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Curing is a chemical process employed in polymer chemistry and process engineering that produces the toughening or hardening of a polymer material by cross-linking of polymer chains. It is strongly associated with the production of thermosetting polymers.

Curing process
During the curing process single macromolecules react to each other to form a tridimensional polymeric network.

In the first part of the reaction branches molecules with various architectures are formed, and their molecular weight increase in time with the extent of the reaction until the network size is equal to the size of the system. The system has reached its gel point (GP) and it has lost its solubility. Its viscosity tends to infinite. The remaining molecules start to coexist with the macroscopic network until they react with the network creating other crosslinks. The crosslinking density increases until the system reaches the end of the chemical reaction.

Curing can be initiated by heat, radiation, electron beams, or chemical additives. To quote from IUPAC: curing "might or might not require mixing with a chemical curing agent." Thus, two broad classes are (i) curing induced by chemical additives (also called curing agents, hardeners) and (ii) curing in the absence of additives. An intermediate case involves a mixture of resin and additives that requires external stimulus (light, heat, radiation) to induce curing.

The curing methodology depends on the resin and the application. Particular attention is paid to the shrinkage induced by the curing. Usually small values of shrinkage (2-3%) are desirable.

Curing induced by additives


Epoxy resins are typically cured by the use of additives, often called hardeners. Polyamines are often used. The amine groups ring-open the epoxide rings.

In rubber, the curing is also induced by the addition of a crosslinker. The resulting process is called sulfur vulcanization. Sulfur breaks down to forms polysulfide cross-links (bridges) between sections of the polymer chains. The degree of crosslinking determines the rigidity and durability, as well as other properties of the material.

Paints and varnishes commonly contain oil drying agents; metal soaps which catalyse cross-linking of the unsaturated oils of which they are largely comprised. As such, when paint is described as drying it is in fact hardening. Oxygen atoms serve the crosslinks, analogous to the role played by sulfur in the vulcanization of rubber.

Curing without additives
In the case of concrete, curing entails the formation of silicate crosslinks. The process is not induced by additives.

In many cases, the resin is provided as a solution or mixture with a thermally-activated catalyst, which induces crosslinking but only upon heating. For example, some acrylate-based resins are formulated with dibenzoyl peroxide. Upon heating the mixture, the peroxide converts to a free radical, which adds to an acrylate, initiating crosslinking.

Some organic resins are cured with heat. As heat is applied, the viscosity of the resin drops before the onset of crosslinking, whereupon it increases as the constituent oligomers interconnect. This process continues until a tridimensional network of oligomer chains is created – this stage is termed gelation. In terms of processability of the resin this marks an important stage: before gelation the system is relatively mobile, after it the mobility is very limited, the micro-structure of the resin and the composite material is fixed and severe diffusion limitations to further cure are created. Thus, in order to achieve vitrification in the resin, it is usually necessary to increase the process temperature after gelation.

When catalysts are activated by ultraviolet radiation, the process is called UV cure.

Monitoring methods
The material, initially liquid, at the end of the process will be solid. This transition can be followed in different way.

The rationale for cure monitoring relies on the various physical or chemical properties that can be used to follow the transformation of an initially liquid material into its final rigid solid form.

Cure monitoring is, for example, an essential component for the control of the manufacturing process of composite materials.

Cure monitoring methods give a significant insight to the chemical process and define process actions towards achieving specific quality indices of the cured resin systems. The relationship between the monitoring output and the requirements for feedback-loop control is the subject of extended research activities including considerations of the modelling of the cure reaction.

Rheological analysis
A simple way to monitor the extent of the reaction in a curing process is to mesure the variation of its mechanical properties in time. One of the mechanical properties that significantly change during crosslinking is the elastic modulus.

To measure the elastic modulus of a system during curing, a rheometer can be used. With dynamic mechanical analysis can be measured the storage modulus (G’) and the loss modulus (G’’). The variation of G' and G" in time can indicate the extent of the curing reaction.

As shown in Figure 4, after an "induction time”, G' and G"  start to increase with different rates. At a certain point they cross each other. This point is recognised by different autors as the gel point, the point in which a continuous network is formed in the polymer. Afterwards, the rate of G' and G" decreases, and the moduli tend to a plateau. When they reach the plateau the reaction is concluded.

The degree of curing, $$ \alpha $$, can be defined as follow:

$$ \alpha = \frac {G'(t) - G'_{min}} {G'_{max} - G'_{min}} $$

The degree of curing starts from zero (at the beginning of the reaction) and grows until one (the end of the reaction). The slope of the curve changes with time and has his maximum about at half of the reaction.

Thermal analysis
If the reactions occurring during crosslinking are exothermic, the crosslinking rate can be related to the heat released during the process. Higher is the number of bonds created, higher is the heat released in the reaction. At the end of the reaction, no more heat will be released. To measure the heat flow differential scanning calorimetry can be used.

Assuming that each bond formed during the crosslinking releases the same amount of energy, the degree of curing, $$ \alpha $$, can be defined as follow:

$$ \alpha = \frac {Q} {Q_T} = \frac	{\int_{0}^{s} \dot Q\, dt} {\int_{0}^{s_f} \dot Q\, dt} $$

where $$ Q $$ is the heat released up to a certain time $$ s $$, $$ \dot Q $$ is the instantaneous rate of heat and $$ Q_T $$is the total amount of heat released in $$ s_f $$, when the reaction finishes.

Also in this case the degree of curing goes from zero (no bonds created) to one (no more reactions occur) with a slope that changes in time and has its maximum about at half of the reaction.

Dielectrometric analysis
The technique of conventional dielectrometry is carried out typically in a parallel plate configuration of the dielectric sensor (capacitance probe) and has the capability of monitoring the resin cure throughout the entire cycle, from the liquid to the rubber to the solid state. It is capable of monitoring phase separation in complex resin blends curing also within a fibrous perform. The same attributes belong to the more recent development of the dielectric technique, namely microdielectrometry.

Several versions of dielectric sensors are available commercially. The most suitable format for use in cure monitoring applications are the flat interdigital capacitive structures bearing a sensing grid on their surface. Depending on their design (specifically those on durable substrates) they have some reusability, while flexible substrate sensors can be used also in the bulk of the resin systems as embedded sensors.

Spectroscopic analysis
The monitoring of curing process can be performed by measuring:
 * changes in the concentration of specific reactive resin species using spectroscopic methods (FTIR & Raman);
 * changes in the refractive index or fluorescence of the resin (optical property);
 * changes in internal resin strain (mechanical property) with the use of Fiber Bragg grating (FBG) sensors.

Ultrasonic analysis
Ultrasonic cure monitoring methods are based on the relationships between changes in the characteristics of propagating ultrasound and the real-time mechanical properties of a component, by measuring:
 * ultrasonic time of flight, both in through-transmission and pulse-echo modes;
 * natural frequency using impact excitation and laser-induced surface acoustic wave velocity measurement.