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Consulting Engineer Gulf Regional Office E.I. DuPont de Nemours Hwy 347 South Beaumont TX 77704 Phone: 1 (409) 727-9722 Fax: 1 (409) 727-9970 (Fax) e-mail: ABSTRACT A Gulf Coast manufacturing unit has three heat exchangers in its reaction overhead off-gas system. All the heat exchangers are once-through condensers with carbon steel shells, zirconium tubes and double tube sheets. There are four reaction trains in the manufacturing unit for a total of 12 condensers. All have many years of satisfactory service except the newest condenser which failed after only four months in service (typical service life is 8 to 15 years). Initially, one tube failed but subsequent inspection found numerous leaks at the rolled joint between the zirconium tube and the zirconium tube sheet. The failure mechanism is stress corrosion cracking initiating at pits due to the presence of ferric ions. Iron was embedded in the tube expansion process during fabrication and subsequent iron corrosion produced ferric ions that lead to SCC and pitting. The fabrication problem occurred despite very detailed and specific quality control plans. This failure reiterates the need for thorough implementation of quality control plans during fabrication. KEYWORDS Corrosion, stress corrosion cracking, pitting, ferric chloride, hydrochloric acid, fabrication, rolling, iron, zirconium, heat exchanger, tubing. BACKGROUND The failed heat exchanger is a condenser in the off-gas system of a batch polymerization process (Figure 1). HX1 and HX2 are condensers and HX3 is a liquid cooler. The failed heat exchanger, HX2, condenses the bulk of the vapors in the off-gas stream.. The remaining vapor is sent to a gas recycle loop (not shown). The batch cycle has portions with oxidizing conditions and other portions with reducing conditions.


Figure 1. Process schematic for the off-gas system from a batch polymerization process. The heat exchangers have zirconium tubes and carbon steel shells with a double tube sheet design. HX1 and HX2 are condensers and HX3 is a cooler. The knock-out pot is fabricated from Zr 702. The reactor and piping are glass-lined. The failed heat exchanger is HX2.

The specific process conditions lead to a greater amount of bad actors absorbing into the liquid phase in the failed heat exchanger than the first off-gas condenser. During polymerization, the condensing liquid includes organic chlorides, a few weight percent HCl and an occasional excursion up to 50 ppm H2SO4. Between batches, the system is swept with chlorine, nitrogen and then air. There is very little water in the failed exchanger during operation or between batches (on the order of a few ppm condensing from the air or nitrogen during sweeps). The service conditions are aggressive to most materials of construction, even zirconium shows moderate attack over time. Service history dating from the 1970s shows the 12 zirconium off-gas condensers (in four reaction trains) have a typical service life ranging from eight to fifteen years.

Figure 2. Schematic of the failed heat exchanger showing the double tube sheet design. 20

The double tube sheet design (Figure 2) has proven very satisfactory for this service. Tubes are only rolled into the tube sheets because service experience shows seals welds fail from stress corrosion cracking. The rolled portion ends at least 3/8 away from the back end of the tube sheet. The heat exchangers are mounted vertically, with the off-gas entering the tube side at the top. The shell side is a glycol mixture entering at the bottom. The failed heat exchanger had numerous leaking tubes in the bottom zirconium tube sheet after only four months of service. No leaks were detected at the top zirconium tube sheet or the carbon steel tube sheets (Figure 2). The leaking tubes are predominantly on one-half of the tube sheet (Figure 3). No leaks were found on the other three tube sheets in the heat exchanger.

Figure 3. Bottom tube sheet. The plugs denote numerous leaking tubes that were found by hydrotesting, distributed over one-half of the tube sheet.

ANALYSIS The failed exchanger was removed from service because a leaking tube was detected. The heat exchanger was sent to the original fabricators shop for assessment. Subsequent hydrotesting found numerous tube leaks. Before plugging tubes, random tubes were measured for the roll depth. Most holes measured the specified 3/8, the minimum distance between the end of the rolled portion and the back of the tube sheet was .


Figure 4. Sample removed from bottom tube sheet, row 4, tube 1. This is one sample removed in two pieces due to the heat exchanger configuration.

A number of samples were removed from the failed heat exchanger, both from the bottom and top zirconium tube sheets (Figure 4). In most cases, corresponding portions of the same tube from the top and bottom were removed. On the leaking tubes, all crack-like indications were at the transition between rolled and unrolled portions of the tube. Tables I and II contain chemistry and mechanical property information for the OD, 0.065 wall ASME SB-523 tubes.
Table I. Chemical Analysis (Weight Percent)

Element Zirconium + Hafnium Hafnium Iron + Chromium Hydrogen Nitrogen Carbon Oxygen

ASTM B523 UNS R60702 99.2 4.5 max 0.2 max 0.005 max 0.025 max 0.05 max 0.16 max
Table II. Mechanical Properties

Sample (Ingot Analysis) >99.2 1.3 0.08 0.00055 0.0047 0.01 0.1370


ASTM B523 UNS R60702

Sample 76 (524) 51.6 (356) 34.5

Tensile Strength ksi (MPa) 55 min (379 min) Yield Strength ksi (MPa) 30 min (207 min) Elongation in 2 (%) 16

Sample 2 (Figure 5) was not initially reported as a leaking tube. However, there are longitudinal cracks in the transition region between rolled and unrolled portions of the tube. This damage pattern is characteristic of all samples showing cracks. The number of longitudinal cracks per tube varies from a

few to numerous with no discernable pattern. Sample 2 has circumferential indications, (Figure 5), visible predominantly in the transition region.
Rolled Transition Unrolled

Circumferential Indications

Longitudinal Cracks

Figure 5. ID surface at the transition between the rolled and unrolled portion of Sample 2. (16.5X).
Rolled Transition Unrolled

General Corrosion

Scanning Artifact (Not Relevant)

Longitudinal Cracks

Figure 6. SEM micrograph of Sample 2 showing the same area as the previous figure. Corrosion in the rolled area is more apparent as are a few additional longitudinal cracks. The circumferential indications in the previous figure are not visible because these indications are only in the oxide layer. (17X).

Scanning electron microscopy (SEM) reveals corrosion in the rolled area (Figure 6) that was not visible in Figure 5, but the circumferential indications are not observable in SEM photo macrograph (ensuing discussion will show the circumferential indications are only in the oxide). SEM will not image the circumferential indications because the oxides are thin and electrically insulating so the

oxides will not produce sufficient secondary electrons at lower magnifications to be imaged with SEM. Figures 5 and 6 emphasize the need to perform both light optical microscopy as well as SEM.
Crack Initiation at ID

Service Fracture (Figure 8)

Lab Fracture (Figure 9)

Figure 7. Longitudinal crack fracture surface showing ID origination. (16.5X)

The fracture surface of a longitudinal crack shows ID origination (Figure 7). Comparing the fracture surfaces of the service and laboratory fractures provides a qualitative check for the zirconium brittleness (Figures 8 and 9, respectively). The service fracture (Figure 8) shows a very brittle appearance while laboratory fracture (Figure 9) has the dimpling characteristic of a ductile fracture. This quick check shows the zirconium tube has ductility in the regions not affected by cracking.

Figure 8. Cleavage facets on the surface of a longitudinal crack showing brittle failure. (2500X).

Figure 9. Dimpling on the laboratory fracture showing the tube material was not initially brittle. (2500X).


.Figure 10. Cross-section of a longitudinal crack from Sample 2 showing ID origination (upper, right corner) with transgranular morphology and very little branching. (100X, Unetched)

Figure 11. Cross-section of another longitudinal crack in Sample 2 originating from the ID surface at the right of the micrograph. The crack is transgranular with a slightly higher degree of branching. (400X, Unetched).

The cracking morphology is transgranular with minor branching (Figures 10 and 11). Another important observation is the internal oxide disruption in the unrolled area compared to the rolled area (Figures 12 to 15). The circumferential indications in Figure 5 are macro features of the disrupted oxide seen in Figures 13 and 15. The other samples from the bottom tube sheet had very similar damage patterns to sample 2.


Figure 12. Oxide on the interior, unrolled surface of sample 2. Compare with the following micrograph. (400X, Unetched).

Figure 13. Oxide on the interior, rolled section of sample 2. Compare with the previous micrograph. (400X, Unetched).

Longitudinal Axis

Longitudinal Axis

Figure 14. A secondary electron image of the surface oxide on sample 8 in the unrolled region. The longitudinal tube axis is parallel to the length of the figure. (1000X).

Figure 15. A secondary electron image of the surface oxide on sample 8 in the rolled region. The circumferential (up and down) cracks were caused by rolling. The longitudinal axis is parallel to the length of the figure. (1000X).

Sample 2G, from the top zirconium tube sheet, is the complementary portion of Sample 2. The internal surface of sample 2G shows pitting and accelerated corrosion (Figure 16 and 17).The interior surface of sample 2G is typical of all the tubes from the top of the tube sheet: Corrosion and pitting, but no

cracking. Contrast the severe corrosion on the rolled portion of sample 2G with minor corrosion on the unrolled portion (Figure 16).
Transition Rolled Unrolled

Figure 16. Internal surface of sample 2G from the top zirconium tube sheet, the complementary portion of sample 2 from the bottom zirconium tube sheet. Corrosion is on the rolled portion of the tube. (7.5X).

Figure 17. Cross-section of pits in the rolled section of sample 2G. (400X, Unetched).

The most significant analysis for this failure is provided by the SEM Energy Dispersive Analysis by X-rays (EDAX) results (Figures 18a to 19b). EDAX of the sample 2 in the rolled region shows an iron peak while the unrolled area has no iron (Figures 18a and 18b). Sample 2G has iron on the interior surface in the rolled region (Figure 19a) and the unrolled region does not have iron (Figure 19b). Iron was 3 wt% to 6 wt% on various rolled tube areas by semi-quantitative EDAX. The rolled region of sample 2G also has nickel, chromium and calcium. The calcium is probably from sample handling, however the iron, nickel and chromium are probably from the tube rolling process. Sample 2 may also have trace amounts of nickel and chromium, but the excitation voltage for sample 2G EDAX was 25 keV while the sample 2 EDAX was only 10 keV, hence the EDAX on sample 2G

can detect slightly smaller amounts of contaminants. The tube rollers are reported to have austenitic stainless steel components.

Figure 18a. Sample 2 EDAX outside of tube sheet in an unrolled area. (10keV).


Figure 18b. Sample 2 EDAX from inside tube sheet in a rolled area. (10 keV). Samples from the bottom tubesheet showed from 3 wt% to 6 wt% iron.

Figure 19a. Sample 2G EDAX from outside the tube sheet in an unrolled area. Ca contamination is most likely from sample handling. (25 keV).

Figure 19b. Sample 2G EDAX from inside the tube sheet in a rolled area showing Fe, Cr, Ni and Ca. The first three contaminants were caused by the rolling process, and the Ca is most likely from sample handling. (25 keV). Samples from the top tube sheet had between 0.3 wt% and 3 wt% Fe.


DISCUSSION Examining the condenser operation explains the differences in corrosion damage at the top and bottom tube sheets. Implicit in the condenser design, most of the condensate forms below the top tube sheet as the process travels from top to bottom. At some point in the body of the exchanger the temperature is low enough for larger concentrations of bad actors like HCl absorb in the liquid on the tube walls. The bottom tube sheets are exposed to higher concentrations of these bad actors than tubes in the top tube sheet. It is also possible that there is less iron in the top tube sheet than in the bottom tube sheet. Even with challenging process conditions, the secondary condensers usually provide years of satisfactory service as long as impurities like iron are not present. The leak pattern on the bottom tube sheet prompted a check of the pipe stress to determine if stresses from external loads contributed to the failure. The pipe stresses were within acceptable limits. The glass-lined piping is very sensitive to misalignment and excessive pipe stresses would likely have also caused spalling and damage of the glass-lined pipe. The failure mechanism is stress corrosion cracking initiating at pits in the protective oxide coating. Zirconium is very resistant to organic chlorides and HCl, even though this is a reducing environment [1]. The presence of oxidizing impurities like ferric ions causes pitting and stress corrosion cracking (SCC) of zirconium because ferric ions polarize the zirconium surface to a potential exceeding the pitting potential [2, 3]. Corrosion of the embedded iron by the condensing process stream created ferric ions that lead to pitting and SCC. Iron on the rolled tube surface is sufficient to cause pitting and stress corrosion cracking. Differences in the corrosion attack in the tubes at the top and bottom tube sheet is attributable to the differences in the amount of HCl absorbing at the two locations. All potential sources of iron, chromium and nickel contamination were investigated. The exchanger has never been hydroblasted, so there is no possibility of iron pick-up from the hydroblasting lance. The glass-lined reactor and glass-lined piping are inspected periodically. After the heat exchanger failure, the inspections of the reaction train equipment were very thorough. The reactor has several tantalum patches that were intact and the remaining glass surface was in very good condition. The glass-lined piping has chips on the flange face, outside the gasket area, which is never in contact with the process. All the instruments and piping components are Teflon lined and all were intact. The raw materials are periodically tested for iron and the final product is always tested for iron because this contaminant has a strong impact on product quality. By a process of elimination, the only potential source of iron contamination is the fabrication process. Supporting evidence for a fabrication problem is the other seven exchangers currently in this service have no leaks or exchanger failures. The replacement for the failed exchanger has been in service for more than one year without any leaks. A leak would be readily detectable by an operator on his rounds because the susceptible location on the tubes is open to the atmosphere between the two tube sheets. An interesting side note is the condition of the protective oxide in the rolled regions. The tubes are purchased with an enhanced oxide to improve scratch resistance during tube handling and bundle insertion. The tube rolling process cracks this thicker oxide (compare Figures 14 and 15). In order to minimize the risk of trapping contaminants in the oxide cracks, the enhanced oxide should be removed by pickling after the rolling process. A post rolling thermal treatment may reestablish the oxide film but the reduction in residual stress may cause loss of seal integrity. Pickling the tubes after tube expansion will be beneficial for removing contaminants. As mentioned previously, this will also eliminate cracked oxide in the rolled regions. The oxide layer will be

diminished, but as long as there is at least 10nm oxide, then this will be sufficient initial protection [4] until service conditions thicken the oxide. There is a portion of the batch polymerization cycle where conditions are oxidizing and the protective oxide can reestablish. This is probably why the off-gas condensers have long service life even in the aggressive process environment. In the case of the failed heat exchanger the cracked oxide lessened the general corrosion resistance and the embedded iron accelerated pitting and cracking. FABRICATION PRACTICES AND QUALITY CONTROL Service history shows the performance of these zirconium heat exchangers is strongly dependent on fabrication practices. Very comprehensive fabrication specifications have been developed over the years to address numerous details needed for successful service. These address the unique issues involved in fabricating zirconium equipment[5]. Tube sheet hole diameter, tube ID and tube OD have very tight tolerances. The percent expansion of every tube is measured and recorded. The average expansion on all the tubes in the failed heat exchanger is 6.05%, which is within the acceptable range for zirconium tube expansion. For reference the hardness in the rolled area ranges from 200 HV to 280 HV, the unrolled area hardness ranges from 170 HV to 200 HV. An inspector follows the fabrication to ensure the specification and quality control details are followed. The fabricator has provided several zirconium heat exchangers for DuPont with acceptable service lives. The failed heat exchanger was purchased on an order for two zirconium heat exchangers. The vendor has two shops and decided to fabricate one heat exchanger at each location. The other heat exchanger on this order has been in service for several years with no reported leaks. Numerous communication and scheduling problems occurred during the failed heat exchanger fabrication. Both shops were supposed to use clean rooms for fabricating these exchangers. One heat exchanger on this order was build in a clean room. The failed heat exchanger was built in the open shop. It is reported that the second shop adamantly refused to build a clean room and successfully delayed fabrication until it was too late to transfer the job to another facility, thereby forcing fabrication to proceed without a clean room. The job was quoted with hydroswage tube expansion, but the vendor subsequently changed to rollers. Both techniques are reported successful, but hydroswaging is preferred because this method has less risk for embedding impurities, a more uniform tube expansion and decreased work hardening of the zirconium tube. The vendor completed the portions of tube rolling without the required and specified oversight. Judging by the embedded iron in the zirconium tubes, the rolling was apparently done in a dirty environment and/or with dirty rollers. The shop had no special control on the rollers, so they could have been used on another job with stainless steel tubes (based on impurities detected by EDAX). The leaking tube pattern (Figure 3) suggests the embedded iron problem may have occurred on one or two shifts. This failure highlights that equipment owners need to be aware of the vendors fabrication processes and must strictly enforce fabrication hold-points to ensure long service life of the equipment. This failure analysis touched on all the key corrosion control factors for a successful zirconium application: a proven design, operation, maintenance (not an issue for this failure) and fabrication [6]. Generally, the service performance of the zirconium tube/carbon steel shell, double tube sheet exchangers has been very good. The failure analysis demonstrates the crucial role of fabrication for a

long, successful service life. The unfortunate consequence of relearning this lesson is a very expensive replacement condenser. CONCLUSIONS 1. The failure mechanism is stress corrosion cracking initiating at pits. The failure mode is iron corrosion. The iron corroded in a process containing organic chlorides and hydrochloric acid thereby creating ferric ions that initiated pitting. 2. Iron is present only in the rolled sections of the tubes which was most likely embedded during fabrication. 3. Chromium and nickel are also present on some samples, but these contaminants did not contribute to the failure. 4. An interesting by-product of this failure analysis is the condition of the enhanced oxide in the rolled portions of the tubes. Cracks in the enhanced oxide are potential locations for contaminants to collect. Cracks in the enhanced oxide occur during rolling, resulting in portions of the surface having lower corrosion protection until process conditions reestablish a thicker oxide. 5. The heat exchanger service conditions are challenging service for many materials of construction including zirconium. Successful service performance requires strict adherence to all the subtle fabrication and quality control details. RECOMMENDATIONS 1. Maintain a very high level of inspection monitoring during fabrication to ensure vigilant adherence to the fabrication and quality control procedures and requirements. 2. Only use hydroswaging for tube expansion. Hydroswaging will lessen the risk for embedding contaminants into the tube ID, provide a more uniform tube expansion and decrease the amount of work hardening in the tubes. 3. Consider pickling tubes after expansion to provide a uniformly clean surface and also to remove the cracked oxides in the expanded regions. ACKNOWLEDGEMENTS The author thanks Jack Tosdale, Wah Chang, Dr. Te-Lin Yau, Te-Lin Yau Consultancy and Dr. Brian Saldanha, DuPont for assistance with the failure analysis and many useful discussions during the preparation of this paper.


REFERENCES [1] T.L. Yau, Zirconium Meeting the Challenges of the New Millenium, Paper 01331, NACE International, Houston, TX, 2001, p.18. [2] R.T. Webster and T.L. Yau, Zirconium, Process Industries Corrosion, edited by B.J. Moniz and W.I. Pollock, NACE, Houston, TX, 1986, p.537. [3] T.L. Yau and R.T. Webster, Corrosion of Zirconium and Hafnium, Metals Handbook, 9th ed., vol. 13, L.J. Korb and D.L. Olson eds., ASM International, Metals Park, OH, 1987, p.710. [4] T.L. Yau, private communication [5] G.J. Lentz and B.J. Sanders, Managing a Zirconium Project, Reactive Metals in Corrosion Applications, Wah Chang, Sunriver, OR, 1999. [6] R.A. Clapp, J.J. Kvochak and B.J. Saldanha, Corrosion of Titanium and Zirconium in Organic Solutions, Paper 95243, NACE International, Houston TX, 1995, p.11.