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WHY IS PARTICLE SIZE IMPURTANT?

art|c|e s|ze |nf|uences many propert|es of part|cu|ate mater|a|s and |s a va|uab|e |nd|cator
of qua||ty and performance
1hls ls Lrue for powders suspenslons emulslons and aerosols 1he slze and shape of
powders lnfluences flow and compacLlon properLles Larger more spherlcal parLlcles wlll
Lyplcally flow more easlly Lhan smaller or hlgh aspecL raLlo parLlcles Smaller parLlcles
dlssolve more qulckly and lead Lo hlgher suspenslon vlscoslLles Lhan larger ones Smaller
dropleL slzes and hlgher surface charge (zeLa poLenLlal) wlll Lyplcally lmprove suspenslon
and emulslon sLablllLy owder or dropleLs ln Lhe range of 23m aerosollze beLLer and wlll
peneLraLe lnLo lungs deeper Lhan larger slzes lor Lhese and many oLher reasons lL ls
lmporLanL Lo measure and conLrol Lhe parLlcle slze dlsLrlbuLlon of many producLs
MeasuremenLs ln Lhe laboraLory are ofLen made Lo supporL unlL operaLlons Laklng place ln a
process envlronmenL 1he mosL obvlous example ls mllllng (or slze reducLlon by anoLher
Lechnology) where Lhe goal of Lhe operaLlon ls Lo reduce parLlcle slze Lo a deslred
speclflcaLlon Many oLher slze reducLlon operaLlons and Lechnologles also requlre lab
measuremenLs Lo Lrack changes ln parLlcle slze lncludlng crushlng homogenlzaLlon
emulslflcaLlon mlcrofluldlzaLlon and oLhers SeparaLlon sLeps such as screenlng fllLerlng
cyclones eLc may be monlLored by measurlng parLlcle slze before and afLer Lhe process
arLlcle slze growLh may be monlLored durlng operaLlons such as granulaLlon or
crysLalllzaLlon ueLermlnlng Lhe parLlcle slze of powders requlrlng mlxlng ls common slnce
maLerlals wlLh slmllar and narrower dlsLrlbuLlons are less prone Lo segregaLlon 1here are
also lndusLry/appllcaLlon speclflc reasons why conLrolllng and measurlng parLlcle slze ls
lmporLanL ln Lhe palnL and plgmenL lndusLrles parLlcle slze lnfluences appearance
properLles lncludlng gloss and LlncLorlal sLrengLh arLlcle slze of Lhe cocoa powder used ln
chocolaLe affecLs color and flavor 1he slze and shape of Lhe glass beads used ln hlghway
palnL lmpacLs reflecLlvlLy CemenL parLlcle slze lnfluences hydraLlon raLe sLrengLh 1he slze
and shape dlsLrlbuLlon of Lhe meLal parLlcles lmpacLs powder behavlor durlng dle fllllng
compacLlon and slnLerlng and Lherefore lnfluences Lhe physlcal properLles of Lhe parLs
creaLed ln Lhe pharmaceuLlcal lndusLry Lhe slze of acLlve lngredlenLs lnfluences crlLlcal
characLerlsLlcs lncludlng conLenL unlformlLy dlssoluLlon and absorpLlon raLes CLher
lndusLrles where parLlcle slze plays an lmporLanL role lnclude nanoLechnology proLelns
cosmeLlcs polymers solls abraslves ferLlllzers and many more

WHICH SIZE TU MEASURE?

spherlcal parLlcle can be descrlbed uslng a slngle numberLhe dlameLer because every
dlmenslon ls ldenLlcal s seen ln llgure 1 nonspherlcal parLlcles can be descrlbed uslng
mulLlple lengLh and wldLh measures (horlzonLal and verLlcal pro[ecLlons are shown here)
1hese descrlpLlons provlde greaLer accuracy buL also greaLer complexlLy 1hus many
Lechnlques make Lhe useful and convenlenL assumpLlon LhaL every parLlcle ls a sphere 1he
reporLed value ls Lyplcally an equlvalenL spherlcal dlameLer 1hls ls essenLlally Laklng Lhe
physlcal measured value (le scaLLered llghL acousLlc aLLenuaLlon seLLllng raLe) and
deLermlnlng Lhe slze of Lhe sphere LhaL could produce Lhe daLa lLhough Lhls approach ls
slmpllsLlc and noL perfecLly accuraLe Lhe shapes of parLlcles generaLed by mosL lndusLrlal
processes are such LhaL Lhe spherlcal assumpLlon does noL cause serlous problems
roblems can arlse however lf Lhe lndlvldual parLlcles have a very large aspecL raLlo such
as flbers or needles Shape facLor causes dlsagreemenLs when parLlcles are measured wlLh
dlfferenL parLlcle slze analyzers Lach measuremenL Lechnlque deLecLs slze Lhrough Lhe use
of lLs own physlcal prlnclple lor example a sleve wlll Lend Lo emphaslze Lhe second
smallesL dlmenslon because of Lhe way parLlcles musL orlenL Lhemselves Lo pass Lhrough Lhe
mesh openlng sedlmenLomeLer measures Lhe raLe of fall of Lhe parLlcle Lhrough a vlscous
medlum wlLh Lhe oLher parLlcles and/or Lhe conLalner walls Lendlng Lo slow Lhelr
movemenL llaky or plaLellke parLlcles wlll orlenL Lo maxlmlze drag whlle sedlmenLlng
shlfLlng Lhe reporLed parLlcle slze ln Lhe smaller dlrecLlon llghL scaLLerlng devlce wlll
average Lhe varlous dlmenslons as Lhe parLlcles flow randomly Lhrough Lhe llghL beam
produclng a dlsLrlbuLlon of slzes from Lhe smallesL Lo Lhe largesL dlmenslons 1he only
Lechnlques LhaL can descrlbe parLlcle slze uslng mulLlple values are mlcroscopy or
auLomaLed lmage analysls n lmage analysls sysLem could descrlbe Lhe nonspherlcal
parLlcle seen ln llgure 1 uslng Lhe longesL and shorLesL dlameLers perlmeLer pro[ecLed
area or agaln by equlvalenL spherlcal dlameLer When reporLlng a parLlcle slze dlsLrlbuLlon
Lhe mosL common formaL used even for lmage analysls sysLems ls equlvalenL spherlcal
dlameLer on Lhe x axls and percenL on Lhe y axls lL ls only for elongaLed or flbrous parLlcles
LhaL Lhe x axls ls Lyplcally dlsplayed as lengLh raLher Lhan equlvalenL spherlcal dlameLer

UNDERSTANDINC AND INTERPRETINC PARTICLE SIZE DISTRIBUTIUN
CALCULATIUNS

Some people prefer a slngle number answerwhaL ls Lhe average slze? More experlenced
parLlcle sclenLlsLs crlnge when Lhey hear Lhls quesLlon knowlng LhaL a slngle number cannoL
descrlbe Lhe dlsLrlbuLlon of Lhe sample beLLer approach ls Lo reporL boLh a cenLral polnL
of Lhe dlsLrlbuLlon along wlLh one or more values Lo descrlbe Lhe wldLh of dlsLrlbuLlon
CLher approaches are also descrlbed ln Lhls documenL
CLn18L vLuLS
O MLn
O MLuln
O MCuL

lor symmeLrlc dlsLrlbuLlons such as Lhe one shown ln llgure 2 all cenLral values
are equlvalenL mean medlan mode 8uL whaL do Lhese values represenL?

MEAN

Mean ls a calculaLed value slmllar Lo Lhe concepL of average 1he varlous mean calculaLlons
are deflned ln several sLandard documenLs (ref12) 1here are mulLlple deflnlLlons for mean
because Lhe mean value ls assoclaLed wlLh Lhe basls of Lhe dlsLrlbuLlon calculaLlon (number
surface volume) See(ref3) for an explanaLlon of number surface and volume
dlsLrlbuLlons Laser dlffracLlon resulLs are reporLed on a volume basls so Lhe volume mean
can be used Lo deflne Lhe cenLral polnL alLhough Lhe medlan ls more frequenLly used Lhan
Lhe mean when uslng Lhls Lechnlque 1he equaLlon for deflnlng Lhe volume mean ls shown
below 1he besL way Lo Lhlnk abouL Lhls calculaLlon ls Lo Lhlnk of a hlsLogram Lable showlng
Lhe upper and lower llmlLs of n slze channels along wlLh Lhe percenL wlLhln Lhls channel 1he
ul value for each channel ls Lhe geomeLrlc mean Lhe square rooL of upper x lower
dlameLers lor Lhe numeraLor Lake Lhe geomeLrlc ul Lo Lhe fourLh power x Lhe percenL ln
LhaL channel summed over all channels lor Lhe denomlnaLor Lake Lhe geomeLrlc ul Lo Lhe
Lhlrd power x Lhe percenL ln LhaL channel summed over all channels 1he volume mean
dlameLer has several names lncludlng u43 ln all PC8l8 dlffracLlon sofLware Lhls ls slmply
called Lhe mean" whenever Lhe resulL ls dlsplayed as a volume dlsLrlbuLlon Conversely
when Lhe resulL ln PC8l8 sofLware ls converLed Lo a surface area dlsLrlbuLlon Lhe mean
value dlsplayed ls Lhe surface mean or u 32 1he equaLlon for Lhe surface mean ls shown
below








1he descrlpLlon for Lhls calculaLlon ls Lhe same as Lhe u43 calculaLlon excepL LhaL ul values
are ralsed Lo Lhe exponenL values of 3 and 2 lnsLead of 4 and 3
1he generallzed form of Lhe equaLlons seen above for u43 and u32 ls shown below
(followlng Lhe convenLlons from ref 2 S1M L 799 )








Where
u Lhe overbar ln u deslgnaLes an averaglng process
(pq)pq Lhe algebralc power of upq
ul Lhe dlameLer of Lhe lLh parLlcle
z Lhe summaLlon of ulp or ulq represenLlng all parLlcles ln Lhe sample
Some of Lhe more common represenLaLlve dlameLers are
u10 arlLhmeLlc or number mean
u32 volume/surface mean (also called Lhe SauLer mean)
u43 Lhe mean dlameLer over volume (also called Lhe ue8roukere mean)

1he example resulLs shown ln S1M L 799 are based on a dlsLrlbuLlon of llquld dropleLs
(parLlcles) ranglng from 240 6332 m lor Lhls dlsLrlbuLlon Lhe followlng resulLs were
calculaLed
u10 1460 m
u32 2280 m
u30 2340 m
u43 2670 m

1hese resulLs are falrly Lyplcal ln LhaL Lhe u43 ls larger Lhan Lhe u30 Lhe volumebasls
medlan value
MEDIAN

Medlan values are deflned as Lhe value where half of Lhe populaLlon resldes above Lhls
polnL and half resldes below Lhls polnL lor parLlcle slze dlsLrlbuLlons Lhe medlan ls called
Lhe u30 (or x30 when followlng cerLaln lSC guldellnes) 1he u30 ls Lhe slze ln mlcrons LhaL
spllLs Lhe dlsLrlbuLlon wlLh half above and half below Lhls dlameLer 1he uv30 (or uv03) ls
Lhe medlan for a volume dlsLrlbuLlon un30 ls used for number dlsLrlbuLlons and us30 ls
used for surface dlsLrlbuLlons Slnce Lhe prlmary resulL from laser dlffracLlon ls a volume
dlsLrlbuLlon Lhe defaulL u30 clLed ls Lhe volume medlan and u30 Lyplcally refers Lo Lhe uv30
wlLhouL lncludlng Lhe v 1hls value ls one of Lhe easler sLaLlsLlcs Lo undersLand and also one
of Lhe mosL meanlngful for parLlcle slze dlsLrlbuLlons

MUDE

1he mode ls Lhe peak of Lhe frequency dlsLrlbuLlon or lL may be easler Lo vlsuallze lL as Lhe
hlghesL peak seen ln Lhe dlsLrlbuLlon 1he mode represenLs Lhe parLlcle slze (or slze range)
mosL commonly found ln Lhe dlsLrlbuLlon Less care ls Laken Lo denoLe wheLher Lhe value ls
based on volume surface or number so elLher run Lhe rlsk of assumlng volume basls or
check Lo assure Lhe dlsLrlbuLlon basls 1he mode ls noL as commonly used buL can be
descrlpLlve ln parLlcular lf Lhere ls more Lhan one peak Lo Lhe dlsLrlbuLlon Lhen Lhe modes
are helpful Lo descrlbe Lhe mldpolnL of Lhe dlfferenL peaks

lor nonsymmeLrlc dlsLrlbuLlons Lhe mean medlan and mode wlll be Lhree
dlfferenL values shown ln llgure 3


DISTRIBUTIUN WIDTHS

MosL lnsLrumenLs are used Lo measure Lhe parLlcle slze dlsLrlbuLlon lmplylng an lnLeresL ln
Lhe wldLh or breadLh of Lhe dlsLrlbuLlon Lxperlenced sclenLlsLs Lyplcally shun uslng a slngle
number answer Lo Lhe quesLlon WhaL slze are Lhose parLlcles?" and prefer Lo lnclude a
way Lo deflne Lhe wldLh 1he fleld of sLaLlsLlcs provldes several calculaLlons Lo descrlbe Lhe
wldLh of dlsLrlbuLlons and Lhese calculaLlons are someLlmes used ln Lhe fleld of parLlcle
characLerlzaLlon 1he mosL common calculaLlons are sLandard devlaLlon and varlance 1he
sLandard devlaLlon (SL uev) ls Lhe preferred value ln our fleld of sLudy s shown ln llgure 4
6827 of Lhe LoLal populaLlon lles wlLhln +/ 1 SL uev and 9343 lles wlLhln +/ 2 SL uev

lLhough occaslonally clLed Lhe use of sLandard devlaLlon decllned when hardware and
sofLware advanced beyond assumlng normal or 8osln8ammler dlsLrlbuLlons

Cnce model lndependenL" algorlLhms were lnLroduced many parLlcle sclenLlsLs began uslng
dlfferenL calculaLlons Lo descrlbe dlsLrlbuLlon wldLh Cne of Lhe common values used for
laser dlffracLlon resulLs ls Lhe span wlLh Lhe sLrlcL deflnlLlon shown ln Lhe equaLlon below
(2)



ln rare slLuaLlons Lhe span equaLlon may be deflned uslng oLher values such as uv08 and
uv02 Laser dlffracLlon lnsLrumenLs should allow users Lhls flexlblllLy n addlLlonal
approach Lo descrlblng dlsLrlbuLlon wldLh ls Lo normallze Lhe sLandard devlaLlon Lhrough
dlvlslon by Lhe mean 1hls ls Lhe CoefflclenL of varlaLlon (CCv) (alLhough lL may also be
referred Lo as Lhe relaLlve sLandard devlaLlon or 8Su) lLhough lncluded ln PC8l8 laser
dlffracLlon sofLware Lhls value ls seldom used as ofLen as lL should glven lLs sLaLure 1he CCv
calculaLlon ls boLh used and encouraged as a calculaLlon Lo express measuremenL resulL
reproduclblllLy lSC13320 (ref 4) encourages all users Lo measure any sample aL leasL 3
Llmes calculaLe Lhe mean sL dev and CCv (sL dev/mean) and Lhe sLandard seLs pass/fall
crlLerla based on Lhe CCv values noLher common approach Lo deflne Lhe dlsLrlbuLlon
wldLh ls Lo clLe Lhree values on Lhe xaxls Lhe u10 u30 and u90 as shown ln llgure 3 1he
u30 Lhe medlan has been deflned above as Lhe dlameLer where half of Lhe populaLlon lles
below Lhls value Slmllarly 90 percenL of Lhe dlsLrlbuLlon lles below Lhe u90 and 10
percenL of Lhe populaLlon lles below Lhe u10

TECHNIQUE DEPENDENCE

PC8l8 lnsLrumenLs lnc dlsLrlbuLes parLlcle characLerlzaLlon Lools based on several


prlnclples lncludlng laser dlffracLlon dynamlc llghL scaLLerlng acousLlc aLLenuaLlon and
lmage analysls Lach of Lhese Lechnlques generaLes resulLs ln boLh slmllar and unlque ways
MosL Lechnlques can descrlbe resulLs uslng sLandard sLaLlsLlcal calculaLlons such as Lhe
mean and sLandard devlaLlon 8uL commonly accepLed pracLlces for descrlblng resulLs have
evolved for each Lechnlque

PARTICLE SIZE RESULT INTEPRETATIUN: NUMBER VS. VULUME
DISTRIBUTIUNS

nterpret|ng resu|ts of a part|c|e s|ze measurement requ|res an understand|ng
of wh|ch techn|que was used and the bas|s of the ca|cu|at|ons Lach techn|que generates a
d|fferent resu|t s|nce each measures d|fferent phys|ca| propert|es of the samp|e
Cnce Lhe physlcal properLy ls measured a calculaLlon of some Lype generaLes a
represenLaLlon of a parLlcle slze dlsLrlbuLlon Some Lechnlques reporL only a cenLral polnL
and spread of Lhe dlsLrlbuLlon oLhers provlde greaLer deLall across Lhe upper and lower
parLlcle slze deLecLed 1he parLlcle slze dlsLrlbuLlon can be calculaLed based on several
models mosL ofLen as a number or volume/mass dlsLrlbuLlon

NUMBER VS. VULUME DISTRIBUTIUN

1he easlesL way Lo undersLand a number dlsLrlbuLlon ls Lo conslder measurlng parLlcles
uslng a mlcroscope 1he observer asslgns a slze value Lo each parLlcle lnspecLed 1hls
approach bullds a number dlsLrlbuLloneach parLlcle has equal welghLlng once Lhe flnal
dlsLrlbuLlon ls calculaLed s an example conslder Lhe nlne parLlcles shown ln llgure 6
1hree parLlcles are 1m Lhree are 2m and Lhree are 3m ln slze (dlameLer) 8ulldlng a
number dlsLrlbuLlon for Lhese parLlcles wlll generaLe Lhe resulL shown ln llgure 7 where
each parLlcle slze accounLs for one Lhlrd of Lhe LoLal lf Lhls same resulL were converLed Lo a
volume dlsLrlbuLlon Lhe resulL would appear as shown ln llgure 8 where 73 of Lhe LoLal
volume comes from Lhe 3m parLlcles and less Lhan 3 comes from Lhe 1m parLlcles















When presenLed as a volume dlsLrlbuLlon lL becomes more obvlous LhaL Lhe ma[orlLy of Lhe
LoLal parLlcle mass or volume comes from Lhe 3m parLlcles noLhlng changes beLween Lhe
lefL and rlghL graph excepL for Lhe basls of Lhe dlsLrlbuLlon calculaLlon noLher way Lo
vlsuallze Lhe dlfference beLween number and volume dlsLrlbuLlons was glven Lo us by a
cusLomer who needed Lo explaln Lhe dlfference Lo her colleagues ln Lhls case beans are
used as Lhe parLlcle sysLem llgure 9 shows a populaLlon where Lhere are 13 beans ln each
of Lhree slze classes equal on a number basls llgure 10 shows Lhese beans placed ln
volumeLrlc cyllnders where lL becomes apparenL LhaL Lhe larger beans represenL a much
larger LoLal volume Lhan Lhe smaller ones

llgure 11 shows a populaLlon of beans where lL may noL be lnLulLlvely obvlous buL Lhere ls
an equal volume of each slze desplLe Lhe wlde range of numbers presenL lL becomes
apparenL ln llgure 12 when Lhe beans are placed ln volumeLrlc cyllnders LhaL each volumes
are equal

TRANSFURMINC RESULTS

8esulLs from number based sysLems such as mlcroscopes or lmage analyzers consLrucL Lhelr
beglnnlng resulL as a number dlsLrlbuLlon 8esulLs from laser dlffracLlon or acousLlc
aLLenuaLlon consLrucL Lhelr beglnnlng resulL as a volume dlsLrlbuLlon 1he sofLware for many
of Lhese sysLems lncludes Lhe ablllLy Lo Lransform Lhe resulLs from number Lo volume or vlce
versa lL ls perfecLly accepLable Lo Lransform lmage analysls resulLs from a number Lo
volume basls ln facL Lhe pharmaceuLlcal lndusLry has concluded LhaL lL prefers resulLs be
reporLed on a volume basls for mosL appllcaLlons (ref 6) Cn Lhe oLher hand converLlng a
volume resulL from laser dlffracLlon Lo a number basls can lead Lo undeflned errors and ls
only suggesLed when comparlng Lo resulLs generaLed by mlcroscopy llgure 13 below shows
an example where a laser dlffracLlon resulL ls Lransformed from volume Lo boLh a number
and a surface area based dlsLrlbuLlon noLlce Lhe large change ln medlan from 1138m Lo
030m when converLed from volume Lo number















SETTINC PARTICLE SIZE SPECIFICATIUNS

1he creat|on of a mean|ngfu| and productappropr|ate part|c|e s|ze spec|f|cat|on requ|res
know|edge of |ts effect on product performance |n add|t|on to an understand|ng of how
resu|ts shou|d be |nterpreted for a g|ven techn|que
1hls secLlon provldes guldellnes for seLLlng parLlcle slze speclflcaLlons on parLlculaLe
maLerlalsprlmarlly when uslng Lhe laser dlffracLlon Lechnlque buL also wlLh lnformaLlon
abouL dynamlc llghL scaLLerlng (uLS) acousLlc specLroscopy and lmage analysls

DISTRIBUTIUN BASIS

ulfferenL parLlcle slzlng Lechnlques reporL prlmary resulLs based on number volume
welghL surface area or lnLenslLy s a general rule speclflcaLlons should be based ln Lhe
formaL of Lhe prlmary resulL for a glven Lechnlque Laser dlffracLlon generaLes resulLs based
on volume dlsLrlbuLlons and any speclflcaLlon should be volume based Llkewlse an
lnLenslLy basls should be used for uLS speclflcaLlons volume for acousLlc specLroscopy and
number for lmage analysls Converslon Lo anoLher basls such as numberalLhough posslble
ln Lhe sofLwarels lnadvlsable because slgnlflcanL error ls lnLroduced 1he excepLlon Lo Lhls
guldellne ls converLlng a number based resulL from a Lechnlque such as lmage analysls lnLo a
volume basls (ref 7) 1he error lnvolved ls generally very low ln Lhls scenarlo

DISTRIBUTIUN PUINTS

Whlle lL ls LempLlng Lo use a slngle number Lo represenL a parLlcle slze dlsLrlbuLlon (Su)
and Lhus Lhe producL speclflcaLlon Lhls ls Lyplcally noL a good ldea ln nearly every case a
slngle daLa polnL cannoL adequaLely descrlbe a dlsLrlbuLlon of daLa polnLs 1hls can easlly
lead Lo mlsundersLandlngs and provldes no lnformaLlon abouL Lhe wldLh of Lhe dlsLrlbuLlon
Less experlenced users may belleve LhaL Lhe average parLlcle slze" can adequaLely descrlbe
a slze dlsLrlbuLlon buL Lhls lmplles expecLlng a response based on a calculaLed average (or
mean) lf forced Lo use a slngle calculaLed number Lo represenL Lhe mldpolnL of a parLlcle
slze dlsLrlbuLlon Lhen Lhe common pracLlce ls Lo reporL Lhe medlan and noL Lhe mean 1he
medlan ls Lhe mosL sLable calculaLlon generaLed by laser dlffracLlon and should be Lhe
value used for a slngle polnL speclflcaLlon ln mosL cases 8aLher Lhan use a slngle polnL ln Lhe
dlsLrlbuLlon as a speclflcaLlon lL ls suggesLed Lo lnclude oLher slze parameLers ln order Lo
descrlbe Lhe wldLh of Lhe dlsLrlbuLlon 1he span ls a common calculaLlon Lo quanLlfy
dlsLrlbuLlon wldLh (u90 u10) / u30 Powever lL ls rare Lo see span as parL of a parLlcle
slze speclflcaLlon 1he more common pracLlce ls Lo lnclude Lwo polnLs whlch descrlbe Lhe
coarsesL and flnesL parLs of Lhe dlsLrlbuLlon 1hese are Lyplcally Lhe u90 and u10 uslng Lhe
same convenLlon as Lhe u30 Lhe u90 descrlbes Lhe dlameLer where nlneLy percenL of Lhe
dlsLrlbuLlon has a smaller parLlcle slze and Len percenL has a larger parLlcle slze 1he u10
dlameLer has Len percenL smaller and nlneLy percenL larger Lhree polnL speclflcaLlon
feaLurlng Lhe u10 u30 and u90 wlll be consldered compleLe and approprlaLe for mosL
parLlculaLe maLerlals
Pow Lhese polnLs are expressed may vary Some speclflcaLlons use a formaL
where Lhe u10 u30 and u90 musL noL be more Lhan (nM1) a sLaLed slze

Lxample NM1 2m
NM1 8m
NM1 2m

lLhough only one slze ls sLaLed for each polnL Lhere ls an lmplled range of accepLable slzes
(le Lhe u30 passes lf beLween 20 and 80m) lLernaLlvely a range of values can be
expllclLly sLaLed

Lxample 2m
7 8m
8 2m

1hls approach beLLer deflnes Lhe accepLable slze dlsLrlbuLlon buL may be percelved as
overly compllcaLed for many maLerlals lL may also be LempLlng Lo lnclude a requlremenL
LhaL 100 of Lhe dlsLrlbuLlon ls smaller Lhan a glven slze 1hls lmplles calculaLlng Lhe u100
whlch ls noL recommended 1he u100 resulL (and Lo a lesser degree Lhe u0) ls Lhe leasL
robusL calculaLlon from any experlmenL ny sllghL dlsLurbance durlng Lhe measuremenL
such as an alr bubble or Lhermal flucLuaLlon can slgnlflcanLly lnfluence Lhe u100 value
ddlLlonally Lhe sLaLlsLlcs lnvolved wlLh calculaLlng Lhls value (and oLher exLreme" values
such as Lhe u99 u1 eLc) aren'L as robusL because Lhere may noL be very many of Lhe
largesL" and smallesL" parLlcles Clven Lhe posslble broad spread of u100 resulLs lL ls noL
recommended for use ln creaLlng speclflcaLlons lnvolvlng a sLaLemenL LhaL 100 of Lhe
parLlcles are below a sLaLed slze

INCLUDINC A MEAN VALUE

ulLlmaLely Lhe sophlsLlcaLlon of Lhe speclflcaLlon should be drlven by how parLlcle slze
lnfluences producL performance Clven LhaL some people ask abouL Lhe average slze" lL ls
noL surprlslng LhaL some speclflcaLlons are based on a mean dlameLer 1hls approach ls
compllcaLed by Lhe facL LhaL Lhere are several mean values LhaL can be calculaLed and
reporLed ln Lhe resulL (ref 8) 1he mosL common mean value noLed when uslng laser
dlffracLlon ls Lhe volume mean or u43 1he u43 ls very senslLlve Lo Lhe presence of large
parLlcles ln Lhe dlsLrlbuLlon lL ls a good ldea Lo use or lnclude Lhe u43 ln Lhe speclflcaLlon lf
producL performance ls senslLlve Lo Lhe presence of large parLlcles 1he oLher mean value
occaslonally used ls Lhe u32 or surface mean 1hls value ls only Lyplcally used when Lhe
producL ls an aerosol or spray


VS. Y AIS

CLher publlshed speclflcaLlons are based on Lhe percenL below a glven parLlcle slze such as
30 below 20m and 90 below 100m 1hls Lype of speclflcaLlon ls based on polnLs along
Lhe y axls (whlch reporLs frequency percenL) as opposed Lo Lhe x axls (whlch reporLs
dlameLer) as ln Lhe prevlous examples lLhough Lhls approach has been used ln many
speclflcaLlons lL ls lmporLanL Lo reallze Lhe dlfference beLween uslng Lhe x (slze) and y
(percenL) axes ll measuremenLs lnclude an error whlch should always be consldered when
seLLlng a speclflcaLlon lor Lhe example shown ln llgure 14 Lhe u30 ls 100m wlLh an error
of +/ 3 on Lhe x (slze) axls 1hls error lncludes all sources such as sampllng and sample
preparaLlon 1he same error becomes +/ 20 when LranslaLed Lo Lhe y (percenL) axls
SLaLlng an error of +/ 3 ls more aLLracLlve Lhan +/ 20 even when expresslng Lhe same
acLual error range 1he degree Lo whlch Lhe y axls error ls exaggeraLed vs Lhe x axls depends
upon Lhe sLeepness of Lhe dlsLrlbuLlon curve 1here are appllcaLlons where Lhe percenL
below a glven parLlcle slze ls an lmporLanL resulL 8ecenLly Lhere has been lnLeresL ln Lhe
presence of nanoparLlcles" (aL leasL one dlmenslon smaller Lhan 100nm) ln producLs such
as cosmeLlcs 1he sofLware whlch calculaLes Lhe Su should be capable of easlly reporLlng
Lhe percenL under any chosen slzeln Lhls case Lhe percenL below 100nm (llgure 13) ln Lhe
L930 sofLware Lhls ls dlsplayed as ulameLer on CumulaLlve " ln Lhe example below Lhe
value for percenL less Lhan 100nm ls reporLed as 9133 Several polnLs are worLh
menLlonlng ln regards Lo seLLlng a speclflcaLlon on Lhe percenL below 100nm as ln Lhls
example speclflcally and for submlcron maLerlals generally 1he parLlcle slze dlsLrlbuLlon ls
dependenL upon many facLors lncludlng Lhe sample preparaLlon meLhod 1he laser
dlffracLlon Lechnlque works besL wlLhln a cerLaln parLlculaLe concenLraLlon range 1hls
someLlmes requlres LhaL samples undergo dlluLlon ln some cases Lhls dlluLlon may change
Lhe sLaLe of Lhe parLlcles and affecL Lhe apparenL slze dlsLrlbuLlon ddlLlonally ulLrasonlc
energy can be applled Lo lmprove Lhe dlsperslon of agglomeraLes whlch can slgnlflcanLly
change Lhe resulL

TESTINC REPRUDUCIBILITY

1here are currenLly Lwo lnLernaLlonally accepLed sLandards wrlLLen on Lhe use of laser
dlffracLlon lSC 13320 (ref 9) and uS429 (ref 10) 8oLh sLandards sLaLe LhaL samples
should be measured aL leasL Lhree Llmes and reproduclblllLy musL meeL speclfled guldellnes
noLe LhaL Lhls means Lhree lndependenL measuremenLs (le prepare Lhe sample measure
Lhe sample empLy Lhe lnsLrumenL and repeaL) 1he coefflclenL of varlaLlon (CCv or (sLd
dev/mean)*100) for Lhe measuremenL seL musL be less Lhan 3 aL Lhe u30 and less Lhan 3
aL Lhe u10 and u90 Lo pass Lhe lSC 13320 requlremenLs 1hese guldellnes change Lo less
Lhan 10 aL Lhe u30 and less Lhan 13 aL Lhe u10 and u90 when followlng Lhe uS429
requlremenLs llnally Lhe guldellnes all double when Lhe u30 of Lhe maLerlal ls less Lhan
10m Whlle followlng Lhe lSC or uS guldellnes Lo LesL reproduclblllLy ls suggesLed lL ls
Lyplcally parL of an lnLernal speclflcaLlon or procedure 1he speclflcaLlons shown Lo poLenLlal
cusLomers Lyplcally don'L lnclude Lhe reproduclblllLy values


INCLUDINC THE ERRUR

1he reproduclblllLy errors dlscussed above should be lnvesLlgaLed and mlnlmlzed because
Lhey play an lmporLanL role ln Lhe flnal seLLlng of a speclflcaLlon Cnce Lhe speclflcaLlon
based on producL performance has been deLermlned Lhen Lhe flnal speclflcaLlon musL be
narrowed by Lhe error range (ref 11) ln Lhe example shown ln llgure 16 Lhe speclflcaLlon
for Lhe u30 ls 100 +/ 20 (or 80120m) based on producL performance lf Lhe LoLal
measuremenL error ls +/ 10 (uslng uS429 guldellnes for Lhe u30 value) Lhe
speclflcaLlon musL be LlghLened Lo 90110m (rounded for slmpllclLy) ln order Lo assure
Lhe producL ls never ouL of Lhe performance speclflcaLlon lor example lf Lhe u30 ls
measured Lo be 110m we are cerLaln Lhe u30 ls acLually less Lhan 120m even wlLh a
maxlmum 10 error 1hls ls why lL ls lmporLanL Lo creaLe robusL sLandard operaLlng
procedures for any maLerlal we wlsh Lo seL a publlshed speclflcaLlon for ny comblnaLlon of
hlgh measuremenL error (usually sLemmlng from nonopLlmlzed meLhod developmenL) and
LlghL speclflcaLlons wlll make meeLlng LhaL speclflcaLlon more dlfflculL
Why make llfe harder Lhan lL need be?




























LASER DIFFRACTIUN TECHNIQUE

1he knowledge LhaL parLlcles scaLLer llghL ls noL new 8aylelgh scaLLerlng of llghL from
parLlcles ln Lhe aLmosphere ls whaL glves Lhe sky a blue color and makes sunseLs yellow
orange and red LlghL lnLeracLs wlLh parLlcles ln any of four ways dlffracLlon reflecLlon
absorpLlon and refracLlon llgure 17 shows Lhe ldeallzed edge dlffracLlon of an lncldenL
plane wave on a spherlcal parLlcle SclenLlsLs dlscovered more Lhan a cenLury ago LhaL llghL
scaLLered dlfferenLly off of dlfferenLly slzed ob[ecLs Cnly Lhe relaLlvely recenL pasL
however has seen Lhe sclence of parLlcle slze analysls embrace llghL scaLLerlng as noL only a
vlable Lechnlque buL Lhe backbone of modern slzlng






8enchLop laser dlffracLlon lnsLrumenLs became pracLlcal wlLh Lhe advenL of hlgh lnLenslLy
reasonably prlced lasers and sufflclenL compuLlng power Lo process Lhe scaLLered llghL daLa
Cnce Lhese barrlers Lo markeL enLry were ellmlnaLed Lhe advanLages of laser dlffracLlon
over oLher Lechnlques were apparenL speed of analysls appllcaLlon flexlblllLy small parLlcle
accuracy and ease of use 1he ablllLy Lo measure nano mlcro and macroslzed powders
suspenslons and emulslons and Lo do lL wlLhln one mlnuLe explalns how laser dlffracLlon
dlsplaced popular Lechnlques such as slevlng sedlmenLaLlon and manual mlcroscopy Such
an lnsLrumenL conslsLs of aL leasL one source of hlgh lnLenslLy monochromaLlc llghL a
sample handllng sysLem Lo conLrol Lhe lnLeracLlon of parLlcles and lncldenL llghL and an
array of hlgh quallLy phoLodlodes Lo deLecL Lhe scaLLered llghL over a wlde range of angles
1hls lasL plece ls Lhe prlmary funcLlon of a laser dlffracLlon lnsLrumenL Lo record angle and
lnLenslLy of scaLLered llghL 1hls lnformaLlon ls Lhen lnpuL lnLo an algorlLhm whlch whlle
complex reduces Lo Lhe followlng baslc LruLh

O L 1LS S11L N1LNSL 1 NJ NLS
O SM 1LS S11L JL 1 JL NLS


1he algorlLhm aL lLs core conslsLs of an opLlcal model wlLh Lhe maLhemaLlcal
LransformaLlons necessary Lo geL parLlcle slze daLa from scaLLered llghL Powever noL all
opLlcal models were creaLed equally

THE IMPURTANCE UF UPTICAL MUDEL

ln Lhe beglnnlng Lhere was Lhe Iraunhofer pprox|mat|on and lL was good 1hls model
whlch was popular ln older laser dlffracLlon lnsLrumenLs makes cerLaln assumpLlons (hence
Lhe approxlmaLlon) Lo slmpllfy Lhe calculaLlon

arLlcles are assumed
O Lo be spherlcal
O Lo be opaque
O Lo scaLLer equlvalenLly aL wlde angles as narrow angles
O Lo lnLeracL wlLh llghL ln a dlfferenL manner Lhan Lhe medlum

racLlcally Lhese resLrlcLlons render Lhe lraunhofer pproxlmaLlon a very poor cholce for
parLlcle slze analysls as measuremenL accuracy below roughly 20 mlcrons ls compromlsed

1he M|e scatter|ng theory overcomes Lhese llmlLaLlons CusLav Mle developed a closed
form soluLlon (noL approxlmaLlon) Lo Maxwell's elecLromagneLlc equaLlons for scaLLerlng
from spheres Lhls soluLlon exceeds lraunhofer Lo lnclude senslLlvlLy Lo smaller slzes (wlde
angle scaLLer) a wlde range of opaclLy (le llghL absorpLlon) and Lhe user need only provlde
Lhe refracLlve lndex of parLlcle and dlsperslng medlum ccounLlng for llghL LhaL refracLs
Lhrough Lhe parLlcle (aka secondary scaLLer) allows for accuraLe measuremenL even ln
cases of slgnlflcanL Lransparency
1he Mle Lheory llkewlse makes cerLaln assumpLlons LhaL Lhe parLlcle
O ls spherlcal
O ensemble ls homogeneous
O refracLlve lndex of parLlcle and surroundlng medlum ls known

llgure 18 shows a graphlcal represenLaLlon of lraunhofer and Mle models uslng scaLLerlng
lnLenslLy scaLLerlng angle and parLlcle slze (ref 13) 1he Lwo models begln Lo dlverge
around 20 mlcrons and Lhese dlfferences become pronounced below 10 mlcrons uL
slmply Lhe lraunhofer pproxlmaLlon conLrlbuLes a magnlLude of error for mlcronlzed
parLlcles LhaL ls Lyplcally unaccepLable Lo Lhe user

measuremenL of spherlcal glass beads ls shown ln llgure 19 and calculaLed uslng Lhe Mle
(red) and lraunhofer (blue) models 1he Mle resulL meeLs Lhe maLerlal speclflcaLlon whlle
Lhe lraunhofer resulL falls Lhe speclflcaLlon and spllLs Lhe peak 1he overreporLlng of small
parLlcles (where lraunhofer error ls slgnlflcanL) ls a Lyplcal comparlson resulL

BUILDINC A STATE UF THE ART LASER DIFFRACTIUN ANALYZER



1he baslcs of whaL needs Lo be measured and how lL's Lransformed lnLo parLlcle slze daLa
are undersLood (ref 14) WhaL consLlLuLes a baslc parLlcle slze analyzer has also been
dlscussed buL Lhere's a wlde gulf beLween bare mlnlmum and sLaLe of Lhe arL 1he laLLer ls
always Lhe lndusLry leader ln accuracy repeaLablllLy usablllLy flexlblllLy and rellablllLy 1he
currenL sLaLe of Lhe arL ln laser dlffracLlon ls Lhe arLlca L930 feaLurlng Lwo hlgh lnLenslLy
llghL sources a slngle conLlnuous casL alumlnum opLlcal bench (llgure 20) a wlde array of
sample handllng sysLems and experL reflnemenLs expecLed from Lhe flfLh revlslon ln Lhe 900
serles uslng Lwo llghL sources of dlfferenL wavelengLhs ls of crlLlcal lmporLance because Lhe
measuremenL accuracy of small parLlcles ls wavelengLh dependenL llgure 21 shows Lhe
360 llghL scaLLerlng paLLerns from 30nm and 70nm parLlcles as generaLed from a 630 nm
red laser 1he paLLerns are pracLlcally ldenLlcal across all angles and Lhe algorlLhm wlll noL be
able Lo accuraLely calculaLe Lhe dlfferenL parLlcle slzes llgure 22 shows Lhe same
experlmenL uslng a 403nm blue LLu ulsLlncL dlfferences are now seen on wlde angle
deLecLors whlch allows for accuraLe calculaLlon of Lhese maLerlals lnLegraLlng a second
shorLer wavelengLh llghL source ls Lhe prlmary means of lmprovlng nanoscale performance
beyond Lhe bare mlnlmum laser dlffracLlon analyzer

SELECTINC A PARTICLE SIZE ANALYZER

1he dec|s|on process may be d|fferent |f the |nstrument |s be|ng purchasedfor a spec|f|c
app||cat|on as opposed to a genera| ana|yt|ca| techn|que formany poss|b|e samp|es
lor speclflc appllcaLlon lL makes sense Lo search Lhe lndusLry llLeraLure Lo deLermlne lf a
parLlcular Lechnlque ls favored over oLhers lf for example Lhe appllcaLlon ls llposomes and
90 of all llLeraLure found ln Lhls fleld ls uLS Lhen Lhe declslon ls slmple Cn Lhe oLher hand
lf Lhls ls Lhe flrsL parLlcle slze analyzer boughL by a company for general purpose use Lhen
flexlblllLy and a wlde dynamlc range should be lmporLanL facLors

SomeLlmes Lhe goal Lo buy a new lnsLrumenL lncludes belng able Lo correlaLe Lo exlsLlng
daLa ccompllshlng Lhls goal can range from easy Lo dlfflculL !usL upgradlng from an older
Lo newer model dlffracLlon analyzer could cause a change ln resulLs 1he changes orlglnaLe
from many sources lncludlng dlfferences ln dynamlc range advances ln algorlLhms and
mechanlc lmprovemenLs Lo samplers SwlLchlng from an exlsLlng Lechnlque such as slevlng
Lo newer Lechnlques llke laser dlffracLlon or dynamlc lmage analysls could also lead Lo
changes ln resulLs uaLa from sleves are Lyplcally smaller Lhan daLa from laser dlffracLlon
dependlng on Lhe shape of Lhe parLlcles 1he less spherlcal Lhe parLlcle Lhe greaLer Lhe
dlfference wlll llkely be 1he CMSlZL8 dynamlc lmage analyzer has mulLlple approaches
bullL lnLo Lhe sofLware Lo faclllLaLe daLa maLchlng wlLh sleves s a general rule daLa can be
manlpulaLed Lo approach exlsLlng resulLs buL undersLandlng Lhls lssue durlng Lhe selecLlon
process can ease Lhe lmplemenLaLlon of a new Lechnlque

arLlcle slze dlsLrlbuLlon ls sufflclenL lnformaLlon for Lhe ma[orlLy of parLlcle characLerlzaLlon
appllcaLlons 8uL some Lechnlques are hlgher resoluLlon Lhan oLhers Lnsemble Lechnologles
lncludlng llghL scaLLerlng and acousLlc specLroscopy are powerful Lechnlques Lhan are
resoluLlon llmlLed" compared Lo hlgh resoluLlon Lechnlques whlch are based on parLlcle
counLlng (such as elecLro zone counLlng or lmage analysls) lf Lhe goal of Lhe measuremenL ls
flndlng small populaLlons of parLlcles larger or smaller Lhan Lhe maln dlsLrlbuLlon Lhen an
lnvesLlgaLlon of Lhe senslLlvlLy Lo second dlsLrlbuLlons should be parL of Lhe selecLlon
process
arLlcle shape lnformaLlon may be elLher deslrable or crlLlcal dependlng on Lhe degree Lo
whlch shape affecLs producL performance arLlcle shape lnfluences bulk properLles of
powders lncludlng flow and compacLlon behavlor and Lhe vlscoslLy of suspenslons lor
speclflc appllcaLlon such as glass beads used ln hlghway palnL shape ls a crlLlcal facLor for
reflecLlvlLy When parLlcle shape lnformaLlon ls requlred mlcroscopy and lmage analysls are
Lhe only Lechnlques LhaL dellvery Lhe deslred daLa Manual mlcroscopy provldes baslc
quallLaLlve slze and shape lnformaLlon buL auLomaLed lmage analysls generaLes
quanLlLaLlve daLa LhaL ls sLaLlsLlcally slgnlflcanL lor Lhls reason boLh dynamlc and sLaLlc
lmage analysls are growlng Lechnlques replaclng manual mlcroscopy Surface charge or zeLa
poLenLlal of suspenslons ls lmporLanL lnformaLlon for formulaLors lor Lhese appllcaLlons
Lechnlques provldlng boLh parLlcle slze and zeLa poLenLlal (along wlLh oLher such as pP or
conducLlvlLy) may be Lhe besL opLlons 1hese opLlons lnclude uLS sysLems wlLh lnLegraLed
zeLa poLenLlal and acousLlc sysLems llke Lhe u11201 LhaL can auLomaLlcally measure many
of Lhe deslred parameLers

Conslder Lhe appllcaLlon of wanLlng Lo measure Lhe parLlcle slze dlsLrlbuLlon of 30 nm
colloldal slllca !usL conslderlng Lhe slze range of Lhe sample lndlcaLes LhaL posslble
Lechnlques lnclude laser dlffracLlon acousLlc specLroscopy and uLS Cne quesLlon worLh
asklng would be wlll l need oLher capablllLles ln Lhe fuLure? lf l mlghL need zeLa poLenLlal ln
Lhe fuLure Lhls removes laser dlffracLlon from Lhe llsL of posslble Lechnlques lf l mlghL have
parLlcles 1m ln Lhe fuLure Lhls would ellmlnaLe uLS 8e forewarned LhaL fuLure
requlremenLs can be dlfflculL Lo ascerLaln and addlLlonal capablllLles always carry
lncremenLal cosL


WHEN TU CHUUSE LASER DIFFRACTIUN

Laser dlffracLlon ls Lhe mosL popular parLlcle slze Lechnlque for reasons lncludlng speed
ease of use and flexlblllLy 1he mosL baslc laser dlffracLlon sysLem can measure solld
parLlcles ln suspenslons and emulslons WlLh Lhe addlLlon of a dry powder feeder Lhe
lnsLrumenL can Lhen also measure dry powders ln alr 1hls ls a low concenLraLlon Lechnlque
so dlluLlon ls ofLen requlred 1he complex refracLlve lndex of Lhe sample and dlluenL musL
be known for opLlmum accuracy buL Lhls lnformaLlon ls easler Lo obLaln Lhan ls ofLen
lndlcaLed (more ofLen by compeLlLors Lhan lnformed sclenLlsLs) 1he PC8l8 L930 has a
wlde dynamlc range capable of measurlng down Lo 30nm and up Lo 3000m 1hls unlque
ablllLy Lo measure parLlcles 100nm as well as agglomeraLes as large as hundreds of
mlcrons makes Lhls a credlble cholce even for nanoLechnology appllcaLlons Slnce Lhls ls
such a powerful flexlble Lechnlque laser dlffracLlon ls ofLen Lhe besL opLlon for companles
buylng Lhelr flrsL analyzer or hoplng Lo saLlsfy mulLlple needs and appllcaLlons

CUNCLUSIUNS

1he parLlcle slze analyzer uses Lhe laser dlffracLlon meLhod Lo measure slze dlsLrlbuLlons
1hls Lechnlque uses flrsL prlnclples Lo calculaLe slze uslng llghL scaLLered off Lhe parLlcle
(edge dlffracLlon) and Lhrough Lhe parLlcle (secondary scaLLerlng refracLlon) 1he analyzer
lncorporaLes Lhe full Mle scaLLerlng Lheory Lo cover Lhe wldesL slze range currenLly avallable
Wlde measuremenL ranges fasL analyses excepLlonal preclslon and rellablllLy have made
laser dlffracLlon Lhe mosL popular modern slzlng Lechnlque ln boLh lndusLry and academla













REFERENCES

1 (CL 3) lSC 927622001 8epresenLaLlon of resulLs of parLlcle slze analysls arL
2 CalculaLlon of average parLlcle slzes/dlameLers and momenLs from parLlcle slze
dlsLrlbuLlons
2 (CL 3 4) S1M L 79903 SLandard racLlce for ueLermlnlng uaLa CrlLerla and
rocesslng for Llquld urop Slze nalysls
3 (CL 3) 1n134 arLlcle Slze 8esulL lnLerpreLaLlon number vs volume
ulsLrlbuLlons avallable aL wwwhorlbacom/us/parLlcle
4 (CL 3) lSC 133201 arLlcle slze analysls Laser dlffracLlon meLhods
3 (CL 7) lSC 133222 arLlcle slze analysls lmage analysls meLhods arL 2
uynamlc lmage analysls meLhods
6 (CLS 89 14) 8urgess ! uuffy L LLzler l Plckey arLlcle Slze nalysls S
Workshop 8eporL Cosponsored by Lhe lood and urug dmlnlsLraLlon and Lhe unlLed
SLaLes harmacopela S !ournal 2004 6 (3) rLlcle 20 (hLLp//wwwaapslorg)
7 (CL 10) 1n134 arLlcle Slze 8esulL lnLerpreLaLlon number vs volume
ulsLrlbuLlons avallable aL wwwhorlbacom/us/parLlcle
8 (CL 11) 1n136 arLlcle Slze 8esulL lnLerpreLaLlon undersLandlng arLlcle Slze
ulsLrlbuLlon CalculaLlons avallable aL wwwhorlbacom/us/parLlcle
9 (CL 12) lSC 133201 arLlcle slze analysls Laser dlffracLlon meLhods
10(CL 12) uS429 LlghL ulffracLlon MeasuremenL of arLlcle Slze
11(CL 13) Wheeler u Pow Lo LsLabllsh ManufacLurlng SpeclflcaLlons posLed on
spcspresscom aL hLLp//www spcpresscom/pdf/ManufacLurlng_SpeclflcaLlonpdf
12(CL 14) neumann eL al WhaL does a mean slze mean?" 2003 lChL presenLaLlon
aL Sesslon 39 CharacLerlzaLlon of Lnglneered parLlcles november 1621 San
lranclsco C
13(CL 16) lSC 13320 arLlcle slze analysls Laser dlffracLlon meLhods arL 1
Ceneral prlnclples
14(CL 17) undersLandlng CalculaLlon Level and lLeraLlve ueconvoluLlon"
wwwhorlbacom/us/parLlcle

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