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Created by Brian Hallee

Partnered by Joseph Oxenham

Performed September 8th, 2010

Historical Background

The idea of a thermistor, or thermally sensitive resistor, has been around for over 150 years. Although one of his lesser-known discoveries, the first documented use of an NTC, (Negative Temperature Coefficient, something to be returned to in the theoretical basis section), thermistor came from Michael Faraday in 1833.

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After the initial discovery, it was

quickly realized that thermistors could be separated entirely into two different categories: NTC and PTC thermistors. Interestingly, the classification didn’t solely depend on metallurgical properties due to the fact that at certain temperatures some types can actually switch categories! Silicon is one such example that exhibits NTC properties until 250K, where a positive temperature coefficient sets in.

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All thermistors are made using

semi-conducting metallic compound oxides such as manganese, copper, cobalt, and nickel, as well as single-crystal semiconductors silicon and germanium.3 Many different types of thermistors exist for different uses. The coated lens type, while not utilized in this experiment, is one example as seen in Fig. 1 on page 2. While Faraday was first to discover the thermistor properties of semiconductors, Samuel Ruben was quickest to perfect it and seal it under a U.S. patent. Almost a century after Faraday’s breakthrough, Ruben released his “Electrical Pyrometer Resistance” findings in which he used a special technique to “cook” a copper base in an oxidizing atmosphere to create a cuprous oxide. After being cleansed in hydrochloric and nitric acid, a thin film of this oxide remained that gave his thermistor a negative

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temperature coefficient without the drawbacks of standard semiconducting materials.4 He explains in his patent that as he experimented with adding heat to the device, its resistance dropped noticeably and reproducibly. As a final notable

Example Coated Lens-Type NTC Thermistors (FIG. 1) http://www.patarnott.com/atms360/pptATMS3 60/CircuitLabThermistors.ppt

mention, Rueben explains similar phenomena occurred when mixing the cuprous oxide with cuprous sulphide, or

melting antimony sulphide with cuprous sulphide. The practicality of this intricate thermistor was widespread, as it drove applications in voltage protection, temperature control, and calorimitry to name a few. The notion of resistance increasing with temperature in regular conducting materials, however, is not a new one by any means. A. E. Kennelly and Reginald A. Fessenden write in 1893 in the Physical Review about the linear relationship between increased temperature and resistance in a sample of copper. In their testing between the ranges of -69⁰C and 123⁰C, the same range we have worked in, they explain how copper’s temperature coefficient is a positive 4.18% per degree Celsius.5 Thus, they seem to have proven very early on that, unlike semi-conductors, wellconducting metals do not exhibit strong, or any, fluctuations in R vs. T linearity. We will prove in later sections that this century-old value for the coefficient of copper (alpha) is quite reproducible.

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Although not explored in this lab, it was only a few decades later when physicists made perhaps the most astonishing discovery relating to electrical conductivity. On April 8, 1911, Kamerlingh Onnes and his cohorts experimented with vapor pressures of liquid helium to drop the temperature of mercury to a level where resistance “practically” disappeared.6 Today, we denote this phenomenon as superconductivity and it involves similar quantum effects explored in the theory section of this report on thermistors. Thus, historical experimenting has proven to us that the relationship between resistance and temperature can take wildly different turns given the circumstances and materials used.

Theoretical Basis

In order to better understand the results presented here, the underlying physical workings of the materials must be grasped. The idea of a negative or positive temperature coefficient is simple. It is the deciding factor as to whether resistance increases with increasing temperature, or decreases. Like Faraday, in this experiment we utilized a negative temperature coefficient thermistor and attempt to grasp the type of curve drawn out over a 10⁰C-90⁰C range. We start by assuming that 150+ years of semiconductor engineering is correct in assuming thermistors exhibit a relationship with temperature as such: RT=k*T (eqn. 1)

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R is naturally the resistance, T is temperature, and k is an unknown “temperature coefficient of resistance”. This k value can, at face value, be either negative or positive depending on whether we are using an NTC or PTC. A significant problem with this simple equation is the fact that most, if not all, thermistors do not wield a simple linear, quadratic, power, or other pre-determined relationship between its resistance and temperature imposed. Thus, naturally, equation 1 above breaks down when large temperature ranges are used. To resolve this, two geophysicists John S. Steinhart and Stanly R. Hart developed a 3rd power logarithmic equation with four coefficients to solve for the inverse of temperature in all semiconductors. The equation is as follows: 7 1 T=a+b*lnR+c*ln2R+d*ln3 (eqn. 2) The lowercase letters are individual Steinhart-Hart temperature coefficients. While in most professional cases, a, b, c, and d can be solved using four data points to solve four simultaneous equations, we can exploit the fact that our thermistor has a negative temperature coefficient and simplify the coefficients. Both c and d will practically fade into insignificance, and we can set a= 1To-1βlnRo and b= 1β to arrive at the β parameter equation: 1T= 1To-1βlnRo+1βlnR Finally, we use logarithmic properties to achieve 1T= 1To+1βlnRRo (eqn. 3)

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where β is the new temperature coefficient of resistance. Before moving on, the final equation used for determining resistance must be derived: 1T= 1To+1βlnRRo → Toβ=Tβ+ToT*lnRRo →

β*To-T= ToT*lnRRo → β*1T- 1To= lnRRo Place both sides as the exponent of e and multiply by R0 to get resistance as a function of temperature: RT= Roeβ(1T- 1To) (eqn. 4) Ro =Resistance at lowest temperature To=Lowest temperature data point e=The Naperian base: 2.781 Equation 2 can be deceiving. As I previously mentioned, we have taken the Steinhart-Hart equation and modified it to work succinctly for negative temperature coefficient thermistors. Thus, in our case, beta will actually come out to be positive. Now, this experiment enabled us to compare a thermistor to an actual conducting wire made from copper. The electrochemical properties of conducting metals such as copper have been fairly well understood for many years now. Excluding the strange nature of semiconductors, most metals exhibit a linear increase in resistance with increasing temperature. To fully appreciate this fact, we have to understand copper at the atomic level. Electric current is simply the passage of electrons through a wire over time somewhat analogously to the flow rate of water passing through a pipe. When we introduce the concept of resistance, you can picture driving thick nails into the pipe to impede the flow of water

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through it. At the atomic level, these “nails” are actually nuclei vibrating around their mean position. The electrons passing through the wire are either smashed into these nuclei, impeding their progress, or deliberately thrown off course due to the strong electric forces present between the positively charged protons and the electrons’ own negative charge. It is fairly simple to visualize and conceive the notion that if these nuclei were to vibrate back and forth quicker and quicker, and with larger ranges, the electrons’ chances of hitting nuclei increases dramatically. This is precisely the phenomenon that occurs when the temperature of the wire is increased. Thus, we can appreciate why conducting metals increase resistance with temperature, and why NTC semiconductors can be labeled as “strange”. The math behind regular conducting metals is a bit simpler relative to thermistors. We expect the temperature coefficient of these metals to be as close to zero as possible, thus we define it as such: α= 1Ro*(dRdT) (eqn. 5) We can easily form a function R(T) by separating variables and integrating demonstrated in the following steps: α*dT= 1Ro*dR → α0TdT= 1RoR0RdR → αT= 1R0 R- R0

Multiply and subtract by R0 to get resistance as a function of temperature:

RT= R0αT+ R0 →

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RT= R0(aT+1) (eqn. 6) The physics behind the strange phenomena exhibited in this experiment on thermistors is somewhat convoluted. Semiconductors exhibit conduction band energy states at the very high energy end. Most electrons in semiconductors are stuck in the low energy band bound by the valence band. Hence, very few charge carriers are available at low temperatures. However, when temperature is increased and heat energy is bestowed to the metal, many of these lower energy electrons begin making the jump to the conducting band and free holes in the valence band. This occurrence overrides the fact that atomic vibrations are increasing simultaneously, and the end result is decreased resistance.

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Apparatus

This experiment was carried out utilizing a relatively simple set of tools and apparatuses. The central piece of this experiment was a tripodsupported, insulated canister used to house the copper coil and thermistor. This canister was electrically supplied by a two-prong wall plug to operate its internal resistance source. This source involved a simple resistance heater with a coefficient of performance = 1. It was hand operated and spring loaded to return to the off state in order to avoid a boiling water or fire

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hazard. Next, the copper coil and thermistor units were both coupled to a lid engineered to seal off the canister and minimize heat loss. These lids came equipped with a sealed access point for a thermometer, and a stirring apparatus to enable uniform heat dissipation throughout the canister. Lastly, the lids were electrically coupled to the thermistor and copper wounds and were subsequently equipped with positive and negative terminals on the top. We utilized these terminals through alligator clips and color-coated wires (Red: positive, Black: negative) that were fed into a Keithley 197 Amp Multimeter. This multimeter allowed us to simultaneously feed current into the copper or thermistor coils and determine the resistance through one device. This multimeter was stated to have an accuracy of 1mΩ.9 Lastly, we had five medium to large beakers at our disposal in order to achieve water just above the freezing point to cool down the canister. As an effort to cut down on unnecessary reproduction, we utilized an HP Pavilion laptop with Excel formulas pre-loaded in order to visualize our trend lines on the spot.

Procedure

We began this experiment by acquiring roughly 1/2 pound of ice (1 large beaker) and mixing it with tap water. The instruments necessary for

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the procedure were conveniently laid out beforehand, and thus we were able to begin immediately. Before connecting the canister to the wall outlet, we brought the metal inside down to roughly 5⁰C by flushing it with ice-cold water from the large beaker. Another pre-experiment task was to determine the lead resistance on the wires we had for use. This was determined by inserting them into the multimeter, ensuring the multimeter was on and reading resistance on a 2Ω scale, and rubbing the leads together to remove a bit of corrosion. While the actual lead resistance was rather “jumpy” and hard to measure, we averaged the value over a roughly ten-second interval. Once satisfied, we left the water inside the canister, plugged in the resistance heater, and opted to begin with the copper coil apparatus. We placed it snugly onto the canister, inserted the thermometer, connected the alligator clips to the terminals, and observed the multimeter to ensure a proper connection had been made. The temperature was brought up to 10⁰C for the first data point, and the data collection was underway. We divided the remaining tasks as such: Joseph Oxenham operated the resistance heater and ensured the temperature was brought up slowly to the next data point. I maintained the homogeneity of the heat in the liquid via the stirring apparatus and inserted the data points into Microsoft Excel. As previously mentioned, the tables, formulas, and graphs were created prior to the experiment. Thus, we were able to observe the linear relationship between Resistance and Temperature on the fly during the copper experiment to ensure all equipment and procedures were optimal. We attempted, and

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mostly succeeded, in taking data points for every 10⁰C increase in temperature. Therefore, a total of nine data points were taken ending with a 90⁰C data point. Once this portion of the lab had concluded, the copper lid was removed and ice-cold water was again flushed in and out of the canister until the water maintained a temperature of 5⁰C. The thermistor device was housed by the same type of lid as the copper device, ergo the same procedures applied. Again, we acquired data points for every 10⁰C increase in temperature beginning with 10⁰C and culminating with 90⁰C. We were able to observe the relationship between (1/T-1/Td) and ln(R/Rd) in real-time to ensure the experiment was correct. As the lab concluded, we dumped out the water, removed all the components, turned off/unplugged electronics, and cleaned beakers in order to prepare for the next usage.

Results

From our experimentation, we gathered data in the form Ohms (Ω), Temperature (⁰C and ⁰K), and unit-less values of (1/T-1/Td) and ln(R/Rd) for the thermistor.

Rd = Resistance at lowest temperature Td = Lowest temperature: In our case 12⁰C (Thermistor)

As far as resistance is concerned, we noted both the raw measured resistance and the actual resistance with the lead resistance taken into account. All of these values can be viewed in the appendix section of this report. We found the lead resistance to be 0.258Ω, thus the actual value of

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resistance was determined via Rmeasured- Rlead=Ractual. With the Ractual and T values in hand, we were able to make a graph demonstrating the linear relationship between the two in copper wire demonstrated below. Now, as we derived earlier, eqn. 6 represents the change of resistance vs. temperature for copper. RT= R0aT+1 → α= 1T*RRo-1= (R- R0)(T-0)R0= SlopeIntercept We can use Excel’s built in algorithms to calculate alpha as follows: α=SLOPE(C6:C14,A6:A14)INTERCEPT(C6:C14,A6:A14).10 This automatically gives us the value α=0.00473112 1℃. This is acceptable, as it closely matches the value given in the lab handout: α=0.00433 1℃.11 However, we wish to verify that excel is indeed performing the calculation correctly. We take the first two data points (10℃ and 20℃ respectively) and use them simultaneously to solve for the slope and intercept as such: 3.577Ω=m*10 ℃+b and 3.691Ω=m*20 ℃+b Subtract Equations → 0.113Ω =m*20℃-10℃ → m=0.0113 Ω℃ Plug in m → 3.577Ω=0.0113 Ω℃*10 ℃+b → b= 3.577Ω-0.0113 Ω℃*10 ℃ = 3.465Ω α= SlopeIntercept = 0.0113 Ω℃3.465Ω= 0.00329 1℃.

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This value of α is fairly close, so we are comfortable with our calculation. As shown in the graph above, our coefficient of determination is practically 100%, so we can again be sure our experimental process was not flawed. Next we deal with our calculations pertaining to the thermistor apparatus. We were informed from our handout that, in this case, R vs. T would not be linear. Instead, what we got seemed to represent an exponential decay as shown below:

The important concept to take away from this graph is the notion that resistance did indeed decline with increased temperature. Temperature was displayed in Kelvins for the reason that an absolute scale was necessary for generating the logarithmic resistance ratio graph to solve for β. To achieve this, all Celsius data points were converted using this formula: T0K=T℃+273.15 We previously derived the relationship for resistance vs. temperature of a thermistor culminating with eqn. 4. Our goal is to solve for β, (the negative temperature coefficient), and that is found via the following two steps: lnRR0=β1T-1To → β= lnRR01T-1To Therefore, we need a graph demonstrating the relationship between lnRR0 and 1T- 1To to solve for β. The graph below exhibits just that.

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Armed with the knowledge that β is a constant, we expect this graph to be perfectly linear (or close to it). Excel tells us we have a coefficient of determination of practically 100%. Thus, our data can be viewed as highly precise. In this case, our slope is our β, and it is rather close to the lab handout’s expected range of 3530⁰K ± 80⁰K. It was acquired using the formula β= SLOPEM6:M14,L6:L14.10 We perform a sample calculation using the first and ninth data points to ensure the quality of Excel’s algorithms: β= ln(4.132Ω52.242Ω)(1363.150K- 1285.150K) = 3,368.27⁰K This value is very close to our experimental value, so we can ensure the calculation is correct.

Discussion

Overall we are very satisfied with the results of our experimentation. Reviewing our coefficient of determination value (0.996) acquired for the copper coil (0.996), we had a very precise set of data points. Knowing the accepted value for copper from the lab handout, we can calculate the percent approximation error using the following formula: δ= αaccepted- αexpirimentalαaccepted*100% = 0.004331℃ 0.004731121℃ 0.004331℃*100%=9.26% While small, an almost ten-percent error has to be accounted for. This is most likely due to the inexperience in working the resistance heater. While it was stressed in class that a gradual increase in heat over the few degrees

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preceding the data point would garner the best results, we may have acted overly ambitious on this first run. Consequentially, we were not allowing for uniform heat dispersion throughout the entire canister. This, in turn, caused resistances to vary throughout the copper coil and subsequently cause our readings to vary. Another problem we ran into on this first run is variance in the multimeter itself. When the time came to take note of a resistance, the multimeter would frequently jump over a range of roughly 0.3Ω. Thus, we were forced to quickly average this value in order to gather a data point. In hindsight, this too may have been caused by the hastily controlled resistance source and non-uniformly resisting copper wire. Returning to the work of Kennelly and Fessenden, we did, however, demonstrate similar values to their experiments dating over a century ago. Their value being 0.004181℃ , we experienced a 13.2% approximation error relative to this α. We had a bit more luck with in determining the temperature coefficient of the thermistor apparatus. The lab handout states that the manufacturer of this thermistor already accepts an absolute error of ±80 ⁰K. Thus we can begin by computing the percent error of the manufacturer’s value, and compare that to our percent approximation error of the experimental value. % Relative Error Manufacturer= errormeasurement*100%= 800K35300K*100%=2.27% δ= |35300K-34220K|3530⁰K*100%=3.06% error

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Thus, our experimental error is less than one percent greater than manufacturing error, so we can be very comfortable with this value acquired. For the error that we did happen to obtain, this, again, is likely due to ambitious resistance heating and other minute issues such as lead corrosion, terminal corrosion, etc. We were, however, intrigued by the fact that our β value came out to be only two ⁰K off from the attempt from the writers of the lab handout. While they were forced to utilize a slide-wire Wheatstone bridge and we were blessed with a digital multimeter, the 0.053% error from their attempt gave us something to further ground our own attempt. While most of the theories behind the behavior of conducting and semiconducting metals have been well understood for, at the very least, decades, this experiment does its job at solidifying certain concepts and implications of these technologies. First, copper’s positive temperature coefficient demonstrates why it makes such a useful tool for widespread use among our communications and energy infrastructure. It self-protects itself from thermal runaway. In layman’s terms, copper and other conductors will “sense” that extra or unruly current is passing through via heat generation and will automatically increase the resistance to this current. While this is not applicable to, say, replacing a fuse, it does function optimally for the uses for which it is designed (e.g. local telephone or power cables). On the other hand, NTC thermistors such as the one experimented on in this lab are vulnerable to such a runaway. However, these units are not exploited for their load carrying capacities so much as they are for their sensitivity. In this

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lab we observed a change in almost fifty Ohms in our thermistor versus roughly 1.2 Ohms in the copper coil. Our conclusion on this device is that it would be very useful in application settings centered on temperature control and compensation. When coupled to a simplified Ohmmeter and computer chip, this devices change in resistance could immediately be relayed to the computer chip and the temperature could be changed according to the algorithm set in place by the software engineer. To no surprise, the thermistor is very heavily used in all areas of temperature control such as thermostats, ovens, refrigerators, A/C units, fire alarms, fever thermometers, coffee makers, and more.5 In summary, both conducting wires and semiconducting thermistors have very practical uses for their R vs. T properties that will likely leave them around for decades, if not centuries, to come.

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APPENDIX – RAW DATA

Copper Coil Lead Resistance = 0.258Ω T (⁰C) 10 20 30 40 50 60 R-meas. (Ω) 3.835 3.949 4.090 4.329 4.487 4.645

α = 0.00473112 (1/⁰C) R-s (Ω) 3.577 3.691 3.832 4.071 4.229 4.387 4.532 4.684 3421.988 4.827 β= 495 R-s (Ω) 52.242 41.089 27.272 19.042 12.948 9.477 7.132 5.536 4.132 (1/T-1/Td) 0 -9.6 x 10-5 -0.00021 -0.00031 -0.00041 -0.00051 -0.00059 -0.00068 -0.00075

)

70 4.790 81 4.942 Thermistor Apparatus 90 5.085 Lead Resistance = 0.258Ω T (⁰C) 12 20 30 40 50 60 70 80 90 R-meas. (Ω) 52.500 41.347 27.530 19.300 13.206 9.735 7.390 5.794 4.390 T (⁰K) 285.15 293.15 303.15 313.15 323.15 333.15 343.15 353.15 363.15

(⁰K)

ln(R/Rd) 0 -0.24015 -0.65003 -1.00924 -1.39495 -1.70702 -1.99130 -2.24461 -2.53713

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**APPENDIX – DISC FILES
**

• Root Directory ○ Lab Report_Brian Hallee_Lab 1.doc Official digital copy of “Finding the Temperature Coefficient for Copper Wire and a Semiconducting Thermistor” lab report. ○ Lab1_Temperature Coefficient_9-8-10.xls Comprehensive spreadsheet containing all raw data entered during the experiment, all three graphs presented in this report associated with the copper wire and thermistor, and calculated values for α and β.

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ENDNOTES

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Cornerstone Sensors. (n.d.). A Brief History of NTC Thermistors. Retrieved September 18, 2010, from Cornerstone Sensors: http://www.cornerstonesensors.com/? LinkIn=http://www.cornerstonesensors.com/About.asp?PageCode=Brief Radio-Electronics. (n.d.). Thermistor. Retrieved September 18, 2010, from RadioElectronics.com: http://www.radioelectronics.com/info/data/resistor/thermistor/thermistor.php Arnott, P. (n.d.). Thermistors: Thermal Resistors. Retrieved September 19, 2010, from PatArnott.com: patarnott.com/atms360/pptATMS360/CircuitLabThermistors.ppt Ruben, S. (1930, March 19). Electrical Pyrometer Resistance. Retrieved September 19, 2010, from FreePatentsOnline: http://www.freepatentsonline.com/2021491.pdf A. E. Kennelly and Reginald A. Fessenden. (1893). Some Measurements of the Temperature Variation in the Electrical Resistance of a Sample of Copper. The Physical Review, 260-273. Kes, D.v. (2010). The Discovery of Superconductivity. Physics Today, 38-43. John S. Steinhart, Stanley R. Hart, Calibration curves for thermistors, Deep Sea Research and Oceanographic Abstracts, Volume 15, Issue 4, August 1968, Pages 497-503, ISSN 0011-7471, DOI: 10.1016/0011-7471(68)90057-0. Nave, R. (n.d.). Band Theory for Solids. Retrieved September 18, 2010, from HyperPhysics: http://hyperphysics.phy-astr.gsu.edu/hbase/solids/band.html#c5 ValueTronics. (n.d.). Keithley 197A Autoranging Digital Multimeter. Retrieved September 19, 2010, from ValueTronics International Inc.: http://www.valuetronics.com/Used_Keithley_197A.aspx See Lab1_Temperature Coeffieicient_9-8-10.xls on accompanying CD-ROM Instructions for the Use of NO. 2836. Thermistor Temperature-Coefficient Apparatus. (n.d.).

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