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Structural Changes in Chocolate Blooming

Is there anything more disappointing than finding a chocolate bar in the back of the desk drawer, anticipating a tasty treat, then unwrapping the bar only to find a dull, grey haze has overtaken your dear candy? Seeing as bloomed chocolate is still edible, yes, there are many things more disappointing than that. But surely you’re curious about how chocolate that was once shiny and perfect came to be filmy and rough. Chocolate blooming, the process that produces the white-grey film that appears on the surface of an old chocolate, is due to molecular migration. More specifically, this imperfection is caused by the movement of fats to the surface of the chocolate followed by a subsequent recrystallization. In a paper published by Applied Materials & Interfaces, a team of researchers dedicated to keeping our chocolates blemish-free has clarified the precise mechanisms that cause chocolate blooming.

The main fat in chocolate is cocoa butter, which is solid at room temperature and melts at 37 degrees Celsius. The proportion of solid to liquid cocoa butter depends on the lipid composition, which depends on which specific triglycerides are present. The solid to liquid proportion also varies with the storage conditions of the chocolate.

As proposed by Aguilera et al, scientists who study this chocolate blooming, consider chocolate as a particulate medium of fat-coated particles such as cocoa solids, sucrose, and milk powder, all suspended in a fat phase with the aid of an emulsifier, which helps to mix fats and oils with water, which usually repel each other. There are six crystallographic polymorphs of cocoa butter molecules, that is, there are six ways the molecules can organize themselves. The structural stability of these polymorphs increases from 1- 6; form 1 is the best at forming solid butter at room temperature, while form 6 tends to arrange in the loose bonds of a liquid. Form 5 is the main form in chocolate, as it possesses the most aesthetically desirable properties. While the phenomenon of blooming is well known to result from melting and recrystallization of chocolate into a less desirable polymorph, it has been unclear how fat moves through the chocolate particle network: Does it move along the fat-particle interface? Does it diffuse through the fat phase (cocoa butter), or through the matrix of assorted particles?

Possible lipid migration pathways in chocolate - Reinke et al

Possible lipid migration pathways in chocolate – Reinke et al

In this experiment, researchers used synchrotron microfocus small-angle X-ray scattering to determine the preferential migration pathway of the cocoa butter molecules surrounded by three different soild components (cocoa solids, skim milk, and sucrose). This technique allows researchers to record the scattering of x-rays through a sample with defects in the nanometer range. They can then extrapolate information about the material’s macromolecules, their shapes and sizes up to 125 nanometers, and distances between partially ordered materials, such as pore sizes. For this experiment, this method is better than more traditional macroscopic techniques as the sample does not need to be dissected in order to examine it, therefore the same sample can be continually analyzed.

Sketch of the experimental setup - Reink et al

Sketch of the experimental setup – Reink et al

The researchers prepared and tempered four different chocolate samples. An initial scattering of x-rays and data collection was performed before the addition of sunflower oil, then 10 uL of oil was pipetted onto the chocolate surface, and a second scan was performed. Images of the droplet were captured through a high-speed camera. These scans were repeated at 5, 10, and 30 minutes after oil addition, and again after 1, 2, 5, and 24 hours.

The results obtained suggest that oil is migrating through pores and cracks in the solid structure driven by capillarity within seconds. This means that the oil can flow in narrow spaces in opposition to gravity. Then chemical migration through the fat phase occurs. The oil doesn’t traverse the fat-particle interface, nor does it move through the matrix of solid particles. This migration disrupts the crystalline cocoa butter, which induces softening.

Because the most immediate migration of oils occurs through the material porous structure, the formation of chocolate bloom could be prevented by minimizing pores and defects in the chocolate matrix. To prevent the longer-term effects of chemical migration of lipids, one must minimize the content of non-crystallized liquid cocoa butter. Tempering chocolate lends to crystalline structures that resist migration, as will reducing the liquid fat content. However, to ensure that you never encounter a sad hazy chocolate again, we recommend eating all chocolate goods expeditiously.

Works Cited

  1. Tracking Structural Changes in Lipid-based Multicomponent Food Materials due to Oil Migration by Microfocus Small-Angle X-ray Scattering. Svenja K. Reinke, Stephan V. Roth, Gonzalo Santoro, Josélio Vieira, Stefan Heinrich, and Stefan Palzer. ACS Applied Materials & Interfaces 2015 7 (18), 9929-9936. DOI:10.1021/acsami.5b02092
  2. Aguilera, J. M.; Michel, M.; Mayor, G.Fat Migration in Chocolate: Diffusion or Capillary Flow in a Particulate Solid?—A Hypothesis PaperJ. Food Sci. 2004, 69, 167–174

 


Elsbeth SitesAbout the author: Elsbeth Sites received her B.S. in Biology at UCLA. Her addiction to the Food Network has developed into a love of learning about the science behind food.

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Fancy Chocolate Treats

Photo credit: Jesús Rodriguez (hezoos/Flickr)

Photo credit: Jesús Rodriguez (hezoos/Flickr)

Chocolate-covered strawberries have an innate beauty in their simplicity, making this snack both sweet and decadent. But this gourmet treat does not have to be expensive nor only savored at special events. Although it’s not quite as simple as dipping strawberries into soupy chocolate sauce, you can easily make chocolate-covered strawberries in your very own kitchen with a basket of strawberries, a bag of chocolate, and a little patience.

To perfect the crafting of chocolate-covered strawberries, it helps to first consider the composition of chocolate. Chocolate contains only a few ingredients: fat, sugars, proteins, and soy lecithin as emulsifier that holds everything together [1,2]. Cocoa butter, a fat that is derived from cocoa beans, makes up the majority of chocolate. Like many vegetable fats, cocoa butter is a mixture of fatty molecules called triacylglycerols. Different types of triacylglycerols—saturated, monounsaturated, polyunsaturated—have their own thermal and structural properties. Roughly 80% of cocoa butter are monounsaturated triacylglycerols [3]. The secret to chocolate perfection lies in the microscopic arrangement of these molecules. The texture (smooth vs. lumpy), appearance (glossy vs. dull), and melting temperature of chocolate (in your mouth at 98°F vs. in your hand at 82°F) all depend on how triacylglycerols pack together in the finished chocolate product.

Triacylglycerols are elongated, spindly molecules that can be packed together in different ways, sort of like long, skinny Legos. The three main ways that triacylglycerols can pack together are named α, β’, and β [3]. A pure mixture of triacylglycerols will form the most stable structure, β [4], and quality chocolate that is hard, smooth, and shiny will predominantly contain this β structure. Unfortunately, cocoa butter isn’t purely one type of triacylglycerol: while the 80% monounsaturated triacylglycerols will tend to pack together nicely into perfect β structures,  the other 20% of cocoa butter fat molecules can interfere and lead to less stable α or β′ structures. As shown in Table 1, chocolate can take on different combinations of α, β′, and β structures, categorized in order of increasing stability as crystals I-VI [2,3]. Crystal V possesses only the β structure, and so it boasts the most desirable chocolate characteristics, such as good sheen, satisfying snap, and melt-in-your-mouth smoothness.

Table 1. Properties of chocolate crystals (adapted from [2]).

Crystal Structure Melting Temp (°F) Chocolate Characteristics
I β′sub(α) 63 Dull, soft, crumbly, melts too easily
II α 70 Dull, soft, crumbly, melts too easily
III β′2 79 Dull, firm, poor snap, melts too easily
IV β′1 82 Dull, firm, poor snap, melts too easily
V β2 93 Glossy, firm, best snap, melts near body temp
VI β1 97 Hard, takes weeks to form

Unfortunately, getting chocolate to form the desired crystal type is easier said than done. When chocolate is melted and then left alone to re-harden on its own terms, uncontrolled crystallization occurs: any and all of the six crystal types will form at random. Chocolate that has been allowed to set this way ends up clumpy and chalky. To control crystallization and select for crystal V, the chocolate must be tempered. Through the tempering process, chocolate is first heated to 110-130°F to melt all the different crystal types. Most importantly, the temperature has to be higher than 82°F to melt the inferior crystals I-IV. Melted chocolate is then cooled down by adding “seeds” of chocolate that already contain only crystal V. These seeds are usually just pieces of chocolate that has already been tempered. Any piece of chocolate—chips, buttons, or chopped— can be used, as the majority of chocolate on the market has already been tempered. These seeds slowly cool the melted chocolate and act as a molecular template from which additional crystal V structures can grow [3]. As the chocolate cools, the stable crystal V will come together into a dense, even network, creating that lustrous, firm chocolate coating.

But beware: a drop of water can ruin all that hard work and perfectly tempered chocolate by causing it to seize. During the manufacturing process, water is removed from the chocolate, leaving behind a blend of fats and sugars. Introducing water to melted chocolate causes the sugar molecules to clump together in a process known as seizing [1]. These wet, sticky sugar clusters result in a grainy, thick batch of chocolate.

Seizing can happen when chocolate is melted in a double boiler, as water from the steam can get into the chocolate. It can also happen when pockets of chocolate are accidentally burnt. Burning is a chemical reaction that oxidizes the fats and sugars to produce carbon dioxide and water. Water that forms in the burnt pockets of chocolate will cause the rest of the batch to seize. But have no fear! Seized chocolate is not completely ruined: it can be saved by adding even more water or other liquids such as cream. Though it may seem counterintuitive, adding more water actually dissolves the sugar clumps, breaking them apart so that the chocolate can become smooth and creamy again [1]. Unfortunately, because there is now moisture in the chocolate, it will not dry and harden into a chocolate shell anymore. Chocolate rescued in this way can be used for hot chocolate, icings, fillings, or ganaches, which means you can still make an impressive chocolate treat even if the chocolate-covered strawberries don’t work out.


Chocolate-Covered Strawberries

1 lb. strawberries
16oz milk chocolate chips
Thermometer (optional, but would be helpful)

1. Melt half to two-thirds of the chocolate chips…

…In a double boiler: Stir constantly. Be sure steam doesn’t escape and sink into the chocolate. Do not cover.

…In the microwave: Heat on high 1 minute. Do not cover. Remove from the microwave and stir. If all the chocolate has not melted, heat again for 5-10 seconds. Repeat until completely melted
Note: If possible, avoid using a heat-retaining container like glass, which may burn the chocolate. Plastic is preferred.

2. Once completely melted, carefully continue heating until the temperature is 90-95°F.

3. Remove from heat, then add chocolate chips. Stir until the chips have melted and the chocolate is 82-88°F.

4. To test if the chocolate is ready, spread a thin layer on the back of a spoon or a piece of paper. It should harden in less than 3 minutes. If it doesn’t, stir in more chocolate chips.

5. When the chocolate is ready, carefully dip in strawberries. Make sure the strawberries are dry, before dipping. Allow dipped strawberries to dry on a sheet of parchment paper.


References Cited

  1. Corriher, S. Chocolate, Chocolate, Chocolate. American Chemical Society: The Elements of Chocolate. October 2007; <http://acselementsofchocolate.typepad.com/elements_of_chocolate/Chocolate.html>
  2. Loisel C, Keller G, Lecq G, Bourgaux C, Ollivon M. Phase Transitions and Polymorphism of Cocoa Butter. Journal of the American Oil Chemists’ Society. 1998;  75(4): 425-439.
  3. Rowat A, Hollar K, Stone H, Rosenberg D. The Science of Chocolate: Interactive Activities on Phase Transitions, Emulsification, and Nucleation.  Journal of Chemical Education. January 2011; 88(1): 29-33.
  4. Weiss J, Decker E, McClements J, Kristbergsson K, Helgason T, Awad T. Solid Lipid Nanoparticles as Delivery Systems for Bioactive Food Components. Food Biophysics. June 2008; 3(2): 146-154

Alice PhungAbout the author: Alice Phung once had her sights set on an English degree, but eventually switched over to chemistry and hasn’t looked back since.