CONCERNING INVESTIGATION OF THE GRAPHITIZATION PROCESS

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP82-00039R000100100041-5
• Release Decision: RIPPUB
• Original Classification: C
• Document Page Count: 28
• Document Creation Date: January 4, 2017
• Sequence Number: 41
• Publication Date: January 22, 1951
• Content Type: REPORT

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CONC~iN1NC? INV~aTICATICN AF TAE C~hITI~ATIQN ~p,QCE9S
~
by P. 8ozhko 1
(Laboratory o~ ~,ectrochQmistryi
Stato Institute Af Applied Chemistry)
submitted far publication on
19 February 1936�
of work on graphitization done by GIPKh (state Institute
r~ome r�eults
in 1 2-1933 ar� included in this paper;]
of Applied Chemistry) 9 3
odifica~~ians of carbon r�present conglomerates of graphite
1 ~ A11 black m
vas in size Ther� is no such thing as amorphous carbon
crystals which may 'Y
n are forn~d as a result of tie decompoeitian of organic
,hen stoma of carbo
5 sate/ become oriented ~ Ny means oi' the free val-
substances= they imm~d y
s formed in this manners adsorption of re-
er~cies of end atoms of crystal
arbons takes place This direction of the pro-
sidues of d�compo~ ng hydroc
ies of the carbon atom referred to as its
cess is determined by t?he prapert
~+met ~~tic quality" ~1)~
s
tion must be regarded as one oi' the growth of '1
't'he process of graphitira
i
oa
ra bite to a lamer size. The basic characteristics of
small crystals of ~ ~
~k ~ in Arndt and ~'ollack + s work on a Wombat of
this process were clarified ,
materials (2). They came to the conclusion that in the process
f;
carbonaceous
n at 2l~~0� } the recrystallization of carbon proceeds in
o� graph~~tizatio ( ~
n in the case af' metals (according to
a manner similar to that occurs g
ry
ferences ~.n the ability to graphitize are due to
Tammann), and triat dif
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i~'~'~r~~~cc~ in the i~it~~ stru~turc tk~o aarbaaF~ccpua zaater~-~c ~ Tho
d
~ tcr~c~oncy ~n tk~a ~-~ar~ a~' ar~~k~ruA~~o cr~l c~~~rooul ~o ~r~.?}n~t~,~c io
lack
duc to i~~uf'ficier~~ ~ro~t~.m~,t~? irdivid~~~ cl~x~cc~~Ge tk~o otructuro
i ~ o ~ ~,~adcauatc dc~~e ity) . l~ the 4 s~ ~ anthracit�a liar a truaturo ~
~ ,
and in the ca~c of charca~l a fibrous atr~cturc pr~vcnt ~ra~l~itl~,atio~~~
s a rccult of studying the ~raphitizatio~ off' ~~Qtxoloum coke ~3), Arnfclat
ca~~tc to the concl~~Aion that the ~rowtk~ ~f ~ra~?hite crystals rQp~~oocnts an
~,nsta~~cc Af the ~roWtkl A~ t.~~.dim~~~cional ~?aral~.cl 1ay~rs fog}~~in~ a layer
latticc~ Acc~rr~~:n~ to Arnfcldt, thQ proeoaa cjf ~ra~k~~ti2,ation is a slow
ar ~'orr~tion A~' ty~~ica1 layer latticco~ {?s tl~c rate of
cr~rstalli~ati~n un~i
di~'~'uolon in aolido ~s slow and the diroctivQ ~'orCQS ~~ctin~ ~~arallal to the
1a Fors tl~o f~~tu~~ lat~?ico aro weak, the ~aroccas off' cryat~lli~ation ~'~ust
bs slow in this ~~articula~~ caso~
the ~r~ hiti~ation a num~~cr of inatcr~.als, V~s~lcvskiy
~:t~vestiGatin~ ~
~~~rx~tsav ~ hnve s~?own that the char~~e cf ~~ropertiQS in the course of
and ( )
trc~`~`~1k~~tl~ation takes ~~lace in a r~artic~larly abrupt manner in a definite
~i P
temt~erctttr~~ ~.ntc~~~val, ~'he9e s~.thors consider tht~~t its tl~e te~,~,erature in-
ttr~~va]. in qur.stiori "a t,rar~s~:tidn of coal From a collnidall~f dis~~ersed stat4
reel dist.crsed state" takes ~lcce~ ~'tsti as ~lrndt and !#ollack,
to a caa Y
tlic are of the apin~cn shat the pr�cess df ~r~?~,hiti~r~ation grocneds according
y
vernin the thermal rr~crystalli~ation of polycrygt~lline substances
to laws ~c ~
e e~'~ect of ash canstit7acnt� w'rL3~ch according; 'to Achescn ~~romote trap.
TE7
is den~,ed ~ Veselorrskiy anr3 1~ertsov, while Arndt and ~c?llack
h~ t~~~ation (5) Y
cons Eder that, they even may l.mpcde ~ra~~hiti~ation ~ Arnfeldt is of the
o in~.on that d~.~'~us~.c~n of carbon is ccnsltlerablf irnl~cded ~.n the liquid phaso,
so that the presence ash in a cart�r~aceo~as material has a favorable
tf~ect an ~raphitixation~
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II
1~
tbo Ar@~�nt ~a~or Dome roeulte on tno ~re~b~tizetion o~ anthracito
end ntk~~r cerboneoaauc m~torielo uro re~~orted~ Tl~e~e results indiceto that
a~k~ constituents uctivoly ~art~.ci~ato in ~re~hit~zetlon, end Chet ~urtk~~ormare
tk~oir ~-~sian end eva~oratinn determine tk~@ sher~ost ck~en~o in ~ number o~
~ro~prtiQ� of tbo matpri~e being gra~~hitiz~d~ This ~pplice ~~ertieul~rly
to entk~racite
~ a
2 ~ t;re~hitiz~tion was cerr-led out in Temme~n #~u~~u1 1'urnae� illustrated '
in ~'i~ura 1. `o'ho ~Qm~~orat4~r� wee controlled by ~~ceno of ~ ~iolb9rn�kurlbe~~
c~~tic~1 ~~~rrometor. The ~rQCiciAn Af ~crnk~eretia~~� moasurement at 200� wa�
30�~ ~n tho sa~~~les undor i~~veetige~ion, t~4~ s~~ci~'ic el~ctrica~. res-k;r;ts ~asir~, 'fable l lists the
o~-;ecific res~:stances, densities, ash content, aYtd igr~~~?i=nn ~~o~.nts ~'or sam~~l~~s
which hc~~te bCOn ha~tcd ct 600� ~'or one haur~~ `J'he ~ies~:s~~nco was determined
can powders ot -?~~12~ mesh on an Arndt a~~jaratus (2) at ~ ~resr~ure of
i1~ ~ 6 kg/cm~
~~ong ~~he mr. f~ralc 1~.~~ted iri that table, petroleum coke and tar coke
were the most uniform, while tine presence df inhomog�neous particles was
ap~arer~t in the cas� of ~~otroleum coke '~hP high res~stf~nce of tar coke
c ke a~~d etrQleum coke is ntly due to its
in compar~.shn with ~'oundzy o ~ ~
lower temr~erature of formation (600�)~ All hf the coises had a~prox~.matel~r
the same deno ~.ty~ ~'hg ash content is highest ~.n Foundry coke 'the ~nt~~racites '
n re and to densit and partict~~.asly as far as electrical
d:~f~'er Pram coke i g Y
res~.stgrice is concgrrred~ Their higher resistance i5 apparently due to the
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k~ ~
c st~botar~aoo which had na~t yot d@oomposod~ Anthraa~t@~
p~�ocono@ Qrg~ni
1 aro dictir~guishcd by a ~'i~o l~yor otruoturo which i~ barely
K, end No
to thQ o e. An broak~.ng troy dorm a cmooth, slightly oocklo-
p~''coC tib'1Q Y
etlapod euri'aoo~
i~itization ~0 gr o~ ~aiaoes having dimonaior~~o~ X0.30 milli-
~or grail
usad~ A cor~proseea packa~� o~ this re~,terial wao placod in tho
r~~ta~a wo~a
!~Q carbon tubo in �~~ch a manner that it ocaupicd approxi~nat�ly
c~entor of t
ers of the tub�~ a ~�ngth~ ~roliminary ox~+erimcnto oatat~liehed
20 centimat
rou ~ distance 2A cer~~time�ter� the ,t�m~,oraturo gradient at
that th g
,
2A0� dose not e~~ceed ~A�
r c~~ar in th� tubo~ tho tempcrat~~re was raised to tho required
{#~to g g
1 ring 1 hour anr2 t~1e samples were then kept for 1 hour at the final
po int d ~ ~
r " some ex ~crimonts are listed in tab~:es and
tem~erature~ lea alts ~
es ~'or cam~arisan tl~e corr~~s~~ondin~, data on the initial materiala~
Tablo 3 cit t
res~~l~~e o~ tl~e exr~eriments show that the initial materials ears bo
The
to two ~rau;~n on the heals o~ the res~~lting grat~hit�~ s electrical
d ivid Qd in 1,
stance; cokes a.~d arithracites~ From this ~~oint o~ view, petroleum
resi
e ds the best results ~ 1'ar soles and ~'aundry coke are slightly in-
voke yi 1
j to Ptroleum colca~ Tar ccl~a exhibits a relatively high ash content
ierior p
a~tcr ra hiti~a-tlon, w~~ich is apparently due to the fact that its bores
~ ~
closed so that the s.sh canna volatil~.~e acid escape From lamer pieces
are ,
a earance ~zs cc~ncdrned, tl~c: samples o~ coke are not
Ag far as external pp
bl in the course of ~raph~.ti~ation~ They also do not
changed perceE~ti y
r
han3cal et~ank;en ~ Auer graphit~.~at:tan the various types off'
undergo any' me c
airs a silvery grey ccalor, wh~.le remaining; very hard
Coke acq
he behav~.or of an~,hrac~.tes is ant3xely d~,~'erent~ As distinguished a
T
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coke anthrac~.teg after graph~.tization split into plates which swell
~ From ,
he 1 erg thug increasing the volume o~ tt~e material
perpend~.culgrly tat ay ~
6 U on owder~.ng graph~.t~.zed anthrac~.te yields a go~t~
by a Factor o~ ~ to p p .
+~e
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p. [
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soak ~rsYphito rosamblin~ n~t~~ ~rapk~ites "with respect tc to~tu~co and
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atr~~oturo�~, taut di~'f@rin~ dram tk~e 1F ttor in that it Q~hibit�a higher
roaotivity, As oan bo assn from tho tablAa~ the �pocifio ~lootriaal ro~-
i�tanc� o~ ~raphit#~e~ ~ep~red from a~thracito is ve~? hi~h~ namely times ~
hi hRr than the resistance Af graphitized petroleum coka~ Thin hi~i~ res-
i~~~anc� is duo to the lsYyer structure of tk~e powdery the platelets ai' which
lie arallel to each othor wk~an the reeistanc� is mcasurad, For that r�ason
P
the resistance meas~rad by this mQthod is not characte~~istic for ~raphi+~i~ed
anthracite� The dens~:ty of graphitized anthracite is not lower, but superior
to that of the graphite obDain�d from coke, fibs ash content of anthracite
remains p~~etty high after graphitization and amounts to ~l�0~� This cir-
cums~tance is due to the difficult removal o~f ash from lame pi~oos and to
the swelling of these piec�a� tip�riments ors Che ~raphitizatior~ of fin�
anthracite powder in an Acheson furnace have shown that in thin case the
ash cont�nt drops to 0.1-0� 3~� While swelling o!' fine anthracite powder
also actors, i4 is not so extensive because of the small size off' the par-
ticles, It is noteworthy that Vino anthracite powder on graphitization has
over resistance than graphitized course pieces (0,010-00160 ohms
a much 1
per centimeter as compared with 0�0315 ohms per centimeter)�
The eculiar behavior of anthracit� in ~raphitiza~ion was no~~iced
3 p
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b ~Yhe author of th~~s pa~~er ~iri his e~:rliest work � ~t was found that
Y a
1; rature is raised slowly in the ~raphitizat~ion of anthracite
e
Wl~ en th@ temp .
i
1.um s in a furnace of the Acheson type (30 kilowatts) with a coke filling
p
yx
f
or on a coke bed, the lumps ni' at~t~~racite do not crack, but swe~.~. ~,n a
k'
n er endicu~.ar to the layers, increasing in volume ~-6 tim�s�
di.rectio p p
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rt~~ ~Lu~?~o
~~~oc�s Q~ antl~rac~.to
~xtrcmoly ao~t and olaatic ~ Ae ~ result
v n ~ im act in the direotion across ttl~ ~,ayoro, the awollcn pieco~
Ai' racQi i ~ ~
is flattened into ~ plate wbiol~ io bighls? flexible and has r~cchanicel prop-
rtie� resembling those of tho ~ra}~hiti~~ed thready obtained ~irani end
has 6 ~ Thin compressed plates obtained Pram swollen pieces can be
~c ( ~
rolled into tubQS kithaut breaking and can bo i'revly cut with a kni~o~
of the clo~~tric~l reeiatanco of a plate cut from awell-
Detarminations
swollen ~~iec� showed that across the layers � 0.032? ohms cm, whilo
along the layers � 0~006~ ohms~em~ ~'has� figures Qxplain the high res-
istance of the product from anthracite powdery and also demonatr'ate that
the resista~tice slang th� layers does not di~'fQr much From the resistance of
ra hiti~ed coke The detern~n�~tions of electrical resistce were carried
C ~
out on a plal;o from a swopon piece of anthrac~:te {~~,thout subnit~ing the
late to any sort of treatfi~?et~t~ Con�eq+~ently rho plate retained hollow
p
spaces insid�~
As has been indicted above a.nt~~racite cracl~s into plates during
ra ~hiti~ation in a '~`ammann f`~rn~c@~ The plates formed in this manner{ then
A number hf experiments has shown that the reason for this is ~
sw@11~
hi h rate of romp@rature increase When anthracit@ of grade
P.?~Ce@~iYbly ~
heated in a Tammann furnace, it begins to crack at 1980~2d00�~
A. K. is
when the experiment was completed at t~?at temperature, solid lumps covered
kith cracks were obtained w~1en an~thraci�~@ was heated up to 2800�, part3�cularly
stron crackin was observed in the re~nge of 2100-2300� ~ As a result of
~ ~
r
this cracking, ae5arate silvery-grey plates are obt~?ined, but they are still
~ t e When the temperature is further raised to 2~~`0-260�s
hard and brit 1
which h~?v@ become soft and resilient are
cracking ceases and swollen plates
obtained. ~y conducting a number of e~rperiments on A. K ~ No ~ 1 anthracite,
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~.t was established that swelling and softening of this t~rpe of anthracite
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y, ~ .
~r
~k s R r
~ ,
takes ?~,~oo only wk~on the ~omp~r~turo io no lowor than 2~00~2600�
a
he reaulto of thc;c o~crim~t~ era a~.ted ire 'rabic
lit fi r ~ e ~M ~~f 1 1? V't' p ~ V ~l ~
~ ' 0
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~'~R , ~ ~tio ~ of ~ la e~6 0 ~~ine try
ap ~ a o � ro 6 a . ~ shgra ~he~~ r 3 ~
,,L 5~
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a ra~~i t 230' 8nd 0'~~4~ �epoot +~1y~:~ ~ o~~~ Qho
gait as b ~p rom ~ insi an i far
f an ~
n� ,
`BAs can be aeon from the oited data artly the dpeci!'io eleotric~. rea-
iat~?ncc is changed wh�n anthracite is heated from 1200� to 2000�~ whil�
other properti�s ar� affected very slightly ~owev�r, the change in �~he
resistanco is due to failure th hold t}~� sample at 1200� for a sufficient
th of tim�: wl~Qn ant~~racite is kept for 6 hours 1200�~ a drop of
leng
the rosystance down to 0~0~~0 ~ahma/cm reeult� (9)~ Thus, the actual change
of the resiatar~ce in the tem~jerature range ender consider�tion must alas
be insi~gnificant~ ~s mentioned abova~ the appearance oi' anthracite does
not change very ~~arceptibly in this temperature range On the other hands
he tem eratt~re b only 300� beyond this range (from 2000�
an increase oft I~ y
� brine about very noticeable changes in the anthracite Table 5
to 2300) g ~
shows that the ash content is strongly reduced (from 3.9 to 1~~~~ while the k
dens ~.ty is strongly increg.sed (cf ~ ~'i~u~~c ~ } ~ ~'o this period Corr�sponds
anted char : � in the appearance of the a~rthracite; there ~.s extensive
a r,rcno ~
craRcking~ With a f'urt~j~r increase of the temper~.ture, modification of the
N
k properties of the anthracite contiRnues, but this modification is no loner
intensive. Cracking of the anthracite stops and is replaced bar swelling
:s
v~,nus that in this particular range (T� ~ 2300�) the brittleness ~ R
It is ob
anthrac~,te disappears and it becomes regilient~ so that the swelling .
of the
brou ht about by the internal pressure of ash vgpore can take place ~
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_~reoite frosted at 2600
x04... tf � . ~ � a'. , e! ? e ~ - .r.. f..}+m., +~r+r~M
. , ' oven ~d oomio l~orio~ Qanvexiti@o are visible on its At tho
appoars un ~
aamo ti~~e the surreoe io vory smoothy oa if it woro poliohcd~ cnd rvflecte
4
1i~ht otrAngly~
h� star ~ ahcn~es in thQ proportion of anthracite in tho ran~o 2000�
T ~
� are accompanied b~F ~ trapntion of the anh conotituants into a molten
2300
ar1d ova ori~od condltion~ Th� prosance oi` th� ash constituentr~in thi� state
A
croatca favorabl� eon~i tio~~a for the ~tecrystalli~ation of carbons which ex~� �
lamb tho abrupt chan~o off' ~~ro~?ortie o me~~tionod cbova, (af ~ ~'i~ure 9)
P
Thin type of ~ra~~h~:ti~,ation in c~~aracteristic not only for anthracites but
~1so for a number ~f varieties of coko~ as wan shown by Vesslovskiy and
pertaov It has been shown t}gat �ven in the ~raphiti~atic~n of
electrodes made of petroleum cokes the electrical reeistuc~ce changes to an '
f,nsi~nificant extent up to 2004�, and that only in the ran~a 2000.3004 ~ �
the resistance drop� from 0~00~0 ohms per cer~timoter to 0~002Cti ohms per
centimeter (cf. Figure 10). This drop is uccom~~ani�d by a sharp reduction '
of the ash content It is obvious that the observed cdru~~~t change in the
~!roperties of a carbonacel~us material that is being grs~~hiti~ed depends on
the nature of t~~e ash constituents and that this change consequently may
i
take .lace in variaus temperature ranges ~ In view of the fact t~1at most
p
carbonaceous materials have app~~oxitnately the scrne a.nh admpos~.tion~ the
temperature rang�s in q~~estion do not di~`fer much from each other
when anthracite was partly de-ached (down to an ash content of 0~9~),
a fair/ hard and brittle product
the swelling was strongly reduced, and y
~ ~
was obtained, although the temperature of gr~?phiti~ation was 260� ~ This
ra hitixed anthracite res�mbles graphite obtained at 2304� from anthrac~.te
~ p
~ which head not been d e-ached
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a ~

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1
3
5
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~ tha roduato was carried out by Y8~ L~
~ ~ An K-ray inv@ati~atian o ~
u trial lnstituto~ Tha oa~~ploa w@ro ground
Khur~in at rho ~onin~rad lnd..~ .
after addition of dextrin past wore pros�od by moan� o~ �
into a ~owdor and
oils Navin a diameter of 0~1~ ? or O~b2 mm~ Thio Q~oa-
a a apil~ cry into r ~
rum of 1~~6 mm diamctQr~ Haddin~
urQS wore made in Aebyo ohar~bors with ~ d
I
r ~F E
r~e~~o ueod~ The exposure wa� continual for 20-
tubQO with iron anticatho~
2}~ hours
od valeea for the dimensions of crystals r�eulting
In Table b are cit
a~~thracite after the materi~il in question lead been
from ~?etrolaum coke and
the t�m ~aratura indicst�d in the table ~'i~ure 11 shows the
homed at ~
a ho~ometric examination of tl~� X.r~ diagrams t~ rn�ans of an
results of p
1 micro hotometer~ The results listed in the
a~~to~natically re6isterin~ X101 p
. ra hitization of anthracite a particularly stro~~~
table show that in the ~
stale sets in at 2300�f i~o~, this growth ba~ine in a temp.
growth of cry
a seam mocification of most of the properties of
erature range in which ~
and the removal of a�h starts 2600� the crystals ~ .
ar~t~~racite takes place
become still larger
from the hotometric curves that reflerion (002) is doubled
One can see p
d and f. This phenomenons ~i~`ich had already been observed
for samples c, ~
rt is a lainc:d by ~~he fact that the (001) planes are slippage
by ~~be ~ ~
~e of ra hite~ `v~hen thg rods are pressed cut of th e
planes in the ca ~ p
the re9ulting orientation is such that xeflexion may take place
capillaries,
cs which are near the surface 'his results in a
. only from (001) ~?1an
of the line Thus the doubling of lines indicates that there are
doubling
stale which have well-developed slippage planes
i sizeable cry
i
nthracite this doubling is first observed in the sample
In thg case of a
e sam le ra hitized
� renounced in th p ~ p
graphitized at 2300 and is especially p
� The se~~e doubling of the line (002) occs.rs in
at 2600 (~i~re ll~ d),
aeon ra hits (Figure 11~ f).
Ach ~ ri
9.
tt
~~~~l~~
t ,,F .
E y
I ~.~k ~ ~ ,i
f ~ '
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 Declassified in Part -Sanitized Copy Approved for Release 2012/05/25 :CIA-RDP82-000398000100100041-5
~'e
a
-
~
t ~
l
3
j~
t
~i~urc 11 a18o Dhows tho gradual increa�o of tho int@naity of l~nea
r ossin rra h~tization~ ~ineo (002), (201), and (200= ~orthoh@xonal
with A o gr g ~ p
~rhombio~ indQxing~ s~o air�ady su~fioi@ntly clear in the drat samplos~
In the cove o~ the sample graphitized at 2300' (figure ll, C)~ the i~tenaity
o~ linQS (4~)~ (020), (021), and ~006~ incroases considerably
The cranking of anthracite into plates, t~~e swelling of these plates,
and the resulting elastic properties have led to the assumption that in the
prACess of graphitization the crystals are orie~,tad with th�ir basal plan�s
f
along the anthracite layers pirani and ~'ehse demonstrated that orier~tod
graphs to crystals are responsible for the high fle~cibility oi' threads ~ �pared
Srom acetyl cellulose Turner a#~d Andorson X11) s~~ow�d that in some r�gions
of ar~t~~racite there is on�ntation of crystals.
In order t4 ~nve4t~gate the orientation- oi' graphite crystals i ;thracite M
layers, X-ray diagrams were teen in the following mannor~ A sample having
the shape of a plate was a}at from th� anthracite pE;rpcndieularly to the
1~yers~ 't'his eampl~ was affixed with an adhesive in a Laja@ ct~ambar~ Madding
t~~bes with iron ar~ticathcdos war� usQd as a so~~rce of X-rays The resulting
X-ray pictures confirmed the assum~~tion which had been ~ms.d� in regard to
the orientation of graphite cryetals~ ~he incom~ilote ring which is visible �
in all four pictj~res cif figure l~ is f'at~rrted by the reflox~.�r~ a~' Kl~~,~fle ~
from plane (001) in the second order (002). The second ring of a smaller
diameter which appears in the pictures of ~~igure 12 is due to the reflexion
of K ~'e from ~tt~e same planes The total da~;a indicate the following ~
strip lure, The hex. ~~;onal axes which are perpendf.cul ar to the (00^) planes
are not aZl perpendicular to the anthracite layers, but disposed within a
t
4
Bonus The axis of this Bonus is ;ernendieular to the anthracite layers, a~
Y P. t
~ wh~.le the inner angle forme=d by its tin i~ d~,Fferen~t for dii'ferent �amplos
r ~ ~cf. Table 7) ? The distribution of the axes within the cones shows a
frequency increasing towards the axis of the cones ~`urthermarQ in samples 1
f
s -lO-i
~ i I;
~ t4~ 3 ir(~~'~~ r 43! ~ f t
1~ ~ { b J~~:, t,~ y~ ~ c3
f t R} a, L f 4 - i
r~ 2 643 V rN,S[ �~i~i~ Si
6 ~
~ EM ti ~F r ~i~'a ~k"1~4' ~6 ` F4~ r~ ~
I ~ ~ f~r r~v1 bs f ~
i ~
i.
L.
A.
While reoryet~lli~ation of carbor~aa�aue matorialo pros�oda in tho oolid
hose at tomporaturee reaol~ing ae high ae ~000'~ this rocryctalli~ation ie
p 4
very olow~ The evaporation of amall cr3r8ta1e o~ carbon ar~d eubeequer~t oand�n-
n the tom orat~~~~~e ran Q 20003000' is
cation of vapors on larger crystals i ~ ~
�xtrQmel unlikely becaueo of trio low vapor pressure o~ oarbon in thot temp-
Y
eratr~re range (cf. van gear, anorg~ allgem. Ch. 1926; Sohn and ~ikkel~
Z. f ~ Phy' ~ Vol ~ ~xVll s 305)
~acording to Plishiga~ma~ � dote (13 incr�asin~ a~' tho time of heating
at a oonstac~t tQm~~�raturo in the ~rAphiti?anon oi' prepared carbon filaments
be ins to havQ an e~ii{ect only at 3000� ~ for th~~a reason the abrupt modifi-
C
cation ai' propertieu off' carbonaceous matc~rials in th@ range near 2000� cannot
be explained by recrystalli~at?ion in t~~o solid phase w~.th�ut taking into
consideration the effort oi' th� ash. `
Sn the li~,ht of the in.Cor~~la.tion given above, one may form tie following
~.deas an tho graphitization of`antl~racite~ `~ihen anthracite is heated up
to 1200�~ decomposition of organic compounds takes dace= leading to th�
growth of the original crystals up to dimens~.ons amounting to scores of
~ strcros~ Thore are no substantial e~~angea between 1200� and 2000� after
g
all organic compounds have c~ecomposed~ when the temperature is raised
f�rther the ash between the dyers cif ar~thricite i'irst melts and then is
i
transmitted into the gaseous state Depending on ~tt~e rate of temperature ~
inc=rease, the prbaese may proceed in two di~'ferent ways at this point if
a
the rate of temperature increase is highs the anthracite crs,cks into plates
~
if the temperature rises at a slow rate, swal~.ing of the anthracite may
X':
1 t'" ~
take place The fact that swollen p~,eces of ar~thraci~t� remain hard when the
experiment is terminated prematur�ly leads to the unavoidable conclusion
that at some higher temperature in this rangA the graphitized anthracite
becomes elastic It is possible that d3.ffusion of ash constituents into the
sayers promotes the formation of the elastic product.
~ a
~4+
~ ~ �
'
- -
- -
r
~ E ~ ,
;c a i ,
f ~
`
c 7 f ,h
ii
j
~ f
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 Declassified in Part -Sanitized Copy Approved for Release 2012/05/25 :CIA-RDP82-000398000100100041-5
j.
i-
~1
q
1
4
k', ~ {
! fff
is
t:
The ~rao@no� o~ Soh oonotituento at thQSa temperatures #'acilitatas the
dif~uslon 0f oarhon; se that an aoooloratod gra~th off` graphite o~yatal8
takoo plaoo~ Duo to the dirooting in~'luenoo of" the anthracite l~aro~ this
growth ~roooado bong the sur~aoe o#' tha lay�rs, oo that the X�ray diagrams
taken d~�~ring thin period show the most prooounoed degree a~ ar#~entation
(picture 3'�0~ Figur� 12)~ When the tomparatur� is raised t'~rthor~ loosening
Af the anthraoit� layers �coura under simultat~ous growth of the crystals,
which at thin eta~e are already oriented Notw~:thetai~ding the greater size
o~ crystals at thi� points th� degree oi' orientation is reduced owing to the
vondin~ c~~ tl~e thin layers one may mention h~yre that ~e pres�nce of orient�d
crystal�~� conductive to crystal growth ~8
)
Tha elasticity ~resiliance~ and greasiness whic~t mr� characteriatio ~
gra~~hitiz�d Anthracite are due precisely to the orientation oi' crystals ~ ,
Partial de-aching oi' anthracite reduces its sw~?lling and the resulting
graphite is hard. tinder the circumstances ono mutt conclude that the soi'tnese
and olastlcity of graphit� are due to the ash constituents which facilitate
orientation in addition tc~ extjcditin~; the growth o~ cryst~.e~ The graphit-
i,~,ation o� oth~lr carbonaceous materials proceeds bas~;cally along the sam�
lines as the ~raphiti~ation o~ anthracite ~owevQr, the properties of the
s~tart~ng material affect the process in a specific mgnner in each individual
4.
CAS~~ r
From the tcchnOlogieal standpoint, wh~;n the aim ig to prorl~~ce ~ra~~hite
!
t~at~der, one moat select the ri~h~t kind ni' anthracitte and ttYen insure, good
r
4
swelling h~~ raising the temperature appropriately and bringing the mgterial
up to the right ~,�mr~erat~e, In order to improve tha mechat7~,ca1 properties ~ �
of electrodes made from anthracite powdar~ one should use the finest anthracite y:~
k
r ~ owder and raise h ~
R p t e temperature in the 2000 X300 range at a part~.cularly

r s1~oa~ rate It is not advisable 'to raise the tam era ~ -
p tore above 2300 ,because
- 15 -
~~~1 ~
1 IY~
!
!
_
r� d., `
i ,
r
! i 4
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 Declassified in Part -Sanitized Copy Approved for Release 2012/05/25 :CIA-RDP82-000398000100100041-5
~ ~

.~~.,,.,.~~~.p..
G,~~;;,.
~s ~
t
~s
,
othor~rJ,oQ tho @loo~rodoQ boo
~a omo too Dolt ~ithou~ and oPP~olablo g ao
far ao im~rovomont oI oloo~rioal oonduo~ivlt is
~ oouoornod,
Tho author takes tho oooaoio~ to thank
Pro, M. s. Max~onko #'or valu�
ablo aaoiatanoo rondorod in tho Douro
�o~ thio inveotigatio~.
8iblio ra h~
1. Debye and 9ohorror, Phyo Z, Val XVIII~ 291 1917 E, Borl
1 , Z Phye Ch~,m
(A), Vol OLVIII, 273, 1932 V. Ho
1 ~mann~ Z, ang~ Ch. ~ Vol VILA 81~=, 1931;
V~ ion and Wilco, Z. Phye? Ch. ~E), Vol XVIZI 0
, ~ 1, 1932; Mukhor~eo~
Z. Phye?, Vol LXIOCVIII, 2~?, 193; H. E. Warr�n~ J. Chem. e. V `
01 II,
5~~,143~,
2. K. Arndt and E~ Pollaok, Z. A~org~ Allgem~ Ch. Vol OCI
31, 1931.
3 ~ ~'~ldt, Arkiv~ Matamatiks Astronomi ooh
~yoik, Vol XXIII~H, No 2, 6,
1932
and Partsa~i Zhu Pig. shim, Vol V, 5~7, 193.
E~ J� Aoheoon, U.S. Patents 568323, 71~t031 6 24
5, et0~ '
b. Arsem, Ind. Eng. Chom, 2~2~ 1911.
7. N. P~ Hoxhko~ Journal ir3ovietslc Ele
iy ktrod (Soviet Eleotrode) pub-
lashed as a ma~~uscript by tl~e Mosoow Eleotro
de P1a~~t.
t
8~ Parana, Fehse, Z. Elektroch~, Vol X~IX, 168 l 23.
,9
9. Bo~hko, ~h, Xh~n~ Pr@m. ~`o ll~ 1935
10. VeoelOVBkiy, "Mineral~~Oye r o~~ Min
Y ~ era/ Crud� Mater~,als), No 7-8,
~1, 1932
ll. 4~ Tumor and N. V. Anderson Fuel in SoienoQ and Pr
a~otioe~ Vol XI;,
No 2b2, 1932.
12. Sehaidhau~, Qerr~an Patent 488929 1 30
9
13. Nishi~ama, Z. Phys~, Vol. LXXT 600W61
~ 5, 1931.
tables ~ ~ fi es and ~ '
a 1 list of Figures follow, ~ ~
,
-~6-
jt ~ ~ ~ ~
r I CS ! ~ '
-~.~i ~t f.6, ~ i r1
i { i
,..,C iY iZ a. _ ~
i~ { ~ x,
` : -
7 ~
t ~ ~
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 Declassified in Part -Sanitized Copy Approved for Release 2012/05/25 :CIA-RDP82-000398000100100041-5
ix
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~ .
at
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2
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3
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