The Investigation of Decarburization In Heat Treated 1095 Steel

Coherency Strain Dr. Chen Mate 370

Abstract The process of decarburization was taken into consideration in order to investigate the low hardness values shown in 1095 steel samples. If allowed to occur, decarburization reduces the carbon content within metal samples and may adversely affect its mechanical properties. A test matrix was designed to investigate the role of temperature and duration of the heat treatment in the process of decarburization. Heat treatments of 1095 steel samples were conducted at three different temperatures (830, 865 and 900oC) and over three different times (1, 3 and 5 hours). The resulting depth of the decarburization layer produced through each of the various heat treatments was recorded and graphed. Upon analyzing the resulting trends in the depth of the decarburization layer for the various heat treatments conducted, it was observed that increasing the duration of the treatment increased the depth of the layer regardless of the temperature at which the samples were treated. The depth of the decarburized layer was greater for treatments held at 865oC than for those conducted at 830oC for each of the three treatment durations. However, a clear, linear pattern between the temperature of the heat treatment and the depth of the layer was not present. Using the Arrhenius Equation, the experimental activation energy required for decarburization was calculated and compared to a theoretical value. The experimental energy was found to be substantially smaller than calculated theoretically.

Introduction In the investigation of undesirably low surface hardness values in 1095 steel samples, potential decarburization occurring during the heat treatment was suspected. Decarburization can negatively impact steel's mechanical properties, causing the metal to exhibit decreased surface hardness and strength. Because of this, it may be important to minimize the amount of decarburization that may take place during the production process. Decarburization occurs when there is a concentration gradient between the steel sample and the furnace environment. Low carbon content in the furnace atmosphere causes its chemical potential to be lower than that of the steel. Thus it becomes thermodynamically favorable for the carbon to diffuse out of the steel. This effectively causes a phase change at the surface of the steel sample where diffusion takes place, and the resulting phase, ferrite, has a lower surface hardness than the pearlite that exists below the decarburized layer. The opposite process, carburization, involves the use of a high carbon-containing source, like gaseous CO, to diffuse carbon into the surface of the steel from the surrounding atmosphere. Carburization can improve surface hardness, wear resistance, and fatigue and tensile strengths because the presence of excess carbon atoms increases lattice strain. A list of the material properties induced by carburization is listed in Table I.

Table I. Effects of carburization on various material properties.

Work material properties

Effects of carburizing

Mechanical

Increased surface hardness Increased wear resistance Increased fatigue/tensile strengths

Physical

Potential grain growth Change in volume may occur Increased surface carbon content

Chemical

Background The diffusion mechanism of decarburization of steel is the concentration gradient between carbon in the surface of the steel and in the surrounding atmosphere. In steel, carbon is trapped in the interstitial sites in the lattice, which causes strain. Diffusion proceeds in an attempt for the material to reach a lower energy state. The type of diffusion that occurs in the decarburization of steel is called inter-diffusion. This occurs on the surface of steel while it is heat treated in a furnace. Since there is a higher concentration of carbon inside the steel, the carbon moves from the steel to the metal's surroundings. The temperature, concentration difference, and lattice size affect the rate of decarburization. As the temperature and the concentration difference increase, the rate of diffusion also increases. The amount of carbon dioxide in the furnace causes either decarburization or carburization to occur in steel1. The equations listed in Figure 1 may be used to calculate the diffusion coefficient D for the various times and temperatures of the each heat treatment.

Equation 1

Equation 2

Equation 3 3

Figure 1. Equations used to calculate diffusion thickness and activation energy, where x = diffusion distance, C = composition, D = diffusivity, Do = pre-exponential constant, Q = activation energy, T = temperature, and t = time.

The calculated diffusion coefficient for each sample can be seen in the table below. The value for Do was taken from Smithells Metals Reference Book. The activation energy Q is held constant throughout the calculations at 80 kJ/mol. These values were calculated using the times and temperatures that were used in the actual experiment. It is apparent that with increasing temperature the size of the decarburization layer also increases. The thickness of the decarburization layer on each sample will increase as the time that the sample spends in the furnace increases.
Table II. Diffusion coefficients and corresponding decarburization layer thickness.

Temp (Deg C) 830 830 830 865 865 865 900 900 900

Diffusion Coefficient D 2.25246E-12 2.25246E-12 2.25246E-12 3.7002E-12 3.7002E-12 3.7002E-12 5.90106E-12 5.90106E-12 5.90106E-12

Distance X (microns) 90.04910229 155.9696203 201.355914 115.4154316 163.2220687 199.9053915 103.0626304 145.7525697 206.1252608

The times and temperatures used to calculate the diffusion coefficient and the thickness of the decarburization layer were carefully selected with the intention of forming a readily measurable region.

PROCEDURE In order to properly measure decarburization, a procedure had to be developed that provided three distinct temperatures and three distinct times in order to calculate the diffusion coefficient and eventually the activation energy. By conducting the heat treatments at three different temperatures, a plot could be generated and the diffusion coefficient extrapolated. The three temperatures allowed for a plot of the data to be observed and the diffusion coefficient and experimental activation energy calculated. It was determined that the samples would be heated at the following temperatures and times: Temperature: 830C; Time(hours):1,3,5 Temperature: 865C; Time(hours): 1,2,3 Temperature: 900C; Time(hours): half hour,1,3 4

After each heat treatment, the samples were normalized to allow an appropriate microstructure to form. Each sample was then cut in half in order to take proper metallographic observations. The samples were placed in QuickSet and polished down to a 1 micrometer finish. Following polishing, initial observations were made to ensure that the samples' microstructure was clearly visible. 50 ml of 2% Nital was used to etch the samples. When etching the samples, they were first swabbed with etchant for 10 seconds, rinsed with ethanol and dried with the blower. The samples were then examined under a microscope. If they appeared over etched, the samples were polished lightly on 1um pad and reexamined. If this step failed to produce a distinguished microstructure, the sample was etched a second time. Directly following etching, the samples were photographed using the optical microscope, taking 3 photographs per sample. The STM E 1077 standards were followed to calculate the decarburization layer. This involved adding the sums of the measured full decarburization layer and partial decarburization layer. These measurements were then used to calculate the diffusion coefficient and activation energy. Results After the samples were heat treated according to the defined experimental procedures, metallography was performed on the samples to determine the width of the decarburization layer. This etch-polish-etch cycle was performed on all of the mounted and polished samples, and the microstructure of the decarburized samples could then be seen (Figure 2).

First, the samples were cut to expose their interior. Then, the cross sectioned samples were mounted in acrylic. The samples were then polished according to accepted metallographic procedures. Once the samples were polished they were etched using a 2% Nital solution. The samples were first swabbed with etchant and then 30 seconds later rinsed with deionized water. Next the samples were polished again with a 1 m polish on a rotating wheel. The samples were then etched again by swabbing with the 2% Nital solution and rinsed after 20 seconds. (Should this go in Procedure?) It was found that the fully decarburized region consisted of a low carbon ferrite phase, and the partially decarburized region had both ferrite and cementite present, as it contained a concentration of carbon similar to the eutectoid composition.

Figure 2. Photomicrograph of mounted, polished and etched sample heat treated at 830C for 3 hours. The decarburization layer can be clearly seen along the left edge of the sample, with the partially decarburized region extending into the interior of the sample. The sample was etched with 2% Nital solution.

Photomicrographs were taken of each of the samples under an optical microscope, and the decarburization layers were measured using image analysis software. The results are summarized in Table III.
Table III. Summary of decarburization layer thicknesses for various heat treatments

Temperature (deg. C) 830 865 900

x after 1h 0.0987 0.113 0.089 (0.5h)

x after 3h 0.16 0.181 0.144

x after 5h 0.24 0.219 0.237

The change in the decarburization layer thickness was representative of the change in the concentration profiles of the different samples. These profiles proved to be a function of both temperature and time (Figure 3).

C (wt. %) C0 t1 t2 t3 t4 t5

CS x (m)
Figure 3. A graph illustrating the change of the concentration profile of a sample with increasing time at a given temperature.

As the duration of the heat treatment increased, the partially decarburized layer shifted further away from the surface, as greater and greater amounts of carbon have had time to diffuse to the surface and leave the sample. Although this trend was apparent, it was also observed that the time required to advance the layer a unit of distance grew exponentially longer as carbon atoms deeper within the samples had to diffuse further toward the surface. This phenomenon is clearly observable from some of the collected data, but is not apparent in each sample. Analysis As mentioned earlier, many of the samples had a distinguishable, fully decarburized layer followed by a slightly less distinguishable partially decarburized layer. The thicknesses of these layers were measured and added together, ten measurements being taken and averaged for each sample. The squares of the average thicknesses were plotted on a graph versus the time the sample spent in the furnace, resulting in one group of three points for each temperature (Figure 4).

x2 vs t
0.07 0.06 0.05 x2 (mm2) 0.04 0.03 0.02 0.01 0 0 1 2 3 time (h)
Figure 4. Plot of measured thicknesses vs. time in furnace for each temperature. Trend-line slopes 2 represent D values in units of mm /h.

y = 0.0188x R = 0.9952

y = 0.0159x R = 0.9827

y = 0.0107x R = 0.9495 830 865 900

This plot clearly displays the trends relating time and temperature to diffusion distance. Longer diffusion distances were observed in samples that were heat treated at each temperature for longer periods of time, and similar diffusion distances were reached at shorter times for higher temperatures. These trends match what would be expected based on both conceptual learning and preliminary calculations. A trend-line was fitted to each group of points and the D values for the three temperatures were read off of the slopes of these lines according to equation 4. These values were then converted into units of m2/s for ease of use in later calculations (Table IV). X2 = Dt (4)

Table IV. Calculated D values (m /s) and the corresponding temperatures.

Temp (C) D (m2/s) 830 2.972E-12 865 4.417E-12 900 5.222E-12 The final step in obtaining an experimental value for the activation energy of carbon diffusing through an austenitic lattice was to plot the natural log of the obtained D values (ln(D)) versus the value of (-1/RT) (Figure 5). From the Arrhenius equation (Equation 5) the activation energy, Q, was calculated. Ln(D) = Q(-1/RT) + Ln(D0) (5)

ln(D) vs -1/RT
-0.00011 -0.000108 -0.000106 -0.000104 -0.000102 -25.9 -26 Series1

ln(D)

-26.1 y = 86942x - 17.027 R = 0.9556 -26.2 -26.3 -26.4 -26.5 -1/RT (mol/J) -26.6

Figure 5. Plot of the natural log of obtained D values vs. (-1/RT) used to find Q. Q is equivalent to the slope of the trend-line.

The value for Q obtained from this plot and thus the conducted experiment is 86.9Kj/mol. This value is 41.2% less than the given theoretical value of 148Kj/mol. Some sources of error that may have contributed to the discrepancy are: Inaccurate measurement of layer thickness Loss of thickness due to flakey oxide layer Inappropriate modeling equations used to obtain values

Conclusion Because of difficulty in determining the endpoint of the partially decarburized layer in some samples, thickness measurements may have been incorrect and skewed the results. Since the error was below the accepted value, it can be assumed that the measured layer thicknesses are lower than they should have been. The flakey oxide layer provided a perfect explanation to why the experimental measurements were low, because some amount of the steel samples was likely lost from the surface when the oxide layer fell off, the material thickness was lessened. The model used to plot thickness versus time was derived from Ficks second law for infinite systems, which modeled a composition value midway between the surface composition and initial composition at the measured thickness. Since the thickness could not be accurately determined, it would make more sense to develop a model from Ficks second law that could relate to a more easily measurable thickness. This model could use a final composition value of 0.77wt %C and the thickness could be measured as the distance from the surface of the sample to the point in the interior after which no more ferrite exists. The rationale behind this method was that any free ferrite formed would be proeutectoid, and the composition at which pearlite begins to form is the eutectoid composition (0.77wt%C). It would follow that the point in the 9

sample at which free ferrite disappears would also be the point at which the composition would equal that of the eutectoid. Following this method, a much more accurate length could be measured and plotted according to a more appropriate model, yielding more accurate results.

Works Cited 2. Verhoeven, John D. "Steel Metallurgy for the non-Metallurgist." ASM International, 2007. 67-69.

Decarburization of Steel R. Cornell and H. K. D. H. Bhadeshia http://www.msm.cam.ac.uk/phase-trans/abstracts/M0.html http://en.wikipedia.org/wiki/Carburizing Carburization

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