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Calculation of Allowable Crack Size of High-Pressure Vessels Considering Effect of H2S Corrosion Fatigue Environment

WANG Jing, ZHANG Yiliang, ZHANG Wei & MIAO Wei

(Department of Mechanical Engineering, Beijing University of Technology, Beijing 100022, China)
Abstract: For leak of testing and evaluation standards of high -pressure compressed natural gas (CNG) vessels, using fracture mechanics approach and probability analysis method, H 2 S stress corrosion cracking tests and corrosion fatigue tests were don e in this paper. Using modified WOL specimens and values of stress corrosion cracking threshold K1SCC of compressed natural gas(CNG) vessel steels 4130X, 30CrMo in two different H 2S environment of 200010 -6 and 20010 -6 with the density were obtained. Considering working environment and stress of vessel, the corrosion fatigue tests of 4130X steel group 2 were K were determined through the Paris fit to experiment data in the case of K below K1SCC and above K1SCC respectively. By ere calculated and the curves between

done in the H2 S solution of moderate concentration (20010 -6) and at a low frequency 0.0067Hz. The relations between fatigue crack growth rate da/d N and the increment of fracture toughness using inverse inferring method, considering critical crack sizes of H 2S stress corrosion cracking, c rack increments of corrosion fatigue, random capability and reliability of data and the practicality of different service period, the allowable crack sizes of different service period w vessels residual life. Keywords: H2S stress corrosion cracking, corrosion fatigue, crack growth rate, allowable crack size, crack evaluation curves allowable crack depth and origina l crack length were obtained, which would supply more accurate data to determine the service period and to evaluate pressure


In the technique phase of natural gas transportation, tube trailers are used to transport gas to vehicle refueling stations. Usually, cylinders are subjected to the working pressure 20 MPa. But now, since we are just star ted to apply this technique, periodical testing skills and the safety evaluation standard are not established, yet. In the process of establishing the standards, these questions must be considered: (1) The major corrosion media in compressed natural gas storage systems are CO 2, H2S, O2 and water, and the most serious problem is that H 2S and water in collaboration with the high working stress and form a wet H 2S stress corrosion cracking environment. (2) The cylinders subjected to the alternating stress that result from gas charge and discharge, and the vibration on the road. Hence the cylinders work in the corrosive environment and under the cyclic load, and corrosion fatigue may occur. (3) In the view of fracture mechanics approach and stress corrosion c racking, KISCC can ensure the critical crack sizes of cylinders, but the crack increments just can be obtained from the experiments of corro sion fatigue; and the difference value of critical crack size and crack increment is the allowable crack size of the ser vice period. In 1980s, as the development of ocean engineering [1] and aeronautical engineering, the study of corrosion fatigue progressed fast and kept focus on practical application. Nowadays, most of the corrosion fatigue experiments are performed in sy nthetic seawater[2],[3] environment. A literature reported corrosion fatigue problem in light water environment [4]. They have conducted the investigations on factors in the crack growth, and on the mechanics and mathematic models [5] . However, there are few reports about the corrosion fatigue of oil and natural gas equipments in H 2S environment. Many literatures calculated components residual life by using probability method [6] , and K.Makhlouf and Shih researched the FCGRs to evaluate residual life of press ure vessels[7],[8] . Xue also discusses the influence of randomness [9]. Considering the requirements of evaluation, three groups of specimens from CNG steels , 4130X and 30CrMo, were studied in this paper. Their stress intensity factors K ISCC in H2S environment are obtained. And the corrosion fatigue property of CNG steels was researched in moderate H 2S solution of 20010-6, low frequency of 0.0067 Hz. The relations between d a/dN and K are figured out. According to fracture mechanics approach and probability method, critical crack sizes of different materials in differen t environment were calculated, and the curves between working pressure or stress and critical crack size are ob tained, critical crack sizes and allowable crack sizes in different service period were also gained, which provide experimental data for the determi nation of allowable crack size and residual life assessment.

Experiment Methodology

2.1 Mechanical Properties and Chemical Composition of 4130X steel Mechanical properties and chemical composition of specimen materials are shown in table 1 and table 2 respectively. Table1 Mechanical properties of materials Youngs modulus Yield strength Tensile strength Elongation Area contraction Material E/GPa H/% ]/% 0.2/MPa b /MPa Group 1 197 638 804 19 74 4130X Group 2 210 653 811 20 72 30CrMo 183 633 788 19 63 Table 2 Chemical composition of materials /% Material C Mn Si Cr Mo S P 4130X 0.25-0.35 0.40-0.90 0.15-0.35 0.80-1.10 0.15-0.25 0.01 0.02 30CrMo 0.26-0.34 0.40-0.70 0.17-0.37 0.80-1.10 0.15-0.25 0.01 0.02 1404

2.2 Experimental Solution Usually, the experimental solution for SSC tests [10,11] should be the NACE standard solution, which is saturated H2S solution with 5% NaCl plus 0.5% CH 3COOH. But in recent years, European federation of corrosion according to tremendous experiments and research productions published a series of new standard. The No. 16 bulletin[12] guidelines on material requirement s for carbon and low alloy steels for H 2S-containing environments in oil and gas production is the latest, most comprehensive and the most authoritative document now. To ensure the results to be adaptable to the requirements of the experiment , the EFCs guideline stipulate that the tested solution should be exactly in conformity with the practical condition. According to GB17820-1999[13] , the H2S concentration in a CNG cylinder should be less than 20 mg/m 3. So, according to the EFCs prescription, meanwhile considering the difference of the natural gas quality, especially the circumstance when the conditions are out of control, the H2S solution of the density 20010-6 is determined, called moderate concentration hydrogen sulfide. 2.3 Specimens The specimens are cut from CNG cylinders. The outer diameter of the cylinder is 559mm and the thickness is 19mm. Modified WOL specimens are used and specimen dimensions are shown in Fig. 1. 2.4 Result 2.4.1 Stress corrosion cracking threshold K1SCC Twenty-two modified WOL specimens were tested for K1SCC, with seven specimens in dense H2S environment and fifteen specimens in moderate H 2S environment. The average K1SCC of three group specimens are shown in Table 2. 2.4.2 Fatigue crack growth rate Four specimens of 4130X group 2 are tested in moderate solution in this work. The fatigue crack growth rate is obtained and the relations between da/dN and K are given in Table 4 based on Paris method. The corrosion fatigue fracture section is shown in Fig.2, the relationship curve da/dN vs K of all specimens in Fig.3. In fracture mechanics, the crack is thought not to grow when K<KISCC under a constant load in a corrosive solution. However, under a cycle load, the crack maybe grow even when K<KISCC because of the fatigue effect. To evaluate the safety and estimate the residual life of defective vessels, the most valuable data for engineer is the FCGR when K<KISCC. We fitted our test data separately and obtained the following relations: when K was above or below the limit KISCC K1SCC=58.6 a m1 / 2 4.33 13 (1) K<K1SCC da/ dN ! 5.75v10 (K K>K1SCC

da / dN ! 5.44 v 10

Table 3 Solution 200010-6 20010


Average Effective K1SCC Material KISCC/( M a m1/ 2 ) 40.4 43.5 58.6 49.1

4130X 4130X

Group 1

Group 1 Group 2 30CrMo



Table 4 No. 1 2 4 5

Relations da/dN(K range /( a m1 / 2 ) 45255 40143 40140 66164

K of each specimen da/dN /(m/cycle)

7 .62 v 10 7 ( K 1 .44 5 .48 v 10 8 ( K 1.78 9 9.03 v 10 ( K 1 . 56 3 .28 v 10  8 ( K

0 . 74

W=48.5 60

Fig.1 Modified WOL specimen /mm

1E -4

(m/cycle)) Corrosion fatigue fracture section

1E -5

1E -6

(K / MPa m1 / 2
1E -7 0 50 100 150 200 250


Standard normal


Fig.2 Corrosion fatigue fracture section

Fig.3 da/dN- K curves of all specimens

distribution of fluent Z




(K 0.95


thickness 15



Analyzing Allowable Crack Size by Probability Method

3.1 Analyzing Critical Stress Intensity Factor Kcr Using Probability Method Considering the randomness of the experimental data, probability method is used to confirm the critical stress intensity fact or Kcr. Consider that K is obeyed normal distribution K N( , 2), and : Z ! K Q ~ N ( 0 ,1) W

Here are 9 valid values of stress corrosion cracking threshold KISCC . Regard those 9 values as the sample of K, then the value of mean and the variance 2 can be obtained. The valid values of KISCC are : k1=41.22, k2=45.71, k3=59.93, k4=58.80, k5=55.94, k6=46.71, k7=44.48, k8=51.3, k9=53.88. Using the maximum likelihood estimation to confirm the value of mean and the variance 2:
^  ^ 2

u ! k ,W

1 n


i !1




k is the average value of k, and n=9.

^ ^

Then we can calculate that: u =50.89, W 2 ! 39.76. And: K~N(50.89, 39.76),

Z !

K  50 .89 ~ N ( 0,1) 6 .3


Define that kq is the stress intensity factor with q reliability, and kq means that there are q stress intensity factor in the ensemble are inclined to safe. Take reliability q=90%, and K90% is the stress intensity factor with 90% reliability. Fig.4 is the standard normal distribution of fluent Z, and the probability of Z appears in the shadow zone is 90%. We can know from the table that Z 0.1=1.28. So

K 90%  50.89 ! 1.28 , and K 90% ! 42. 83MPa m 6 .3

Analyzing Corrosion Fatigue Crack Growth Rate Using Probability Method The crack growth rate da dN ! C ((K ) n in Paris Equation doesnt include the effect of the random capability of d a/dN, and only represents 50% reliability. In engineering field, 90% reliability of d a/dN should be gotten by considering of the random of experimental data. Then Equation of d a/dN and K can be written as follows at certain p reliability and believability[14]

Where, k ! u p  ur

u u u 1 [1  ]  [1  ] , n is the n 2 n  1) ( 2 n  1) ( 2 n  1) (

2 r

2 p

2 r

da d (m c ycle


number of observed values (n=5 in this experiment), up, ur is the standard normal deviator of the reliability and the believability separately. In our experiment, C=5.7510-13; n=4.33 and believability is 2.585.
30 35 40 45 50 55 1E-6

W ! 0. 287 , and k with 90% reliability


The fatigue crack growth rate equation with 90% reliability and believabil ity is

(K ( MPa m )

da / dN ! 3.01v 10 12 ( (K ) 4.33


Fig.5 Relationship of da/dN-(K 9 K<KISCC da/dN-(K when K<KISCC

When K<KISCC, fatigue crack growth rate equations with different reliability see Fig.5. l 3.3 Allowable Crack Size 2 Most of the crack defects of high pressure vessels are surface crack, definition of a crack size see Fig.6. t 1 where: t is thickness of vessel, a is depth of crack, l is length of crack. We measured KISCC values of 22 specimens in this paper, and obtained critical crack size a cr with different material in different sour solution; and the curves between Fig.6 Surface crack working pressure or stress and critical crack size are obtained. In order to ensure the original allowable crack size of different service period (for example: 1, 3, 5years, assuring cycle per year is 300, then co rrespond to 300, 900, 1500 cycles), the fatigue crack growth values in the service period must be considered. 1406

(da / dN ) p ! 10 ( kW ) ( (K ) n





Due to the different shape of the crack, the fatigue crack will grow along the deep as well as the length direction. In the v iew of fracture mechanics approach, str ess intensity factor K is the main factor which decide crack growth. Then the real growth direction at any time should be determined according to the values of the Kmax along the different directions at the risk point. Ellipse surface crack is considered in this paper, and the real growth direction is confirmed according to the changing conditions of Kmax. Using inverse inferring method, according to ASME XI [4] , the relationship between stress intensity factor and crack size is:
K I ! [(W  Ap )M  W b M b ] Ta Q


where: KI is stress intensity factor; Ap is the internal vessel pressure ( Ap=0 in this paper); Wm is membrane stresses, equal to PD/2t; Wb is bending stresses (can be ignored in this paper); Mm is correction factor for membrane stress, and can be o btained from table; Mb is correction factor for bending stress (can be ignored in this paper); a is crack depth; is crack shape parameter, equals to 1+4.593(a/l)1.65-qy, qy=0. To those CNG cylinders, the working pressure p=20 MPa, inside diameter D=521 mm, thickness t=19 mm, membrane stress Wm=274.2 MPa m1 / 2

K I ! (274.2 M m ) Ta [1  4.593( a / l ) 1.65 ]

In Equation (8), KI=Kcr=42.83 MPa, and the allowable crack size acr , lcr can be determined. According to Equation (6), using inverse inferring method, crack size that after some cert ain circle can be calculated. When the number of circle determines the service period, this crack size is the allowable crack size. The allowable crack size can be calculated as the following steps: Step 1: Determine the critical crack size acr , lcr for different shape crack (different crack length l values). Step 2: Calculate a, l after N circles according to Equation (6). Step 3: Calculate next a, l and K values of point 1, 2, as shown Figure 6.

a=a- a, l=l- l, KI ! W mMm

a, l.

Step 4: Compare K at two points and select the larger one to calculate next Step 5: Repeat step 2-4 to find aN, lN after certain N circles. Crack evaluation curves with different service period see Fig.7.


4.1 Two Parameters of Crack Evaluation Curvethe Effect of Crack Size From Fig.7 it can be seen that when crack length lN is small, a(mm) 6.5 or crack depth aN is similar with length lN, the gradient of the aN/mm N=300 crack evaluation curve is big, a N is sensitive to the change of lN, 6.0 5.5 and the critical stress intensity factor K cr is determined by two N=600 5.0 parameters, crack length and crack depth. When lN reaches 4.5 * N=900 critical length lN0, aN goes to a constant value, plane asymptotes 4.0 occur. At that time, K cr is determined by crack depth a N0. N=1500 3.5 Critical length lN is related to circle numbers. When circle 3.0 numbers N=1500(service period is 5 years), lN0 is about 13mm, 2.5 aN0=0.85mm. When circle numbers N=900(service period is 3 2.0 years), lN0 is about 18mm, a N0=1.24mm. When circle numbers 1.5 N=300(service period is 1 year), lN0 is about 30mm, 1.0 aN0=2.44mm. we can obtain that with the different circle 0.5 numbers, when lN/aN>15, the curve affected only by one 0.0 l /mm 0 Fig.7 Crack evaluation curves30 5 10 15 20 25 50 with35 40 45 N l(mm) different parameter. In the process of overhaul, when the crack length is 10 circle numbers large than lN0, the influence of crack length can be ignored, the allowable crack depth a N0 is the only parameter to be considered. 4.2 Safety Region of Crack Evaluation Curve Fig.7 shows the crack evaluation curves with different circle numbers. Each curve divides the crack size into two regions. Th e under region is the safety region and the above region is dangerous region, the spots on curves mean the critical condition of allowable crack. To evaluate the residual life of the vessels, it is more safety to use the allowable crack depth a N0 when lN< lN0. 4.3 The Influence of H2S Density From Table 3 we can find that there are 10 times difference of H 2S densities of those two environments, but the difference of SCC properties are not so large. For the 4130X group 2, when the density are 10 times difference, the difference of K1SCC values is just 1.34 times. In the farther corrosion fatigue tests we can al so see that when the densities are 10 times different, the FCGRs are just 2.39 times different. The results showed that when the destiny of H 2S reaches a certain value, the influence of destiny to the SCC properties is not so large, and the relationship be tween destiny and KISCC values is non-linear.

(1) The curves da/dN- K are obtained through data fit based on Paris method. The relation d a/dN- K with 90% reliability and 1407


believability when K<K ISCC is given by: da / dN ! 3.01v1012 ((K )4.33 . (2) The H2S solution of moderate concentration (20010 -6) and a low frequency of 0.0067 Hz are used in our experiments. Our experimental conditions are conformable to the practical condition. Our results can be used for the determination of allowabl e crack size and life evaluation of CNG cylinders. (3) Crack evaluation curves are obtained based on experimental data, considering critical crack sizes in H 2S stress corrosion cracking environment, crack increments of corrosion fatigue, random capability and reliability of data and the practicality o f different service period. The crack evaluation curves are fit for engineering application.
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Corrosion Fatigue Crack Propagation of a duplex Stainless Steel X6 Cr Ni Mo Cu 25 -6 in Air and in