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Non-Destructive Measurement of Gelatin Content of European Papers: 1400-1800
An Honors Thesis (HONRS 499)
by
Brenda S. Fuller
Patricia Lang, Advisor
Ball State University
Muncie, Indiana
Date of Graduation
May 4, 1996
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Purpose of Thesis
The broad purpose of our research is to determine the effect of gelatin
concentration on paper permanence, in collaboration with paper scientist Tim
Barrett of the University of Iowa. Our specific research goal is to use attenuated
total reflectance (ATR) infrared spectroscopy and various factor analysis methods
to characterize historical papers in a non-destructive manner. We have tested
and developed the infrared sampling techniques and have compared several
factor analysis methods to determine a method which can best be used to analyze
properties of the paper samples.
The method that proved most useful allows
gelatin properties to be estimated by their infrared spectras, provides accurate
predictions of sulfur and potassium content, and estimates the paper's date.
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INTRODUCTION
HISTORY OF PAPER-MAKING IN EUROPE
In Europe between fourteen hundred and eighteen hundred, gelatin was commonly used in
the paper-making process for several reasons. Gelatin was used as a sizing agent, and it helped
prevent bleeding of the ink. Gelatin also increased the strength of the paper and made the paper
more resistant to abrasion. Some studies suggest gelatin acts as a buffering system against
environmental pollutants that catalyze the acidic degradation of paper. It is still unclear what
effect, if any, gelatin has on paper permanence.
FIRST STUDIES OF GELATIN CONTENT OF HISTORICAL PAPERS
Tim Barrett of the University of Iowa originated the study of the effect of gelatin on
paper permanence. He took forty historical papers and divided them into two groups according
to their light values that were measured using a Minolta Chroma-meter. Surface pH, calcium
content, iron content, sulfur content, and potassium content, as well as the gelatin content were
all measured. The gelatin content, or percent hide glue, was determined by the concentration of
4-hydroxyproline. A significant correlation between these values and the light values was
found, indicating that these properties aid in the preservation of paper. This also means that
gelatin may aid in the preservation of paper. However, in order to validate this notion, a nondestructive method for determining gelatin for a larger number of samples would need to be
employed. This is the primary purpose for our study.
EXPERIMENTAL METHODS
PRINCIPLES OF ATR
We have chosen an infrared sampling process known as attenuated total reflectance
(ATR). ATR is a non-destructive method of internal reflectance spectroscopy, meaning that the
paper sample is not destroyed when the spectrum is taken. The paper sample is placed directly
.1
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against two sides of a crystal with a high refractive index (See Figure 1). A KRS-5 element was
used in this research. Complete internal reflection occurs at the interface of the sample and
element, given that the angle of incidence is less than the critical angle. Some radiation
inevitably penetrates the surface of the sample, and the sample absorbs particular frequencies.
These absorptions provide the infrared spectra and characteristic peaks.
Gelatin has several characteristic infrared absorption bands (See Spectrum 1). The
main two bands are the amide I band and the amide II band. The amide I band is caused by the C=O
stretching of the amide bonds (found at approximately 1650 cm- 1), and the amide II band is a
result of the C-N-H bending (found at approximately 1550 cm- 1).
PROCEDURE
First, acceptable spectra from both sides of each sample had to be taken using the ATR
accessory coupled to a Perkin-Elmer 1760X FT-I R spectrometer. Care had to be taken so that
enough pressure was applied to the sample to obtain a good spectrum without fracturing the
crystal. The spectra from the two sides of the sample were averaged together to decrease the
effect of the inhomogeneities of the paper.
The spectra of 25 of the 40 historical paper samples were then run through the
statistical package (Quant +, Perkin-Elmer software), principle components regression (PCR)
as a calibration set.
(The remaining 15 samples were not used because visible evidence showed
damage sustained during previously performed pH measurements.) The PCR algorithm attempts
to express the variation in the spectral data in as few terms as possible. PCR takes the raw
spectral data and breaks it down into a set of weighted factors. Then, the computer drops those
factors that do not correlate to the given properties. This produces a set of factors that are then
compared to the properties of the standard set. Factors may be either positive or negative. The
first factor is approximately the weighted average of all the original spectra. The rest of the
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factors account for the residual variation in the data set (See Figure 2).
2
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When the significant factors are recognized, their contributions to the calibration
spectra are calculated. These contributions are called the factor loadings. A set of loadings
corresponds to the contributions of each factor to its calibration spectrum.
Multiple linear
regression is then used to identify correlations between the factor loadings and the properties of
the samples.
Factors that show little correlation to a property are eliminated until the
remaining factors show a significant correlation. By using graphs, known values of properties
in the calibration set are compared with those predicted by the regression equation. The linear
regression of the graph provides a correlation factor for the set.
To generate the best model possible, the expert assist option was used for our models.
Expert assist automatically rejects abnormal or eschewed standards until the best possible
model is generated.
RESULTS AND DISCUSSION
Graph 1 shows the correlation for the computer's predictions of gelatin concentration
from the regression equation vs. the "known" gelatin concentration obtained by the wet
chemical hydroxyproline method. From a calibration set of 25 historic paper samples, we have
a multiple correlation of 0.8057, a significant R value considering the calibration set was
constructed with a wide variety of paper samples of different natural origin. In addition, we find
that five factors were extracted from the set of 25 spectra and three correlate with gelatin. In
addition, since our collaborators had characterized each of these papers with regard to surface
pH, calcium, sulfur, iron, potassium, fluorescence, and light, we entered these values for those
properties into our statistical package and did a regression to see if any extracted factors
correlated with them. This is shown in the lower portion of Table 1. We can see that sulfur,
potassium, and date correlate with an R value of about 0.7 or higher. In addition, or perhaps
more interesting, some extracted factors are common among different properties. For example
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3
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factor four and five correlate with gelatin, sulfur, and potassium. We speculate that this
relationship might be related to the fact that alum (unalum potassium sulfate) was often used in
conjunction with gelatin sizing.
To validate this method, the factor analysis package performed a full cross-validation
test on the data set. Using information from the validation report, graphs of estimated
validation values vs. specified values were constructed for each property (See graphs 2-10).
Gelatin, sulfur, and potassium concentrations showed high correlations, indicating that this
method showed promise for the predictions of these properties.
In order to evaluate the effect aging had on our prediction capabilities, we analyzed a set
of three papers from an earlier study: a Whatman filter paper, the same paper after gelatin
sizing, and the same paper gelatin sized after accelerated aging (exposure to auto exhaust
followed by heat). We obtained spectra using the same procedure as outlined for the historical
papers in our calibration set, then used the factor analysis model previously developed. The
results can be seen in Table 2: IR Predicted Properties of Artificially Aged Filter Papers.
There is essentially no difference between the aged and unaged samples when we estimate
the error in our ability to calculate gelatin concentration as being approximately equal to the
concentration calculated for the 0% gelatin sample. This implies that the spectral
characteristics detected in our method that are not connected with gelatin are not changed by the
aging method. The properties of L*, pH, date, and calcium all show little differences between
aged and unaged samples as well. It should be noted that there is a significant difference in the L*
values of the paper with no gelatin and the papers with gelatin.
In an attempt to increase prediction capabilities, a new calibration set was created by
adding known flax standards. The flax samples included flax with 0% , 0.5%, 1.0%, 2.0%,
4.0%, 6.0%, and 8.0% gelatin. After the new calibration set was run through the factor
analysis program defined earlier, factors one and two were plotted against each other since they
4
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are the two factors that show the most variance. Circles were drawn around each cluster of data
points, and only one data point was chosen from each cluster. (See figure 3). This provided a
new calibration set, with a mor-e even distribution of values, making the data less weighted.
Graph 11 shows an estimated vs. specified plot for gelatin concentration after the flax samples
were combined with the 25 paper samples, and after the "clustering" procedure was performed
on the new set. The R value for gelatin was found to be 0.9298. The R values for the other
properties are as follows:
potassium, 0.5391;
pH, 0.4560;
iron, 0.9985;
L', 0.6020;
calcium, 0.7227;
sulfur, 0.8665;
fluorescence, 0.9687; and date, 0.8165.
(See Table 3 for
a breakdown of each of the contributing factors.) The samples deleted as a result of the
clustering method were then used as test samples to validate the computer's ability to
accurately predict gelatin content and the other properties using our new calibration set. This
information was converted into graphs showing estimated vs. specified values for each of the
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properties. In some of the graphs, outliers decreased R values, so they were removed. The R
value of gelatin for this validation set was 0.27925 (See Graph 12). After the outlier (Sample
117T) was removed, an R value of 0.62835 was obtained (See Graph 12B). The other R values
are as follows:
pH, 0.17543 (See Graph 13); L', 0.20006 (See Graph 14) - After the
outlier (Sample 82T) was removed, an R value of 0.50562 was obtained (See Graph 14B);
calcium, 0.23225 (See Graph 15) - After the outlier (Sample 82T) was removed, an R value
of 0.37593 was obtained (See Graph 15B); sulfur, 0.43382 (See Graph 16);
0.55501 (See Graph 17);
potassium,
iron, 0.30236 (See Graph 18); fluorescence, 0.55588 (See Graph
19); and date, 0.29721 (See Graph 20) - After the outlier (Sample 157W) was removed, an
R value of 0.70115 was obtained (See Graph 20B).
The flax samples were then removed from the "clustered" calibration set to observe the
effect of the flax samples in our new method. The R value of gelatin was significantly lower
(R=0.3614. See Graph 21) for this data set than the set with the flax samples added
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band (See Spectrum 1). The relative pathlength of the standards were then determined from the
reference band.
CONCLUSIONS
The use of factor analysis allows an automated, objective method of extracting the
spectral features which are responsible for the variance among the samples in the calibration
set. These features may not be apparent visually to the analyst, are often overlapped, or are
affected by baseline variations, noise and impurities. Once a method's parameters have been
established, sample prediction is simplified greatly. Now, the analysis can be performed
repeatedly to analyze other samples. The multiple linear regression allows more than one
factor to be used in the calculation of a property value. This usually improves the results.
Overall, factor analysis has the potential for use as a non-destructive and simultaneous method
of determining several properties: pH, calcium, etc. Factor analysis also shows promise for
providing insights on the relationship between various paper constituents.
It can be concluded that instruments that would analyze the pH of papers without causing
as much damage as current methods would improve the results. Portable instruments for
measuring ultrasonic wave propagation, infrared, and x-ray fluorescence would be very helpful
in the non-destructive determination of these properties of historical papers as well. The
horizontal ATR accessory shows promise for a more non-destructive method of analyzing the
papers. The paper can be placed directly on the crystal, and clamped into place. This means that
the paper does not need to be cut. Also, the clamp is calibrated, so the pressure on each sample
can be equal. This allows for better reproducibility. We have not done intensive research using
this accessory, but a few samples were examined, and the spectrum obtained appear to be
acceptable as well. Therefore, this study deserves further research.
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7
(R=0.9298). The R values for pH, calcium, and date were lower than the previous set as well
(See Table 4 for a breakdown of each of the contributing factors). This method was then
evaluated in the same manner as with the method that included flax. The information obtained
was converted into graphs showing estimated vs. specified values for each of the properties. The
R value for gelatin for this calibration set was 0.23975 (See Graph 22). The other R values
are as follows:
pH, 0.08476 (See Graph 23);
0.0013642 (See Graph 25);
Graph 27);
L*, 0.10065 (See Graph 24);
sulfur, 0.35944 (See Graph 26);
iron, 0.35923 (See Graph 28);
calcium,
potassium, 0.53877 (See
fluorescence, 0.45948 (See Graph 29); and date,
0.38299 (See Graph 30).
The testing of the three methods shows that there is not a significant difference in the
first two methods. The validation tests indicate that both of these methods allow a reasonable
estimated of gelatin, sulfur, and potassium concentrations. The clustering seems to improve on
the date predictions, while decreasing the accuracy of the sulfur and potassium predictions. The
last method showed a significant decrease in the prediction capabilities of most all the
properties. Overall, our validation tests show that the first method is generally the most
useful.
Throughout our research, inhomogeneity within a given sample has limited the
reproducibility of our predictions. Since one side of a sample might have a higher gelatin
content than the other, we compensated by averaging the spectrum from each side together.
The other factor that affects reproducibility is the penetration depth the radiation. This
penetration depth differs between samples for two reasons. The surfaces of the samples are
different, and the pressure applied to the sample against the crystal is also variable. Since the
path lengths of the standards are unknown, normalization parameters were adjusted to overcome
thickness variations by using the cellulose absorptions from 900 t01250 cm- 1 as a reference
6
ACKNOWLEDGEMENTS
I would like to take this opportunity to thank everyone who has helped me in any way
with my thesis. First, I would like to thank my advisor Dr. Lang for all of the guidance she has
given me. Her excellent teaching abilities triggered my interest in research.
Timothy Barrett for initiating the research on historical papers.
I am grateful to
I would also like to thank the
Honors college undergraduate fellowship program for providing funding for our research.
Finally, I would like to thank my parents and my family for supporting me in every way, and
for always believing in me.
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8
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CORRELATIONS BEFORE FLAX SAMPLES WERE ADDED TO CALIBRATION
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PROPERTY
PCR FACTOR
CORRELATION
COEFFICIENT
GELATIN
3
4
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0.3325
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0.4633
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LIGHT
CALCIUM
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1800
Validation Test of Date
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Graph
10
IR PREDICTED PROPERTIES OF ARTIFICIALLY AGED FILTER PAPERS
SAMPLE
PREDICTED
PREDICTED
PREDICTED
PREDICTED
PREDICTED
% GELATIN
L*
pH
DATE
CALCIUM
.4
73.6
5.8
1663
-496.5
2.5
85.9
5.4
1646
2623
2.0
83.2
5.5
1676
1928
PAPER WITH
NO GELATIN
PAPER WITH
GELATIN
PAPER WITH
GELATIN,
SIZED
Table 2
-
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Principal Component 2 vs 1
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ctS
C.
·0
c:
0.3
0.2
0.1
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0
(0
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a..
-0.1
,
LI[)6~,
I G . . • ·.·•• ··0 . • ·.• • ·.• • •
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. ....
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18
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G)
I
-0.6
-0.4
-0.2
0.0
Principal Component 1
-
I
I
I
0.2
I
I
0.4
Figure 3
-
Gelatin
Flax I After
(After
2.5
.....co
-
E
.....
en
W
:
:
,
'
iL~."
3
CD
;
.
..... > . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
2
IT:I,I
1.5
·· .. ·..·..·.....·· .. ·.. ·.. ··T·~ .. ·.. ·.. ·.. ·· .................. ,!................................... ,................................... ,!................................... :
:.'
.
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1
,
.
'.
'.
!
!
R=O.9298,
,
.. ------.. --------------- ---t---------------------_···--_······-:------------------................. :....... ------------------.--.--._.-:-.... _-----------------------------:
:
~
0.5
:,
:~
:~
.
:
!
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:
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0
-0.5
0
12345
Specified
-
.
·· ..........·· ..·...... ·.. ·.. ·T ..·..·..·........·..·..·..·..·.. ··~·· .. ·.. ·.. ·.. ·......................,...............................,................... ..
3.5
"'C
..
Clustering)
Graph
11
CORRELATIONS AFTER FLAX SAMPLES WERE ADDED TO CALIBRATION
AND AFTER CLUSTERING
PROPERTY
PCR FACTOR
CORRELATION
COEFFICIENT
GELATIN
1
3
4
5
-0.3132
-0.4562
0.5464
0.5096
pH
LIGHT
CALCIUM
I
I
I
IRON
FLUORESCENCE
DATE
5
5
I
I
I
3
4
SULFUR
POTASSIUM
4
I
4
-0.4560
0.6020
0.7227
MULTIPLE
CORRELATION
(IF APPLICABLE)
0.9298
I
I
I
0.5105
0.4919
I
-0.5391
0.8665
I
1
2
4
5
-0.0409
-0.9937
-0.1925
-0.0378
2
4
5
0.8262
0.3358
0.3825
0.9687
1
2
3
0.4376
-0.2422
0.4407
0.8165
0.9985
Table 3
Validation Test of Gelatin
(After Flax I After Clustering)
3 . ----------------,----------------------.----------------------.----------------------,--------.-------------.----------------------,------------.-----------.
.'
T~·~'.~T·r+
.
t
'
,
.
•
2
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Q)
1
:
:
:
.. ------;--_ ... ----------------l-----.......... ------;---------..... ------.L----... -------------
1
ctS
E
en
W
.•
o
------------.-~---------------------i----------------- -----,---------------------i---------------------+------ ---------------f--------------------------------------------~
R=O.27: 925
~
:
:
:
:
:
:
:
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- 1
•
•
•
-2~++rH~++rH~++~~++~~++~~++~
o
0.5
1
1 .5
2
Specified
-
2.5
3
3.5
4
Graph
12
-
(After
3
Validation Test of Gelatin
Flax/After Clustering/Outlier
....................,....................................................,.........................,.................................................,.........................,
: . i."l , ·
2
....................
+-'
en
W
. .
'
----_ .............. -:. __ . __ .. _--------- .......:- .. __ .. ----
1
• .
;............................................... ;....................... ;........................ ;:.................. ;.........................:
,
-
Removed)
,
,
---.- ........
-~----
,
.
:
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:
:
--------_ .. _------- .----.-------------- ... .
_
o
- 1
-2
-1--1-+-+-+-+-+--+-+-+-+---+--11--+-+-+-+--+---+-+-+-+-+--+-1--1-+-+-+-+-+--+-+-+--+--1
o
0.5
1
1.5
2
Specified
-
2.5
3
3.5
Graph
128
,-
Validation Test of pH
(After Flax I After Clustering)
.::
9
-----------------1----.··.··.··---------,------------.·_-------f----------------------,---------------------r-----------,
,
,
.
.
.........................L........!.........., . . . . . . . l............l . . . . . . . . . .
•
••
R=O,17543
•
8
W
:
:
____ . __ ._ ... _.. _.j_ .. _.. __ . __ . ________ ._~ ______ .___________ .__ l__ .__ .__ .________ .__ .L. _____ .. _______ .__ .__ ~ ____________ ._ .. __ .__ l__ .________ .. __ .__ .__ .~ ________ .__.____ .""
7
.....
en
6
:
5
:
I.
:
:
:
:
5.5
6
6.5
7
.•'.
i
:
:
7.5
8
' ......•...... +.~...............: .................... ; .....•..... "."; .............. ".,, .. ;..................... , ............... "."; .............. ,, .. :
•
4
4
4.5
5
Specified
-
----.-,------..
--------------,...... ------------.--.. ,,
,
Graph
13
-
98
96
94
-
"'C
Q)
+-'
ctI
Validation Test of Light
(After Flax I After Clustering)
...................................1.................. ··················1··································· ...... ,...............................:
....................................... ;................................•.......i...........................······· ..·.....··i········ .. · ....... ·········· ........ ........ ~
............... _-_._------_. __ . __ ...... ,,~ ........ __ ._-------- ........ __ . __ ._------ ... ,i, ....... __ . __ . __ .............. _------_. __ .... ,i, ...... __ ._--_._--_ ....... _----_.--'----'-'--,:,
R=O.20006
92
...... ---._. -_. ------'- --.-. ---........ ~.- ... ------.. -............ --- -------..... j. -_. -------_. -.. _.......... ---------_. -..... ;... -------_ .. _. -_."-' _... ----_. _. -_........ :
E
+-'
en
UJ
90
. ----.
--- ........... ------- --- ---- -- ..
-~
:
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~
.
-~
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i
:
:
.
..
.
.:. .
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~
~
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86
................................
:
"
...... _. --- --- --- _._. -....... ----------- ....... -- ---- -_. --- _............ ---------.- .... ------_. _... -..... _.. _. ------- _.... _.- -.:
:
88
:
;
............................................
• •
,
:
:
~.......................
.:-:-
.
....•....................................•.......................................
84~~-+~+-~-r~+-~~4-~-+~~
75
80
85
Specified
-
90
95
Graph
14
-
Validation Test of Light
Flax/After Clustering/Outlier
(After
89
.
i~':
•
~
88
.
,
R=O,50562
.-
-
87
W
86
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Q)
m
E
en
-
-- --- --- --- -. -_ .. _. -------- --- --- --- --- --..... _.. _. -- --- --- _.-' -_ .. .. _. --- --- --~-
"
-~.
••
--- --- ----- --- --- --- ----... _. --- ----
•
•
•
,
--.- ---. -----_. -- ---- --_. -_ ..... -_. -- ----- -_. -.,
••
••
•
···---···-f--------------------·------------········--";-• ------ ... --._ .. ------------.. -----------•
.
:
•
...
,
...........L.........................................:.......................................,..........................................:
85
•
75
•
80
85
Specified
-
Removed)
.....................................................................................,..........................................,...........................................
90
95
Graph
148
Validation Test of Calcium
Flax I After
7000 (After
..................................................
-.-.- .......Clustering)
- .... -. . "-- .... .
"'C
Q)
+-'
ro
:
.
6000
-_. ---.--.. _.. _. -----' _. ~-- ---------. --... -_._. ----_. -~. ---_. ---. -_. --...... --_ .. -.-~. _... _... ---------_. _.- -.--- .~- ... ---_.- .. -----.... -----_. -t· ,." -_. -_. -----_. -_. _. -' --.-~
5000
j
:
---_ ... --------------... ,-.: ........ --------------_ .. _.,------_·--------·----------·'T···-----·---·········--------T·------···_·--------···-·····,---··----------·-------------,
.:
.:
.!
,
,
-
R=O.23225
4000
. ..
- . - . . . . . . . . . . . . . . . . . , .. - ..... - . . . . . . . . . . . . . . . . . . . , ... - . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . --.-- . . . . . . . . . . . . . . . . . . - . . . . . . . . . . . . . . . --.; . . . . . . . . . . - . - . . . . . . . . . . 1
:
E
+-'
en
:
_~__.•..~ .. -.. --
......... _.. _..
w 3000
-
:
2000
:
..
:
:
:
....... j.........-........ _............ _.. __ ..... 1........ __ ._ ......... __ ............ _...... .
-
~
.....: .......... ---.• .......... --.... j
-
-
;
-
______ .; _______ ... ________ ... _____ ...1________________ -------------l--..... --_._---- ...... _____ ._i
ill
1000
•
0
0
4000
8000
Specified
-
-
1.200 1 0
Graph
15
4
Validation Test of Calcium
Flax/After Clustering/Outlier
{After
3500
"'C
Q)
,-.
+'"
m
E
+'"
en
w
Removed)
························r····························r ............................ ]......................... ····;····························T·····.·············· .... j
..I · '
.
,
i.
'
,
,.
,.
3000
.......................J ......................... L. ........................... L........................ !.............................;.............................:
2500
..................,........·. · . ·. ]". . . ·. ··. ·.............. ,··. ·......·....·. ·. ·. ·T. ·• ................,··..............·......
2000
i·..··....·..·..·..·..··j·I..·..····..·..·..··.........,': .............................I:-............................I,.............................:,
.. ·· ..•··.... ···· ..·.. ···1··.·
•
•
•
:j
:
!:
:
:
:
1
!:
._. --------_. -_. --,." --~ .. -.. -. ------ -_ .. " --'--' -- .-~ --_. -- _.' -----_ ....... -------j-'.... _.. _. -------_. '.' ----- .~ .. --------_. ----_. ------_.. --~. _...... -_. -----_. '.. _. -----·i
1500
.......................!.............................,..................................8 . ;::..0.....3. 7. 5..9.3., ............................
1000
1
I
500
I
•
•
!
····.·---.--·--·--·-,1'-·---------····.····-------'1·.·_·····_-----------_···--_·t---------···-------- --.. --.~-.--.--.-- .. -.. --.--.--.-- .. -;.--.-- --------------_.-- ....
0
0
4000
8000
Specified
-
1.200 1 0
Graph
4
158
Validation Test of Sulfur
(After Flax I After Clustering)
4000
-- ---- ---- -- _... -...
~.
.
--_. -- ---- -_. ----- .. -. ":" _. --- --------- .. -. .. ----:- ---- --- _._ .. -.. ----- -_. -:--- --- _.- --_. -- ------.. --:" -_. -_. -----_. --- -_. _. _. -: --_. -- -"-' -_. -- ----' -_.":
_
'
. . . . . . . . . . ,.; . . . . . . . . .J. . . . . . . . . . . . ,. . . . . . . . . . . [ . . . . . . :. . . . . . . . . . . . i . . . . . . . . . . •
..
3000
:
2000
,-
:.
;
.................. ........................................ ;.........................•........................ .........................
:...•...................
"'0
Q)
+-'
co
E 1000
+-'
en
...
~ ............. ;.........................:.......... ··············;·························t·············............~......................... ;.........................•
ill~=O.43~J21
UJ
0
-1000
•
o
1 000 2000 3000 4000 5000 60007000
Specified
-
Graph
16
-
2000
1 500
"C
2co
1 000
Validation Test of Potassium
(After Flax I After Clustering)
-------------------------,-----------------------------,-----------------------------,-----------------------------,------------ - ------,
i
'
:
:
:
i
.i
------------ - _ _ 1..._______________________1___________ --------------;-------------------------;-------------------------,------------------------------ j
.
•
--
CJ)
500
:.'.
-----------------------r-------------------------'-----------------------------------------
: ..
,
.
E
w
]
• .,
:.
:
:.
: . .:
:
------------------------.------------------------------------------------------------------------------------------------------- ---:----------------------------.
:
•
o
:
R=O.55501
------------------------L---------------------------<-----------------------------i-----------------------------i-----------------------------i-----------------------------
o
500
1000 1500 2000 2500 3000
Specified
-
:
----.--+-----------------.------i---------------------------:
Graph
17
170
Validation Test of Iron
(After Flax I After Clustering)
...................................................................................;........................................,..................... :.....................•
I
-
"'0
Q)
.......
ctS
150
E
.......
(/)
UJ
~
•
I·.il;·~i:r·i-.:
160
...............•.....
.............................•..........
........................•...................•...................•................
~
140
.................~ ..................•..•...............L..... ............;......................l..................···:····················,,·····················1
130
.................................l~,·, .~~p.~ot~~
1.1
•
120~~~~~~~~~~~~~~~
o
50 100 150 200 250 300 350 400
Specified
Graph
18
100
Validation Test of Fluorescence
(After Flax I After Clustering)
80
----------------------------------,-------------------------
.
CD
,-
+-'
co
E
+-'
en
w
,
.
,
,
,
••
!
.
!
•
!
.
--------------------;-----------------------.-----------------------:------------------------:-------------------------j"------------------------;-------------------------,
60
"'C
•
•
--------------------,-------!--------------~----.----------------,------------------------+---------
.~
40
1··. . . .1·············.·..
•........................... ,........................1......................
.
·····1 ..................•
•_____________________~___________________ ~ ___________________ ----L-----__________________
• R=OJ555Sls
.______________________ L ____________ _
20
:
.
.
.
.
.
.
:,
:.
[
~
:
:
~:~r::T:j
0
- 20
•
-40~~~++++++~~~~HH~~~++++~
o
50
100 150 200 250 300 350
Specified
Graph
19
2100
Validation Test of Date
(After Flax I After Clustering)
--------------------,.--------
----------------.--.-.----------.--.--.--.--.--,---------------------.---.------------.---------.--,--.------.--
2000
-
~
+-'
1900
ctI
E
+-'
t.TI
1800
!~:~,~~;J1ir:;:
_____________ ._ ._ ._ ._________ ____ ._ L. _____ .______________ ~------------------------ :-- ____________________ ,________________________ L____ .----___________,
:
.
1700
..
.
----------------+--------------------->-----_.
:
•
i-
------+------------------------'--------------;-----r-------
,
:
• ••••
•• ••
-----.--'-~----------
• I
160044++~~~++~~~4+++~~~++~
14501500155016001650170017501800
Specified
-
Graph
20
-
(After
Validation Test of Date
Flax/After Clustering/Outlier
Removed)
1900
..................................................................,.........................,.........................,................. .
1850
------------___ .____ ;.-- ---------_. -_. _-. --~ --.--.--.--.--.--.--.. -.J. ------------.--.. - ---: -----_. --. -----.--------~- --_-_. --.-- ----.--.. -;.--.--.-----_. __ .. __ ---.-~
•
:
!
!
j
R=O.!70115
-
(])
co
E
en
1750
+-'
1650
.
.
.,~lL
UJ
1700
i
••
'I'·
1800
"'C
+-'
:
................... : ..................... , ....................
.................;
..
•
,
..
• ~;~
~
.................... : .................... '....
.............. , ..................... .
:
,
............................................. : ........................ :.........................
,••
...... ..
1600~~~~~~~~~~~~~~~
14501500155016001650170017501800
Specified
-
Graph
20B
-
2.5
Gelatin
Flax I After
(Before
•
•
••
Q)
-
W
•
•
---------------- . -----.-----""._.
1 .5
ro
E
en
•
..............................;................................... j...................................:.......................................................................•
2
"'C
Clustering)
.....................................................................................................,...................................,................................... :
:
-- --- --- ----.- ~--. -- .... -------- ---------- ----- --- ;-- --- .. --_. _.- .. _.- --- ---- -_. -- --~ ---- .. _. ----- --- ---- --- --- -_
:
:
:.:
:
1
.
:
:
_
--"""
]
:
::
;
.........•...............•......................................................................................................... ................................ .
•
I
• R=O.3614
----_. --.---". -.--_... --_._. ---j--------_."' ----_. -----. --_._. --- --~-- ---------. -... ".. _.. _.. _. -------- ~--- ----_. -.... -----_. _.. -- ----- -~. -_. -_ ... _. ----- ---_. -_. ------. -.
0.5
o
1
2
3
Specified
4
5
Graph
21
CORRELATIONS WITH NO FLAX ADDED TO CALIBRATION
AND AFTER CLUSTERING
GELATIN
pH
LIGHT
CALCIUM
I
I
I
I
SULFUR
-
POTASSIUM
IRON
I
3
2
3
1
I
I
I
I
I
0.3614
-0.3960
0.4374
-0.3123
1
2
3
4
0.5890
-0.2416
-0.6785
-0.7481
1
4
5
0.4938
-0.4457
-0.4910
2
I
1
-0.9199
MULTIPLE
CORRELATION
(IF APPLICABLE)
I
I
I
I
0.9965
0.8170
I
-0.3658
0.2633
-0.3137
-0.6279
2
3
4
5
FLUORESCENCE
DATE
CORRELATION
COEFFICIENT
PCR FACTOR
PROPERTY
I
0.4241
0.8558
I
Table 4
-
-
Validation Test of Gelatin
(Before Flax I After Clustering)
3
.. ----.-.- .. ---.-.--.-- ... -.............,.......................--_._-----------------,------.-- ........................... _---_. __ .,---------_._----_ .....,... __ .... _------------,
2.5
-----.--------.--------------------"--------------------,--------------------L----------------.---------.--.--•. -, .... --.---.--.--.--.- .. -.--.... -.-
.
,
,
2
,-
1.5
E
1
w
0.5
Q)
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.....
C/)
[
1
'
i,
t
,
. . ..
~
"'C
,
~
~.
:
~
.
-----------------i------------------- : ----.-.
.
~
.
.:
.
,
~
-.. -.. -.. -.. --.-~ .. -.................•... _._------_. __ ._-.-_._ ............... .
-_. __ . __ .. _........ _.. _.. __ . __ . __ . __ .. _. __ ......•......................... -
:
~
,
, .
~'
:
:
:
:
... -.-~ ... -..... -.--.-------{.---------------------~-----.- .. --.... --.--.~-.------------.
:
:
------+-------_._._----.---- i
.............L.................. -+ ........... -.... -: .. -................ .!..............·..·....i-· .. ·.. ··-··-·······i....................... -.. -....... -..... i
.
,
.
. . . . -.-.- .............-.. . . . .-.......................-.. . . . . .
:
a
:
:
:
:
f
f
ri:f~·{f[·2·3
:
.
'
. 9·"7-5. ····-··· ..........•-·· . ·:
:
:
ii:!I+::
-0.5
- 1
a
0.5
1
1.5
2
Specified
-
2.5
3
3.5
4
Graph
22
-
Validation Test of pH
(Before Flax I After Clustering)
...................................... :...............······[·r········································,···············;····················i
7
- -------_. _._ .. _;.- --- --- --- ---------- -------_. -----. _.- -----------.. _. ---i'- -----------. --. ".- -----------_.- ---.. '- i --- -_._-
6.5
-
1:)
Q)
+-'
co
E
•
,
~-.
--~--.
,
,
en
,
1
6
,
,
.. ..
'
5.5
- -- -
•
-.. _, .. ---- - -- -- -- --
~.
••
_. -------- -- -- --.-- ._------ - - --.- ----------- -- --
••
--~.-
'._-_...... ----j-- .. -.-- .... ---------.~-.-- .. --.------------:
\
j
~
1
6.5
7
••
................. ,..................... j, ....................,..................... j ...................l.....................:.......................................
5
•
4
4.5
j
5
5.5
R=~.08476
6
Specified
-
1
................•..................•..................···················.·T···································r················.···················:
••
'
,
:
'
i
'
,
+-'
W
--------- ... -----:
--~
7.5
8
Graph
23
-
92
Validation Test of Light
(Before Flax I After Clustering)
.
.
:
:
:
:
-------------.----------------------i--------------------------------------------~----.------------------------------------,------------.----------------------------'
90
•
:
•
: ••
:
• •
:
:
i
•
I
---------------------------------------j-------------------------------------------+-.--------------------------------------,--------------------------------------------~
"'C
86
ro
E
en
84
_. -----------------------.-............ "i-"" ..... _-----------_. _.. _.............. --~--. -_. -_. ----_. ---.-................. ----- -·i --_. ----......... --- _... -------_ .. ----_ ..... :
82
---------------------------------------~---------------.-------------------------:----------------,---------------------------.------------.---.---------------------------i
80
---.-....................... -.. --------~-------.-- ............... ---------------.... ;............ -------------_ .................. ;-----_. __ .-_ ........ __ .... _--------------_ .. !
78
.................. _... _---------------_.j-_._ .......... _-------------_._-_ .......... _;---------------_ .. _........... _---_._-------; ......... _._ .. _..... __ ._ ......... __ .__ ..... -!
- -Q)
W
75
• •
•
i
:
,
- R=O.10io65
80
85
Specified
-
•
....................................... ~.- --- ._ ..... _......... -............. __ . _.- -- ;--- -- --_. --- ---- .. -.................. ----- --~- -_. _.. -............ _.... ---_. -_. _. ----' -- .. :
88
:
90
i
'
95
Graph
24
-
3500
Validation Test of Calcium
(Before Flax I After Clustering)
...............................•.................................................;.............................,.............................;...........................
•
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4000
8000
Specified
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Graph
25
4
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4000
Validation Test of Sulfur
(Before Flax I After Clustering)
....................,.........................,.........................,........................,.........................,........................,.........................;
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1000 2000 3000 4000 5000 60007000
Specified
-
Graph
26
-
5000
Validation Test of Potassium
(Before Flax I After Clustering)
.........................:.............................,.............................,.............................,.............................,.............................:
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Specified
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Graph
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220
Validation Test of Iron
(Before Flax I After Clustering)
.................[......................•.............······T···················T··················r····················;-····················T······················
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Graph
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12 0
Validation Test of Fluorescence
(Before Flax I After Clustering)
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0
50
100
150
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Specified
-
250
300 350
Graph
29
1770
1760
1750
-
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1740
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Validation Test of Date
(Before Flax I After Clustering)
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1700
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1690
14501500155016001650170017501800
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Graph
30