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What is it exactly?

I have heard a lot about them, mostly in the form of elephant guns in .500, .600 and .700NE; however I have also seen smaller ones such as .224NE.

Is NE the powder used, or the name of the company, or another name for magnum, or what?

And has anyone tried using a small rimless NE round in a military rifle?
 

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The cartridges you mention came into being in the latter 19th and early 20th century (with the exception of the 700 NE). Black powder cartridges were commonly in use and smokeless powder was just coming into play. The Nitro Express (NE) designation was used to differentiate the new loadings from the old black powder loadings. Some early NE loads were simply a former black powder cartridge loaded with smokeless powder. The new loadings were intended for new firearms stressed to handle the higher pressures produced by smokeless powder. If you look at some older rifles and shotguns, you will see "Nitro-Proofed Steel" stamped on the barrel. This was to indicate that the weapon was safe to use with the new loadings. The early smokless powders were nitro cellulose extruded into spaghetti-like strands called cordite. Cordite was the forerunner of modern smokless powders and was used even up into the early '60's by some British manufacturers (Kynoch in particular). Its major drawback is it is highly erosive and tends to eat barrels more quickly than modern powders.

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