Proceedings of the 18th Plastic Pipes Conference

PPXVIII
September 12-14, 2016, Berlin, Germany

THE INFLUENCE OF BETA- CRYSTAL CONTENT IN PP-RCT

MATERIALS AND CALCULATIONS OF THE TEST PRESSURE
OF PIPE

Tu Xiang-qun Wang Chao

Wuhan Kingbull Economic Wuhan Kingbull Economic
Development Co.，Ltd Development Co.，Ltd
Wuhan City, Hubei Province, China Wuhan City, Hubei Province, China

Cheng Zhong-lin Dong Bo-bo

Wuhan Kingbull Economic Wuhan Kingbull Economic
Development Co.，Ltd Development Co.，Ltd
Wuhan City, Hubei Province, China Wuhan City, Hubei Province, China

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 Proceedings of the 18th Plastic Pipes Conference
PPXVIII
September 12-14, 2016, Berlin, Germany
ABSTRACT
This paper is to verify the impact of different contents of nucleating agent and annealing
processes on the content of β-crystal. By using four-parameter equation of PP-RCT with
requirements in different application conditions, different temperature coefficients and Miner's rules
the design stress of PP-RCT materials under different applications and the calculation process of test
pressure of the PP-RCT pipes have been deduced, which can facilitate the better understanding and
learning of relevant standards for plastic piping engineers. Moreover, it provides reference for the
research and development of plastic pipe materials and quality control method.

KEYWORDS
β crystalline polypropylene; PP-RCT; design stress; test pressure

INTRODUCTION
As the third generation of polypropylene material, random copolymer polypropylene (PP-R), with
good mechanical properties, non-toxic, good heat resistance and long-term creep resistance etc., has
been widely used as the hot & cold water pipe system in construction buildings. However, when the
installation is taken under at low ambient temperature, the brittle fracture could happen. In order to
increase the low temperature impact resistance and heat resistance of PP-R pipes, the improvement
of crystal structure of PP-R pipe by adding the nucleating agents has been proposed by many
researches. The PP-R with modified crystalline structure is called PP-RCT. It is found from the long-
term hydrostatic pressure test curve of PP-RCT, obtained by material modification, no knee point is
observed before 8760h at any temperature, including 110 ℃, which indicates there is no brittle
failure.

EXPERIMENTAL AND DISCUSSION

1 Influence of β-crystal content in PP-RCT materials
As well known, the polypropylene in different crystallization conditions can form 5 kinds of crystal
structures: α, β, γ, δ, and the pseudohexagonal state. The α-crystalline is the most common and has
the best thermal stability, and the β -crystalline is the thermodynamically metastable [1].
In this paper, the pipe materials analyzed is mainly the PP-RCT of β crystalline form. Since the β
crystalline form is thermodynamically metastable, the formation of β crystal is kinetically unfavorable;
the main factors for the content of β-crystal are as follows:
(1) Type and content of nucleating agent;
(2) Machining processes parameters such as temperature and shear rate;
(3) Type and grade of polypropylene base resins.
Nowadays, adding β crystal nucleating agents is the most effective way to obtain high content of
β crystalline form [2]. The impact resistance and heat resistance of materials can be increased by
adding the nucleating agents, the slow crack propagation and the notch sensitivity tubes are also

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 Proceedings of the 18th Plastic Pipes Conference
PPXVIII
September 12-14, 2016, Berlin, Germany
superior to traditional products. The test of nucleating agent quantity and annealing processes on
crystalline content is presented following.
1.1 The calculation method for determining the content of β-crystal by DSC
The determination of the content of β-crystal in PP-RCT pipes is significant for evaluating the
pipe tenacity and heat resistance. Generally, DSC and XDR test methods are used. According
to calculation process, the DSC test method can be calculated using two methods: formula method
and multi-modal Gaussian fitting method [3]. This article introduces the determination of relative
content of β-crystal using DSC formula method.
Firstly, under the protection of nitrogen, sample was heated to 180 ℃ at a heating rate 10 ℃
/min and kept in 180 ℃ for 5 mins to clear the thermal history , cooled it to 40 ℃ at rate of 10 ℃
/min, and then heated again with a heating rate 10 ℃/min to 210 ℃, obtaining the material DSC
curves.. The melting enthalpy (△H) can be calculated by integrating the DSC curve from 80 ℃ to
165 ℃, by taking a vertical line of the baseline at the lowest points in valleys of two peaks of α and β,
the melting enthalpy area can be divided into two regions, corresponding two melting enthalpies, △Hα
and △Hβ.Choosing the lowest points in valleys of two peaks of α and β, the temperatures are marked.
By finding the corresponding temperatures in the integrated curve, the percentages can be obtained,
that is, the percentage of melting enthalpy area of β-crystal (m). The crystallinity of α-crystal (Xα), the
crystallinity of β-crystal (Xβ) and the relative percentage of β-crystal (φβ) can be calculated using the
following equations (1)-(5):
△Hβ=m×△H (1)
△Hα=△H-△Hβ (2)
Xα=△Hα/△Hα0×100% (3)
Xβ=△Hβ/△Hβ0×100% (4)
φβ= Xβ/（Xα+ Xβ）×100% (5)
Where △Hα0 is the standard melting enthalpy of α-crystal (178 J/g) [3], △Hβ0 is the standard melting
enthalpy of β-crystal (170 J/g) [3].
To take an example, a certain grade of PP-RCT material, the DSC curve is obtained and integrated
with the software, showing in Figure 1.

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 Proceedings of the 18th Plastic Pipes Conference
PPXVIII
September 12-14, 2016, Berlin, Germany

Figure 1—The DSC curve of β-crystal polypropylene.

The second step is to find where the boundary is between α peak and β peak and to know
the critical temperature. The integral area ratio (m) of β-crystal of melting enthalpy can be thus
calculated, as shown in Figure 2.

Figure 2—The DSC curve after integration.

It can be observed in Figure 2, that the critical temperature is 137.55℃ (△H=52.05 J/g, m=50.92%).
The calculated φβ is 52.07% through the equations (1)-(5).
Table 1—The calculated values of the content of β-crystal for a certain grade PP-RCT material
△Hα △Hβ Xα Xβ φβ
（J/g） （J/g） (%) (%) (%)
calculation resul
25.55 26.50 14.35 15.59 52.07
ts

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 Proceedings of the 18th Plastic Pipes Conference
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September 12-14, 2016, Berlin, Germany
1.2 Analysis of the results
1.2.1 Effect of nucleating agent amount on the content of β-crystal

The previous DSC formula method helps us to analyze and evaluate more accurately during
the design and development of new raw materials. Figure 3 shows the DSC re-heating curves of PP-
RCT materials with different amounts of nucleating agent (JN2012). The effect of the amount of
nucleating agent on the content of β-crystal is presented in Table 2.

Figure 3—The DSC re-heating curves of PP-RCT with different amounts of nucleating agent
(JN2012).
Table 2—The effect of the amount of nucleating agent on the content of β-crystal.
Amount of
△H
nucleating age Xα Xβ φβ
J/g
nts
0.2wt% 69.72 8.20% 28.56% 79.60%
0.4wt% 61.60 6.64% 29.28% 81.50%
0.7wt% 51.48 4.72% 25.34% 84.30%
1.0wt% 51.50 4.62% 25.45% 84.63%
1.3wt% 50.48 4.53% 24.47% 84.25%
1.6wt% 48.48 4.46% 23.85% 84.24%
From Table 2, it can be found that JN2012 is an efficient nucleating agent. More than 30% β-
crystallinity and a relative percentage of β-crystal (φβ) of 30% are got by adding JN2012. With the
increase of amount of nucleating agent, the melting peak of β-crystal moves to right side, the melting
point of β-crystal increase. It is due to the fact that there are more crystal seeds and
smaller grain size, thus generating more fine crystal structure. In addition, with the increase of
amount of nucleating agent, the β-crystallinity and α-crystallinity are reduced obviously, indicating that
after a limit value of amount, continuing to increase the amount of nucleating agent, the β-crystallinity

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 Proceedings of the 18th Plastic Pipes Conference
PPXVIII
September 12-14, 2016, Berlin, Germany
can be decreased. When the amount of nucleating agent exceeds a certain range the speed of
crystallization is increased and β-crystal has not enough time to grow, thus reducing the β-
crystallinity.
The experimental results indicates that the crystallinity of β-crystal increases with decreasing
the amount of JN2012. The best dosage of JN2012 is between 0.2 wt% and 0.4 wt%. This formula
provides optimal form of β-crystal with 30% of β crystallinity, 6.6% of α crystallinity and 80% of φβ.

1.2.2 Effect of annealing processes on the content of β-crystal

Figure 4—Effect of
annealing time on the crystallinity of PP-RCT pipe

Figure 4 illustrates the change of DSC curves after different annealing times. With the increase
of annealing time, the outermost point tends to the high melting point direction. As the annealing is
carried out in the pipes, imperfect spherulites gradually melt and recrystallization become perfect, so
that the thickness of the lamella increases, the melting point becomes higher, β crystallinity and total
crystallinity of the pipe gradually increase. However, after 4h’s annealing, the crystal cannot be further
improved at the annealing temperature, with the final stable β-crystal content at 62%. Therefore, the
2-4h annealing time is highly recommended.

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 Proceedings of the 18th Plastic Pipes Conference
PPXVIII
September 12-14, 2016, Berlin, Germany

Figure
5 -Effect of annealing temperature on the crystallinity of PP-RCT tube

Figure 5 shows the effect of different annealing temperatures for the crystallinity of PP-RCT
pipes. It can be seen that after the annealing temperature reaches 100 ℃, with further increase of
temperature the increase of the pipe total crystallinity and β crystallinity becomes relatively slowly.
After the annealing temperature reaches 120 ℃, β-crystal content decreases, while α-crystal content
increases. It is because that this metastable crystalline β portion is transformed into α-crystal at the
high temperature, resulting in the decrease of β-crystal. Therefore, the annealing temperature should
not exceed 110 ℃.

2 Permissible design stress calculation of PP-RCT

The β-crystalline polypropylene pipe material, named PP-RCT for short in the international standard
referred to as ISO 15874:2013, was released on February 15, 2013 [4]. The grading curve of PP-RCT
is designed and developed in the standard. As shown in Figure 4, there has no turning point in all
temperature ranges. Generally, it can be found approximately the permissible stress (experimental
ring stress) at different temperatures and different life (experimental times).

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 Proceedings of the 18th Plastic Pipes Conference
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September 12-14, 2016, Berlin, Germany

Figure 4—PP-RCT reference intensity curves predicted by ISO15874-2:2013.

According to the PP-RCT model equations of four-parameter, conditions of use of the material
level, different temperature coefficients and Miner's rule, it can be calculated the design stress (σD) of
the different using conditions.

2.1 Four-parameter model of PP-RCT

1 log 
For PP-RCT： log t  119 .546  52176 .696  31.279 log(  )  23738 .797 [4] (6)
T T
2.2 Selection of grade of using conditions

Under the provisions of GB/T 18991, selection of class 1, 2, 4, 5 by using conditions, as shown
in Table 3, each level corresponds to a specific range of applications and 50 years of its design life.

Table 3—Grades of using conditions

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 Proceedings of the 18th Plastic Pipes Conference
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September 12-14, 2016, Berlin, Germany
Time,a Time,
Time,at
Application TD t Tmax at Tmal Typical field
Tmal
class ℃ TD ℃ Tmax ℃ of application
h
years years
Hot water
1 60 49 80 1 95 100 supply
（60 ℃）
Hot water
2 70 49 80 1 95 100 supply
（70 ℃）
Underfloor
20 2.5 heating and
4 40 20 70 2.5 100 100 low
60 25 temperature
radiators
20 14 High
5 60 25 90 1 100 100 temperature
80 10 radiators
Note: 1) when time and temperature are more than one, should be stacking.
Because the system is not always a continuous operation at design time,
so for the life of 50, actual operating time has not exceeded 50, other times
at 20 ℃ to consider.
2) TD，Tmax and Tmal value is out of range in this table cannot be used in this table.

2.3 Design coefficients of different temperatures

Table 4—Design coefficient of PP-RCT [4].
Temperature coefficient
℃ C
TD 1.5
Tmax 1.3
Tmal 1.0
Tcold 1.4

2.4 Miner's rules calculate design stress σD

Miner's rules is a calculation method of cumulative damage, its principle is following:

(1) Total loss of material with complete damage is set for 100%;
(2) Produced damage is proportional to the time of erosion;

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 Proceedings of the 18th Plastic Pipes Conference
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(3) Given that the material in working temperature (T）can be continuously used for t years,
the annual damage rate is 1/t;
(4) In different temperature T conditions, the material's total year damage is:
a
TYD   i (7)
ti
(5) In variable temperature conditions, the material's using life is:
1
t (8)
TYD

For example, calculate the design stress σD under PP-RCT material level 1, designing the form
through the Excel and introducing relating equations, showing in Table 5.

Table 5—The calculation form of design stress σD of level 1 criteria

desig Calculati
T T t t'
C n on of Log t a TYD
（℃） （K） （y） （y）
stress stress
60 333.15 1.5 σ1 t1 a1
80 353.15 1.3 σD σ2 t2 a2
95 368.15 1.0 σ3 t3 a3
Note：① σ1=1.5*σD ；σ2=1.3*σD ；σ3=1.0*σD
② according to formula (6), log t is calculated.
③ convert t by log t calculated power of 10.
④ a is the percentage of time, such as a1=49y/(49y+100h +1 years) = 0.9798, likewise
a2=0.0200; a3=0.0002
⑤ according to the formula (7) to calculate TYD .
⑥ according to the formula (8) to calculate t'.
The iteration method is used to calculate design stress. As shown in Table 6, the valued of
σD is 3.636Mpa. As presented in Table 7, the valued of σD is 3.635Mpa.
Table 6
T T desig Calculat t t'
C log t a TYD
（℃） （K） n ion of （y） （y）

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 Proceedings of the 18th Plastic Pipes Conference
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stress stress
333.1
60 1.5 0.9798
5 5.454 7.619 4746.464
353.1
80 1.3 3.636 0.0200 0.0201 49.64
5 4.727 3.956 1.031 4 34
368.1
95 1.0 0.0002
5 3.636 3.567 0.421

When valuing σD for 3.635Mpa, looking at the Table 7:

Table 7
T desig
T Calculatio
（ ℃ n t t'
（K C n of log t a TYD
） stres （y） （y）
） stress
s
333.1 7.62 4798.94
60 1.5 5.453 0.9798
5 4 5
353.1 3.96 0.019 50.13
80 1.3 3.635 4.726 1.041 0.0200
5 0 95 62
368.1 3.57
95 1.0 3.635 0.425 0.0002
5 1

In order to meet the request of the service life at least 50 years for pipes, σD value should keep
at 3.635 Mpa. Generally, the design stress values accurate to two decimal digits, the value σD is thus
3.64 Mpa. Using the same method, other 3 level conditions of design stress σD can be also obtained,
as can be seen in Table 8.

Table 8—PP-RCT different levels of design stress of material.

Application
1 2 4 5
class

σD（MPa） 3.64 3.40 3.67 2.92

3 Checking calculation of the PP-RCT materials’ testing pressure

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With the design stress calculation method for PP-RCT material, it is able to determine the tube s
value though the design stress and the design pressure, also calculate the test parameters in pipe
performance test, such as hydrostatic stresses in hydrostatic testing, hydrostatic stresses in thermal
stability test, test pressure of internal pressure test.

3.1 Calculation of pipe hydrostatic stress

There are four Pipe hydrostatic test conditions: 20℃*1h、95℃*22h、95℃*165h、95℃*1000h.

Under hydrostatic state, the thermal stability test condition of is 110℃*8760h. Taking an example of
20 ℃ *1h, according to four-parameter model and static hydraulic test conditions of PP-RCT
material, the hydrostatic stress can be calculated, shown in Table 9:
Table 9 Hydrostatic stress calculation parameters
hydrostat
T T t
C ic stress Calculation log t
（℃） （K） of stress （h）
（MPa）

1 14.99 14.99
20 293.15 0.0037899 1.01
Generally, the hydrostatic stress value is accurate to one decimal place, and the hydrostatic
stress value is thus 15.0Mpa. According to the same method, 3 other hydrostatic stresses under test
conditions can be calculated, showing in Table 10:

Table 10—Hydrostatic testing stress

Hydrostatic test 110℃
20℃*1h 95℃*22h 95℃*165h 95℃*1000h
conditions *8760h
hydrostatic
15.0 4.2 4.0 3.8 2.6
stress（MPa）

3.2 Calculation of internal pressure test pressure

The test condition of internal pressure test is 95 ℃ *1000h, the hydrostatic stress has been
calculated from Table 10, which is 3.8Mpa. According to the formula (9), the test pressure of different
series S can be also calculated, as shown in Table 11.

P （9）
S
Table 11—Test pressure of PP-RCT pressure test

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 Proceedings of the 18th Plastic Pipes Conference
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Tube series
S6.3 S5 S4 S3.2 S2.5 S2
S
test pressure（
0.60 0.76 0.95 1.19 1.52 1.90
MPa）

CONCLUSIONS
With the release of international and national standards ISO 15874:2013, new PP-RCT materials
will be further promoted and applied in building hot & cold water pipes, and other fields. The
calculation method of design stress for engineers is crucial, not only to validate new materials, but
also become process design and calculation reference to draw up new international standards,
national standards, industry standards and enterprise standards.

ACKNOWLEDGMENTS
The authors acknowledge Dr. Cindy Xin Wang from Borouge for the special contribution to this
paper.

REFERENCES
[1] Wang Rong-he, Qu Yun-chun. β-special analysis on developing prospect of PPR pipe.
petrochemical technology economy, 2007,23 (3): 39-41.
[2] Xie Jian-ling, Wang Xiou-li. Polypropylene pipe standard and development trends.
[3] Zhao Bo, The analysis and evaluation of relative amount of β-form in βPP-R. Plastic
technology. 2012,40(8): 88-92.
[4] Plastic piping systems for hot and cold water installations-Polypropylene (PP)-Part 1:General,
ISO 15874-1:2013.
[5] Plastic piping systems for hot and cold water installations-Polypropylene (PP)-Part 2:Pipes,
ISO 15874-2:2013.

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