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Influence of the Processes Parameters on the Properties of The ...

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Chapter 2.<br />

<str<strong>on</strong>g>Processes</str<strong>on</strong>g> to Manufacture Foams and to Functi<strong>on</strong>alize <str<strong>on</strong>g>the</str<strong>on</strong>g> Surface<br />

Ano<str<strong>on</strong>g>the</str<strong>on</strong>g>r approach to create microcellular materials was dem<strong>on</strong>strated by Shi et al. [1999]. First,<br />

<str<strong>on</strong>g>the</str<strong>on</strong>g>y syn<str<strong>on</strong>g>the</str<strong>on</strong>g>sized a number <str<strong>on</strong>g>of</str<strong>on</strong>g> chemicals soluble in scCO 2 or liquid CO 2 . <strong>The</strong>se chemicals comprise a number<br />

<str<strong>on</strong>g>of</str<strong>on</strong>g> “m<strong>on</strong>omers” c<strong>on</strong>taining <strong>on</strong>e or two urea groups and fluorinated “tail” groups that enhance solubility <str<strong>on</strong>g>of</str<strong>on</strong>g><br />

<str<strong>on</strong>g>the</str<strong>on</strong>g>se compounds in CO 2 . When <str<strong>on</strong>g>the</str<strong>on</strong>g>se compounds were dissolved in CO 2 , <str<strong>on</strong>g>the</str<strong>on</strong>g>ir self-associati<strong>on</strong> led to <str<strong>on</strong>g>the</str<strong>on</strong>g><br />

formati<strong>on</strong> <str<strong>on</strong>g>of</str<strong>on</strong>g> gels. <strong>The</strong> removal <str<strong>on</strong>g>of</str<strong>on</strong>g> CO 2 via depressurizati<strong>on</strong> resulted in <str<strong>on</strong>g>the</str<strong>on</strong>g> formati<strong>on</strong> <str<strong>on</strong>g>of</str<strong>on</strong>g> foams with cells<br />

with an average diameter <str<strong>on</strong>g>of</str<strong>on</strong>g> less than 1 m. Shi et al. [1999] reported that <str<strong>on</strong>g>the</str<strong>on</strong>g> bulk density reducti<strong>on</strong> <str<strong>on</strong>g>of</str<strong>on</strong>g> <str<strong>on</strong>g>the</str<strong>on</strong>g>se<br />

foams was 97% compared to <str<strong>on</strong>g>the</str<strong>on</strong>g> parent materials. Sheridan et al. [2000] studied <str<strong>on</strong>g>the</str<strong>on</strong>g> effects <str<strong>on</strong>g>of</str<strong>on</strong>g> several<br />

processing parameters (such as polymer compositi<strong>on</strong>, molecular mass, and gas type) <strong>on</strong> preparing threedimensi<strong>on</strong>al<br />

porous matrices from copolymers <str<strong>on</strong>g>of</str<strong>on</strong>g> lactide and glycolide and dem<strong>on</strong>strated that crystalline<br />

polymers did not produce foamed materials via this approach, while gas treatment <str<strong>on</strong>g>of</str<strong>on</strong>g> amorphous copolymers<br />

produced matrices with porosity up to 95%. This work also dem<strong>on</strong>strated that <strong>on</strong>ly CO 2 am<strong>on</strong>g <str<strong>on</strong>g>the</str<strong>on</strong>g> o<str<strong>on</strong>g>the</str<strong>on</strong>g>r<br />

gases used (e.g., N2 and He) created highly porous polymer structures in <str<strong>on</strong>g>the</str<strong>on</strong>g>se copolymers [Sheridan et al.,<br />

2000] and explained this by <str<strong>on</strong>g>the</str<strong>on</strong>g> possible interacti<strong>on</strong>s between CO 2 and carb<strong>on</strong>yl groups in PLGA [Kazarian<br />

et al., 1996a].<br />

5 Manufacturing <str<strong>on</strong>g>of</str<strong>on</strong>g> <str<strong>on</strong>g>the</str<strong>on</strong>g> Composite Biomaterials<br />

5.1 Fundements <str<strong>on</strong>g>of</str<strong>on</strong>g> Co-grinding Process<br />

5.1.1 Mechanism <str<strong>on</strong>g>of</str<strong>on</strong>g> Size Reducti<strong>on</strong><br />

<strong>The</strong> properties <str<strong>on</strong>g>of</str<strong>on</strong>g> a material may be c<strong>on</strong>siderably influenced by <str<strong>on</strong>g>the</str<strong>on</strong>g> particle size and, for example,<br />

<str<strong>on</strong>g>the</str<strong>on</strong>g> chemical reactivity <str<strong>on</strong>g>of</str<strong>on</strong>g> fine particles is greater than that <str<strong>on</strong>g>of</str<strong>on</strong>g> coarse particles. In additi<strong>on</strong>, far more intimate<br />

mixing <str<strong>on</strong>g>of</str<strong>on</strong>g> solids can be achieved if <str<strong>on</strong>g>the</str<strong>on</strong>g> particle size is small [Richards<strong>on</strong> et al., 2002]. Practically every solid<br />

material undergoes size reducti<strong>on</strong> at some point in its processing cycle.<br />

Also reducti<strong>on</strong> in size causes [Richards<strong>on</strong> et al., 2002]:<br />

<br />

<br />

<br />

<br />

<br />

Both an increase in area and a reducti<strong>on</strong> in <str<strong>on</strong>g>the</str<strong>on</strong>g> distance.<br />

Separati<strong>on</strong> <str<strong>on</strong>g>of</str<strong>on</strong>g> c<strong>on</strong>stituents, especially where <strong>on</strong>e is dispersed in small isolated pockets.<br />

<strong>Properties</strong> <str<strong>on</strong>g>of</str<strong>on</strong>g> a material may be c<strong>on</strong>siderably influenced by <str<strong>on</strong>g>the</str<strong>on</strong>g> particle size.<br />

Chemical reactivity <str<strong>on</strong>g>of</str<strong>on</strong>g> fine particles is greater than that <str<strong>on</strong>g>of</str<strong>on</strong>g> coarse particles.<br />

In additi<strong>on</strong>, far more intimate mixing <str<strong>on</strong>g>of</str<strong>on</strong>g> solids can be achieved if <str<strong>on</strong>g>the</str<strong>on</strong>g> particle size is small.<br />

<strong>The</strong> mechanism <str<strong>on</strong>g>of</str<strong>on</strong>g> <str<strong>on</strong>g>the</str<strong>on</strong>g> process <str<strong>on</strong>g>of</str<strong>on</strong>g> fragmentati<strong>on</strong> is extremely complex. If a single lump <str<strong>on</strong>g>of</str<strong>on</strong>g> material<br />

is subjected to a sudden impact, it will generally break so as to yield a few relatively large particles and a<br />

number <str<strong>on</strong>g>of</str<strong>on</strong>g> fine particles, with relatively few particles <str<strong>on</strong>g>of</str<strong>on</strong>g> intermediate size. If <str<strong>on</strong>g>the</str<strong>on</strong>g> energy in <str<strong>on</strong>g>the</str<strong>on</strong>g> blow is<br />

increased, <str<strong>on</strong>g>the</str<strong>on</strong>g> larger particles will be <str<strong>on</strong>g>of</str<strong>on</strong>g> a ra<str<strong>on</strong>g>the</str<strong>on</strong>g>r smaller size and more numerous and, whereas <str<strong>on</strong>g>the</str<strong>on</strong>g> number <str<strong>on</strong>g>of</str<strong>on</strong>g><br />

fine particles will be appreciably increased, <str<strong>on</strong>g>the</str<strong>on</strong>g>ir size will not be much altered. It <str<strong>on</strong>g>the</str<strong>on</strong>g>refore appears that <str<strong>on</strong>g>the</str<strong>on</strong>g><br />

size <str<strong>on</strong>g>of</str<strong>on</strong>g> <str<strong>on</strong>g>the</str<strong>on</strong>g> fine particles is closely c<strong>on</strong>nected with <str<strong>on</strong>g>the</str<strong>on</strong>g> internal structure <str<strong>on</strong>g>of</str<strong>on</strong>g> <str<strong>on</strong>g>the</str<strong>on</strong>g> material.<br />

During <str<strong>on</strong>g>the</str<strong>on</strong>g> course <str<strong>on</strong>g>of</str<strong>on</strong>g> <str<strong>on</strong>g>the</str<strong>on</strong>g> size reducti<strong>on</strong> processes, much energy is expended in causing plastic<br />

deformati<strong>on</strong> and this energy may be regarded as a waste as it does not result in fracture. Only part <str<strong>on</strong>g>of</str<strong>on</strong>g> it is<br />

retained in <str<strong>on</strong>g>the</str<strong>on</strong>g> system as a result <str<strong>on</strong>g>of</str<strong>on</strong>g> elastic recovery. It is not possible, however, to achieve <str<strong>on</strong>g>the</str<strong>on</strong>g> stress levels<br />

necessary for fracture to occur without first passing through <str<strong>on</strong>g>the</str<strong>on</strong>g> c<strong>on</strong>diti<strong>on</strong> <str<strong>on</strong>g>of</str<strong>on</strong>g> plastic deformati<strong>on</strong> and, in this<br />

sense, this must be regarded as a necessary state which must be achieved before fracture can possibly occur<br />

[Richards<strong>on</strong> et al., 2002].<br />

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