A.D. Moore,  Doubleday & Co., Inc., Garden City,
        N.Y., 1968.  An  entertaining  account, particularly of electro-
        static machines.

        L. Cheng and S.L. Soo, J. Appl. Phys. 41. 585 (1970).  Charging
        of dust particles by  Impact.

       "Static Electrification, 1971", Proceedings of the Third Con-
        ference on Static Electrification organized by the Static
        Electrification  Group of  the  Institute of Physics held in
        London, May 1971.  Conference Series, Number 11, The  Institute
        of Physics, London and Bristol.  These proceedings and the
        1967 proceedings listed below constitute excellent reviews of
        the status of the field.

       "Dynamics of Charged Suspensions", S.L. Soo. Topics in Current
        Aerosol Research, Vol. 2, International Reviews in Aerosol
        Physics and Chemistry, Pergamon Press Ltd., Oxford, 1971.

       "Electrostatics and Its Applications", A.D. Moore, Ed., John Wiley
        and Sons, N.Y.,  1973.  A  very recent review of the field by
        authoritative authors.

                                  -38-

-------
II.  Experimental Work and Contact Electricity Monitors

         R.E.  Volrath, Phys. Rev.  42, 298 (1932).  Development of a
         high voltage generator reaching 260 kV using blown dust.

         W. B. Kunkel, J. Appl. Phys. 2^, 820 (1950), "The Static
         Electrification of Dust Particles on Dispersion into a Cloud".

         J.A.  Medley, Br. J. Appl. Phys. Supp 2, S28 (1953a).  Investi-
         gated the effect of applied electric field on contact potential.

         D. Keefe, P.T. Nolan and T. Rich, Proc. R. Irish Acad. 60_ (4),
         27 (1959), Charge equilibrium in aerosols according to
         Boltzmann's Law.

         D.H.  Grindell, Proc. Inst. Elec. Engrs. (London) IOTA:  353-
         365, Jan. 1960.  Particles charged in a high-voltage corona
         were collected on an electrode.

         K. Min, B.T. Chao, and M.E. Wyman, Rev. Sci. Instr. 34,
         529  (1963).  Measurement of charge on single particles in solid
         gas suspension flow.

         R. Prochazka, Staub 24, 353 (1964).  Data on the mass cor-
         relation of the Konitest current, early Konitest reference.

         A. Schutz, Staub 24, 359 (1964).  New arrangement for dust
         measurement.

         A. Schutz, Staub 26, 18  (1966).  Principal reference for the
         measurement by Schutz.

         A. Schutz, Staub-Reinhalt der Luft, Band 26  (1966) No. 5,
         Seite 198/201, 1-4, Registrierendes kontactelektrisches
         Staubmessgerat mit logarithmischer Anzeige.

         R. Prochazka, Staub 26, 22  (1966).  Recording dust measure-
         ment with the Konitest.

         W. Coenen, Staub 2_7_, 32  (1967).  A battery-powered device
         charging particles by causing them to bounce between high-
         voltage plates.

         E.E. Weaver and Clyde Orr, Jr., "Atmospheric Contamination
         and Triboelectrification", Georgia Inst. of Tech., Atlanta,
         GIT-B-366, APTD-0629, 1 June 1968—31 May 1970.  Investigated
         triboelectrification between various substrates and platinum
         in the presence of various gases and vapors.

         W.J. Megaw and A.C. Wells, Nature 224.  689  (1969).  "Pro-
         duction of Monodisperse Submicron Aerosols of Which Each
         Particle Carries a Specified Number of  Electronic Charges".
                                   -39-

-------
II.  Experimental Work, and Contact Electricity Monitors (Continued)

         J. Kolar, Tech, Ueberwach (Duesseldorf) 10 (6):  188-190,
         June (1969).  The functioning of a Konitest in heating plant.

         N.A. Fuchs and F.I. Murashkevich, Staub 30. 1 (1970).  Dust
         generator with automatic feed and method for reducing particle
         charging.

         G.J. Sem, et  al, "Instrumentation for Measurement of Particu-
         late Emissions from Combustion Sources, Vol. I:  Particulate
         Mass, Thermo-Systems,  Inc. Report No. APTD-0733, 1971.  In-
         cludes a critical discussion of the Konitest.

         J.R. Melcher  and K.S.  Sachar, "Electrical Induction of
         Particulate Agglomeration", Mass. Depart, of Tech., Cambridge,
         APTD-0869, 10 Aug, 1971.

         T. Ito, H. Saito, and  N. Furuya, Proc. Symp. Japan Soc. Air
         Pollution, 13th, 1972, p. 72.  Continuous Dust Collection
         Measurement Konitest.  (in Japanese)

         S. YA. Kisler, Mekh. Avtomat. Proizvod., 26_ (9):  27-28, 1972.
         Monitoring of Concentration of Disperse Phase of Aerosol
         Flows by Electric Contact Method.  (in Russian)

         A.K. Kamra, J. Appl. Phys. 44, 125 (1973).  "Experimental
         Study of the  Electrification Produced by Dispersion of Dust
         into the Air".
                                 -40-

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                            SECTION VIII


                              APPENDIX


          THEORY OF CONTACT CHARGING  OF AEROSOL  PARTICLES





Review of the Theory





The theory developed by Cheng and  Soo^8'     involves  the transfer of


charge during a collision between  two elastic  spheres of radii a,  and


a, .  During the impact there will  be  a mean  area of contact  A^  last-


ing for At, both of these quantities  depending on  the kinematics of


the collision and the elastic properties of  the  materials.   While the


spheres are in contact, the current density  will be proportional to


the voltage difference between the two spheres.  If the current is


integrated over the period of impact, the  charge transferred is


obtained:        ^ = _^f_ ^ .  cpl}  p x . ^orA^





where   C,,2 are the electrical capacities of  the  spheres


        <)>!,2 are the work functions of the materials
                                      Ci+C2
and                     a  =  A2lh2l •
        h2i, the charge transfer coefficient,  is given by


                                 CTl CT2
                               di 
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    The transfer lengths are defined by the equations



                   CTi                CT2
where J2,  is  the current density and Vc is the potential at the point



of contact.   Thus dj_ and da  are the effective distances in the material



over which current is transported.
    Now Cheng and Soo derive the following expressions for A21 and At

                              rt aj,a2

                              - -  ' a
                              &! + aa     i

                                 2.9*+

                                -
i   COS 9     "i
 21




   I* nns O /  ~J-~*= 1 / ~1™2 \ ~ fv.j.V_
 21,
                  „            u     cos 9      .              (ki+k
                                           v

     (note:   ce   is distinct from <* )
              i


    with   r* the ratio of the rebound speed to the incoming speed
           ,,  is the velocity of approach



          0   is the angle of impact



         nij  2   are the masses of the spheres
           )


    an<^  k,  2  are elast^c parameters given by



                              k =     *

                                    TT E




and   x^  is Poisson's Ratio, E the modulus of elasticity.







Application to the Present Problem







It is instructive to evaluate numerically some of the above quantities



using reasonable values of the parameters.  Take sphere 1 to be  the  aerosol




                                   -42-

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 particle and sphere 2 to be the probe.  Then
     Using k,  = k, = 3.10~13 cm2 /dyne

             0=0

             p~!  = 8g/cm3 (density)

             aj  = 10  cm
                        f\
           AU2,  = 1.5-10 cm/s (typical for the IKOR AQM)

             r* = 1
    we find that
                  3 • 10  cm
                      -10,
At - 6-10
               '= Tra^j  = l*10~i:Lcm2
The short duration  of  the impact implies that the theory applies only
                                         f\
to metals or  good semiconductors (p Z 10  ohm* cm) since only then will

there be appreciable current flow.   The area of contact has a diameter

roughly 1/20  of  the particle diameter.



Dependence of Q2i on the  Parameters



The coefficient  ex  depends  on,h21 .   If  we take di"=3 and d^ =  a2   ,  the

remaining variable  is  o^  ,  since (T2  is fixed (metal probe).



    When P,<  10 ohm-cm, l-e"aAt = !>
and

                                   -43-

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This equation results because  the  resistivity is small enough to allow



complete charge  transfer within  the  contact  time At.
If pl > 10 ohm-cm, Q2 j  is  reduced  by the  factor  (1-e a  ).  For example,



when Pt = 10  ohm»cm,  (l-e"Q^ |t)  =  0.05  and  only  5% of  the charge is trans



ferred within At.  The theory,  therefore, applies only to metals or very



good semiconductors.
Q21 is  the  charge  transferred per particle.   The  total  charge  transf-



erred to or from the probe is given by



                     QT * N,  Q21



where N, , the  number of aerosol particles,  is given  in  terms of  the  total



mass of particles,  MI , by

                              M
                          •*    3 _
                          — IT  a  p
                          3    1 Kl



                           _2

For PI  <  10  ohm-cm, QjX? ai  •   Thus the theory predicts that the total




charge  transferred to the probe is inversely proportional to the par-




ticle radius squared.  Also, for Pj  < 10 ohm* on, the charge transferred




is predicted to be independent of the velocity of the particles rela-



tive to the  probe.








Magnitude of the Charge Transferred
 Consider metal particles with a radius of O.OSum.  Assume that cp2-cp



      1 volt.   Then QJI = 10~17 C/particle.  Furthermore, QT = 2000
                                   -44-

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This is three orders of magnitude greater than observed (See Table 2).




The calculated charge could be brought into agreement with experiment




by assuming that the particles had an effective resistivity of 5.10




ohm-cm which is in the semiconductor range.
The oxide layer on the particle surfaces could easily increase the




effective resistance, not to mention contaminant layers on the surfaces




of the particles as well as on the probe surface.








Summary of the Theory








While the theory is not quantitative, the model may still be useful




in understanding the dependence of the charge on the physical para-




meters.  However, the theory cannot as yet be regarded as verified by




experiment.








The above theory applies only to metals or good semiconductors.  For




materials with f> > 10  ohm-cm, which includes most semiconductors and




all insulators the charge transferred is that already on  the surface




in the area of contact.  In the absence of detailed knowledge of the




physical processes involved, it is not possible to carry  out the




analysis for  the charging of insulating materials.
                                  -45-

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing}
1. REPORT NO.
  EPA-650/2-75-043
                                                           3. RECIPIENT'S ACCESSIOWNO.
4 TITLE AND SUBTITLE
       Investigation of Participate Matter
       Monitoring Using Contact Electrification
           5. REPORT DATE
             Feb ruary 1975
           6. PERFORMING ORGANIZATION CODE
7 AUTHOR(S)
       Dr. Walter John
                                                           B. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORG MMIZATION NAME AND ADDRESS
       California State College, Stanislaus
       Turlock,  CA  95380
           10. PROGRAM ELEMENT NO.

              1AA010
           11. CONTRACT/GRANT NO.

              802726
12. SPONSORING AGENCY NAME AND ADDRESS
  Chemistry  and Physics  Laboratory
  National Environmental Research Center
  Research Triangle Park
  North  Carolina  27711
            13. TYPE OF REPORT AND PERIOD COVERED
              Final Report	
            14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
  The theory of the charging of aerosol particles by contact electricity  is  reviewed,
  as well as the development of monitors for particulate matter "based  on  this
  principle.  Data on the  performance of these monitors is scarce and  sometimes
  contradictory.  In the present work, laboratory tests were carried out  with  a
  variety of test dusts.   The results show that the dynamic response of the  contact
  electricity monitor tracks well with that of an optical detector.  The  total charge
  correlates well with  the gravimetric mass.  Humidity or precharge on the particles
  did not influence the detector.  Some evidence was obtained  showing  that particle
  size  does not have an important effect on the response, although there  is  a cutoff
  for very small particles.  Results for the sensitivity of the instrument can be
  grouped according to  the electrical resistivity of the material.  It is found that
  the condition of the  surface of the Inconel probe has a major effect on the
  sensitivity.  Additional work is necessary on this aspect of the detector.  The
  theory of Cheng and Soo  for the charging of metal particles  is discussed.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                              b.lDENTIFIERS/OPEN ENDED-TERMS
                           COS AT I Field/Group
  Monitors, Electrostatic charge, Dust,
  Particles, Fly ash,  Konimeters, Sampling
  probes,  Electrostatic measurement methods,
  Electric charge,  Triboelectric charging
Pollution measurement
methods, Continuous
monitoring methods,
Particulate sampling,
Contact electricity
 1302, 2003,
 1711, 2102
18. DISTRIBUTION STATEMENT

   Release Unlimited
. SECURITY CLASS (ThisReport}
Unclassified
21. NO. OF PAGES
      52
                                              20 SECURITY CLASS fThis page)
                                                Unclassified
                         22 PRICE
EPA Form 2220-1 (9-73)
                                             46

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