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04/01/2011

Nickel and Ccopper Switch Places

 CHAPTER 8 - OFF TO NACA IN CLEVELAND
 
In this column I take my leave of Pitt and head for NACA's Lewis Flight Propulsion Laboratory, now the NASA John H. Glenn Research Center at Lewis Field in Cleveland, Ohio. Apropos of the flight theme, one of my favorite things to do on a cruise was to sit on deck looking for flying fish leaping out of the water. Accordingly, I was intrigued by a brief article in the October 2010 issue of Scientific American. The article, by Ferris Jabr, discussed the sighting of a flying marine creature by marine biologist Silvia Macia off the coast of Jamaica in 2001. To her surprise, it was a squid!  It was a small squid, only about 8 inches long, but  managed flights of around 11 yards while attaining heights over 6 feet high in the air. Her sighting of squid flying resulted in a collaboration with other workers and a paper in 2004 in the Journal of Molluscan Studies reviewing previous observations of flying squids dating back to 1924. 
 
The squid uses jet propulsion to launch itself into the air by squirting seawater out a "funnel" under its head. In the water, it uses this funnel, which can swivel in almost any direction to propel itself towards or away from prey or predator. I've often discussed in these columns the flying dinosaurs among us, namely birds. Some accounts of the squid flights mention the spreading of fins and even flapping of fins while in flight and I can't help wondering if millions of years from now squids will have developed wings and will join birds flying around. Will they also evolve to walk around on those "legs"? Hey, you never know!
 
So much for flying squid. Let's begin to take leave of Pitt.   In my last column, I had just passed the last hurdle for my PhD, the defense of my error-laden thesis. In another major life-altering event, I had proposed to my dance partner, Vicki, and she accepted. I was to become a member of the rather large Novak family.  Vicki is the youngest of 10 children, including two half-brothers. She grew up in the very small town of Mutual, a suburb of Greensburg, Pennsylvania. Her mother and father were immigrants from what then was either Austria-Hungary or Czechoslovakia and is now the Slovak Republic. Her father was a mason, who built coke ovens in this coal mining district. I only met him only once and he died soon after that meeting. I could write a book about the very warm and generous Novak family. At the time, Vicki had some 21 nieces and nephews - it would be no small matter keeping track of this family over the years!
 
With my imminent departure from Pitt, what was to come next? I went to a meeting of the American Chemical Society to explore employment possibilities. As I recall, I got an offer from a college in New England at a salary of $3400 a year and there was the possibility of an offer from Monsanto. However, someone from NACA (National Advisory Committee for Aeronautics) came recruiting at Pitt and I went to Cleveland for an interview. NACA's  Lewis Flight Propulsion Laboratory was an impressive place, with a huge wind tunnel and facilities dedicated to such things as rockets, fuels and lubrication, ramjet studies and other flight problems. It directly adjoins what is now the Cleveland Hopkins International Airport and people would often drive out and park along the road just to watch the planes come in to land. As I recall, a plane once clipped a NACA flagpole as it came in a bit low on landing! 
 
I interviewed in several areas at NACA but the place I ended up was in the Materials and Stresses (M&S) building. There I encountered my future boss, Sidney Simon, a tall, somewhat overpowering fellow, who said that I would be studying the effect of radiation on materials. The goal was to build an airplane powered by nuclear energy! Whoa! This sounded like a really cool project and my unbridled enthusiasm for nuclear stuff returned. Imagine an aircraft powered by a nuclear reactor that could stay up in the air for days or weeks at a time! I took the job. You have to remember that this was back in 1950, when anything nuclear was glamorous and exciting. Today, especially in view of the horrible nuclear situation in Japan, the prospect of a nuclear powered airplane is ridiculous. Think of such an aircraft, if it could actually be built, crashing with attendant scattering of radiation. But I was young, 22, and such a thought never occurred to me. 
 
At the time, I was more concerned with another mode of transportation. Heading for Cleveland, I needed a car. In 1950, getting a car wasn't that simple. Although the war had been over for some 4-5 years, the pent up demand for wheels was still not that easily fulfilled. However, Vicki's brother "Cop" used his influence to convince a dealer to sell me a new 1950 maroon Plymouth, a car I still remember fondly. Vicki found herself a nursing job at Crile Veteran's Administration Hospital in a suburb of Cleveland. She lived in the nurses' quarters there while I found myself digs at Lettie Dobson's house on Bradgate Avenue, just off Rocky River Drive in Cleveland ( I'm proud of myself that I actually remember the name of the streets!). Lettie was a very nice spinster lady who rented rooms to two other NACA employees. The arrangement was great because Lettie's neighbor, Ella Kerkeek, was a great cook who served dinners in her house to a handful of NACA employees.  
 
In fact, just last week, I baked my first pecan pie from a recipe that Vicki got from Ella 60 years ago! It was delicious, even though I cheated and used a purchased pie crust. I still remember Vicki, by then my wife, using Ella's recipe for the first time. Vicki likes thin crusts and apparently that one was a bit too thin and the Karo syrup filling ended up leaking through the crust, raising it and the pecans up on top of the crust! Regular readers may recall my own unique broiled blueberry pie resulting when I set the oven temp at 400 degrees on broil instead of bake!
 
But enough about cooking; let's get to my new job at NACA. Being involved in a program related to nuclear studies, I had to get an Atomic Energy Commission Q clearance, which required the FBI to check me out.  I'm not sure now whether or not I knew it before arriving on the scene, but there was a missing link in our group's objective to study the effect of radiation on materials. GE was building a cyclotron in the basement of our building and the cyclotron was not yet finished. So, without a source of radiation, we were free to essentially do anything we wanted! As a newly minted PhD, this sounded great. What to do?  Why not continue my work at Pitt on electrochemical cells with magnesium-cadmium alloy electrodes on another alloy system? 
 
I shared a lab with an older NACA employee, George Fryburg, who had made a name for himself in the field of the prevention and control of fires in a plane crash. George and I agreed that we would collaborate in an emf study of the copper-nickel alloy system. I'm not sure why we chose that system but assume it might have been because copper-nickel alloys were more akin to the kinds of materials that might be used in aircraft engines? The copper-nickel alloys were harder to work with than the magnesium -cadmium alloys. It took higher temperatures to make the alloys and, at a given temperature, the copper and nickel atoms did not move (diffuse) as fast as the magnesium and cadmium atoms did in their alloys.
 
Why should this make a difference? You may remember that I mentioned previously that I used a potentiometer (pot) to measure the emfs (voltages) at Pitt. The way this works is that you dial in a voltage on the potentiometer and then push a button to close a circuit pitting the pot voltage against that of your cell. If the two voltages are the same, your galvanometer needle stays in its neutral, normal position. If not, the galvanometer needle swings one way or the other, depending on whether the pot voltage is above or below the voltage of the cell. I haven't mentioned before that a key point in emf measurements is that the voltage of a cell is a surface phenomenon; that is, the voltage is determined by the composition of the surface of your alloy. When I dialed in the wrong voltage on my pot at Pitt, atoms of magnesium would either leave or deposit onto the surface of the magnesium-cadmium alloy. Now, even though the number of atoms that came or went is small,  the composition of the surface is not the same as that in the bulk of your alloy. 
 
But the goal of these types of studies is to measure the emf corresponding to the bulk composition of the alloy; hence you must wait until the atoms diffuse into or out of the surface and everything is back to the same composition. The next time you adjust your pot voltage you'll know to make it closer to the "equilibrium" voltage of your cell. By zeroing in on this "true" voltage you finally have measured the voltage you're after. With the magnesium-cadmium system, the atoms move around relatively quickly at the 270-300 degree Centigrade temperatures we used. In copper-nickel alloys, we had to go significantly higher in temperature but even at 400-500 degrees, the atoms didn't move very quickly. As a result, George and I found that we sometimes had to wait an hour or even several hours between measurements. Not great if you don't have much patience!
 
That was bad enough, but there was something much more fundamental that was giving us a problem. To appreciate this particular problem, think back to your first chemistry course. Chances are you learned about the so-called standard electrode potential series. If you didn't, you may remember an experiment in which you plated an iron nail with a coating of copper. It was a simple thing to do - you just stuck the nail into a solution of a copper salt, perhaps copper sulfate. Stick the nail into the solution and take it out and you have copper plated on the nail. The iron in the nail goes into solution, plating out the copper. Well, if you look at this standard electrode series you will see that iron is above copper in the series (in chemical terms, it has a more negative reduction potential). Nickel is also above copper in the standard electrode potential series so, if you stick a nickel nail in a copper sulfate solution you should get copper plated out on it, just like on the iron nail.
 
What does all this have to do with our work at NACA? Remember, we have two electrodes in an electrochemical  cell, an anode and a cathode (as in a battery). Our cathode is the copper-nickel alloy. What should the anode be?  Obviously, to those trained in the art, it's nickel and the electrolyte should be a fused salt mixture containing a nickel salt. Think about it. If we used copper and a copper salt in our electrolyte, the nickel in our alloy would plate out copper spontaneously and we have loused up our surface making it copper, not an alloy. So, George and I used for our electrolyte a mix of potassium and lithium chlorides with a modicum of nickel chloride added. Our anode was nickel.
 
As time progressed, we realized that something drastic was wrong. Our voltages were all over the place and made no sense. Finally, we opened up our cells and were shocked to find that the surfaces of our alloys were coated with crystals of nickel! The copper in the alloys was plating out nickel, not vice versa. The standard electrode potential series in textbooks is for aqueous solutions and here we have found that in fused salt solutions, at least the ones we used, copper and nickel appear to have switched positions, copper lying above nickel! I don't remember how long it took to realize this fundamental problem but imagine it must have been several months. So, we had to regroup and make cells with copper anodes and copper salt in our electrolyte. I'll get back to this work next month and explain how it was perhaps the reason I ended up leaving NACA for Bell Labs in New Jersey.
 
Meanwhile, items of a more personal nature were also occupying my attention. I was going to be married, on January 20, 1951. My parents, especially my mother, were very opposed to my marrying a Catholic. (I may have mentioned that my parents were active in a church in Denver prior to my birth but seemed to have stopped attending church after my birth! I grew up having no religious affiliation.) I had agreed with Vicki that we would be married by a priest and that our children would be raised Catholic. But Vicki's old-school priest in her home area would not marry us! However, Father Tully, in Cleveland, agreed to perform the ceremony. Father Tully was a great guy and he and I spent most of the time during my "instructions" periods talking about his experiences in the army.  
 
Vicki and I were married by Father Tully in the library of the cathedral in Cleveland. We were not allowed at that time to be married at the altar. It was a very small wedding, with nobody from my family in attendance. My best man was Al Weber, whom you may recall was the guy who refused Vicki's dance invitation, suggesting me instead. Prof. Hurd Safford, with whom I shared an apartment in Pittsburgh, also was there, in addition to Vicki's brother "Bunsie" and her best friend from Magee Hospital, Estelle. (Later that year, Bunsie and Estelle, who was not Catholic, were married by that same local priest who wouldn't marry us!)   Two of Vicki's nurse friends from Crile Hospital, Ruthie and Yolanda, were also there and just this past week, Vicki spoke to both of them on the phone. 
 
Where to honeymoon in January? Obviously, someplace warm such as Florida. But hey, I had only been working for about half a year and could only afford train tickets to Chicago, with the temperatures hovering around zero or below! We stayed at what was then the biggest hotel in the world - the Stevens, now the Hilton Chicago. The Stevens had a lot to offer. We saw an ice show in the hotel and also saw actress Janet Blair in a touring production of "South Pacific".  We even braved the frigid weather on one icy day to visit the aquarium, the first I had ever seen. Another first was my first experience with imbibing alcohol; we bought a bottle of wine in the hotel. My parents probably would have been shocked; not only had I married a Catholic but I had violated our teetotaling tradition. At any rate, we had an interesting honeymoon, if not in a tropical locale - that would come a few years later, when we did get to Florida.
 
Next column, hopefully, will be posted on or about May 1. I'll probably discuss a time of mixed emotions regarding our stay in Cleveland and the events leading to our move to New Jersey and Bell Labs.
 
By the way, I started this column with flying squid. Did you see the item in the news this past week about the jumping spotted eagle ray? You may remember that some time ago, a ray had killed a person when the ray jumped onto the boat, stabbing the victim with its venomous barb. This time a family had been watching this ray when it jumped onto the boat, striking the woman in her chest. The ray was a 200-pound critter with a wingspan of over five feet! Fortunately, the lady got out from under the ray unhurt. And I thought flying squid sounded dangerous!
 
Allen F. Bortrum



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-04/01/2011-      
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04/01/2011

Nickel and Ccopper Switch Places

 CHAPTER 8 - OFF TO NACA IN CLEVELAND
 
In this column I take my leave of Pitt and head for NACA's Lewis Flight Propulsion Laboratory, now the NASA John H. Glenn Research Center at Lewis Field in Cleveland, Ohio. Apropos of the flight theme, one of my favorite things to do on a cruise was to sit on deck looking for flying fish leaping out of the water. Accordingly, I was intrigued by a brief article in the October 2010 issue of Scientific American. The article, by Ferris Jabr, discussed the sighting of a flying marine creature by marine biologist Silvia Macia off the coast of Jamaica in 2001. To her surprise, it was a squid!  It was a small squid, only about 8 inches long, but  managed flights of around 11 yards while attaining heights over 6 feet high in the air. Her sighting of squid flying resulted in a collaboration with other workers and a paper in 2004 in the Journal of Molluscan Studies reviewing previous observations of flying squids dating back to 1924. 
 
The squid uses jet propulsion to launch itself into the air by squirting seawater out a "funnel" under its head. In the water, it uses this funnel, which can swivel in almost any direction to propel itself towards or away from prey or predator. I've often discussed in these columns the flying dinosaurs among us, namely birds. Some accounts of the squid flights mention the spreading of fins and even flapping of fins while in flight and I can't help wondering if millions of years from now squids will have developed wings and will join birds flying around. Will they also evolve to walk around on those "legs"? Hey, you never know!
 
So much for flying squid. Let's begin to take leave of Pitt.   In my last column, I had just passed the last hurdle for my PhD, the defense of my error-laden thesis. In another major life-altering event, I had proposed to my dance partner, Vicki, and she accepted. I was to become a member of the rather large Novak family.  Vicki is the youngest of 10 children, including two half-brothers. She grew up in the very small town of Mutual, a suburb of Greensburg, Pennsylvania. Her mother and father were immigrants from what then was either Austria-Hungary or Czechoslovakia and is now the Slovak Republic. Her father was a mason, who built coke ovens in this coal mining district. I only met him only once and he died soon after that meeting. I could write a book about the very warm and generous Novak family. At the time, Vicki had some 21 nieces and nephews - it would be no small matter keeping track of this family over the years!
 
With my imminent departure from Pitt, what was to come next? I went to a meeting of the American Chemical Society to explore employment possibilities. As I recall, I got an offer from a college in New England at a salary of $3400 a year and there was the possibility of an offer from Monsanto. However, someone from NACA (National Advisory Committee for Aeronautics) came recruiting at Pitt and I went to Cleveland for an interview. NACA's  Lewis Flight Propulsion Laboratory was an impressive place, with a huge wind tunnel and facilities dedicated to such things as rockets, fuels and lubrication, ramjet studies and other flight problems. It directly adjoins what is now the Cleveland Hopkins International Airport and people would often drive out and park along the road just to watch the planes come in to land. As I recall, a plane once clipped a NACA flagpole as it came in a bit low on landing! 
 
I interviewed in several areas at NACA but the place I ended up was in the Materials and Stresses (M&S) building. There I encountered my future boss, Sidney Simon, a tall, somewhat overpowering fellow, who said that I would be studying the effect of radiation on materials. The goal was to build an airplane powered by nuclear energy! Whoa! This sounded like a really cool project and my unbridled enthusiasm for nuclear stuff returned. Imagine an aircraft powered by a nuclear reactor that could stay up in the air for days or weeks at a time! I took the job. You have to remember that this was back in 1950, when anything nuclear was glamorous and exciting. Today, especially in view of the horrible nuclear situation in Japan, the prospect of a nuclear powered airplane is ridiculous. Think of such an aircraft, if it could actually be built, crashing with attendant scattering of radiation. But I was young, 22, and such a thought never occurred to me. 
 
At the time, I was more concerned with another mode of transportation. Heading for Cleveland, I needed a car. In 1950, getting a car wasn't that simple. Although the war had been over for some 4-5 years, the pent up demand for wheels was still not that easily fulfilled. However, Vicki's brother "Cop" used his influence to convince a dealer to sell me a new 1950 maroon Plymouth, a car I still remember fondly. Vicki found herself a nursing job at Crile Veteran's Administration Hospital in a suburb of Cleveland. She lived in the nurses' quarters there while I found myself digs at Lettie Dobson's house on Bradgate Avenue, just off Rocky River Drive in Cleveland ( I'm proud of myself that I actually remember the name of the streets!). Lettie was a very nice spinster lady who rented rooms to two other NACA employees. The arrangement was great because Lettie's neighbor, Ella Kerkeek, was a great cook who served dinners in her house to a handful of NACA employees.  
 
In fact, just last week, I baked my first pecan pie from a recipe that Vicki got from Ella 60 years ago! It was delicious, even though I cheated and used a purchased pie crust. I still remember Vicki, by then my wife, using Ella's recipe for the first time. Vicki likes thin crusts and apparently that one was a bit too thin and the Karo syrup filling ended up leaking through the crust, raising it and the pecans up on top of the crust! Regular readers may recall my own unique broiled blueberry pie resulting when I set the oven temp at 400 degrees on broil instead of bake!
 
But enough about cooking; let's get to my new job at NACA. Being involved in a program related to nuclear studies, I had to get an Atomic Energy Commission Q clearance, which required the FBI to check me out.  I'm not sure now whether or not I knew it before arriving on the scene, but there was a missing link in our group's objective to study the effect of radiation on materials. GE was building a cyclotron in the basement of our building and the cyclotron was not yet finished. So, without a source of radiation, we were free to essentially do anything we wanted! As a newly minted PhD, this sounded great. What to do?  Why not continue my work at Pitt on electrochemical cells with magnesium-cadmium alloy electrodes on another alloy system? 
 
I shared a lab with an older NACA employee, George Fryburg, who had made a name for himself in the field of the prevention and control of fires in a plane crash. George and I agreed that we would collaborate in an emf study of the copper-nickel alloy system. I'm not sure why we chose that system but assume it might have been because copper-nickel alloys were more akin to the kinds of materials that might be used in aircraft engines? The copper-nickel alloys were harder to work with than the magnesium -cadmium alloys. It took higher temperatures to make the alloys and, at a given temperature, the copper and nickel atoms did not move (diffuse) as fast as the magnesium and cadmium atoms did in their alloys.
 
Why should this make a difference? You may remember that I mentioned previously that I used a potentiometer (pot) to measure the emfs (voltages) at Pitt. The way this works is that you dial in a voltage on the potentiometer and then push a button to close a circuit pitting the pot voltage against that of your cell. If the two voltages are the same, your galvanometer needle stays in its neutral, normal position. If not, the galvanometer needle swings one way or the other, depending on whether the pot voltage is above or below the voltage of the cell. I haven't mentioned before that a key point in emf measurements is that the voltage of a cell is a surface phenomenon; that is, the voltage is determined by the composition of the surface of your alloy. When I dialed in the wrong voltage on my pot at Pitt, atoms of magnesium would either leave or deposit onto the surface of the magnesium-cadmium alloy. Now, even though the number of atoms that came or went is small,  the composition of the surface is not the same as that in the bulk of your alloy. 
 
But the goal of these types of studies is to measure the emf corresponding to the bulk composition of the alloy; hence you must wait until the atoms diffuse into or out of the surface and everything is back to the same composition. The next time you adjust your pot voltage you'll know to make it closer to the "equilibrium" voltage of your cell. By zeroing in on this "true" voltage you finally have measured the voltage you're after. With the magnesium-cadmium system, the atoms move around relatively quickly at the 270-300 degree Centigrade temperatures we used. In copper-nickel alloys, we had to go significantly higher in temperature but even at 400-500 degrees, the atoms didn't move very quickly. As a result, George and I found that we sometimes had to wait an hour or even several hours between measurements. Not great if you don't have much patience!
 
That was bad enough, but there was something much more fundamental that was giving us a problem. To appreciate this particular problem, think back to your first chemistry course. Chances are you learned about the so-called standard electrode potential series. If you didn't, you may remember an experiment in which you plated an iron nail with a coating of copper. It was a simple thing to do - you just stuck the nail into a solution of a copper salt, perhaps copper sulfate. Stick the nail into the solution and take it out and you have copper plated on the nail. The iron in the nail goes into solution, plating out the copper. Well, if you look at this standard electrode series you will see that iron is above copper in the series (in chemical terms, it has a more negative reduction potential). Nickel is also above copper in the standard electrode potential series so, if you stick a nickel nail in a copper sulfate solution you should get copper plated out on it, just like on the iron nail.
 
What does all this have to do with our work at NACA? Remember, we have two electrodes in an electrochemical  cell, an anode and a cathode (as in a battery). Our cathode is the copper-nickel alloy. What should the anode be?  Obviously, to those trained in the art, it's nickel and the electrolyte should be a fused salt mixture containing a nickel salt. Think about it. If we used copper and a copper salt in our electrolyte, the nickel in our alloy would plate out copper spontaneously and we have loused up our surface making it copper, not an alloy. So, George and I used for our electrolyte a mix of potassium and lithium chlorides with a modicum of nickel chloride added. Our anode was nickel.
 
As time progressed, we realized that something drastic was wrong. Our voltages were all over the place and made no sense. Finally, we opened up our cells and were shocked to find that the surfaces of our alloys were coated with crystals of nickel! The copper in the alloys was plating out nickel, not vice versa. The standard electrode potential series in textbooks is for aqueous solutions and here we have found that in fused salt solutions, at least the ones we used, copper and nickel appear to have switched positions, copper lying above nickel! I don't remember how long it took to realize this fundamental problem but imagine it must have been several months. So, we had to regroup and make cells with copper anodes and copper salt in our electrolyte. I'll get back to this work next month and explain how it was perhaps the reason I ended up leaving NACA for Bell Labs in New Jersey.
 
Meanwhile, items of a more personal nature were also occupying my attention. I was going to be married, on January 20, 1951. My parents, especially my mother, were very opposed to my marrying a Catholic. (I may have mentioned that my parents were active in a church in Denver prior to my birth but seemed to have stopped attending church after my birth! I grew up having no religious affiliation.) I had agreed with Vicki that we would be married by a priest and that our children would be raised Catholic. But Vicki's old-school priest in her home area would not marry us! However, Father Tully, in Cleveland, agreed to perform the ceremony. Father Tully was a great guy and he and I spent most of the time during my "instructions" periods talking about his experiences in the army.  
 
Vicki and I were married by Father Tully in the library of the cathedral in Cleveland. We were not allowed at that time to be married at the altar. It was a very small wedding, with nobody from my family in attendance. My best man was Al Weber, whom you may recall was the guy who refused Vicki's dance invitation, suggesting me instead. Prof. Hurd Safford, with whom I shared an apartment in Pittsburgh, also was there, in addition to Vicki's brother "Bunsie" and her best friend from Magee Hospital, Estelle. (Later that year, Bunsie and Estelle, who was not Catholic, were married by that same local priest who wouldn't marry us!)   Two of Vicki's nurse friends from Crile Hospital, Ruthie and Yolanda, were also there and just this past week, Vicki spoke to both of them on the phone. 
 
Where to honeymoon in January? Obviously, someplace warm such as Florida. But hey, I had only been working for about half a year and could only afford train tickets to Chicago, with the temperatures hovering around zero or below! We stayed at what was then the biggest hotel in the world - the Stevens, now the Hilton Chicago. The Stevens had a lot to offer. We saw an ice show in the hotel and also saw actress Janet Blair in a touring production of "South Pacific".  We even braved the frigid weather on one icy day to visit the aquarium, the first I had ever seen. Another first was my first experience with imbibing alcohol; we bought a bottle of wine in the hotel. My parents probably would have been shocked; not only had I married a Catholic but I had violated our teetotaling tradition. At any rate, we had an interesting honeymoon, if not in a tropical locale - that would come a few years later, when we did get to Florida.
 
Next column, hopefully, will be posted on or about May 1. I'll probably discuss a time of mixed emotions regarding our stay in Cleveland and the events leading to our move to New Jersey and Bell Labs.
 
By the way, I started this column with flying squid. Did you see the item in the news this past week about the jumping spotted eagle ray? You may remember that some time ago, a ray had killed a person when the ray jumped onto the boat, stabbing the victim with its venomous barb. This time a family had been watching this ray when it jumped onto the boat, striking the woman in her chest. The ray was a 200-pound critter with a wingspan of over five feet! Fortunately, the lady got out from under the ray unhurt. And I thought flying squid sounded dangerous!
 
Allen F. Bortrum