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Manuscript_8b7fdcff436f9f89c4b0f67fda243ded

Effects of several retarders on setting time and

strength of building gypsum
Yuanyuan Zhang a, Jiansen Yang a,*, Xiangyang Cao a
a
School of Civil and Hydraulic Engineering, Ningxia University, Ningxia 750021, PR China.
* Corresponding author: yjs508@163.com, Tel.: +8613895090329
HIGHLIGHTS
 Eight retarders on setting times and strength of building gypsum were investigated.
 Microstructure and retarding mechanism were analyzed by SEM and XPS.
 The retarding effects of citric acid on building gypsum were the most significant.
 The negative effects of citric acid on strength were the largest.
 Bone glue can increase the strength of gypsum within a certain range.
Abstract: The effects of eight retarders, including tartaric acid, sodium tartrate, salicylic acid,
melamine, sucrose, white cement, sodium triphosphate, and citric acid, on setting times and strength of
building gypsum were investigated under different dosage. The retarding mechanism of that was
analyzed by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), and
the crystal morphology and characteristics of the samples mixed with citric acid and bone glue under
different setting times were observed and compared. The results show that all eight kinds of retarders
have a different degree of retarding effect on building gypsum, and at the same time, they all have
different degree of influence on strength of gypsum, among which citric acid has the most significant
influence. Due to the selective adsorption of citric acid, dihydrate gypsum crystals are changed from
the original needle-like to the short column and the plate-like, the overlaps between the crystals are
weakened, and the pore structure is deteriorated, and the strength are reduced. The addition of bone
glue causes the crystals become coarse, the length become shorter, and the aspect ratio decreased, and
it is mainly by delaying the dissolution of gypsum semihydrate and the growth of gypsum dihydrate
nucleus to achieve retarding effect in building gypsum.
Key words: Building gypsum; Retarders; Setting; Retarding mechanism

1. Introduction

With the improvement of living standards, people's requirements for living environment are
getting higher and higher. To this end, many scholars have done a lot of research, including
“sterilization and humidity control [1], temperature adjustment [2], insulation [3]” etc. However, only
improving the comfort of the environment is not enough for sustainable development, so it is also
necessary to consider the rational use of resources. The structural adjustment of traditional building
materials, especially wall materials, the rise of building energy conservation, and the implementation of
sustainable development strategies have injected new vitality into the development of gypsum-based
materials and bought unprecedented development opportunities. China’s total amount of gypsum is
huge, and it has the capacity to become a gypsum power [4]. In 2013, emissions of gypsum were about
1.84×1012t in China, but the comprehensive utilization rate was only 48.1% in that year. The
accumulation of gypsum has potential hidden danger to groundwater and the surrounding environment.
Therefore, expanding utilization of gypsum is the only way to enhance its comprehensive utilization

© 2019 published by Elsevier. This manuscript is made available under the Elsevier user license
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rate [5].
At present, building gypsum, as an indispensable and important decorative material in building,
became more and more commonly used in the plastering of interior walls of buildings. Compared with
traditional cement plasters, gypsum plasters have the advantages of energy-saving, short construction
period, good construction quality and excellent performance [6]. However, the setting and hardening
characteristics of the building gypsum are also affected to some extent by the composition, the time of
delivery and the dampness of storage of the gypsum. The initial setting time of some gypsum is less
than 5 minutes, and the final setting time of hemihydrate gypsum is just (6～30) minutes, operating
time of that is only 5 to 10 minutes which often cannot meet the requirements of molding and
construction of gypsum-based materials to great restrictions on application. The survey results for some
decoration companies in Yinchuan showed that the problem of gradual retardation of gypsum is mainly
solved by adding retarders to the gypsum during the process of construction. At present, the mainly
retarders, such as citric acid and its salts, tartaric acid, sodium polyphosphate, and calcium acetate, are
utilized in the building gypsum[7]. However, a large number of practices have found that gypsum
retarders have diverse effects on strength of gypsum hardened body during the process of retarding.
A large number of scholars have studied the retarders mentioned above. Peng Jiahui et al. [8], for
instance, studied the influencing factors of citric acid on the retardation of building gypsum. The results
showed that pH and temperature had a great influence on retardation. Huang Yuyan et al [9] found that
black tea alters the gypsum hydration process, decreases the hydration rate and prolongs the setting
times of gypsum. Moderate black tea has the positive role in improving the strength of gypsum, but the
excessive black tea poses a negative effect. Chongqing University had prepared a kind high-efficiency
composite retarder based on the characteristics of various retarders [10]. Chinese Forestry University
developed a series of HG gypsum retarders according to the defects of strength retarders [11]. Kong
Xiangfu [6] et al. found that retarding effect of glucose was weak, while retarding effect of sodium
hexametaphosphate and citric acid were better, but the strength of gypsum hardening would be affected
significantly with high dosage. Feng Chunhua [12] et al. studied the effects of citric acid, tartaric acid
and SG-10 on setting times, strength and microstructure of demilitarized building gypsum, and found
that retarding effect of citric acid was the best, but it had large effects on strength. Li Haoxin [13] et al
found that the cost of hemi-hydrate gypsum based material would be saved, as well as modulated the
setting times of this material to the ideal one, would be resolved if desulfurized ash from semi-dry flue
gas desulfurization can be applied as a admixture into hemihydrate gypsum based material. In general,
the longer the setting times are, the greater the strength reduces [14]. The previous research on gypsum
retarders mainly focused on small molecule retarders, and there were a few studies on macro retarders
for different retarding mechanism, the researches of macromolecular retarder on the hydration process
of building gypsum, the microstructure of hardened body, intrinsic cause of strength loss and retarding
mechanism were still lack[15]. Therefore, it is of great significance to study the influence of different
retarders on setting times and strength of building gypsum under different dosages.
The effects of eight kinds of retarders, such as tartaric acid, sodium tartrate, salicylic acid,
melamine, sucrose, white cement, sodium tripolyphosphate, and citric acid on setting times and
strength of building gypsum were investigated under different dosages through experiments in this
study. The crystal morphology and characteristics of the samples mixed with citric acid and bone glue
under different setting times were observed and compared. The mechanism of building gypsum was
analyzed and discussed by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy

2
(XPS).

2. Materials and methods

2.1Materials and equipment

β-type building gypsum produced by Yinchuan Yaotian Gypsum Factory in Ningxia was selected
as the main raw materials in this study. It has the following characteristics: strength grade of 2.0, initial
setting time of 4.0 minutes and final setting time of 6.0 minutes. The main physical performance
indicators are shown in Table 1.
Polymer: Tartaric acid (AR, Tianjin Kemiou Chemical Reagent Co., Ltd), Sodium tartrate(AR,
Tianjin Damao Chemical Reagent Factory), Salicylic acid(AR, Tianjin Oubokai Chemical Co., Ltd),
Melamine(CP, Sinopharm Chemical Reagent Co., Ltd), Sucrose(AR, Tianjin Oubokai Chemical Co.,
Ltd), Sodium tripolyphosphate(AR,Tianjin Guangfu Fine Chemical Research Institute), Citric acid(AR,
Yantai Shuangshuang Chemical Reagent Co., Ltd), Bone glue (Commercially available industrial bone
glue is heated to a glue solution in a water bath at a ratio of 1:8), White Portland cement(AR, Tianjin
Kemiou Chemical Reagent Co., Ltd)
YAW-300B microcomputer controlled compression and flexure synchronous testing machine
(Hangzhou Xingao Technology Co., Ltd), ISO cement standard consistency setting times measuring
instrument (Vicat instrument, Beijing Road Construction Machinery Technology Co., Ltd), Scanning
Electron Microscopy (SEM, Zeiss, Germany (EVO18)), XSAM×800 Multifunctional Electron
Spectroscopy(XPS, KRATOS Company, UK), Cement paste mixer (Shanghai Leiyun Test Instrument
Manufacturing Co., Ltd), TD10002 electronic balance (weighing accuracy of 0.01g, Yuyao Jinnuo
Tianping Instrument Co., Ltd).

Table 1
Physical performance of building gypsum

Setting time /min 2h Strength/MPa 1d Strength/ MPa 3d Strength/MPa

Flexural Compressive Flexural Compressive Absolute dry Absolute dry

Initial Final
strength strength strength strength flexural strength compressive strength
4 6 2.25 3.05 2.62 4.46 2.74 5.42

2.2 Methods

2.2.1 Test of setting time and strength

Firstly, the water requirement for the normal consistency was determined according to the sixth
chapter of GB/T17669.4-1999 (Determination of physical properties of building gypsum paste). The
setting times were determined according to the seventh chapter. The specimens were prepared
according to 4.3 of GB/T17669.3-1999 (Determination of mechanical properties of building gypsum),
and the specimens were stored according to 4.4. The compressive and flexural strengths of the
specimens after contacting with water for two hours were measured according to fifth and sixth
chapters. The whole experimental process was carried out according to GB/T9776-2008(Building
Gypsum) [16]. The water immersion compressive and flexural strengths were determined by the same
method after soaking for 5 hours at room temperature tap water at the corresponding ages. The effects
of different component on setting times of gypsum were investigated by means of a continuous
distribution method, and the relationship between setting time of gypsum and dosage of conditioning
aid was established. The dosage of each raw material in the test is gypsum of 500g, water of 360g,
water paste ratio of 0.72, and the ratio of citric acid is shown in Table 2. The proportion of bone glue is
2.76% (10min) and 5.2% (30min) respectively. The test procedure is as follows.

3
 Test mold of the Vicat apparatus (upper small and lower big) was placed on the glass plate, the
pointer was adjusted to the zero point when the test bar contacted the glass plate. The water and
retarders were poured into the stirring pot, gypsum was added into the stirring pot within 5 to10
seconds. The stirring pot was stirred at a low speed for 2 minutes, stopped for 15 seconds and then
continued to stir at a high speed for 2 minutes to form gypsum slurry. The gypsum slurry was poured
into the test mold quickly and inserted the slurry to remove the excess gas. The surface of the slurry is
smoothed and moved to the Vicat apparatus, lower until the gypsum surface was in contact, and then
the test rod was vertically and freely sank into the interior of the slurry, repeated the above operation. It
was regarded as initial setting time of gypsum (calculated it from stopping stirring) when the test
needle was 5±1 mm away from the bottom plate, and then the test mold was flipped by 180 degrees
while changing the test needle, it was regarded as final setting time when the test needle sank into the
interior of the gypsum about 0.5 mm. The gypsum slurry should be tested every two minutes at first
when the dosage of retarder is large, it should be tested every 30 seconds when it was going to setting,
it should be tested every 30 seconds when the dosage of retarder is small. After repeating tests, initial
and final setting time of gypsum were determined with different retarders under different dosage.
The flexure and compressive test pieces of gypsum were standard test piece with
40mm×40mm×160mm. After the test pieces were formed, they were cured for one day with mold
under natural conditions, and then compressive and flexural strengths of them were tested by a
compression and flexure synchronous testing machine. In the flexural strength test of test pieces, the
standard test pieces were placed on the two support bars of the test machine, and the molding surface of
the test pieces were laterally stood, each edge of the test pieces were perpendicular to the respective
sticks, and the loading stick and the two supporting sticks were kept equidistant, the test machine was
gradually loaded after starting, and finally the test piece was broken. In compressive strength test of test
pieces, the molding surface of the test pieces were laterally stood in the compression clamp, and the
center of the compression clamp was placed on the central axis of the upper and lower clamping plates
to ensure upper clamping plate ball shaft pass through the center of the pressure receiving surface of
the test piece, and then started the compression test machine, the test pieces should be damaged within
20 to 40 seconds after starting loading.

2.2.2 SEM test

A small piece of dry and clean gypsum was intercepted and adhered to the sample holder with a
conductive adhesive, and kept observation surface of it flat, then the sample holder was placed into an
ion sputtering equipment to coat a conductive film (Au), and the processed sample was placed in the
sample chamber. After the vacuum degree less than 5x10-5Pa, setting the electron gun acceleration
voltage to 15KV, the probe current to 50μA, the working distance to 8～10mm, and then opening the
beam to observe the image.
2.2.3XPS analysis
A certain amount of β-hemihydrate gypsum was dried to absolute dryness, pressed into a thin film
under a certain pressure, then immersed in a certain concentration of water reducing agent solution
adsorption for 4 minutes, terminated with hydration anhydrous alcohol, and then baked at 45 °C until
absolutely drying. It was tested by XSAM×800 multi-function electronic energy spectrum with energy
of 3.5KV, the stream of 30μm, the etching rate of 10 Å/min. Conditions of XPS are: 12kV high voltage,
16mA emission current A1Kα (1486.6eV) X-ray gun, the analyzer adopts fixed reduction ratio (FPR)
mode. The spectrometer is calibrated by Ag (BE = 386.3 eV) and Au (BE = 84.0 eV) standard samples,
the background vacuum of the analysis chamber is 6×10-7Pa.

3. Results and discussion

4
3.1 Effects of retarders on setting time of building gypsum

With building gypsum as basic raw material, different dosage of retarders were added into it
respectively to determine its influence on setting time of gypsum, as shown in Table 2. In order to
visually observe the influence of various retarder dosages on initial and final setting times of gypsum,
according to the data in Table 2, the influence curves are drawn and shown in Fig. 1.
Table 2
Effects of various retarders on setting time of building gypsum under different dosages

Setting time/min
Retarders
Dosage/% 0 0.010 0.025 0.050 0.100 0.250 0.500

Initial 4.0 18.0 15.0 12.0 13.0 14.0 18.0

Tartaric acid
Final 6.0 27.0 24.0 23.0 24.0 25.0 26.0
Initial 4.0 7.0 12.0 13.0 13.0 7.0 8.0
Sodium tartrate
Final 6.0 18.0 21.0 25.0 23.0 19.0 15.0
Initial 4.0 15.0 10.0 10.0 9.0 6.0 8.0
Salicylic acid
Final 6.0 27.0 16.0 18.0 18.0 11.0 16.0
Initial 4.0 10.0 12.0 10.0 12.0 12.0 13.0
Melamine
Final 6.0 20.0 21.0 17.0 16.0 19.0 17.0
Initial 4.0 10.0 14.0 15.0 14.0 11.0 13.0
Sucrose
Final 6.0 20.0 19.0 22.0 22.0 22.0 27.0
Initial 4.0 13.0 12.0 13.0 5.0 8.0 11.0
White cement
Final 6.0 24.0 24.0 24.0 16.0 19.0 22.0
Sodium Initial 4.0 19.0 27.0 11.0 65.0 >120.0 >120.0
tripolyphosphate Final 6.0 36.0 40.0 33.0 85.0 >120.0 >120.0
Initial 4.0 16.0 20.0 40.0 91.0 >120.0 >120.0
Citric acid
Final 6.0 21.0 29.0 47.0 100.0 >120.0 >120.0

100
(a) Initial setting time

80

Tartaric acid
Sodium tartrate
60 Salicylic acid
Setting time/min

Melamine
Sucrose
White cement
40
Sodium tripolyphosphate
Citric acid

20

0
0.0 0.1 0.2 0.3 0.4 0.5

Dosage%

5
 (b) Final setting time
100

Tartaric acid
80
Sodium tartrate
Salicylic acid
Melamine
60

Setting time/min
Sucrose
White cement
Sodium tripolyphosphate
40 Citric acid

20

0
0.0 0.1 0.2 0.3 0.4 0.5

Dosage%

Fig.1.Effects of different retarders on setting times

of building gypsum under different dosages
Fig.1 (a) and (b) show that all eight kinds of retarders play different degree on setting times for
building gypsum, among which citric acid demonstrates the most significant retarding effect, followed
by sodium tripolyphosphate. When the dosage of citric acid is only 0.1%, the initial setting time of
gypsum has been more than 60min, i.e. a stronger retarding effect can be achieved with a small dosage
of citric acid. With the increase of dosage, the retarding effects of gypsum increase obviously, and the
setting times increase linearly. Therefore, citric acid is considered as a high-efficiency retarder for
building gypsum.
The chemical shift of the electronic binding energy of calcium on the surface of gypsum indicates
that [17] citric acid complexes with calcium ions to form calcium citrate, which covers the surface of
the nucleus of dihydrate gypsum, inhibits the growth of crystal nuclei, and changes the crystal habit of
dihydrate gypsum crystals. Therefore, the crystal morphology of dihydrate gypsum is changed from
needle to short column, and then plays a role in retarding.
In order to further understand the relationship between the dosage of citric acid and the setting
times of gypsum, the effect of the citric acid dosage on the setting times of gypsum under 0.72
water-to-binder ratio was studied, which provides a reference for the future selection of citric acid.

100

80

60
Setting time/min

40

20 Initial setting time

Final setting time

0
0.00 0.02 0.04 0.06 0.08 0.10

Dosage%

Fig.2.Effects of citric acid on setting times of building gypsum

Fig.2 shows that citric acid can delay the setting times of gypsum obviously, and a stronger
retarding effect can be achieved with a smaller dosage. When the dosage of retarders is within 0.1%,

6
the setting times are constantly prolonged with the increase of citric acid content, when the dosage of
retarders is over 0.025%, the trend of setting times increases linearly with the increase of the dosages.

3.2 Effects of retarders on strength of building gypsum

Eight kinds of retarders were added into building gypsum to determine the flexural and
compressive strengths of it under different dosages. The results are shown in Table 3.
Table 3

Effects of different retarders on strength of building gypsum

Strength/MPa
Retarders Dosage (%) 0 0.010 0.025 0.050 0.100 0.250 0.500

1d Flexural 2.62 2.29 2.06 2.38 2.42 2.15 1.63

Tartaric acid
strength Compressive 4.46 4.62 4.33 4.62 4.80 4.25 3.12

1d Flexural 2.62 2.33 2.43 2.36 2.58 2.05 1.78

Sodium tartrate
strength Compressive 4.46 4.93 4.98 4.61 5.18 4.38 3.92

1d Flexural 2.62 2.44 2.19 2.27 2.39 2.30 2.34

Salicylic acid
strength Compressive 4.46 5.42 5.45 5.00 5.20 4.33 4.12

1d Flexural 2.62 2.48 2.36 2.53 2.56 2.30 2.20

Melamine
strength Compressive 4.46 4.80 4.67 5.23 4.43 4.48 4.78

1d Flexural 2.62 2.86 2.60 2.94 3.01 3.07 2.80

Sucrose
strength Compressive 4.46 5.53 4.67 5.17 5.52 6.05 6.08
1d Flexural 2.62 2.39 2.45 2.74 3.01 2.69 3.12
White cement
strength Compressive 4.46 5.52 6.65 6.60 6.82 6.30 7.10

Sodium 1d Flexural 2.62 2.26 2.26 2.22 2.15 1.39 -

tripolyphosphate strength
Compressive 4.46 4.40 3.98 4.10 4.98 3.13 -
1d Flexural 2.62 2.12 2.32 2.06 1.40 0.52 0.50
Citric acid
strength Compressive 4.46 4.05 4.02 4.27 2.8 0.93 0.87

In order to visually observe the influence trend of different retarders on flexural and compressive
strengths under different dosages, according to the data in Table 3, the influence curves are drawn and
shown in Fig.3.

(a) 1d flexural strength

3.0

2.5

2.0
Flexural strength/MPa

tartaric acid
1.5 Sodium tartrate
Salicylic acid
Melamine
sucrose
1.0 White cement
sodium tripolyphosphate
Citric acid

0.5

0.0 0.1 0.2 0.3 0.4 0.5

Dosage%

7
 (b) 1d compressive strength
7

Compressive strength/MPa
4

tartaric acid
Sodium tartrate
3
Salicylic acid
Melamine
sucrose
2
White cement
sodium tripolyphosphate
Citric acid
1

0.0 0.1 0.2 0.3 0.4 0.5

Dosage%

Fig.3.Effects of different retarders on flexural and compressive strengths

of building gypsum under different dosages.
Fig.3 (a) shows that when the retarder dosage is within 0.01%, except sugar, the flexural strength
of other gypsum all decreases with the incorporation of retarders, the main reason is that a slight
amount of sugar-calcium complex is formed when the sucrose dosage is small. Therefore, the flexural
strength of gypsum has a slight increase instead of decrease. Among them, citric acid demonstrates the
most significant reduction, which decreases from 2.62 MPa to 2.12 MPa and reduces by 19%. When
the retarder dosage is between 0.1 to 0.5%, the flexural strength of gypsum decreases slightly with the
dosage increase of tartaric acid, sodium tartrate, salicylic acid and melamine. However, the flexural
strength decreases obviously with the dosage increase of citric acid and sodium tripolyphosphate. The
sucrose and white cement generally show as reinforcing the flexural strength of the gypsum.
Fig.3 (b) shows that when the retarder dosage is within 0.01%, except sodium tripolyphosphate
and citric acid, the compressive strength of other gypsum all increase in different degree with the
incorporation of the retarders. When the retarder dosage is between 0.1 to 0.5%, the compressive
strength of gypsum decreases in different degree with dosage increase of tartaric acid, sodium tartrate,
sodium tripolyphosphate and citric acid. Citric acid demonstrates the most significant reduction, which
decreases from 1.4 MPa to 0.5 MPa and decreases by 69%, followed by sodium tripolyphosphate,
which reduces by 37%, other retarders have different degree of enhancement effects on strength with
increase of dosage.
Combined with Fig.1 (a) and Fig.3 (a), a stronger retarding effect can be achieved with a small
dosage of citric acid, but the strength of the building gypsum will be drastically decreased with a large
dosage of citric acid. The more the retarder dosage is, the longer the setting times are, and the more
obviously reduce strength. For example, citric acid can make the setting time of β-hemihydrate gypsum
extend to 1 hour, but its strength losses more than 50% [18]. In general, for most retarders, gypsum
strength is reduced to different degree during the process of retarding, especially citric acid, which has
the most significant effects, and with the increase of dosage, the relationship between retarding effect
and strength loss is directly proportional. Citric acid selectively adsorbs on the long axis which grows
fast to affect the superposition rate of crystalline elements in the axial direction and inhibit the growth
of crystals in the axial direction, thereby changing the relative growth rate of different crystal faces and
resulting in transformation of the crystal form, which ultimately leading to the reduction of strength

8
[19].

4. Microstructure and retarding mechanism

4.1. Microstructure of hardened gypsum with citric acid and bone glue
The microstructures of building gypsum were analyzed by scanning electron microscopy (SEM).
It can be seen from the SEM image of 2000 times that the crystal morphology of dihydrate gypsum
changes significantly before and after the incorporation of citric acid and bone glue.

（a）blank sample 2000× （b）with citric acid(10min)2000×

（c）with citric acid(20min)2000× （d）with bone glue(10min)2000×

（e）with bone glue(30min)2000×

Fig.4. SEM image of building gypsum hardened
Fig. 4 (a) shows that gypsum crystals without any retarder are mainly needle-like, with many
overlap points among the crystals, compact structures and better pore structure.
Fig.4 (b) and (c) show that the gypsum crystals with citric acid are changed from the original
needle-like to the short column and plate-like, and the size of crystals becomes smaller obviously, some
crystals almost become angularity sharp cubes. The growth of crystals is strongly inhibited, the growth
rate inhibition in all directions is not consistent, and the more the dosage of citric acid is, the more
obvious inhibitory effect on the crystals is. It is inferred that this phenomenon is related to the selective
adsorption of citric acid, which reasonably regulates the setting times from the macroscopic level by
controlling the growth direction and growth rate of the crystals.

9
 Fig.4 (d) and (e) show that the growth of the crystals with the incorporation of bone glue are more
developed, the diameter of the crystals are larger obviously, and the length slightly reduce, therefore,
the amount of overlaps between the crystals are reduced, the porosity rate of the hardened body is
increased, and the setting times of gypsum are prolong. It is inferred that the dissolution of dihydrate
gypsum crystals are inhibited with the incorporation of bone glue, the dissolution rate of crystals slow
down, the concentration of Ca2+ and SO42- in the solution are reduced and decreased, the formation rate
of dihydrate gypsum is slow down to achieve retarding effect. The 1d absolute dry flexural and
compressive strength of building gypsum with bone glue of 2.8% were tested. The results show that 1d
absolute dry flexural and compressive strength increased from 1.67 MPa and 4.75 MPa to 1.7 MPa and
7.00 MPa, respectively, after the addition of bone glue. It indicates that within a certain range, the
improvement of single crystal whisker skeleton strength overcomes the negative impact of the decrease
in the number of crystal contacts [20], so the compressive and flexural strengths show an increasing
trend instead of decreasing, then began to decline beyond this range.

4.2 X-ray photoelectron spectroscopy analysis of crystals

Dihydrate gypsum belongs to monoclinic system, Ca2+ and SO42- tetrahedron are connected to
form a double structure layer, and H2O molecules are distributed in the middle of it, forming a layered
structure which composed of water-molecular alternating layer and ion binding layer consist of Ca2+
and SO42-[21]. There are different elementals in different crystal faces [22]. Chemical shifts of the
elements are judged by XPS analysis, and infer whether the elements have chemical reaction [17], the
results are shown in Table 4.

Table 4

XPS analysis of building gypsum surface.

2P electron binding
Samples Elements Chemical shift /eV
energy/eV

Gypsum Ca 351.595

Gypsum + Citric acid Ca 350.945 -0.65

Table 4 shows that after the citric acid is absorbed to the surface of the dihydrate gypsum crystals,
the chemical shift of the calcium element 2P electron binding energy is changed -0.65 eV which is
enough to indicate that the citric acid has a certain chemical reaction with the calcium element on the
surface of gypsum. The researches show that this chemical reaction is mainly complex reaction, citric
acid, a hydroxyl-containing monocarboxylic acid molecule, can react with Calcium on the surface of
gypsum to form a stable calcium citrate complex to affect the surface energy of the crystal nucleus, as
well as the congruent rate and spatial orientation of Ca2+ and SO42- in each surface of crystal. Because
citric acid preferentially adsorbs in the direction of the long axis which grows quicker, makes the
surface energy of the axis decrease and inhibits its growth, therefore, achieving the aims of changing
the relative growth rate of each crystal face of the crystal and slowing down the hydration process,
eventually leading to the crystal form change from needle-like to short column and plate-like.
Citric acid is one of the commonly used high-efficiency retarders in building gypsum, and its
outstanding feature is that a strong retarding effect can be achieved with a smaller dosage [23-24]. It
can react with calcium to form a calcium citrate complex which adheres to the surface of the dihydrate
gypsum nucleus to inhibit its growth, change crystallization habit, and change the crystal from the
original needle-like to the short column and plate-like. Therefore, the overlap between the crystals is
weakened, the pore structure is deteriorated, and the growth of crystals is inhibited to achieve retarding
effect. The retardation of bone glue is another situation, by binding with calcium ions in building
gypsum, bone glue covers the surface of gypsum crystals, delaying the formation of crystals and

10
slowing down the hydration process, thus extends the setting time of building gypsum [25-26].

5. Conclusions

(1) The retarding effect of building gypsum is closely related to the type and dosage of retarders,
most retarders could have a different degree of the effects on the strength of building gypsum while
playing a retarding effect. Among them, the retarding effect of citric acid is the most obvious, and an
excellent retarding effects can be achieved with a small dosage of citric acid, the more dosage it is, the
better retarding effects it will produced, and the great strength will also be missed.
(2) When the dosage of tartaric acid, sodium tartrate, salicylic acid, melamine, sucrose is 0.1%,
they can not only meet the requirements of retardation, but also reach the maximum value of the
strength. Therefore, it can be concluded that the optimum dosage of the six retarders to gypsum is 0.1%
at the age of 1day.
(3) Owing to the selective adsorption of citric acid, the size of the dihydrate gypsum crystals in the
long axis direction become reducing, while the size in the short axis direction is increasing, The
coarsening of crystals, the weakening of overlap between crystals and the deterioration of pore
structure lead to the decrease of strength of citric acid while playing a retarding effect. However, bone
glue reaches the aim of retarding effect by inhibiting concentration of Ca2+ and SO42- in the solution.
(4) Under the same condition of retarding effect, bone glue has a better retarding effect on
building gypsum, the negative effects of that on strength are far less than citric acid, and it can even
enhance the strength of gypsum within a certain range.
Author Contributions: I would like to thank my tutor, Jiansen Yang, for guiding me throughout the
trial process and the process of writing the paper, including the test methods, research ideas, analysis
angles, paper revisions and supervision completion, as well as my brother Xiangyang Cao who taught
me specific method of operation during my experiment, as well as the revision of my manuscript
during the writing process of the subsequent paper, I was responsible for the implementation of the
experiment, data analysis and the writing of the paper.
Funding: This research is funded by National Natural Science Foundation of China, grant number
51568056.
Acknowledgments: The authors gratefully acknowledge the support provided by the National Natural
Science Foundation of China (NO. 51568056).and the authors would also be grateful to the teachers of
the Structural Engineering Laboratory of the School of Civil and Hydraulic Engineering of Ningxia
University for their guidance on our experiment.
Conflicts of Interest: The authors declare no conflict of interest.

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