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Journal of Cultural Heritage 15 (2014) 144–150

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Original article

The identification of organic additives in traditional lime mortar


Shi Qiang Fang a,c , Hui Zhang b , Bing Jian Zhang a,b,∗ , Ye Zheng a
a
Department of Chemistry, Zhejiang University, 310027 Hangzhou, China
b
Department of Cultural Heritage and Museology, Zhejiang University, 310028 Hangzhou, China
c
College of Chemical Engineering and Materials Science, Zhejiang University of Technology, 310014 Hangzhou, China

a r t i c l e i n f o a b s t r a c t

Article history: Organic-inorganic lime mortars were widely used in many ancient buildings due to their good perfor-
Received 3 December 2012 mance in some fields (such as caking property, water repellency, weatherability, etc.). However, many
Accepted 8 April 2013 ancient buildings and sites are suffering from various degrees of damage with the development of the
Available online 14 May 2013
economy and society and appropriate conservation and restoration are needed. The application of tradi-
tional construction materials, such as organic-inorganic lime mortars, attracts more and more attention
Keywords: in the conservation and restoration of ancient buildings in the recent years. So, the understanding of the
Lime mortar
components of original lime mortar which remained in ancient sites is of fundamental significance. In this
Organic additives
Chemical analysis
work a set of analytical procedures to identify the organic additives in lime mortars by classical chemical
Detection analysis is proposed. The results show that using iodine-potassium iodide reagent, Benedict’s reagent,
Historic preservation reduction phenolphthalein reagent, Coomassie brilliant blue and sodium periodate oxidation glycerin
acetyl acetone method could effectively detect a small amount of starch, reducing sugar, blood, pro-
tein and fatty acid ester that remained in ancient buildings’ lime mortars, respectively. These analytical
methods are easy to operate with low detection limit, high accuracy and some other advantages.
© 2013 Elsevier Masson SAS. All rights reserved.

1. Introduction and research aims Different lime mortars have different compositions, ratios, appli-
cations and properties. So, a reliable detection method could help
During the long history, lots of architectural sites were us deeply understand the materials used in different construction
remained. They reflected our ancestor’s wisdom and provided valu- sites, and also could provide a guide to select appropriate repair
able materials to study our history for later generations. However, a materials.
lot of historical buildings and sites are facing huge threat because of As far as we know, the studies of inorganic additives in lime
the explosion of modern industrial and traffic activities, man-made mortars are abundant [4,5,9–11], while the research about organic-
destruction and increasing tourism pressure. Therefore, protecting inorganic lime mortar is scarce. At present, the analytical methods
these precious cultural relics is urgent. for organic additives in mortars mostly rely on instrument analysis
Cement paste as modern building material has been used for the and biological analysis. However, the instrumental analysis may
restoration of ancient architecture in the past few decades. But the not be feasible for the in situ analysis of mortar in ancient sites
disadvantages of cement, such as too high strength, low porosity, because of the limitation of instruments, such as their requirement
poor compatibility with ancient buildings and the introduction of of professional and complicated analysis, high costs, etc. Even the
soluble salts, have been revealed by conservation scientists [1–3]. portable instruments may not be able to detect the tiny amount
However, lime mortars, the traditional construction cementing of additives in complicated mortar mixtures. But a reliable analyt-
materials had been widely applied around the world. Today, lots ical result about the information of additives in mortar is always
of lime mortars which were used in ancient sites are still working. needed as soon as possible in archaeological field work for the con-
For instance, hydraulic mortar prepared by lime with ash, clay and sideration of in situ handling and future conservation. So, a simple
brick powder [4,5], organic-inorganic lime mortar prepared by lime and effective method to analyze ancient mortars is important to
with sticky-rice, blood, juice of plants, drying oil or egg white [6,7], study and understand the original mortar’s content and structure
and reinforced mortar prepared by lime with straw and fiber [8]. in ancient architectures.
In this work, a simple and effective method to analyze the
organic additives in ancient building lime mortars is proposed using
∗ Corresponding author. Tel.: +86057187997523. classical chemical analysis. This method, combining with other
E-mail addresses: fangshiqiang@gmail.com (S.Q. Fang), huizhang@zju.edu.cn analysis means, could provide the original information about the
(H. Zhang), zhangbiji@zju.edu.cn (B.J. Zhang), 704747260@qq.com (Y. Zheng). ancient sites for future conservation and restoration.

1296-2074/$ – see front matter © 2013 Elsevier Masson SAS. All rights reserved.
http://dx.doi.org/10.1016/j.culher.2013.04.001
S.Q. Fang et al. / Journal of Cultural Heritage 15 (2014) 144–150 145

2. Experimental methods 2.2.1. Sugar lime mortar and egg white lime mortar
Weigh certain amount of brown sugar (or egg white) and make
2.1. Reagents different concentrations of solutions (0.1, 0.25, 0.5, 1.0, 2.0, 4.0, 6.0%
(w/w)). Then mix the solution with Ca(OH)2 completely (the ratio
Iodine-potassium iodide reagent: 3 g potassium iodide dissolv- of H2 O/Ca(OH)2 is 0.8) and daub the mortar on the glass plate. The
ing in 100 ml distilled water. And add 1 g iodine after the potassium samples were stored in laboratory for 3 months before test.
iodide was completely dissolved. This reagent was kept in brown
bottle before test. 2.2.2. Sticky-rice lime mortar
Benedict’s reagent: dissolve 85 g sodium citrate and 50 g anhy- Weigh 4 g sticky-rice and 94 g distilled water, and boil for
drous sodium carbonate in 400 ml distilled water. This solution was 4 hours. During the boiling process add sufficient water to keep
marked as reagent 1. Weigh 8.5 g anhydrous cupric sulfate and the ratio of sticky-rice/water unchanged. The concentration of this
dissolve into 50 ml hot distilled water. And mark this solution as sticky-rice slurry is 6%. Use the same method to prepare other
reagent 2. Add reagent 2 into reagent 1 and stir. Then keep it in sticky-rice slurry with different ratio (0.1, 0.25, 0.5, 1.0, 2.0, 4.0%).
bottle after filtered. Mix the aforesaid sticky-rice slurry with Ca(OH)2 (the ratio of
Coomassie brilliant blue reagent: weigh 100 mg Coomassie bril- H2 O/Ca(OH)2 is 0.8) and daub the mortar on the glass plate. The
liant blue G250 and dissolve in 50 ml 95% ethanol. Add 100 ml 85% samples were stored in laboratory for 3 months before test.
phosphoric acid and distilled water to reach 1000 ml. This solution
was kept under 4 ◦ C after filtered. 2.2.3. Tung-oil lime mortar
Reducing phenolphthalein reagent: add 100 ml 20% KOH solu- Add certain amount of tung-oil and Ca(OH)2 into iron container.
tion, 2 g phenolphthalein and 1 g zinc into 250 ml round bottom Then grind the mortar repeatedly until the mortar become fine
flask. Heat the solution until colorless. Add some zinc powder into and smooth. The samples should also be stored in laboratory for
the colorless solution and keep in brown bottle. 3 months before test.
Takayama’s reagent: weigh 3 g glucose, 3 ml pyridine, 3 ml 10%
NaOH solution and 7 ml distilled water and mix them completely.
2.2.4. Blood lime mortar
The solution should be stored for 24 hours before test.
Squeeze the fresh animal blood clot with the help of gauze. Then
Sodium periodate solution: weigh 1.065 g sodium periodate,
mix the blood with 17% lime water (the ratio of blood and lime
4.8 g and 15.4 g acetic acid ammonium acetate, then add water to
water is 10:7). Place the mixed solution in water bath (30 ◦ C) for
reach 100 ml. The concentration of sodium periodate solution is
3 hours. At last, mix the above products with appropriate Ca(OH)2
0.05 mol/L.
completely. This kind of mortar is called blood lime mortar. The
Acetyl acetone solution: add 4 ml acetyl acetone into 96 ml iso-
mortar was daubed on the glass plate and stored in laboratory for
propyl alcohol and mix them completely.
3 months before test.

2.2. Preparation of simulated mortar samples 2.3. Methodology

The preparation of simulated mortar samples refers to the pro- In this paper, the classical chemical analytical methods
duction technology of Chinese traditional mortar [7,12–14]. were selected to detect the organic additives in lime mortar.

Fig. 1. The analytical flow diagram of blood and starch in lime mortar.
146 S.Q. Fang et al. / Journal of Cultural Heritage 15 (2014) 144–150

Fig. 2. The analytical flow diagram of protein and sugar in lime mortar.

Iodine-potassium iodide reagent, Benedict’s reagent, reduction additives. Usually this value is under 5% (the content of drying
phenolphthalein reagent, Coomassie brilliant blue and sodium oil in traditional mortar could reach 25%). Nonetheless, the actual
periodate oxidation glycerin acetyl acetone method were selected quantity of organics in real ancient mortars is lower than 5% due
to detect the starch, reducing sugar, blood, protein and fatty acid to the degradation processes proceeding for hundreds and even
ester respectively in lime mortar. The analysis flow diagrams are thousands years. Therefore, only the methods with lower detection
shown in Figs. 1–3. limit could be used for detecting the organic additives in ancient
mortar. The detection limits of the test methods in this paper were
3. Results and discussion shown in Table 1. From the data we can see that except egg white
lime mortar, the detection limits of the rest four kinds of mor-
3.1. Negative control tests tar could satisfy the requirement of microanalysis. The detected

The analytical results of five simulated traditional lime mortar


were shown in Fig. 4 according to the above methods. From the
results we can see in the iodine starch test, reducing sugar detec-
tion and blood stain test only sticky-rice lime mortar, sugar lime
mortar (the sugar had been changed to glucose and fructose in the
test) and blood lime mortar present positive reaction, respectively
(Fig. 4E, D and C). Since blood and egg white both contain protein,
the blood lime mortar and egg white lime mortar present positive
reaction in the protein test (Fig. 4B). Similarly, because the tung-
oil and blood contain glyceride, both of tung-oil lime mortar and
blood lime mortar present positive reaction in the glyceride test
(Fig. 4A). However, the sugar lime mortar also presents weak fluo-
rescent yellow in the glyceride test. This is a false positive reaction.
In this paper, the mortar prepared by 6% sugar solution was sug-
gested as the reference sample because the concentration of organic
additives was usually below 5% in traditional lime mortars [15]. The
mortar contains drying oil or blood if the observed fluorescent yel-
low is much deeper than the reference. If the color change is similar
to the reference, further analysis should be performed to confirm
whether the sample contains glyceride.

3.2. Limit of detection

The content of organic additives in traditional lime mortar is


based on the application of mortar and the characteristics of organic Fig. 3. The analytical flow diagram of putty.
S.Q. Fang et al. / Journal of Cultural Heritage 15 (2014) 144–150 147

Fig. 4. Pictures of the negative control tests. A. Glyceride. B. Protein. C. Blood. D. Reducing sugar. E. Starch.

concentrations of organic matters were one to two orders of mag- the growth of bacteria. In addition, it was found that some types
nitude smaller than the added organic additives in the simulated of mortar (for instance, sticky-rice lime mortar and tung-oil lime
mortar samples. So, this method could meet the requirement of mortar) had smaller pores after curing (Fig. 5). This structure may
analysis from the view of detection limit. reduce the risk of decay and loss of organics.

3.3. Analysis of ancient samples


3.4. Accuracy evaluation of the method
In this part, several real ancient samples were tested by our
In order to test the accuracy of the established method in
method. All of the ancient samples were gathered from different
this study, the simulated and ancient samples (which have posi-
areas or ages in China. The detailed information of the samples was
tive reaction through the above chemical analytical method) were
listed in Table 2. The detected results showed that there were more
also analyzed by Fourier transform infrared spectrometer (FT-IR,
than two-thirds of the ancient samples containing one or more
NICOLET 560). In the infrared spectral analysis the samples were
organic targets. It proved that in ancient China people using these
prepared in KBr pellet with the resolution of 2 cm−1 and test range
organic-inorganic compound mortars in architecture and engineer-
from 4000 to 400 cm−1 . The results were shown in Fig. 6.
ing was common. At the same time, the test results coincided with
The chemical compositions of brown sugar and starch are
the records in ancient documents. For instance, part of the Nanjing
mainly sucrose and polysaccharide, respectively. Sucrose and
old city wall was built with sticky-rice lime mortar according to
polysaccharide have absorptions between 1000 and 1200 cm−1
records [16]. Sticky-rice and tung-oil usually were used to prepare
because they contain C O bonds [19]. In the FT-IR patterns, pure
mortars when building tombs or dams due to their good water-
brown sugar and sticky-rice have three peaks in this region (1000
proofness [17]. And blood lime mortar was used to make the base
to 1200 cm−1 ). While the samples prepared by sugar or sticky-
layer of frescoes [18].
rice with Ca(OH)2 only had one broad peak (Fig. 6A and B). This
Organics are easily to rot and degrade in the natural environ-
phenomenon may be caused by chemical reaction between sugar
ment. How could the organic additives in ancient mortars remain
and lime [20]. Comparing the curves of ancient samples in Fig. 6A
more than hundreds years? Through the study of sticky-rice lime
and B it can be seen that all of them have one broad peak in
mortar, Yang et al. [16] suggested that there were two reasons why
1000–1200 cm−1 wavenumber range. Through the FT-IR analysis,
the sticky-rice could preserve from decay in mortar in such a long
sucrose and polysaccharide in mortar couldn’t be distinguished.
time: first, the quick lime digestion process during the preparation
But the broad peak appearing between 1000 and 1200 cm−1 still
of mortar will release lots of heat and active oxygen. These heat and
confirms that there are sugar or other organics with C O bond in
oxygen could help kill bacteria. Secondly, Ca(OH)2 is converted into
ancient mortar when compared with simulated samples.
CaCO3 in the interior of the mortar very slowly. Thus, lots of ancient
The FT-IR results of pure blood, blood lime mortar, common lime
mortars still remain strongly basic, which could effectively inhibit
mortar and ancient mortars were shown in Fig. 6C. Since the ani-
mal blood contains lots of protein, there are three characteristic
Table 1 absorption peaks in the curve of pure blood (amide I, II, III bands)
The limit of detection of different lime mortars. [21]. These characteristic absorption peaks were also found in curve
Serial number Organics Organic content in Limit of detection of simulated blood lime mortar. But in the curve of common lime
mortar (%) (mg/ml) mortar no peak was found in these regions. Thus, these three peaks
1 Sticky-rice 0.04 0.4a
were chosen as characteristic peaks of blood lime mortar or egg
2 Blood 0.001 0.001 white lime mortar. In the curves of samples CCHJ and DZC2 there
3 Egg white 1.6 0.8 were two absorption peaks at 1651 cm−1 and 1559 cm−1 (belong to
4 Red sugar 0.4 0.087 amide I and II, respectively). While no obvious peak was found at
5 Tung oil 0.4 0.1
amide III region. Considering that no obvious broad peak was found
a
Unit: mg/g. at 3000–2250 cm−1 region, ammonium salt didn’t exist in these two
148 S.Q. Fang et al. / Journal of Cultural Heritage 15 (2014) 144–150

Table 2
Information and analytical results of ancient samples.

Serial number Date Sample sources Starch test Blood test Reducing sugar test Protein test Glycerides test
AD

SHT1 1368–1644 Hakka Earth Building in Fujiang – – – – –


Province, China (world cultural
heritage)
SHT2 1636–1911 Hakka Earth Building in Fujiang – – – – –
Province, China (world cultural
heritage)
MZHJ1 1127–1279 A tomb in Zhejiang Province, China +++ – – ++ +++
MZHJ2 1368–1644 A tomb in Jiangxi Province, China ++ – – – –
MZHJ3 1368–1644 A tomb in Jiangsu Province, China – – – – –
CQHJ1 1368–1644 Walls of Nanjing city in China – – – – –
CQHJ2 1368–1644 Walls of Nanjing city in China ++ – – – –
GTHJ1 959–961 Tiger Hill Pagoda in Jiangsu Province, ++ – – – –
China (word cultural heritage)
GTHJ2 959–961 Tiger Hill Pagoda in Jiangsu Province, – – +++ – –
China (word cultural heritage)
DZC1 1368–1644 The overall layer of Drum Tower of / – ++ – /
Xi’an in Shanxi Province, China
DZC2 1636–1911 The overall layer of stalagnate in an old – +++ – – +++
stage in Zhejiang Province, China
CCHJ 1127–1279 “Huaguang No. 1” ancient wood ship – – – + +++
SLHJ 1127–1279 A sluice gate in Zhejiang Province, ++ – – – –
China

–: negative reaction; +: weak positive reaction; ++: median positive reaction; +++: strong positive reaction; /: no test due to the limited amount of sample.

samples. Thus similar matters containing protein exist in these two in the curve of tung-oil lime mortar. However, the C O adsorp-
ancient samples. On the contrary, no peak was found at amide I tion band in the spectrum of tung-oil disappeared in the IR curve
region on the curve of MZHJ1 sample. Therfore, the existence of of tung-oil lime mortar. So the two strong bands appearing at
protein couldn’t be confirmed in this sample from FT-IR. 1610∼1560 cm−1 and 1440∼1360 cm−1 could be the evidence of
The FT-IR spectrum of tung-oil, modeling lime mortar and the existence of stretching bonds in alkyl esters (tung-oil’s main
ancient samples was shown in Fig 6D. Comparing pure tung-oil with component is alkyl ester [22]). In the FT-IR curves of three ancient
modeling lime mortars it was found that there were two charac- samples, it can be seen that samples CCHJ and MZHJ1 had two
teristic strong bands at wavenumber range 1610∼1560 cm−1 and strong absorption peaks at 1576 cm−1 and 1460 cm−1 . This means
1440∼1360 cm−1 which correspond to the following stretching that these two samples may contain lipids. While in the curve of
bonds (␯as (COO− )) and (␯s (COO− )) of carboxylate functional group DZC2, one peak was found at 1610∼1560 cm−1 or 1440∼1360 cm−1

Fig. 5. The SEM pictures of internal structure of different mortars. A. Lime mortar. B. Sticky-rice lime mortar. C. Putty.
S.Q. Fang et al. / Journal of Cultural Heritage 15 (2014) 144–150 149

Fig. 6. The Fourier transform infrared spectrometer (FT-IR) patterns of different lime mortar. A. Sugar lime mortar. B. Starch lime mortar. C. Protein lime mortar. D. Putty.

which can be ascribed to the existence of lipids in blood. Based on in acid which leads to the failure of iodine starch experiment. So,
the above phenomena it can be stated that DZC2 sample might in this work, CaCO3 was used to be mixed with mortar completely
contain blood. While little glyceride exists in blood. before test. This measure reduced the color interference in the test.
Through the above analysis it can be concluded that the FT-IR Fibers in mortar is another factor that would cause the test
test results were generally consistent with the method mentioned present false positive result. Because fiber could also decay into
in this research except samples MZHJ1 and DZC2. The FT-IR results reducing sugar under alkaline environment. For instance, the
can be regarded as a reference in addition to the common chemical ancient sample GTHJ2 (contain fibers, lime and soil) presented
analysis. But the results still could demonstrate that our method positive result in reducing sugar test. But there was no reference
is relatively reliable. In addition, this method has same advantages showing that it was prepared by sugar. Moreover, by analyzing
over the FT-IR spectrum measurements. For instance, the chemical the simulated lime mortar containing fibers it was found that the
analysis could can unequivocally distinguish sugar and starch in reducing sugar content around fiber was two to five times higher
mortar. than the area away from fiber. Therefore, the sample used for reduc-
ing sugar test should be selected from the area far from fiber in order
to get reliable results.
3.5. Interferometric analysis At last, the animal and plant debris, the loss and rot of the organic
additives also will influence the analysis. Thus, the sample used for
In this work, the analytical method mostly rely on observing test should be the internal mortar which still retain alkalinity.
color change or precipitation to judge whether organic additives
exist in mortar. Therefore, the color interference will seriously
impact the analytical results. There are three major interference 4. Conclusion
factors to perform the analysis in this work. The first factor came
from the aggregate and soil in mortar. It was discovered that the In this work, iodine-potassium iodide reagent, benedict’s
dark brown gravel, soil and red brick powder seriously influence the reagent, reducing phenolphthalein, Coomassie brilliant blue and
iodine starch experiment. Strong acid has to be used in the com- acetylacetone development process were used to identify starch,
mon decolorizing method of soil, while starch could be hydrolyzed reducing sugar, blood, protein and esters exist in mortar,
150 S.Q. Fang et al. / Journal of Cultural Heritage 15 (2014) 144–150

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