Professional Documents
Culture Documents
26 (2002) 253-260
TBTAK
Received: 11.02.20002
Abstract: There have been some problems reported associated with the use of alkyl ketene dimer (AKD) in alkali papermaking.
Excessive use of size emulsion, poor size performance when filler used, problems with back water contamination, poor retention,
and formation of pitch deposits on machinery are some of the problems experienced during papermaking operations. In addition,
paper containing AKD is reported to lose its resistance, over time against liquid penetration and tends to become slippery. Therefore,
in this study, the retention and reaction mechanisms of AKD internal sizing agent in a paper matrix were investigated by capillary
gas chromatography (GC) in an attempt to better understand paper sizing with AKD. Results are expressed as the mean value of at
least three repetitive tests along with standard deviation (SD) and coefficient of variation (COV). A number of different paper samples
were made on a pilot paper machine with different AKD addition levels. AKD levels in wet and machine dry paper were extracted
and analysed in GC. Precipitated calcium carbonate (PCC) loading was observed to increase AKD retention. The amount of bound
AKD in wet paper significantly increased as a result of drying. Nevertheless, in general the reacted AKD only constituted a very small
portion of the total retained AKD. Paper sizing was found to be achieved by bound AKD. This means that an even lower additional
level of AKD would be sufficient to ensure good paper sizing provided that it forms a chemical bond with furnish. This result is
believed to be important in solving some problems associated with AKD sizing.
Key Words: Alkali paper, AKD sizing, retention, gas chromatography
Alkil Keten Dimer (AKD)in Pilot Kat Makinasnda Yaplan Katlardaki Tutunmasnn
Kantitatif Olarak Belirlenmesi
zet: Alkali kat yapmnda Alkil Keten Dimer (AKD) kullanlmas ile balantl olan bir takm problemler olduu bildirilmektedir.
Aflr dozda emulsiyon kullanm, dolgu maddesi kullanldnda dflk i yapfltrma performans, elek alt suyu kontaminasyon
problemleri, zayf tutunma ve makinalarda yapflkan benekcikler oluflumu gibi problemler kat yapm srasnda karfllafllan
problemlerden bazlardr. Ayrca AKD ieren katlarn zaman ierisinde svlara olan direnlerini kaybettikleri ve kaygan bir yapya
ulafltklarda bildirilmektedir. Bu nedenle bu alflmada, alkil keten dimer (AKD)in kat ierisindeki tutunma ve reaksiyon
mekanizmas, AKD ile i yapfltrmay daha iyi anlayabilmek iin kapilar gaz kromatografisi (GC) kullanlarak arafltrlmfltr. Sonular
en az testin ortalamas olarak, standart sapma (SD) ve varyasyon katsays (COV) ile verilmifltir. Bir seri kat rnekleri, pilot kat
makinasnda farkl AKD katlmlar ile retilmifltir. Islak ve makina kurusu katlar ierisinde bulunan AKD ekstrakte edilmifl ve GCde
incelenmifltir. Kat hamuruna keltilmifl kalsiyum karbonat (PCC) eklenmesi AKD tutunmasn artrmfltr. Islak katlar ierisindeki
selloz liflerine balanmfl olan AKD miktarnda katlarn kurutulmas sonucu nemli bir artfl gerekleflmifltir. Bununla birlikte genel
olarak, bal AKD miktar kat ierisinde tutunmufl olan toplam AKDnin ancak ok kk bir yzdesini oluflturmaktadr.
yapfltrmann balanmfl AKD tarafndan saland bulunmufltur. Bu selloz lifleri ile kimyasal ba yapt srece ok daha az bir AKD
katlmasnn iyi bir i yapfltrma iin yeterli olacan gstermektedir. Bu sonucun, yukarda bahsedilmifl olan AKD i yapfltrmasnda
karfllafllan baz problemlerin zm asndan nemli olduuna inanlmaktadr.
Anahtar Szckler: Alkali kat, AKD i yapfltrma, tutunma, gaz kromatograf
Introduction
Over the last two decades the paper industry has
witnessed a rapid conversion from an acid to
neutral/alkali system where alkyl ketene dimer (AKD) is
the main sizing agent extensively used in the pH range of
7-10 (Dumas, 1980; Abell, 1985; Wiley, 1989; Crouse
and Wimer, 1990). AKDs are waxy materials which are
253
Quantitative Determination of Alkyl Ketene Dimer (AKD) Retention in Paper Made on a Pilot Paper Machine
R1
H2 O
C
R1
CH 2
H
H
C H(R 2)
Beta-keto Acid
R2
CO 2
Cellulose
R1
R1
C H2
C H(R 2)
Cellulose
Beta-keto Ester
Figure 1.
254
C
Ketone
C H2
The proposed reaction mechanisms of alkyl ketene dimer with cellulose fibre and water.
C H2
R2
A. KARADEMR
Figure 2.
C-35
C-33
10.0
15.0
mU
70.0
65.0
60.0
55.0
50.0
45.0
40.0
35.0
30.0
25.0
20.0
15.0
0.0
5.0
minutes
C-31
C-29
Papermaking
HEXADECANE
20.0
255
Quantitative Determination of Alkyl Ketene Dimer (AKD) Retention in Paper Made on a Pilot Paper Machine
Table 1.
Retention
Mean
(%)
SD
26
COV
(%)
AKD
Addition
(mg/g)
Retention
Mean
(%)
SD
12
58
11
COV
(%)
21
11
56
31
60
45
63
51
75
A. KARADEMR
AKD
Addition
(mg/g)
Retention
Mean
(mg/g)
SD
COV
(%)
AKD
Addition
(mg/g)
Retention
Mean
(mg/g)
SD
COV
(%)
0
1
2
3
4
5
0.00
0.22
0.39
0.86
1.71
2.40
0.00
0.04
0.06
0.04
0.07
0.10
0
16
14
4
4
4
0
1
2
3
4
5
0.00
0.53
1.06
1.72
2.38
3.61
0.00
0.06
0.09
0.09
0.10
0.13
0
11
9
5
4
4
Form of
AKD
Extracted
AKD
Addition
(mg/g)
Retention
Mean
(mg/g)
SD
COV
(%)
AKD
Addition
(mg/g)
Retention
Mean
(mg/g)
SD
COV
(%)
0
1
2
3
4
5
0.00
0.04
0.04
0.07
0.09
0.13
0.00
0.01
0.01
0.01
0.02
0.02
0
25
25
16
18
16
0
1
2
3
4
5
0.00
0.05
0.06
0.09
0.14
0.16
0.00
0.01
0.01
0.02
0.03
0.03
0
20
20
18
18
16
Bound AKD
(mg/g)
Form of
AKD
Extracted
Form of
AKD
Extracted
AKD
Addition
(mg/g)
Retention
Mean
(mg/g)
SD
COV
(%)
AKD
Addition
(mg/g)
Retention
Mean
(mg/g)
SD
COV
(%)
Unbound AKD
(mg/g)
0
1
2
3
4
5
0.00
0.19
0.27
0.77
1.36
1.81
0.00
0.04
0.05
0.09
0.10
0.13
0
19
19
12
8
7
0
1
2
3
4
5
0.00
0.37
0.84
1.31
1.70
2.83
0.00
0.08
0.12
0.13
0.13
0.17
0
21
14
10
8
6
Form of
AKD
Extracted
AKD
Addition
(mg/g)
Retention
Mean
(mg/g)
SD
COV
(%)
AKD
Addition
(mg/g)
Retention
Mean
(mg/g)
SD
COV
(%)
0
1
2
3
4
5
0.00
0.09
0.16
0.28
0.28
0.33
0.00
0.02
0.02
0.04
0.04
0.05
0
16
13
13
13
14
0
1
2
3
4
5
0.00
0.24
0.39
0.76
0.81
0.77
0.00
0.05
0.06
0.10
0.09
0.07
0
19
16
13
11
9
Bound AKD
(mg/g)
Table 3.
Unbound AKD
(mg/g)
Table 2.
257
Quantitative Determination of Alkyl Ketene Dimer (AKD) Retention in Paper Made on a Pilot Paper Machine
0.10
1800
1600
1400
Hercules Sizing Degree (second)
0.08
0.06
0.04
0.02
0.00
0.0
1200
1000
800
600
400
200
0.1
0.2
0.3
0.4
258
1
2
3
4
Bound and Unbound AKD Extracted (mg/g)
Figure 4.
A. KARADEMR
Table 4.
HST
Mean
(Second)
SD
COV
(%)
AKD
Addition
(mg/g)
682
39
1430
57
1533
50
1601
61
1607
60
HST
Mean
(Second)
SD
COV
(%)
46
222
15
523
37
660
40
664
41
Conclusions
AKD retention at the wet end was quantitatively
determined by employing capillary GC. Retention was
thought to be due to opposite charge attraction rather
then any strong chemical formation. Interaction between
References
Abell, S. 1985. Alkaline papermaking and rosin size. In: Proceedings of
TAPPI Alkaline Papermaking Conference, TAPPI Press. pp. 31-36.
Bartz, W.J., W.E. Darroch, and F.L. Kurrle, 1994. Alkyl Ketene Dimer
Sizing Efficiency and Reversion in Calcium Carbonate Filled
Papers. Tappi J. 12: 139-148.
Bottroff, K.J. and M.J. Sullivan, 1993. New insight into the AKD sizing
mechanism. Nordic Pulp and Paper Research J. 8: 86-95.
Gill R.A. 1990. PCC fillers: High opacity and a whole lot more.
Neutral/Alkaline Papermaking Short Course, Tappi press. pp. 9197.
259
Quantitative Determination of Alkyl Ketene Dimer (AKD) Retention in Paper Made on a Pilot Paper Machine
Roberts, J.C. 1996. Neutral and alkaline sizing. In: Paper Chemistry, 2nd
ed. (Ed. J.C. Roberts), Blacklie A&P, Glasgow, UK, pp. 140-159.
Roberts, J.C., D.N. Garner and U.D. Akpabio. 1985. The mechanism of
alkyl ketene dimer sizing of paper, part I. Tappi J. 4: 118-121.
260