Otto-Von-Guericke-University Magdeburg D Mechanical Process Engineering

OTTO-VON-GUERICKE-UNIVERSITY MAGDEBURG
PROCESS ENGINEERING DEPARTMENT

Mechanical Process Engineering Figure 1.1
1. Dispersity of particulate systems,

1.1 About rocks, gravel, lumps, nuggets, corn, particles, nanoparticles and
colloids
1.2 Particle characterisation - Granulometry,
1.3 Particle size distributions,
1.4 Physical particle properties
Fig_MPE_1.doc © Mechanical Process Engineering - Particle Technology Disperse Systems Prof. Dr. J. Tomas 16.03.2010 Figure 1.1
Size Scale of Polydisperse (Material) Particle Systems
10-10 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-1 1
o
1A 1 nm 1 µm 1 mm 1 cm 1m
visual ability of human eye
wave length of visible light:
ultra-
X-rays and electron interferences microscope light microscope
electron microscope
capacitive und inductive sensors
dispersity molecular-disperse colloid- high-disperse, fine-disperse coarse-disperse

disperse ultra-fine
pore dispersity microporous mesoporous macroporous
dispersed molecules makromolecules, ultra-fines fines medium grain coarse

elements colloids
one-dimensional surface coatings, liquid films, membranes

two-dimensional chains of macromolecules, needles, fibres, threads
Blatt 2
Mixtures of Polydisperse (Material) Particle Systems
10-10 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-1 1
disper- disperse
sant phase 1 Ao 1 nm 1 µm 1 mm 1 cm 1m
gas gas gas mixture

liquid aerosol, fog
solid aerosol, smoke
transition l-g foam
4B
liquid gas solution, lyosol, bubble system

liquid hydrosol micro-emulsion 5B emulsion
solid suspension 6B
solid gas xerogel, porous membrane

7B rigid-foam insulation
liquid gel 8B liquid filled, porous solid material
solid mixed crystal, solid solution, s-s alloy
9B
monodisperse = uniform-sized elements
Size Scale and Properties of Nanoparticles
Bioavailability
Quantum effects
Strongly developed
surface effects
10–9 10–6 m
0,001 0,01 0,1 1 µm
1 10 100 1000 nm
Polymers
Proteins
Metal powders
Virus, DNS
Ceramic powders
Tobacco smoke
Atmospheric
aerosols
Nanoparticles for
life sciences
Expression of the Particle Size
characte- Eq./sketch measuring method,
ristic size quantity r = 0...3
breadth: b b + 1 b + l + t ⎛ b ⎞1 / 3 r = 0 number basis
, ,⎜ ⎟ , b
length: l 2 3 ⎝t⎠ r = 1 length
thickness: t 3 ⎛ 2lb + 2bt + 2lt ⎞
1/ 2
r = 2 area
, lb , ⎜ ⎟ t
1/ l + 1/ b ⎝ 6 ⎠ r = 3 volume basis
(1) equivalent diameter d, for b ≈ l ≈ t ¾ image analysis d0

(2) equivalent length l, for rods l >> b ≈ t ¾ geometric anal. d0
(3) equivalent area b ⋅ l , for chips, plates ¾ geometric anal. d0
b ≈ l >> t
(4) equivalent mass ρ s ⋅ b ⋅ l ⋅ t , for extreme
¾ mass balancing d3
shaped clusters:
Feret image analysis,
diameter number basis d0
Martin image analysis,
diameter A = A1 + A 2 number basis d0
sieve a1 a2
1
(a 1 + a 2 ) or a 1a 2 sieving, mass or
diameter 2 volume basis d3
volume V equivalent volume diameter Coulter counter
equivalent 3
6⋅V/π electrical method,
area A equivalent projection area light extinction,
equivalent diameter 4A / π number basis d0
diameter
surface area equivalent surface area diameter AS / π light extinction,
AS equiv. specific surface diameter V / A S number basis d0
diameter
physical Stokes diameter gravitational, centri-
feature v s ⋅ 18 ⋅ η fugal sedimentation
d St =
equivalent (ρ s − ρ f ) ⋅ a vs and impactor, mass
diameter basis d3
v s ⋅ 18 ⋅ η sedimentation, mass
aerodynamic diameter da =
a or volume basis d3
equivalent low angle laser light-
light-scattering scattering method,
Characterisation of Disperse Material Systems
Characterisation of granulometric properties
1. Particle size characteristics by 2. Particle size distribution function

image analysis (cumulative distribution curve)
direction of measurement
1
Qr(d)
dM dF 0,5 ΔQr(d)
dS
Qr(d2)
Qr(d1) Δd
0
dF FERET chord length du d1 d2 d0
dM MARTIN chord length d
dS maximum chord length
4. Example of measured particle size distribution

3. Frequency distribution of particle size
particle size mass mass cumulative
(distribution density curve)
fraction fraction fraction
di-1 ... di in kg Q3(di)-Q3(di-1) Q3(d) in%
in mm in %
- 0.16 0.180 1.7 1.7
qr(d) dQr(d)
qr(d) = d(d) 0.16 ... 0.63 0.648 6.1 7.8
0.63 ... 1.25 0.919 8.7 16.5
1.25 ... 2.5 1.920 18.1 34.6
2.5 ... 5.0 3.021 28.6 63.2
5.0 ... 6.3 1.084 10.3 73.5
6.3 ... 10 1.748 16.6 90.1
10 ... 16 0.761 7.2 97.3
16 ... 20 0.232 2.2 99.5
du di-1 di di+1 d0 + 20 0.054 0.5 100.0
d
10.567 100.0
5. Particle size distribution function Q3(d) and frequency distribution of particle size q3(d) of
the above example 4.
0.20
a) b)
100 qr(d) ≈ Qr(di) - Qr(di-1)
0.15 di - di-1
q3(d) in mm-1
80
Q3(d) in %
60 0.1
di-1 + di
40 Qr(d*<di) dm,i =
2
0.05
20
0 0
0 4 8 12 16 20 0 4 8 12 16 20
particle size d in mm particle size d in mm
6. Three - parameter logarithmic 7. Comparison of particle size distribution functions
normal distribution (L) with upper in a full-logarithmic, RRSB and log - normal
limit do and transformation (T) diagram (net)
99.9 99.9 99,9

99.90 3 - parameter 99.5 95
60
cumulative distribution Q(d) in %

99.50 distribution 98 40
96 1 2 3 1 2 3 1 2 3 50
97 90 20
full-logarithmic net
RRSB - net
90 80 10 full-logarith- RRSB-net
L mic -net log - normal
Qr(d)
60 6
net
50 T transformed 40 4 10
distribution 20
2 5
10
10 5
5 1
1
1 0.5 0.5
0.20 100 101 102 103 104
10-1 100 101 102 103
0.02 10-2 10-1 100 101 102
1 5 10 50 100 500
d50 do particle size d in µm
δ16 δ50 δ84 d or δ in µm
1 Log-Normal distribution
2 RRSB-distribution
3 GGS-distribution
8. RRSB - distribution in a double - logarithmic diagram
7.0 7.5 8 9 10 15 20 25 30
AS,V,K · d63 in m3/ m3
40
n 4.0 3.5 3.0 2.5 2.0 1.8 1.6 1.4 1.3 1.2 1.1 1.0 60
0.9 80
99.9 100
99 x 120
cumulative distribution Q3(d) in %
x 0.8 150
95
90 x 200
0.7 300
x 500
63.2 x 1000
50 0.6 2000
x 5000
0.5 10000
x
10 0.4
x
0.3
0.2
x
1 0.1
0.5 0
Pol -1
10 -3 10 -2 10 10 0 101 10
2
particle size d in mm
Probability Distributions
Normal Distribution:
⎡ 1 ⎛ x − μ ⎞2 ⎤
q (x ) =
1 σ2< σ1
exp ⎢ − ⋅ ⎜ ⎟ ⎥ q(x)
σ⋅ 2⋅π ⎢⎣ 2 ⎝ σ ⎠ ⎥⎦ (1)
x
⎡ 1 ⎛ t − μ ⎞2 ⎤ σ1
Q (x ) =
1
σ ⋅ 2π
∫ ⎢⎢ − 2 ⋅ ⎜⎝ σ ⎟⎠ ⎥⎥ dt
exp (2)
−∞ ⎣ ⎦
normalised :
u
⎡ t2 ⎤
Q (x ) =
1
2π
∫− ∞ ⎢⎣ − 2 ⎥⎦ dt
exp (3) Q(x) = 0.5
with
x − x 50 x 84 − x 16 μ = xh = x50 x
u= (4 ) σ= (5) 0 x16 x84
σ 2
Four - Parameter Log - Normal Distribution:
⎡ 1 ⎛ ln x − μ ⎞
2
⎤
q (x ) =
1 (6) q(x)
⋅ exp ⎢ − ⋅ ⎜⎜ ln
⎟⎟ ⎥
σ ln ⋅ x ⋅ 2 ⋅ π ⎢⎣ 2 ⎝ σ ln ⎠ ⎥⎦ 0.3
μln = 1, σln = 1
x ⎡ 1 ⎛ ln t − μ ⎞
2
⎤ (7) 0.2
Q (x ) =
1 1
σ ln ⋅ 2⋅π
∫0
t
⋅ exp ⎢ − ⎜⎜
⎢⎣ 2 ⎝ σ ln
ln
⎟⎟
⎠
⎥ dt
⎥⎦ μln = 3, σln = √3
d − d min (8) 0.1
μln = 3, σln = 1
x= ⋅ d max for d min ≤ d ≤ d max
d max − d
ln x − μ ln ⎛x ⎞ (10)
u= (9 ) σ ln =
1
⋅ ln ⎜⎜ 84 ⎟⎟ x
σ ln 2 ⎝ x 16 ⎠ 0 5 10 15
WEIBULL (RRSB) - Distribution:
q(x) xu = 0
n = 0.5 n = 5.5 x* = x63 = 1
⎛ x − xu ⎞
n −1
⎡ ⎛ x−x ⎞
n
⎤
q (x ) = ∗
n 2.0
⋅ ⎜⎜ ∗ ⎟
⎟ ⋅ exp ⎢ − ⎜⎜ ∗ u
⎟
⎟ ⎥
(11)
x − xu ⎝ x − xu ⎠ ⎢⎣ ⎝ x − x u ⎠ ⎥⎦ n=3
n=2
⎡ ⎛ x−x ⎞
n
⎤ 1.0
Q (x ) = 1 − exp ⎢ − ⎜⎜ ∗ u
⎟⎟ ⎥ (12) n=1
⎢⎣ ⎝ x − x u ⎠ ⎥⎦
for xu = 0 and n = 1 follows the 0 1 2 x

1
Exponential Distribution if λ =
x63
Q(x) = 1 - exp(-λ·x) (13)
Statistical Moments of Particle Size Distributions
Complete k-th Moment of Particle Size Distribution Qr(d*<d) related to Quantity r:
do do
( )
N
∫ (d − d ) ∫ (d − d ) ⋅ dQ r (d ) ≈ ∑ d m,r ,i − d ∗
k
* k * k
d*
M k, r = ⋅ q r (d ) d (d ) = ⋅ μ r ,i (1)
du du i=1
First Initial Moment (k = 1, d* = 0) or Expected Value

do do N
M 1, r = d m,r = ∫ d ⋅ q r (d ) d (d ) = ∫ d ⋅ dQ r (d ) ≈ ∑ d m,r ,i ⋅ μ r ,i (2)
du du i =1
Central Moment related to expectation (mean) dm,r

do
d m, r M k , r = Z k ,r = ∫ ( d − d m ,r ) k q r ( d ) d ( d ) (3)
du
Second Central Moment or Variance

do do N
Z 2 ,r = σ = ∫ (d − d m,r ) q r (d ) d (d ) = ∫ (d − d m,r ) 2 dQ r (d ) ≈ ∑ (d m,r ,i − d m,r ) 2 ⋅ μ r ,i
2
r
2
(4)
du du i =1
Variance according to “Satz von Steiner”

N
σ 2r = Z 2 ,r = M 2 ,r − M 12,,r ≈ ∑ d 2m,r ,i ⋅ μ r ,i − d 2m,r (5)
i=1
Incomplete k-th Initial Moment du...d, i...n and Complete Initial Moment du...do, i...n...N
d n do N
∫ d q r (d) d (d ) ≈ ∑ d m,r ,i ⋅ μ r ,i ∫ d q r (d) d (d ) ≈ ∑ d km,r ,i ⋅ μ r ,i

k k
k
(6) (7)
du i =1 du i =1
Conversion from given quantity r to a searched quantity t of Frequency Distribution

d t − r ⋅ q r (d )
q t (d ) = (8)
M t − r ,r
and Cumulative Distribution

d n
M t − r ,r
d
du
∫
du
d t − r q r (d ) d (d ) ∑d
i =1
t−r
m , r ,i ⋅ μ r ,i
Q t (d ) = do = do ≈ N (9)
M t − r ,r
du ∫d t−r
q r (d ) d (d ) ∑d
i =1
t−r
m , r ,i ⋅ μ r ,i
du
Conversion of cumulative distributions from number to mass basis or from mass to number
basis
d n d n
∫
du
3
d q 0 (d ) d (d ) ∑d
i =1
3
m , 0 ,i ⋅ μ 0 ,i ∫
du
d −3 q 3 (d ) d (d ) ∑d
i =1
−3
m , 3,i ⋅ μ 3,i
Q 3 (d ) = do ≈ N (10) Q 0 (d ) = do ≈ N (11)
∫d 3
q 0 (d ) d (d ) ∑d
i =1
3
m , 0 ,i ⋅ μ 0 ,i ∫d −3
q 3 (d ) d (d ) ∑d
i =1
−3
m , 3,i ⋅ μ 3,i
du du
Conversion of k-th complete initial moment of a known quantity r in a searched quantity t

M k + t − r ,r
M k ,t = (12)
M t − r ,r
Cumulative Particle Size Distribution, Mass and Number Basis
d n
mass basis: Q 3 (d ) = ∫ q 3 (d ) ⋅ d(d ) ≈ ∑ μ 3,i
dU i =1
100
Verteilungsfunktion Q3(d) in %
90
80
70
60 Masseverteilung
50
40
30
20
10
0
0.5 1 5 10 50 100 500 1000
Partikelgröße in µm
d n μ 3 ,i
∫ d ⋅ q 3 ( d ) ⋅ d( d ) ∑d
−3
3
i =1
number basis: Q 0 (d ) = du
≈
m ,i
do N μ 3 ,i
∫d
−3
⋅ q 3 ( d ) ⋅ d( d ) ∑d
i =1
3
du m ,i
100
Verteilungsfunktion Q0(d) in %
90
80
70
60
Anzahlverteilung
50
40
30
20
10
0
0.5 1 5 10 50 100 500 1000
Partikelgröße in µm
Multi-modal Frequency Distribution
1.8
1.6
frequency distribution q*(log d)
1.4 subcollective 1
1.2
1.0 subcollective 2
0.8
0.6 subcollective 3
0.4
0.2
0
0.1 1.0 10.0 100.0
particle size d in mm
total frequency distribution: μSC,k(t) mass fraction of the k-th
[ ]
N
subcollective (subpopulation)
q3,tot (d, t) = ∑ μ SC,k ⋅ q3,k d, do,k , d50,k , σ ln,k
k =1
q3,k frequency distribution
truncated log-normal distribution:
of the k-th subcollective
do,k − d ⎛ u2 ⎞ do,k upper limit of the particle size
q3,k (d) = ⋅ exp⎜ − ⎟
2 π ⋅ σ ln,k ⋅ do,k ⋅d ⎝ 2⎠ of the k-th subcollective
with d50,k median particle size of the
1 ⎡ ⎛ do,k ⋅ d ⎞ ⎛ do,k ⋅ d50,k ⎞ ⎤ distribution function
u= ⎢ln⎜ ⎟ − ln⎜ ⎟⎥
σ ln,k ⎢⎣ ⎝ do,k − d⎠ ⎝ o,k
d − d 50,k ⎠ ⎥
⎦ σln,k standard deviation of the
normalisation: k-th subcollective
dQ 3 (log d) ΔQ 3 (log d) μ 3,i N total number of subcollectives

q*3,tot = ≈ =
d(log d) Δ log d ⎛ d ⎞
log⎜ i ⎟
⎝ di−1 ⎠
∞
⎛ u2 ⎞
lim ∑ μ SC,k ⋅ Q 3,k [d, d o,k , d 50,k , σ ln,k ] =
u
1
N→∞
k =1 2π ∫−∞exp⎜⎜⎝ − 2 ⎟⎟⎠ d(d) = Q3,tot (d, t)
Mass Fraction Related to the Number of Stressing Events
discrete mass balance model:
dμ sc ,1
= −S n ,1 ⋅ μ sc ,1
n
dμ sc,3 N
n
= S n ,3,1 ⋅ μ sc,1 + S n ,3, 2 ⋅ μ sc, 2 ∑μ
k =1
sc , k =1
n number of stressing events
Sk,j kinetic constants for mass transfer from j to k subcollective
measured
3
model
mass fraction µsc,k
1,0
0,8
0,6
0,4
1
0,2
2 0,0
k-th subcollective 2 3 4
3
0 1
number of stressing events n
Application of Image Analysis to Characterise Particle Size
0B
1. Image of Microscope by CCD-camera

1B
direct- trans-
light mitted
direct-light light
transmitted
light
particle
pixel number
2. Definition of Threshold Value
2B
Definition of grey tone limits

for particle detection in a 8-bit
grey tone image
0 grey tone distribution 255
3. Conversion of Grey Tone Image in a (black) (wite)
Binary Image (Binarisation)
Binary image means: which

pixel of original image is shown
by 0 (black) or by 255 (white)
4. Classification of Particles
• min. and maximum Feret diameter
dF,ma • equivalent circle diameter
d = 2⋅ A/π ,
A
dF,mi • shape factor ψ U = 4 ⋅ π ⋅
U2
dequ U = circumference, A = projection
area
Presentation of Particle Size Fractions

in a Colour Code
Principle of Laser Light Diffraction
large diffraction for particle size d ≈ λ wavelength, small diffraction for d >> λ
sample cell
Fourier detector
lense system lense
r
laser
f
focal distance
principle of laser light diffractometer

computer
¾ light diffraction pattern detector

Fourier lense
¾ radial light intensity
distribution at detector r
d max
I tot = ∫N
d min
tot ⋅ q 0 (d ) ⋅ I( r , d i ) d (d )
¾ particle size distribution prinziple of Fourier lense

cumulative distribution Q3 in %
frequency distribution q3 in 1/mm

particle size distribution
100
Intensity I
50
r 0
particle size
In-Line Particle Size Analysis (Sympatec)
feed opening
particle loaded air stream
inductive sensor
drive for rotating

sampling device
on-line sampling
dispersion air
detector with
sensor array
laser beam
low-angle laser
light-scattering
instrument
(LALLS)
d = 0.5 – 1750
µm
nozzle and
sample cell
isokinetic sampling device for a split particle stream:

rotating sector moving pipe
d
α
D D
In-Line Particle Size Analysis (Malvern)
isokinetic sampling
particle
stream
laser particle
feed back
Injektion nozzle detector
pressurized air
monitoring of size ranges: 0.5 - 200 µm

1.0 - 400 µm
2.25 - 850 µm
Principle of Photon – Correlation Spectrometer (PCS)
¾ in suspensions at rest: light scattering at dispersed particles, that oscillate by Brownian
molecular motion
Laser Optik Probenbehälter
Photomultiplier Korrelator
Optische Einheit
¾ Determination of intensity – time function of scattered light (reasons: interferences,

change of particle number concentration within the charac-teristic volume element)
and calculation of autocorrelation function:
intensity of scattered light
autocorrelation function RI,I(τ)
fine particle
coarse particle
time t retardation time τ
• Autocorrelation function (Dp – particle diffusion coefficient, K – scattered light vector,

τ - retardation time)
T
R I, I (τ) = lim ∫ I( t ) ⋅ I( t + τ) dt = e
− 2⋅ D p ⋅ K 2 ⋅ τ
kB ⋅T
T →∞ with d =
−T 3 ⋅ π ⋅ η ⋅ Dp
• EINSTEIN equation (d – particle size, kB – BOLTZMANN constant, T – absolute
temperature, η - dynamic viscosity)
page 1
1. Physical Principle
Laser diffraction technique is based on the phenominon that particles scatter light
in all directions (backscattering and diffraction) with an intensity that is dependent
on particle size
2. Measurement setup
Using two laser beams with different wavelength (red and blue light) additional
information to particles smaller 0,2 µm is obtained
red light setup large angle

Detectors
forward angle
backscatter
Laser Θ
Fourier lens Sample chamber
- scattering light hits only forward angle detectors

- the angle of the deflected laser beam is inverse proportional to the particle size
large angle
Detectors
blue light setup forward angle
backscatter
Laser
Θ
Fourier lens Sample chamber
- blue light (wavelength 466 nm) leads to a scattering signal for small particles
(isotropic scattering pattern) which can be detected from large angle- and
backscatter- detectors
Device features: - range: 20 nm to 2000 µm page 2
- high resolution
- dilute suspension, (low particle concentration)
3. Data Analysis Technique

Light Scattering
1000
Light scattering data 500
0
0 5 10 15 20 25 30 35 40 45 50
De t e c t or Numbe r
Determining the Particle Size Distribution (equivalent sphere radius) by means of

MIE -Theory
∞
light intensity distributionwhich receive each detector
I(Θ) = ∫I(r,Θ) q(r) dr r - particle radius
0 q(r) - frequency distribution of particles
Θ - angle of scattered light
at finite num ber of detectors the above integral equation induce to a system of
linear equations (area m atrix)
⎡f1 ⎤ ⎡c11 ⋅ c1n ⎤ ⎡r1 ⎤

⎢ ⋅ ⎥ = ⎢ ⋅ ⋅ ⋅ ⎥⋅⎢ ⋅ ⎥ f - vector for measured detecor intensity
⎢ ⎥ ⎢ ⎥ ⎢ ⎥ c - Solutions of above equation I(Θ)
⎢⎣fn ⎥⎦ ⎢⎣cn1 ⋅ cnn ⎥⎦ ⎢⎣rn ⎥⎦ r - vector for particle size
Particle Size Distribution

10
100
9
8
80
7
V o lu m e ( % )
Result Report 6 60
5 Θ
4 40
3
2 20
1
0 0
1 10 100 1000 2000
Particle Size (µm)
Principle of Acoustic Attenuation Spectroscopy
¾ during acoustic wave penetration, amplitude and intensity attenuation (damping) of
ultrasonic frequency spectrum (1 to 100 MHz) in high concentrated particle
suspensions with sizes d = 10 nm – 1 mm
Suspension
Level sensor
HF Transmitter HF Receiver
LF Transmitter LF Receiver
Stopper motor
and digital
encoder
Transducer
Positioning Table
Stirrer Discharge
Control
module
Microwave
and
DSP module
¾ detection of attenuation (damping) spectrum

¾ correlation between attenuation
RF generator RF detector
characteristics and particle size distribution
(K = 2⋅π/λ suspension wave number, k fluid x << λ
entrainment
wave number, ϕs particle volume
concentration, i = 1...n particle size fraction,
ri particle radius, Ami reflected compression
wave coefficient, ARe real contribution, m
number of acoustic dispersion coefficient):
3 n i ⋅ ϕs ,i ∞
2
⎛K⎞
⎜ ⎟ = 1 − ∑ 3 3 ∑ (2m + 1)A Re ⋅ A mi
⎝k⎠ 2 i=1 k ⋅ ri m=0 λ x >> λ
scattering
measuring zone
cumulative distribution Q3 in %
frequency distribution q3 in 1/mm
particle size distribution

damping
100
50
frequency 0
particle size
Determination of Particle Size Distribution and Zeta-Potential using
Electroacoustic Effect - Electrokinetic Sonic Amplitude (ESA)
1. Physical Principle
Alternating electric field (frequency range 1 to 20 MHz) generates particle oscillations
at velocities that depend on their size and zeta potential (O' Brien- Theory)
Δρ
Δρ ∼ Δp ESA = A(ω ) ⋅ ϕ s ⋅ ⋅ Z ⋅ μE
ρp
A(ω) calibration function

ϕs volume fraction of particles
Δρ suspension density difference
acoustic signal (ESA) as response ρp particle density
Z acoustic impedance (complex resistance)
2. Measurement Setup electrophoretic mobility (µE)

r
v ζ
μE = r = ε0 ⋅εr ⋅
ESA-Signal
Processing
E η
ε0 permittivity of vacuum
εr permittivity
v particle velocity
E electric field strength
η viscosity
suspension
μ m = ∫ μ E (d , ζ , ϕ s ) ⋅ q(d )d (d )
3. Data Analysis
Particle motion in an electric field
E;v
μm measured dynamic mobility

Tim e
ζ zeta-potential
applied electric field particle velocity d particle diameter
ϕs volume fraction of particles
q(d) particle size frequency distribution
Mobility Spectrum
phase lag
µm
adjusting q(d) and zeta-potential ζ from
phase lag
dyn. mobility
the measured mobility spectrum
frequency
Photoluminescence
Wavelength of visible light
UV IR
400 500 600 700
wavelength λ in nm
a) Phosphorescence, life time > 10-5 s, here t ≈ 20 min
energy level
inradiation transition
light radiation
initial particle particle after
excitation quasi transparent grinding
b) Fluorescence, wavelength shift λ↑, life time <10-5s
initial particle particle after grinding
Online Size Measurement by Particle Photoluminescence
MIR
1
feed
particle
activation v discharge
cell
cuvette D
stirred tank mill

phosphorescence cell
photomultiplier
a) Phosphorescence reduction (decreasing of transparency) due to
stressing, cracking, surface displacement and defects
2
I0 - initial intensity (J/m )
phosphorescence intensity ratio I/I0
1.0
I - current intensity
0.8
0.6
0.4
0.2
0.0
0 5 10 15 20 25
surface diameter dST in μm
b) Fluorescence spectra of zinc sulfide particles to determine the surface
diameter
HeCd Laser
excitation at λ = 325 nm
Mono- Sample
chromator
CCD Camera
⎛ I(λ ) ⎞
Normalised fluorescence intensity i = I / ∫ I(λ)dλ and d = f ⎜⎜ ⎟⎟ 1
λ
3B
⎝ I ( ) ⎠ 2
surface diameter dST

0.012
20 μm
8.1μm
0.010
initial line 1.5μm
Normalised intensity i
0.79μm
0.008 0.54μm
defect line
0.006
0.004
0.002
0.000
400 425 450 475 500 525 550 575 600 625 650
Wavelength λ in nm
Advantage: Online measurement of crystalline particles without

agglomeration influence.
Particle Density Measurement by HELIUM-Pycnometer
¾ Determination of pore–free particle volume by gas pressure measurement in a double-
chamber system by HELIUM gas (migration access of internal pores dPore > 0,1 nm)
probe chamber P pressure
feed valve discharge valve

Helium
filter
prep./ test valve
overpressure
valve
5
VProbe
VCell 5, V Exp
35
VCell 35,
V Exp
VCell 150
150
V Exp
• Pressure measurement in probe chamber: (VCell –VProbe) p1
• Pressure test in probe and expansion chamber: (VCell –VProbe) + VExp p2
• Calculation of probe volume and solid density, pre-measurement of particle mass ms

by balance
VExp ms
VPr obe = VCell − and
ρs =
p1 / p 2 − 1 VPr obe
Measurement of Particle Surface by Gas Adsorption according to
BRUNAUER, EMMET and TELLER
¾ Physical adsorption of gas molecules at particle surfaces in multi-layers due to VAN
DER WAALS interaction
gas supply vacuum
P
adsorbed gasv olume Vg

desorption
dosing
valve T P
adsorption
standard vessel
BET range
sorption isotherms
0 0.35 1
probe chamber relative partial pressure of gas p/p0
dewar vessel adsorbed
T p0 - test chamber gas molecules
(adsorpt)
liquid nitrogen adsorptiv
N2 at T = 77 K
p0 = 101 kPa particle surface
(adsorbens)
¾ BET- line, valid for: 0.05 < p/p0 < 0.3
• Adsorpt mono-layer coverage:
p / p0 1 C BET − 1
= + ⋅ p / p0 1
Vg (1 − p / p 0 ) Vg ,mono ⋅ C BET Vg ,mono ⋅ C BET Vg ,mono =
a+b
p / p0
• BET- constant:
Vg (1 − p / p0 ) ⎡ ΔH m − ΔH multi ⎤ a + b
C BET = exp ⎢ ⎥= a
b=
(CBET −1) ⎣ R⋅ T ⎦
ΔH m free molar adsorption enthalpy of
Vg,mono⋅ CBET mono-layer
ΔH multi molar bonding enthalpy of n
multi-layers ≅
1 ΔHcondensation
a=
Vg,mono⋅ CBET • Particle Surface:
A S = A M ,g ⋅ N A ⋅ Vg ,mono / Vm ,l
relative gas pressure p / p 0 AM,g cross-sectional area of adsorpt
molecule
NA AVOGADRO-number
Vm,l molar volume of condensed adsorpt
z c
Regular Packing Structures
β α
b
y porosity ε, coordination number k
x γ
a
lattice type primitive basic face- face-centred space-centred

centred
cubic
a=b=c
α = β = γ = 90 °
a0
a0 ≈ 0,1nm k = 6 k = 12 k=8
monodisperse
sphere
packing
d = const.
d
ε = 0,4764 ε = 0,3955
hexagonal
a=b=c
α = β = 90 °
γ = 120 °
k = 12
octahedron
sphere vacancy
packing
tetrahedron
vacancy
ε = 0,2595
PROCESS ENGINEERING DEPARTMENT E.g. influence of packing density:
Stressing and Flow of Wet Particle Dispersions
particle in liquid dispersion (suspension) paste liquid in particle packing
diluted concentrated liquid saturated moist packing
τ τ σ τ σ τ
suspension ux
and particle
dy dy ux vx
flow pattern y
. du dy
x γ = dyx ux vx
flow function τ τ τ τ
τ ≠ f (σ) σ τ ≈ f ( γ. )
. . .
shear rate γ γ γ normal stress σ
cubical cell σ
τ d
packing d
τ τ d
model τ
d
a a
ϕs a
=
εs,0
( 1+ )
a -3 a
d
τ d
d τ
d τ τ
a a a
a
particle a a a a contact
separation >1 0 < d < 0.2 =0 contact -0.01 < <0
d d d deformation
particle π εs > π
volume ϕs < 0.066 π εs,0 =
0.3 < ϕs < 6 6
fraction
s
6 pore saturation S = 1 S<1

particle
friction ϕi = 0 ϕi = 0 ϕi ≥ 0 ϕi > 30°
Sampling

Otto-Von-Guericke-University Magdeburg D Mechanical Process Engineering

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Otto-Von-Guericke-University Magdeburg D Mechanical Process Engineering

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OTTO-VON-GUERICKE-UNIVERSITY MAGDEBURG

PROCESS ENGINEERING DEPARTMENT

1. Dispersity of particulate systems,

Size Scale of Polydisperse (Material) Particle Systems

capacitive und inductive sensors

dispersity molecular-disperse colloid- high-disperse, fine-disperse coarse-disperse

pore dispersity microporous mesoporous macroporous

dispersed molecules makromolecules, ultra-fines fines medium grain coarse

one-dimensional surface coatings, liquid films, membranes

gas gas gas mixture

liquid gas solution, lyosol, bubble system

solid gas xerogel, porous membrane

monodisperse = uniform-sized elements

Size Scale and Properties of Nanoparticles

(1) equivalent diameter d, for b ≈ l ≈ t ¾ image analysis d0

Characterisation of granulometric properties

1. Particle size characteristics by 2. Particle size distribution function

4. Example of measured particle size distribution

99.9 99.9 99,9

cumulative distribution Q(d) in %

8. RRSB - distribution in a double - logarithmic diagram

Four - Parameter Log - Normal Distribution:

WEIBULL (RRSB) - Distribution:

for xu = 0 and n = 1 follows the 0 1 2 x

First Initial Moment (k = 1, d* = 0) or Expected Value

Central Moment related to expectation (mean) dm,r

Second Central Moment or Variance

Variance according to “Satz von Steiner”

∫ d q r (d) d (d ) ≈ ∑ d m,r ,i ⋅ μ r ,i ∫ d q r (d) d (d ) ≈ ∑ d km,r ,i ⋅ μ r ,i

Conversion from given quantity r to a searched quantity t of Frequency Distribution

and Cumulative Distribution

Conversion of k-th complete initial moment of a known quantity r in a searched quantity t

dQ 3 (log d) ΔQ 3 (log d) μ 3,i N total number of subcollectives

Mass Fraction Related to the Number of Stressing Events

discrete mass balance model:

mass fraction µsc,k

1. Image of Microscope by CCD-camera

Definition of grey tone limits

Binary image means: which

Presentation of Particle Size Fractions

principle of laser light diffractometer

¾ light diffraction pattern detector

¾ particle size distribution prinziple of Fourier lense

frequency distribution q3 in 1/mm

drive for rotating

isokinetic sampling device for a split particle stream:

Injektion nozzle detector

monitoring of size ranges: 0.5 - 200 µm

Laser Optik Probenbehälter

¾ Determination of intensity – time function of scattered light (reasons: interferences,

autocorrelation function RI,I(τ)

time t retardation time τ

• Autocorrelation function (Dp – particle diffusion coefficient, K – scattered light vector,

red light setup large angle

Fourier lens Sample chamber

- scattering light hits only forward angle detectors

Fourier lens Sample chamber

- dilute suspension, (low particle concentration)

3. Data Analysis Technique

Light scattering data 500

Determining the Particle Size Distribution (equivalent sphere radius) by means of

⎡f1 ⎤ ⎡c11 ⋅ c1n ⎤ ⎡r1 ⎤

Particle Size Distribution