Recommendation of Piping Material in a Corrosive Environment

By Austin Hangartner

Material Science 057:015:A01 Professor Audrey Butler 7/5/2012

Abstract In this lab, the task was to determine the best material for piping hydrochloric acid from a special stainless steel alloy reactor for Kauffman Enterprises. The acid fluid traveling through the pipes will be approximately at 525C. Due to hydrochloric acids corrosive nature, volatility, and temperature, a suitable material must be able to withstand the pressure, temperature, and reactivity effects associated with piping the acid. The property investigated in this lab was the coefficient of linear expansion for several materials: copper, brass, aluminum, and stainless steel. The materials considered for the piping material were those tested with the addition of bronze. Of these materials, bronze and brass exhibit the best corrosion resistance under the assumption that it is not concentrated hydrochloric acid or in a hydrated environment, and most importantly a low linear coefficient of expansion. The high corrosion resistance combined with the low linear coefficient of expansion will increase life expectancy and lower the possibility of material failure in a thermally active environment. Hence, this report is on bronze and brass as acceptable selections for piping material.

Introduction and Background Kauffman enterprises wishes to pipe hydrochloric acid at 525C from a special stainless steel alloy reactor. With hydrochloric acids high corrosive nature, high vapor pressure, and high toxicity, it is imperative for the piping material to withstand all these properties for the safety and financial success of Kauffman Enterprises (Sigma Aldrich, 2012). With piping fluid in a thermally active environment, it is necessary to be aware of the properties that are associated with temperature changes. One such property is thermal expansion. Generally when materials are heated, this energy causes vibrations in their molecular bonds which macroscopically results in expansion. Thus, different materials with different molecular bonds will experience larger or smaller quantities of expansion depending on weaker or stronger molecular bonds, respectively. Engineers can quantify this relationship with the coefficient of linear expansion whose equation is shown in Figure 1. This essentially can give engineers an estimation of how much a materials linear dimension will change based on temperature difference (Tf - To) and the initial linear dimension of the material (Lo).

Figure 1: The equation for calculation the coefficient of linear expansion for a material (Callister & Rethwisch, 2008) In designing a piping system, the piping materials coefficient of linear expansion is a useful tool. It allows for engineers to estimate the linear dimension change based on design temperatures or vice versa. This estimation can increase the safety and life expectancy of a system by identifying a problem before it becomes catastrophe. An engineer can be inclined to make adjustments to a piping systems

problem areas such as where the pipe meets another material (i.e. joint) with a different coefficient of linear expansion in order to avoid a future problem. With this knowledge, systems of materials with different and similar coefficients of linear expansion have been implemented for the utilization of the expansion characteristics. For example, in most household thermostats there is a bimetallic strip within the device. This strip is composed of two metals, one which has a high coefficient of linear expansion and the other a low coefficient of expansion. On hot summer days, thermostats automatically engage the air conditioning by utilizing their thermal expansion properties. When the temperature of the room gets hot enough and causes the metal with the higher coefficient to expand, the expanded material completes an electrical circuit which engages the air conditioner. After the air conditioner has cooled the room and metal enough to cause it to retract and disrupt the circuit, it will stop the air conditioner from cooling the room any further. The process is analogous to a cold room being heated (Science Clarified, 2008). A situation where two metals with similar coefficients of linear expansion are generally desirable is in any construction situation. For example, when building a skyscraper or road out of concrete with rebar it is necessary for the concrete and rebar have similar coefficients of linear expansion. The similarity in coefficients will reduce the chance of internal fractures which will allow the material to serve its purpose completely. This concept can be applied to pipe systems. When joining a pipe to a reactor, it would be an ideal situation to have both materials have the same coefficient of linear expansion. So when the system heats up, the pipe and reactor will expand at the same rate evading potential problems such as fractures and leaks (Thomson, 2006). Thus in this recommendation it is not only important to consider the materials corrosion resistance but its coefficient of linear expansion. In room 3249 of the Seamans Center, the coefficient of

linear expansion was experimentally tested for copper, brass, aluminum and stainless steel. The theoretical values for these materials are listed in Table 1. Table 1: Theoretical values for the materials tested in the lab. (Callister & Rethwisch, 2008) (x10^-6 1/C) 12.0 23.6 20.0 17.0 18.0

Material Steel Aluminum Brass Copper Bronze

Experimental Methods In lab, the property investigated was the coefficient of linear expansion. This was done with a deluxe linear expansion apparatus where the steam or cold water could be connected to the equipments inlet in order to heat or cool, respectively, the material placed in the apparatus. This apparatus is shown in Figure 2. For measuring the coefficient of linear expansion safely and effectively, the procedure here was used.

Figure 2: Deluxe linear expansion apparatus was used for determining the coefficient of linear expansion for copper, aluminum, brass, and stainless steel. For effectively measuring the linear coefficient of expansion the first step was to inspect the equipment. This mainly pertained to checking the steam generator to see if it contained enough water

to run the experiment. If it was low or became low during the experiment it was refilled with water. The generator was plugged in after inspection. While the steam generator was warmed up, the length of material was measured with a meter stick and recorded in a lab notebook. All materials were shaped or molded into the shape of a rod for use in the linear expansion apparatus. Before the material was inserted into the linear expansion device, the jacket or shell was examined to see if it was securely attached to the base of the instrument. Also the outlet for either cold water or steam was placed in a nearby sink to drain away the fluids. Once the rod was inserted, the micrometer screws dial was set to zero and cold water was connected to the linear expansion device to homogenize the temperature throughout the material. After approximately three minutes, the cold water was replaced with steam from the steam generator started earlier and allowed to heat the material for approximately five minutes. This procedure insured that the temperature of the materials between cold and hot treatments was kept to a nearly constant value between experiments. Once the five minutes were passed or the material stopped expanding, the displacement dial read the change in length and was recorded in a lab notebook. This procedure was repeated twice for two different materials. Collaboration with the lab section yielded the data set used in this report.

Results The raw data collected from the experimental trials is shown in the Appendix. The calculated coefficients of linear expansion are presented in Figure 3.
Experimental Coefficients of Linear Expansion
Coefficient of Linear Expansion (mm/mm oC )
30x10-6

25x10-6

20x10-6

15x10-6

10x10-6

5x10-6

ee St

er pp Co

a Br

ss um Al

um in

Br

e* nz o

Figure 3: A visual representation of the statistical averages for the data collected in lab and the error bars representing the standard deviation in the experimental trials. * - Bronze is considered in the piping material recommendation but was not experimented with in this lab.

By the experiment, the lowest coefficient of linear expansion was steel and the highest was aluminum, which is what was expected from the theoretical values in Table 1. The deviation of the experimental value from the theoretical value will be the error estimate defined by equation in Figure 4.

Figure 4: Equation for Estimation of error in experiment from theoretical values. As shown in Figure 5, the theoretical and experimental values of the materials tested with their estimated error from the theoretical value for the coefficient of linear expansion. This figure shows that the error was relatively low but in a design project an error greater than five percent could correspond to a length change greater than desired. (x10^-6 1/C) Material Theoretical Experimental % Error 12 Steel 12.81 6.75 23.6 Aluminum 22.46 4.83 20 Brass 20.46 2.3 17 Copper 18.34 7.89

Figure 5: Theoretical and experimental values tested with percent error calculated for each material.

Discussion and Conclusion The corrosion resistance of materials is another important factor when selecting a pipe material for these parameters. Hydrochloric acid is quite reactive in an ambient temperature environment so being at a temperature of 525C makes hydrochloric acid more reactive and corrosive ( ).

Stainless steel is prone to corrosion by hydrochloric acid through multiple mechanisms. The first is the phenomena where hydrogen atoms can diffuse into the surface of the pipe decreasing the pipes ductility and strength. This phenomenon also acts as a stress concentrator so once the process starts it rapidly increases corrosion in the affected area (Corrosionist, 2000). Another form of corrosion stainless steel experiences is pitting/crevice. This is where an acid creates a pit/crevice in the surface of the material by an electrochemical mechanism (Health and Safety Executive, 1999)

Copper is a relatively corrosion resistant metal. Its non-reactive in low temperature and low concentrations of hydrochloric acid. According to the University of North Carolina (2001), a high concentration of hydrochloric acid will dissolve copper with the combination of high temperatures. Bronze with a typical composition of 88wt% copper and 12wt% tin has also some corrosion resistance but depends on the environment. If in an acidic and hydrated environment, the stability of bronze is weakened due to chlorine ions reacting with copper ions starting a chain reaction. This chain reaction is termed the bronze disease which corrodes bronze materials severely. Also an alloy containing copper is brass with a composition of 72wt% copper and 28wt% zinc with other trace elements. Brass can undergo a similar corrosion pathway as bronze. Chlorine ions can react with copper atoms and form copper chloride salts which react with water to form hydrochloric acid continue to wear away the surface. If all water can be isolated from the system bronze or brass would be an acceptable piping material Aluminum is non-resistant to the corrosive properties of hydrochloric acid (British Stainless Steel Association, 2012). The thin layer of oxidized aluminum typically provides good resistant to corrosion but this layer is soluble in hydrochloric acid (Metalstone Technologies, Inc.). Once hydrochloric acid breaches the oxidized aluminum layer it will undergo a replacement reaction creating hydrogen gas. This can be a concern since hydrogen gas is flammable so danger of explosion in the reaction vessel is high (Sigma Aldrich, 2012). The construction of the pipe system with the observed error could be compensated by giving the points which are in contact with other materials that may have different coefficients of linear expansion some expansion room. Essentially making sure that the system can comfortably handle the expansion of the materials without fracturing. One way to incorporate this idea is to use gaskets or Orings in joints connecting two materials. Another way is to combine the previous idea with slots for bolts

to slide. That way when the pipe or reactor expands there will be minimized stress due to the nuts and bolts being able to slid within the slot provided. Although the best method is to try and match the materials coefficient of linear expansion so avoid these adjustments. The pipes should be added near the bottom of the reaction vessel. This ensures that liquid hydrochloric acid is being pumped and lessens the chance for water vapor and vapor lock of the pump (i.e.cavitation). Based on all data and research, the materials to choose from would be inadequate in todays world. Although in spirit of the assignment, the best material for piping from the materials given would be either brass or bronze. From a corrosion resistance stand point sources say these will withstand hydrochloric acid in low concentrations and in a water-free environment. The main difference is in the cost per foot of pipe. In the Appendix, values for the cost of materials is listed and brass is cheaper than bronze by 0.60$ per foot of pipe. My recommendation outside of the assignment parameters would be either to have a polymer coated austenite steel, nickel, or high weight percent nickel alloys (Chlorine Institute, 2011).

References British Stainless Steel Association. (2012 , June). Selection of stainless steels for handling hydrochloric acid. Retrieved from http://www.bssa.org.uk Callister, W. D., & Rethwisch, D. G. (2008). Fundamentals of materials science and engineering. (3rd ed.). Danvers, MA: John Wiley & Sons, Inc. Chlorine Institute. (2011). Hydrochloric acid storage and piping systems. Retrieved from www.chlorineinstitute.org Corrosionist. (2000). Hydrogen embrittlement. Retrieved from http://www.corrosionist.com/Corrosion_Type_Hydrogen_Embrittlement.htm Health and Safety Executive. (1999). Corrosion: selection of materials. Retrieved from http://www.hse.gov.uk Metalstone Technologies, Inc. (2010). Metal. Retrieved from http://www.metalstone.com/ Thomson, G. (2006). Thermal expansion. Retrieved from http://www.scienceclarified.com/ Sigma Aldrich. (2012). Material safety data sheet for hydrochloric acid. Retrieved from http://www.sigmaaldrich.com/united-states.html University of North Carolina. (2001). Copper. Retrieved from http://uncp.edu/

Appendix

Trial 1 2 3 4 Average Std. Dev.

Lo(mm) 600 600 600 601

Steel Lf-Lo (mm) 0.51 0.52 0.49 0.51 5.075E-01 1.258E-02

1.288E-05 1.313E-05 1.237E-05 1.286E-05 1.281E-05 3.165E-07

Trial Lo(mm) 1 599 2 599 3 600.5 4 600.5 Average Std. Dev.

Brass Lf-Lo (mm) 0.82 0.82 0.8 0.8 8.100E-01 1.155E-02

2.074E-05 2.074E-05 2.019E-05 2.019E-05 2.046E-05 3.213E-07

Trial 1 2 3 4 Average Std. Dev.

Aluminum Lo(mm) Lf-Lo(mm) 612 0.895 612 0.97 600.5 0.89 600.5 0.87 9.063E-01 4.385E-02

2.216E-05 2.401E-05 2.246E-05 2.195E-05 2.264E-05 9.363E-07

Trial 1 2 3 4 Average Std. Dev.

Lo 599 598 600 599

Copper Lf-Lo(mm) 0.73 0.71 0.74 0.72 7.250E-01 1.291E-02

1.847E-05 1.799E-05 1.869E-05 1.821E-05 1.834E-05 3.029E-07

Material Steel Aluminum Brass Copper Bronze

Price (USD) 2.65 3.25 2.76 1.24 4.65