Cocoa Butter Crystallisation

Kees van Malssen Introduction

In this paper the crystallisation and polymorphism of cocoa butter will be discussed. It might be thought that this is well understood already. However, recent studies suggest that a re thin! is necessary. Introduction CB Polymorphism CB Crystallisation Individual crystallites Summary References

Chocolate and the role of Cocoa Butter

Cocoa butter plays a significant role in the overall performance of chocolate. "at is the continuous phase of chocolate and it is the cocoa butter that provides the snap, gloss and pleasant, cooling mouthfeel. #o obtain these desirable $ualities from the cocoa butter, proper crystallisation is crucial. Incorrectly produced chocolate will have the wrong melting profile, warmer mouthfeel, poor gloss and a very short shelf life. It also will be sub%ect to bloom formation. #he difficulty in obtaining the correct crystallisation lies in the polymorphism of the fat. #he composition of the cocoa butter depending on origin, harvest and processing as well as the chocolate recipe, will affect the polymorphic characteristics of the product.

Cocoa Butter Polymorphism

&espite numerous structures presented for the principal cocoa butter #'(s, St)St, P)St and P)P, it must be stressed that no structure has yet been determined. #o date, the structures presented for these #'(s are suggestions only. *any clues have been gathered from + ray diffraction and spectroscopic methods but wor! is hampered by the difficulty in obtaining a single crystal. #hese three main #'(s themselves have a complicated polymorphism so it is no surprise that cocoa butter,s polymorphism is also complicated. However, the fact that cocoa butter is a mi+ture of #'(s adds another layer of comple+ity. -ille . /utton are often credited with the discovery of the complete polymorphic scheme, naming the polymorphs using Roman numerals 0I 1I2 in order of increasing melting point 0see #able 32.

#he phases have melting points anywhere between 45 and 467C, depending on composition. #he 1I melting point usually being about 37C higher than that for 1. 8ote that the 1 melting point of a hard cocoa butter can be higher than the 1I melting point of a softer cocoa butter. Similarly, it is possible for the , melting point of a hard cocoa butter to be higher than that of the form of a soft cocoa butter. 's an identification of the polymorphic form, therefore, melting points are not reliable. )nly + ray diffraction provides an une$uivocal means to determine the polymorphic form.

Crystallisation of Cocoa Butter

#he different polymorphs not only have different melting points, but will crystallise at different temperatures. *oreover, different components in the cocoa butter may crystallise independently, depending on their solubility in the remaining li$uid phase. Crystallisation begins with nucleation, of which two types of nucleation can be distinguished9 heterogeneous and homogeneous. #he former means that crystal growth is initiated on :foreign: particles. #hese may be the sugar, cocoa powder particles, emulsifiers or even dust. Crystals from a different polymorph might be considered heterogeneous nuclei. Homogeneous nucleation occurs without such :foreign: particles and re$uires significant super cooling 0cooling below the melting point2. It is important to note that Sat ) Sat #'(s will grow easily on crystals with similar #'( structure and much less on other #'(s, such as trisaturated ones, whatever the polymorph. Increasing the amount of fully saturated #'( in cocoa butter does not increase overall crystallisation performance, but increase of St)St 0or even B)B2 does. 'lthough the crystallisation of cocoa butter depends on the formation of nuclei, temperature and physical motion 0e.g. stirring2 have an influence too. #here are two counteracting phenomena. Higher melting, more stable polymorphs have a higher activation energy for crystallisation and so re$uire more time for crystallisation. )n the other hand, they have a greater degree of super cooling at any given temperature, compared to less stable polymorphs. ;ffectively, it is the temperature that decides which polymorph will form. It is only when cooling is so slow that higher polymorphs find time to crystallise that

lower polymorphs are prevented from crystallising. <nder static conditions, only crystallises $uic!ly 0within minutes2 straight from the melt, at temperatures below 357 C 0see "igure =2. In fact, (sub ) will also crystallise $uic!ly if a temperature below 57C is achieved following rapid 0>37C?min2 cooling. 't any cooling rate the crystallisation of will be accompanied by partial crystallisation of, and?or transformation to, . 't temperatures between 3= and 3@7C, , will slowly

crystallise. 't higher temperatures the cocoa butter will remain li$uid. ;+periments maintaining cocoa butter at 457C for several months yielded a minor part of the highest melting #'( floating as solids in an otherwise completely li$uid fat.

Phase Transformations
It is a characteristic of fat polymorphism that polymorphic transformation is monotropic, ta!ing place in one direction, from less stable to more stable. )nce a fat is in a more stable phase, it must be dissolved or melted in order to regain a less stable phase. In general, polymorphs are easier formed by transformation from a lower polymorph than by crystallisation straight from the melt.

&epending on the temperature, polymorphs will generally transform to the more stable forms after some time. #he phase will transform into a , phase, which will, in turn, transform into . &epending on the temperature at which the transforms into ,, or the , crystallises by itself, the physical

properties 0melting point, diffraction pattern2 will differ. "or e+ample, with no difficulty whatsoever, it is possible to generate A or more different , polymorphs, each with its own melting profile and + ray diffraction pattern 0see "igures 3 . 42. ' thorough e+amination of this phase range demonstrates it cannot be reduced to simple combinations of two different phases e+isting in various ratiosB it is truly a continuum of , polymorphs. &epending on temperature, the , will eventually transform into . 't lower temperatures 0up to about 337C2, , will transform into 1. 't higher temperatures 0from about 367C2, , will transform directly into the 1I form 0see "igure C2. 't intermediate temperatures, a mi+ture of 1 and 1I will be formed. -ithout seeding of some description, it is impossible to crystallise the polymorphs directly from the melt. Suitable seeds are fat crystals, preferably in the desired polymorphic state and built from #'(s which are similar to those in cocoa butter. #hus cocoa butter seeds or

 St)St seeds will accelerate

crystallisation much more than , cocoa butter seeds. #hese latter, however, still will be much faster than any seed of tripalmitin or tristearin, even though these have much higher melting points. ' special type of seeding, or rather of having the right nuclei for fast crystallisation, is the memory effect. If cocoa butter in the phase is melted 0no visible solid2, but remains below C57C, it maintains a :memory: of the crystal structure. )n subse$uent cooling, the crystallisation speed of the phase is increased, apparently forming from the melt. #his temperature of C57C applies irrespective of cocoa butter composition. #hat is, whether the cocoa butter has a melting point of 437C or 467C, the memory effect for both is lost at C57C but not below. #his implies that the invisible nuclei have similar compositions, irrespective of the cocoa butter source.

Concept of crystallites as individuals

' !ey to understanding phase transformations, the e+istence of a , phase range, memory effects and other :mysteries: of cocoa butter is the phenomenon of mi+ed crystals. If we consider a simple phase diagram 0"igure D2 in which there is complete miscibility in both li$uid and solid phases, we can follow what happens on cooling of a mi+ture. If we cool a molten mi+ture with 45E B from 0=2 we eventually reach the li$uidus at 032. 't this point crystallisation begins. However, the composition of the crystallising material is read off by ta!ing a horiFontal 0isothermal2 line across to 042 and finding the composition by dropping a vertical line to 0C2, i.e. about A4E B. &uring subse$uent cooling, the composition of the

crystallised material will follow the solidus line down to 0D2, while the composition of the remaining li$uid will follow the li$uidus down to 062. #he process described above assumes that the system remains at e$uilibrium at all times and that there is sufficient time for the solid phase to remain homogenous. In practice, of course, this never happens. "re$uently crystallisation is rapid meaning that there is no time for the solid phase to e$uilibrate to the thermodynamically stable composition. Crystallisation can be imagined to ta!e place in several stages, building up each crystal li!e the s!ins of an onion 0see "igure 6, left2. In reality, the composition probably will vary continuously from the centre to the outside 0"igure 6, right2. )f course, the crystals or crystallites that form will be of varying siFes as well as varying compositions. #he phase behaviour of binary combinations of fats need not be as simple as that shown in "igure D. If partial immiscibility occurs, as it commonly does with #'(s, a situation similar to "igure A arises. #his leads to much more comple+ crystallisation. #he #'(s present in cocoa butter have a range of melting points. #hese relate to differences in saturation and chain length. -hen li$uid cocoa butter is cooled, each of these #'( will perceive a different !ind of super cooling. It seems obvious that the :higher melting: #'( will crystallise first, but remember that we must thin! in terms of the phase diagram. #he first solid will, of course, be rich in the higher melting #'(s but will also include some of the softer #'(s. ' group of molecules will stic! together to form an embryo 0a nucleus too small to survive2. *ost embryos will dissolve $uic!ly

again, but some will grow. 'round the !ernel of this embryo, different #'( may %oin. In such a process, a nucleus and later a crystallite will grow with an individual composition. 8umerous crystallites will develop, differing slightly in composition due to micro fluctuations of composition and temperature in the li$uid and due to formation at slightly different times. ;ventually, each crystallite will have a uni$ue composition, melting point and structure related to that particular composition. #he overall melting range and polymorphic form of the solidified cocoa butter will be the average of all those individual crystallites. Since the force driving crystallisation is affected by changes in temperature, variation in crystallite composition will occur. #his could be the cause of the phenomenon of the , phase range variation in melting point and diffraction pattern noted above.

Summary
'ssignment of melting points to the polymorphs of cocoa butter has been mista!en, perhaps due to rapid polymorphic transformation. ' thorough investigation of cocoa butter polymorphism demonstrates that it is the actual crystallisation temperature, not the cooling rate, that determines the polymorph that crystallises. In case of machinery, one should realise it is the temperature at the walls that is of interest. "rom this starting polymorph transformations into more stable polymorphs will ta!e place. Phases develop more rapidly via transformation than from the melt. phases do not form from the melt e+cept via the memory effect. #o destroy any memory of previous states of cocoa butter, heating to above C37C is necessary. Since composition may have a bigger effect on melting points than the polymorphs alone and with a continuous , phase range, it should be clear that melting point determination 0e.g. by &SC2 cannot always be reliable for polymorph identification of cocoa butter. "or an unambiguous result, + ray diffraction is re$uired.

References
=. Hachiya I, Goyano #, Sato G, Seeding effects on solidification behavior of cocoa butter and dar! chocolate .=. Ginetics of solidification, H. 'm. )il Chem. Soc. 669 0=32 =ADA =A63, 0=I@I2 3. 1an /angevelde '.H., 1an *alssen G."., Peschar R. and Schen! H. ;ffect of temperature on recrystalliFation behavior of cocoa butter, H. 'm )il Chem. Soc A@9 0I2 I=I I3D, 0355=2 4. 1an *alssen, G."., 1an /angevelde '.H., Peschar R. and H. Schen!, Structural and compositional aspects of fat polymorphism, invited review paper. Recent Research &evelopments in )il Chemistry, ;ditor9 S.(. Pandalai, #ransworld Research 8etwor! 0#rivandrum, India29 =C= =DD 0=III2 C. 1an *alssen, G."., 1an /angevelde '.H., Peschar R. and H. Schen!, Phase Behavior and ;+tended Phase Scheme of Static Cocoa Butter investigated with Real #ime J Ray Powder &iffraction, H. 'm. )il Chem Soc. A60629 66I 6A6 0=III2 D. -ille, R/ and ;S /utton, Polymorphism of cocoa butter. H 'm )il Chem Soc C40@29 C=I CI6, 0=I662