A material in 3ds max is a feature of 3DS max that allow for an object to have "skin" so called. By applying a material to any object in 3DS max you are changing how the object appears and this is very important because you will want your objects to look like certain elements in real life such as brick, grass, water, glass etc. Let me clear this up in 3DS max materials are also called shaders and you will hear people use these two words very often. There are many materials in 3ds max by default and so these are referred to as 3ds max materials. When you add a renderer such as Vray to 3ds max you add more materials to vray and thus gives you more options to give your object even more appearances. Now what can get confusing with vray materials is the the term "Vray material" because within the list of Vray materials there exists a specific material called the "Vraymtl or vray material" this is Vray's basic material and with this single material you can give the appearance of glass, water, bricks, dirt etc to an object within 3ds max.
The other Vray materials are not labelled "Vray materials" within 3DS max and so the only way to know them is by the word "Vray" at the beginning and "mtl" at the end of the word, also they come very last in the selection rollout of all materials within 3ds max.These other vray materials are used to give special effects or looks to your objects and require extra practice in using them. All materials whether Vray or 3ds max materials have the ability to use what are called "MAPS" inside specially grayed out areas inside each material. These maps again are divided between vray maps and 3ds maps and the vray maps appear with the word "Vray" at the beginning.
Another confusing thing people often ask is what are textures? textures are images or pictures, whether you download them online, take them with your camera, make them in Photoshop or some other softwares. Textures are used within a specific 3ds map called "bitmap" and this is very common practice so you will see a 3 tier structure alot of the time in 3ds max consisting first of a material, then in a material is a map then in the map is a texture. This is all very easy withing 3ds max an dis the only way to achieve high quality Realistic Render within 3ds max.
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