CA1163496A - Food supplement concentrate in a dense glasseous extrudate - Google Patents

Abstract

FOOD SUPPLEMENT CONCENTRATE IN
A DENSE GLASSEOUS EXTRUDATE

ABSTRACT OF THE DISCLOSURE

A food supplement concentrate of an ingestible agent such as a seasoning, flavoring, oleoresin, essential oil, vitamin, mineral, and mixtures thereof encapsulated, enveloped or otherwise encased as a dispersed microphase within but recoverable from a matrix of encapsulating medium such as a starch, protein, flour, modified starch, gum, and mixtures thereof. The concentrate is prepared by mixing the edible agent and the encapsulating medium with a limited quantity of water adequate to permit conversion of the mixture, under applied extrusion pressure and controlled heat, to pro-vide a dense, essentially unexpanded glassy extrudate with said ingestible agent dispersed therethrough in microform.

Description

3 ~ ~ 6 BACKGROUND OF T~IE INVENTION
Encapsulation, an old art, is playing an ever increasing role in the food and in related industries. Many patents and other publications deal with the encapsulation of ingredients used in foods. In modern food processing it is essential that products have long shelf life and have excellent stability. Encapsulation plays a major role in satisfying these requirements.
For example, encapsulation makes it possible to stabilize and to protect essential oils from deteriora~ion and loss during storage.
Encapsulation may protect the potency and greatly incre`ase the shelf llfe o oxidation-sensitive materials such as Vitamin A. Another imp-ortant application relates to the stabilization of metallic compounds such as ferrous sulfate as well as copper salts and other minerals which may act as pro-oxidants.
The major encapsulation process in use today involves dissolving a gum or a modified starch in water, adding, for example, an essential oil ~ith suitable agitation to produce an emulsion, and spray drying.
In other procedures a solution of a protein such as gelatin serves an an emulsifying ~--, i~
~, ~ 1 ~34 96 agent. A gel is formed and this is carefully dried and ground. Other techniques use sugar melts as protective en-coating agents. Many applications use starches or flours These are gelatinized followed by emulsification and spray drying. Fats have also been used as protective coatings.
Applicants' present invention constitutes a new ap-proach to encapsulation. The method of the inventivn, using an extrusion step, is extremely simple and has many advantages over prior art processes.
o In the last decade hundreds of patents have issued which deal with the structurlng of vegetable proteins~ The eforts in this area have been exte~sive. Extrusion has been a favorite technique for making many food products such as breakfast foods, snacks and ~readings.
In such prior art extrusion processes, the products produced are friable and essentially ready to eat. All are expanded or "puffed"~ similar to a product such as puffed rice.
In more recent years textured vegetable protein products have been developed. In Atkinson, U.S. Patent No.3,488,770, soy ~lour, moistened with about 30~ by weight of water, is passed through an extruder in which heat and applied pressure convert the moist mass to a molten state or melt. This material is then exploded into the atmosphere to produce what is known as textured vegetable protein (TVP). The product is porous and friable, and is intended to simulate or replace meat.
In searching for new forms of vegetable protein which could be used ~or the food supply, Sair & Quass U. S. Ratent No. 3,968,268 devised an extrusion process for forming a dense transluscent, glassy protein. This product was quite different from the prod~cts produced by Atkinson, and different rom the extruded breakfast cereals, snacks, and breadings. The glassy llS34~

protein was hard and vitreous and not edible in this form.
Additional cooking or hydration was needed as in the case of rice, wheat or o~her grains. The protein glass of Sair & Quass was produced by applying heat and pressure to a moist protein mass and extruding under conditions which pxevent puffing.
In prior art encapsulation processes, as commercially practiced, the xatio of water to encapsulating agent has been, for example, 2 to 1, to 5 to 1. Sufficient water is added to produce a solution, followed by suitable emulsification. In reviewing the technology used in developing simulated meat pro ducts such as textured vegetable protein the inventors herein queried whether ther~ might not be a completely new encapsula-tion procedure constituting a major advance over the prior art.
Specifically, if one could utilize the extrusion process to produce a molten, unpuffed glass or melt of a polymeric material to effect encapsulation, the development would have the follow-in~ advantag~s:
1. Extrusion is a continuous process, and it is simple.
~ 2. During extrusio~ one could use minLmal water, whereby drying conditions would be greatly simplified. Spray driers could be eliminated.
3. The finished product could be shaped to any de~
sired orm. One would not be limited to fine (spray-dried) particles.
4. Extrusion would result in a microencapsulation within a matrix of controlled solubility. Release o~ the en-capsulated agent would be gradual, dependent on hydration of - the matrix.
S~ill other advantages become evident.

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Glass for~ation is not unique to proteins. Mercier and Feillet in Cereal_Chemistry, Vol. 52, page 283 ~1975) describe glasses formed from cereal-like materials.
It was known that certain polymer films such as poly-ethylene may serve to protect hygroscopic materials but afford very little protection for the essential oils of ~lavorings.
It was also known that other polymer films such as cellophane are suitable to protect essential oils. The essence o the present invention is the surprîsing discovery that protein and cereal polymer matrices behave like cellophane, providing excellent protection of encase~ agents, including essential oils, in an encapsulation process. It was also found thatr upon hydration of the polymer matrix, the encased agent was gradually released in a hi~hly effective form.
In the conventional prior art extrusion procedures being used to prodùce ¢ereals, snacks, breadings and textured vegetable proteins, it is known that if a flavoring is added to the material prior to extrusion much of the flavoring agent is lost during the puffing expansion. Accordingly, the accepted method has been to add the flavor oil or other flavoring agent only after extrusion. An exàmple is a product sold under the name BACOS. The product consists of small chunks of vegetable protein made by the process described for producirlg textured vegetable protein. The small porous chunks of material are then treated with vegetable oil to which the selected ~lavor ayent has been added. The snack industry has continued its search for flavoring materials that can be added ~ to the extrusion step, but with no succ~qs. The extruded polymer glasses of the present invention, in which expansion or puff~
~o iny is deliberately prevented, provide a novel and unobvious encapsulating medium to produce valuable concentrates of flavors and other agents.

~ ~63'~ 96 Typical of prior art methods is that describ~d in Xatzen U. S. Patent No. 3,786,123 which teaches an extrusion process for stabilizing and preserving nutrients and other in-gestible agents. But the Katzen process is totally unsuited to pxoduce the flavor concentrates of the present inven ion, because Katzen resorts to explosion ~uffing, to form a porous product. In controlled tests, it has been found that when 4% of oil of sage is incorporated in a mixture and then ex-truded following the Katzen teachings, half of the essential oil is lostu In contrast, the process of the present invention, produces an unpuffed, vitreous glass, o~er 90~ of the essential oil being retained in the final product. Katzen teaches only an expanded, porous product. He suggests no dense glasseous extrudate. The Katzen process, for producing a porous product, cannot be used to encapsulate an agent having volatile con-stituents.
In accordance with the practice of the present in-vention it has been found that for some applications one type of extrudate glass is superior to another as the matrix. For example, it has been found that certain flavor oils such as mustard flavor oil (containing allylisothiocyanate) undergo objectionable reactions with functional groups o~ proteinaceous materials to yield final products which do not have the odor and flavor of mustard. On the other hand when a cereal base material is used as the glasseous matrix for the allylisothio-cyanate, the final concentrate has true mustard flavor. In the encapsulation of lemon flavor for use with tea, it ha~
been found that the citric acid in the lemon flavor agent re-acts with alkaline functional groups of a proteinaceous glass so that the citric acid is not released when the flavor con-~ 1~3'~ 9~

centrate is added to hot water. In contrast, when a cerealglass encapsulating matrix is used, no ~unctional groups interfere, and the citric acid is immediately released to the tea along with the other lemon flavor elements.
Still other eonsiderations may dictate the selection of special encapsulating agents in particular applications o the present invention. When more rapid solubilization and re-lease are re~uired, a cereal glass is used in preference to protein. When still more rapid solubilization is~desired, a gum glass or a modified starch glass may be used as the ex-trudate matrix.
~ n the encapsulation of iron for incorporation in cereal products, the aim of industry has been to add the iron prior to extruding. Several approaches to dealing with the problem have been unsuccessful. For example, when hard fats are used to encase minerals such as iron, the high cereal pro-cessing temperatures cause the fat to melt and to liberate the mineral pxematurely. Some proteinaceous encapsulating materials dissolve during the processing and release the minerals. In accordance with the practice of the present invention, the use of wheat gluten as an encapsulating material effectively solves the problem. Wheat gluten is quite insol-uble in water. When iron is encapsulated in a water-insoluble wheat gluten glass, in comb~ination with an additional water-proofing agent such as ~inc stearate, in accordance with the present invention, the ground product withstands processing intact7 the iron being retained within the fused, water insoluble protein matrix.
Depending upon the agent to be encased, concentrations of up to a~out 40% or more may be effectively encapsulated in .

1 ~3~9~

the polymeric matrix~ The food supplement concentrations of the invention may be added to food products in concentration o up to about 15%, or higher.

SUMMARY OF THE INVENTION
The present invention is based upon the disco~ery that it i5 possible effectively to encase or encapsulate an essential oil or other edible agent as a dispersed microphase in a polymer matrix derived rom starch, flour, gum, cereals, or protein, by mixing the encapsulating material and the agent to be encased with a minimal quantity of water and, through application of heat and pressure in exkrusion, to form a dense, glass-like extrudate melt in which the encased agent is uni-formly distributed in micro-form as a protected dispersed phase to provide a food supplement concentrate of the encased agent. The release of tha encased agent is ultimately effected through hydration or through digestion o the enveloping matrix~
The concentrate of the present invention is substant-ively different from the products of Sair et al Patent No.
3,968,268, which is directed to an extrudate intended to be and which is an ultimate food product. The products of the subject invention are not foods, per se, but are flavor and nutritional food supplement concentrates for incorporation into food pro-ducts~ Whereas the retention of structural integrity, even under retorting conditions, was the principal goal and an im~
portant feature of the products of Patent No.3,968,268, there is no such requirement for the encapsulated concentrates of the present invention.

1 ~6~3~96 The method oE the presen-t invention has been found particularly useful in the encasement of essentia~ oils or artificial flavors. Flavorings for the food industry may be either natural spices or soluble seasonings, or essential oils.
For many applications, the essential oil or oleoresin derived from the spice is preferred to the natural spice. One prior art technique is to deposit the e~sential oil or the oleoresin on a carrier such 2S salt or sugar. The inherent marked vola-tility of the essential oils in the soluble seasonings has prompted research directed to preventing the escape or loss of the "active" ingredients.
It is an important feature o~ the present invention that there are provided methods and products whereby the essen-tial oils or oleoresins of natural spices are encased in dense, polymeric glasseous melts (about 55 to about 90 pounds per cubic feet) of polymeric materials derived from natural sources to provide a stable microdispersion in a protective enveloping matrix.
It is a related feature of the invention that the solid extruded glass-like material containing the microdispersion of essential oil (or other asent~ may be ground to provide a particulate product in which the encased component is time and atmosphere protected and maintained in a stable condition.
The enzyme systems of many natural flavor agents are subject to premature chemical breakdown with resulting destruction of the flavoring componants. Moreover, certain of the prior art encapsulatins or encasing agents undergo re-actions with the active agent of the flavor, again destroying the latter. Typical of susceptible flavoring agents is natural mustard in which flavor is derived largely from allylisothio-_g_ .

1 163~9~ -cyanate. When oil of mustard is encapsulated in a protein or protein-derived system, chemical groups on the protein molecule react with the allylisothiocyanate to convert the flavor to something quite differen~ from what is desired. In contrast, it has been discovered that encasement of the oil of mustard in a carbohydrate-derived glasseous polymeric extrudate matrix does not cause such objectionable changes in the flavoring.
The final, ground product exhibits excellent stability and un~
expectedly long shelf life.
The glass-like, unexpanded extrudate produced in accordance with the present invention has also been found to be an excellent matrix fox the incorporation of a mixture of lemon flavoring and citric acid. The resulting product, re-duced to the appropriate particle size and introduced into boiling water, effects an immediate release of the encased citric acid and the lemon flavor so as effectively to simulate the use of lemon itself.
In marked and important contrast to encapsulation by spray drying, in which the final products are very fine particles, the present invention produces extrudate materials which may be fashioned, physically, to simulate "natural" products. For example, using the process of the invention it is feasible to extrude a product in which the flavoring agent of black pepper is dispexsed and encased, with appropriate coloring matter, so that the extruded, solid, glass-like ribbon can be ground or otherwise reduced to any desired particle size, for example, corresponding to a coarse black pepper or a fine black pepper~
The final product will, thus, have not only the flavoring capa-bilities but also the overall vi~ual appearance of the natural material7 --1:0-- .

~ ~3~96 The method of the invention also lends i-tself to the production of "simulated" natural vegetables. For example, it is possible to incorporate suitable coloring as well as green bell pepper flavoring in a carbohydrate material which is then extruded as a molten glass ribbon. This ribbon i~ then further processed through a rollex mill to an ultimate thickness corres~
ponding generally to that of natural green bell pepper. The sheet material is cut to shape to pro~ide a product which may be used in food and food preparations in the same manner in which its natural counterpart is used.
An important property of certain products of khe pre-sent invention is that the encasing or matrix material has a lesser soluhility than do many en~apsulation agents used hexe-tofore. As a result, the essential oil or other active agent in the encasement system is released and distributed more slowly.
That is, the present invention provides products which exhibit a slower extended, and more controlled flavor release.
When using starch-derived material as the encapsulating medium, the processing conditions of the invention are critical to obviate the transformation of the starch-like material into a sticky unwieldly mass. This undesirable result is avoided, in accordance with the practice of the invention, by carefully controlling and limiting the addition of water. Specifically, the water used is provided in-a concentration which is insuffi-cient to promote conventional gelatinization~ The invention relies upon the combination of controlled pressure with limited moisture and further requires that the extruded glass-like product be discharged from the extruder head at a temperature below the boiling point of water, so as to obviate puf~ing or expansion. The method is unique and unobvious as an encapsulat-ing technique. The extrudate is discharged as a dense-opaque--11~

-1 ~63~96 to-translucent glass-like material in which the essential oils or other flavoring ingredients are dispersed in micron size and locked in the glass-like ma~rix. The product is new.
When a gum such as gum acacia is used, it has been found that it is not necessary to put the gum into solutio~.
It has been found feasible to blend the gum with a limited quantity of water. The essential oil or other nutrients can then be added and the mixture introduced into the extruder `to form a dense glass in which ~he nutrient is a microdispersion~
Upon discharge from the extruder, the product is shaped and dried.
The term "ingestible material" as used herein is in-tended to encompass broadly any dispersible, soluble, or emul-sifiable, or dispersible, edible material such as~seasonings, flavor ingrediants, essential oils, vitamins and minerals, nutrients, and components thereof or mixtures or blends of the above both solids and liquids, but particularly liquids.
In all cases the agent is substantially uniformly distributed as a protected, stable, but recoverable dispersed micxophase within a polymeric matrix derived from a natural material.
Since the ultimate product is for the most part added to ~oods or food products at a level of 0.1 to about 2%, and ordinarily less than 15%, to impart flavor or special nutritional pro-perties thereto, or for some similar purpose, the final products of the present invention are appropriately designated "con-centrates."
The essence of the subject invention does not lie in the selection of any particular agent to be encasecl, or in any unique combination of such agents, or in the selection of any specific encapsulating material as a protective matrix.

-3 4 ~ ~

Rather, ~he invention comprises a dense, glass-like organic polymeric extrudate, for example, casein, flour, yluten, gelatin, gum,starch, modified s~arch, and cereal material in which a dispersed ingestible agent is-retained as a stable, protec~ed, microparticulate, which agent is releasable upon hydration or digestion of the enveloping matrix.
The novel encapsulation method of the invention has important advantages over prior art procedures. The process, which consists in mixing an ingestible agent such as an essential oil or flavoring with a moist pol~meric materîal and ~hen heating and forcing the mixture through an extruder to effect encapsula-tion of the ingestible agent as a microdispersed phase is ele-gantly simple and remarkably effective. Compared with spray-drying, the present invention effects important savings in energy requirements. The usual need, as in spray-drying, to vaporize three or more parts by weight of water to produce one part of final product is obviated. The ratio of water to encapsulation media, as practiced in the present invention (ordinarily less than 1:1), is markedly reduced as compared with the high dilu-tion ratio required in spray-~drying. Providing options as to particle` siæe, the method of the invention is further dis-tinguishable from and superior to spray drying.
Whereas in spray-dried products the resulting envelope is highly soluble in aqueous systems, an important feature of the invention is that some of the coating media have signifi-cantly limited water solubility and release the encased material over a xelatively extended time period, correlated with the time required for hydration of the polymeric matrix. The en-cased agent is released in a controlled manner.

3 ~

By utilizing the process of this invention it is possible to simulate the natural spices. If desired, suitable colorings can be added along with the proper level of essential ` oil and oleoresin and simply ~hrough ~xtrusion followed by suitable sizing, products can be made which look remarkably like black pepper or sage or oregano or like any other spices.
The products, of course, show excellent stability on storage whereas in the natural spices the essential oil may be lost unless special provisions are made for protection through 10 packaging. Whereas the natural spices may contain substantial levels oE insect fragments and other normal contaminants ~ound in spices, these contaminants are virtually absent in the product of this invention. Whereas normal spices may have extremely high bacterial counts and may require gas sterilization to reduce the count, this treatment is not nec-essary with the simulated products of the present invention.
This invention makes possible the manufacture of a completely new line of seasoning products. Normally, soluble seasonings are prepared on a salt or sugar base and the level of essential oil or olèoresin that can be added to salt or sugar is relatively-low, rarely approximating more than 5%, because the products become too wet. By utilizing the process of the invention one can make products with 2,3, or even 10 times the strength of the soluble seasonings with the added advantages of complete stability, and free-Elowing capability, together with protection of the flavorings during storage.

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Such concentrates, from an economy standpoint, have great ad-vantages in reducing freight costs, warehouse storage space de-mands, ets. The effective, simple encapsulation procedure of the invention has many uses which render old seasoning prac-tices obsolete.

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In the usual encapsulation procedures the product is spray-dried and the finer, often more fragrant, volatile constituents are lost. By utilizing the glass extrusion encapsulation proccss of the invention one can grind the product in the "moistl' state to the desired shape.
Since there is relatively little moisture, the produc~ may be dried at temperatures as low as 100~. so that the fine flavor volatiles remain in the encapsulated product.
Thus, in accordance with one broad aspect of the invention, there is provided an encapsulated product in the form of spice consen-t:rates and simulated spices, comprising from about one-half to about forty percent by weight of an agent selected from the group consisting of essential oils, oleoresins, and mixtures thereof, said agent being dispersed throughout and encased within but recoverable from an enveloping matrix comprising a fused encapsulating material selected from the group consisting of starches, cereal flour, modified sta~ches, gums~ proteins, and mixtures thereof9 said agent being distributed throughout said encapsulating material as a micro dispersion of from about five microns to sub~icron in size, and said encapsulated product having a density in the range of from abou.t fifty-five to about ~net~ pounds per cubic foot;
said encapsulated product containing said micro dispersion being the pro-duct obtained by blending said encapsulating material, said agent, and from about ten to about forty percent by weight of water based on the total weight of encapsulating material and water to provide a friable blend, subjecting said blend through extrusion to pressure and to heat to form a glasseous melt, and extruding said melt under non-puffing conditions, the resulting said product constituting a substantially homogeneous, dense, essentially unexpanded, translucent-to-glassy extru-date, each said encapuslated product exhibiting excellent stability on long-term storage, and being suitable for adding to foods a~ a flavoring therefor.

1~3~

In accordance with another broad aspect of the invention, there is provided the method of flavoring and of enhancing the nutritional value of a food product, said method comprising the steps of preparing a storage-stable~ dense, glassy concentrate of an encapsulated agent selected from the group consisting of essential oils, oleoresins, vit~mins, min-erals, and mixtures thereof, said encapsulated agent being dispersed throughout and encased within but recoverable from an enveloping matrix comprising a fused encapsulating material selected from the group consisting of starches, cereal flour~ modified starches, gums, proteins, and mixtures thereof, said concentrate comprising from about 1/2 to about 20% by weight of said encapsulated agent distributed as a micro-dispersion throughout said encapsulating material, said concentrate containing said micro-dispersion being prepared by blending said encap-sulating material, said encapsulated agent, and from about 10 to about ~0% by weight of water based on the total weight of encapsulating material and water, to provide a friable blend, subjecting said blend through extrusion to pressure and to heat to form a glasseous melt, and extruding said melt under non-puffing conditions, thereby to yield a substantially homogeneous, dense, essentially unexpanded, translucent-to-glassy extrudate having a density in the range of from about 55 to about 90 pounds per cubic foot, said encapsulated agent being distributed substantially uniformly throughout said extrudate as a dispersed phase of micro particles of from about 5 microns to sub-micron in size in an enveloping matrix of said encapsulating material to provide a concentrate of said encapsulated agent in which said encapsulated agent is stable against loss and deterioration, a.nd incorporating up toabout l/2 percent by weight of said concentrate in a food product.
DETAILED DESCRIPTION OF PREFERRED EMBODIMF.NT
, _ The products of the invention and the methods of producing the same are typified by the specific examples set forth below, provided for illustration only, and not in any limiting sense.

- 15a -h ~3~6 It is a critical feature of the products of the present invention ~hat they are dense glasseous extrudates produced under conditions to obviate puffing or expansion. Although processing temperatures in the extruder may reach 300~. or higher, the product as discharge~, from the extruder to atmosphere, is at a temperature essentially below the boiling point of water. The necessary pre-cooling may be carried out in the extruder or in an auxiliary attached cooling conduit. Processing pressures may be in the range of about 500 to 3000 psi. In all cases, holYever, the exit pressure at the die orifice is essentially zero and the temperature is below that which would produce puffing. The density of the virtually unexpanded glasseous extrudate is in the range of from about 55 to about 90 pounds per cubic foot.

- 15b -1 163~6 The aims and objects of the i~venti.on may be accom-plished through the use of commercially availa~le extrusion equipment. Accoxdingly, no detailed description of apparatus is provided h~rein. A Brabender Pilot Plant Extruder was use~
in some of the work reported below.
In initial experiments using the Brabender which culminated in the discovery which produced the novel products .
of the prssent invention, a series o~ materials including starches and flour were su~jected to the c~mbination of heat and pressure, in the presence of moisture, to determine the process parameters for forming extruded '2glasse~." Typical data are set forth in Tables I and II below.

- TABLE
. . .
EXTRUSION CONDITIONS EFFECTIVE TO
FORM STARCH AND FLOUR GLASSES
.. .. _ % Moisture % Water in Die Temp~r- After Drylng Carbohydrate_.the Blend ature (F and Grindin~

Corn S~arch26.6 217 7.6 Potato Starch34.9 203 7.2 Waxy Maize Starch 40~7 . 203 10.5 Hard Wheat Flour 25.1 220 9.2 Yellow Corn Flour 26.7 203 9.3.

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T~BL~ II
EXTRUSION OF STARCH~S AND FLOURS
TO FORM GLASSES
% Moisture Die Pressure Appearance in the Tempera- at the of Cooled `faterial ' aterial ture % Die (psi) Extrudate Waxy Maize Starch 18.2 203 4,000+ Opaque to Glassy 26.9 2031,500 Opaque to Glassy 40.7 203800 Glassy Potato Starch 27.2 203 1,800 Glassy 27.2 2201,800 Glassy 34.9 2031,500 Glassy 34.9 2201,800 Glassy Co~n Starch 26.6 2031,600 Opaque 26.6 2201,750 Opaque to Glassy 35.6 2031,450 Glassy 35.6 2201,350 Glassy Corn Flour 17.5 2034,000+ Glassy 17.5 2204,000+ Glassy 26.7 2033,000 Glassy 26.7 2202,400 Glassy l~eat Flour 17.2 2554,000+ Opaque 17.2 2~44,000+ Glassy 25.2 2032,300 Opaque 25.9 2203,000 Almost Gl~ssy The data establish that for various starch and cereal products there are differences in the moisture concentration and in processing temperatures conducive to forming extruded glass-like products. For example, wheat flour exhibits a lesser tendency for glass formation. In general, it has been found that, within limits, increased moisture and the use of higher temperatures promote the formation of glasseous products.
In all experimental runs recorded above, a 1:1 transfer screw was used in conjunction with a barrel temperature of 140F.
The extruder was fitted with a 7 inch die extension which was flattened at its exit orifice to a 1/8" by 5/8" slit. The ex-tension was air cooled so that the extrudate was discharged in long, continuous, normally glass-like, unexpanded sheets or ribbons.

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Example Modified Potato Starch as an Encapsulating ~Composition for Oil of Sage Potato Starch* 675 grams Water 225 ml. ~25%3 Oil of Sag& 27 ml. (4 ~) ~Product of Penick & Ford, sold under trademark "CROWN n .

The modiied starch was placed in a mixer, water added, and oil of sage blended in. The blend was then fed .~ -into a Brabender extruder using a 1:1 ~ransfer screw at 100rpm and a barxel temperature 140F. The die temperature was 203F and the pressure at the die was 1,000 p5i. A die exten-sion 7" long and ~lattened ~o 1/8" x 5/8" at the tip was attached at the exit port of the die and was air cooled so that the potato starch glass extruded a continuous unexpanded ribbon or strip. The glass strips were dried in an air oven for 1 hour at 200F. and the dried material then ground using the Fit~patrick mill fitted with a 1/8" screen. The finished pro-duct all passed through a 40 mesh screen.

TABLE III

Length of Storage !
of`the Carbohydrate ~ Essential Oil Extrudate Containing Content on Storage Oil of Sage _ at 100F
~ . _ .
0 Days 3.3 4 Days 2.9 14 Days 3~0 The essential oil transferred in~o the extrudate was in excess of 80~, and the product stability excellent, as shown .

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in Table III. When used at a level of 4 ozs. per pound of meat, an excellent sage ~la~or was imparted.
Using the same extruder, with a 1:1 transfer screw at 100 rpm, a barrel temperature of 140F., a die temperature ow 203F, and pressure in the range of from 500 to 3000 psi at the die, other carbohydrate materials yielded comparable results, as shown in Table IV.

-TAsLE IV
Conc. of Mo~sture Oil of Conc. of Essential Essential Oil the Feed Sage Oil in Dried Ground After Storage Carbohydrate Blend(%) Added(%) Extrudate at 100F(%) .. . . .. .. . . _ 4 Days 14 DaY~
___ Waxy Maize 37 4 3 2.3 2.i Waxy Maize 39 6 4 4~3 3.9 Potato Starch 35 4 3.3 2.9 3.0 Potato Starch 35 6 3.9 3.7 ~.9 Yellow Corn Flour 24 4 3.4 2.2 2.5 Yellow Corn Flour ~8 6 4.2 3.9 4.2 The essential oil converte~ approximated 70 to 802. Stability was excellent.
*That is, 70-80% of the essential~oil used was found in the final product.

. Similar data for encapsulated oil of nutmeg are shown in Table V, for extruder settings and operation corresponding to conditions used for the oil of sage runs.

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~ABLE V
-Moisture Oil of Conc. ~f Oil C~nc. of Essential of the Feed Nutmsg in Dr~ed Ground Oil after Storage Product Blend~%)Added Extrudate (X) at 100F(%) 4 Days 14 Days ~axy Maize 36 5 3.1 3.2 3.0 Potato Starch 35 5 2.5 2.4 2.7 Yellow Corn Flour 27 S 2.9 3.0 3.2 Oil~ conver~ion approximated 60~ and the stability in all case~ wa~ almo~
perfect.

It will be appreciated that the.percent of oil transferred into the extruded product is affected by the particular equip-ment used, since there must be intimate mixing in the molten state in order to subdivide the essential oil to the micron state. In all cases stability studies were conducted on pro-duct which had been ground to pass a 40 mesh screen.

Example _2_ Combination of High Protein Flo~rs with Starch 20 A blend was prepared using: ~

Soy Flour . 27Q gms.
Potato Starch 180 gms.
Water 150 ml. (25%) Oil o~ Sage 18 ml. ( 4%) The protein content of the dry blend was 30~
The blend was extruded using the pilo~ plant Brabender extruder which was run at 50 rpm using a 1:1 screw with an æ~
.cooling extension. The barrel temperature was 150F. and the die temperature was 300F. The extension was cooled with air at 2 psi. The unexpanded extrudate was glassy and the pressure at the die was 2,000 psi~

1~3~

The glass extrudate was dried for 30 minutes at 210F.
and then ground in a Raymond mill to pass a 20 mesh screen.
The essentiai oil content of the dried product was 3.05~ on a dry basis indicating a 76~ conversion, and the sample, when stored for 4 days at 100F., showed 3.03% essential oil on a dry basis, and indlcating excellent stability. After 14 days the oil content on a dry basis was 2.95~.
Three ounces of the concentrate when added to 100 pounds of`meat gave an excellent sage flavor.

Example 3 Encapsulation of Citric Acid and Lemon Oil for Iced Tea It is practical, in accordance with the present in-vention, to compound an encapsulated lemon product which can simply be added to a tea bag to make a lemon iced tea. Since lemon juice, which is normally used in the home, has a ~ery high citric acid content, one should preferably also include, in lemon juice substitute, an acidi factor as well as the lemon flavor factor.
A composition found to be -ex~ellent for the purpose described is the following:

Potato Starch 46 lbs~
Citric Acid 47 lbs.
Spray Dired Lemon (20% oil)* 7 lbs.
100 lbs.

Water added Based on Formula 5 lbs.(5 .~ Sethness B 6 C Carmel~ 2.5 lbs~
BHA 0.1 lbs.
*Manufactured by MCP Foods, Inc~, Anaheim, California. (There was no-need to use a spray dried product except that the parti- -cular lemon flavor used was desirahle. Dixect encapsulation of lemon oil could have been carried out, according to the method of the invention) ~ 1~349~

The extrusion conditions using a laboratory Brabender extruder, Model 100, were as follows:

Screw 1:1 ttransfer) Barrel Temperature 140F.
Die Temperature 185F.
Extension 3/8" I.~.x 7" long, last 6" flattened to 1/8"
Extension Cooling 0- 2 psi air The extrudate, a warm, shiny, ribbon, was cooled to provide a glassy strip. The strips were placed on a tray and dried at 200F. for 30 minutes. Dry ice was added to the dried product prior to grinding to minimize an~ gu~niness.
The fraction going through a 14 mesh screen and remaining on a 40 proved to be an excellent granule size for addition to tea bags. The moisture content of the dried pro-duct was 6.5~ and the essential oil content was 1.4%. On storage for 14 days at 10~F., there`was no discernible change in essential oil content, showing excellent stability. 78~
of the citric acid in the composition dissolved in the boiling water~.~n making iced tea 0.53 gms. of the encapsulated product, of this example, was mixed with 2.25 gms. of tea normally used in a tea bag. The tea bag was submerged in 100 ml. boiling water, brewed or 5 minutes, and then removed. Ice was added to a final volume of 160-165 ml. In making tea at home ~ne often adds lemon juice equivalent to 2/3 teaspoon and this im-parts not only a lemon flavor but also the acidity character-istic of good lemon tea.
The citric acid which dissolved during preparation of iced tea gave an acidity comparable to that obtained when using lemon juice. Thus, in both flavor and acidity, the pro-duct of this example was found to be e~ual to the product obtained using lemon juice~

.

-2~

~3~g~

In developin~ the above product for flavoring tea with lemon ana acidity, it was found that encapsulation of the lemon oil and citric acid in a ~taxch base is preferable to encapsulation using a protein base. The dif~erence is be-lieved to be due to the tendency of the protein to bond the citric acid, probably chemically, resulting in a poor release of the citric acid when added to the boiling water.

Example 4 Encapsulation of Mustard Oil in Starch . . . . .

` There has been a recognized nee~ to separate the mustard oil flavoring from the natural mustard containing enzyme systems which tend to impair the stability of the mustaxd oil in storage.
Encapsulation of mustard oil in protein bases results in a flavoring change to provide something that resembles garlic rather than mustard. In contrast, it has been found, in ac-cordance with the present invention, tha~ encapsulation of mustard oil in starch or in a starch derivative or modified starch yields products which~have true flavors with good stability, The formulation used was as follows:

Mustard Oil 5 lbs.~5%) Waxy Maize Starch* ~5 lbs.
Water 44 lbs.~32~) *A starch phosphate ester cross-linked throuyh phos-phorous oxychloride.(Product of American Maize).
A Brabender extruder was operated at 100 rpm using a 1:1 trans-fer screw with a barrel temperature of 140F. and a die tem-perature of 212F. The cooling extension was 5" long flattened to 1/8. The pressure at the die was 500 psi and the glassy _23-.

1 ~3~36 extrudate was dried for 40 minutes in an oven at 200F. with circulating air and was then ground in a Raymond mill to pass a 40 mesh screen.
The ground product contained 10% moisture and 1.9%
essential oil and showed excellent stability since ~he value remained unchanged after 4 days and even after 18 days of in-cubation at 100F. The encapsulated mustard productO when tasted against a No. 2 mustard flour which has a high pungency, was found to be quite comparable in flavor.

It is quite difficult to work with mustard oil commercially because of its ex~remely disagreeable pungent odor. Converting it on an encapsulated cereal base produces a product which can be used with a minimum of difficulty, and the initial odor problems can he controlled în the commercial operation of encapsulation.

Example 5 Cereal Encapsulation to Make Green Bell_Péppers Dehydrated vegetables are extremely costly and are utilized more as a garnish than as a flavor.
By utilizing the process of the invention, one can form products with controlled size, shape, and thickness, to simulate almost any natural vegetable product.
An example to simulate green bell peppers is as follows:

Artificial Green Bell Pepper Flavor 0.8 lbs.
Wheat Flour (Eckhar~ No.3) 86. lbs.
Cane Sugar 11.2 lbs.
Salt 0.8 lbs~
Monosodium Glutamate 0.9 lbs.
30 Food Color* 0.3 lbs.
Water 17.0 lbs.~15~) *Combination of four different Warner-Jenkinson F.D. ~ C.
Color Lakes give a medium green color.

~ 1~34 9&

A blend of the above was extruded using a Brabender extruder at 100 RPM and using a 1:1 transfer screw. The barrel temperature was 140F. and the die temperature was 185F. The extension was 7" long flattened to 1/8 inch. The product came out in a long glassy strips requiring no additional cooling.
The pressure at the die was 2,150 psi. The extruded 1/8"
ribbons were flattened to 1~32" using smooth compaction roll5 and were then dried for 30 minutes at 22QF~ and screened to pass a 1/~ screen and remaining on a 10 mesh screen.
The product resembled quite closely, natural dehy-drated green`bell peppers which are manufactured by California Vegetable Concentrates (Division of General Foods) in appearance, flavor, and bite.
Storage studies over a period of 7 weeks showed no change in appearance or flavor.
This process makes it possible to control size which `
relates to the physical appearance of different dehydrated vegetablas, making this a ver~ important at~r~ute of the process.
The addition of 5~ by weight of the product to stews and-soups gives good ~reen pepper flavoring.

Example 6 Cereal Encapsulation to Make Artificial - Horseradish Flavor .
The formulation was as follows:

Artificial Horseradish Flavor 3 lbs.
Potato Starch 97 lbs.
Water 33 lbs.t25%) A Brabender extruder was used at 100 RPM, with a 1:1 transfer screw. The barrel temperature was 140F. and the die temperature was 185F. The extension was 4" long ~ 1~3496 flattened to l/8" at the tip. No outside cooling was required.
The pressure at the die was l,600 psi.
The''extruded glassy strips were dried for 60 minutes at 220F. and then ground to pass a 20 mesh and to remain on a 40 mesh screen. The moisture of the product was 8~.
The product, of this example, was tasted in a tri-' angle test at a level of 500 mg.-to 8 oz. of soup against horseradish powder (a product made from natural horseradish1 manuactured by California Vegetable Conentrates. Five ex-l0 'pert tasters felt the flavors of the two products were'comparable.

Example 7 Modified Corn Starc~ as an Encapsulating Agent _ _ ~

Following generally the procedure o Example l,in accordance with the'principles of the invention, oil of sage was encapsulated in a modified corn starch, using a formu-lation consisting o~

Modified Corn Starch* 315 grams Water 135 ml~(30%~
Oil of Sage ~ '12.6 ml.~3.8~) *Product of National S arch and Chemical Corporation,' sold under the trademark "CRISP FILM"
Extruder settings were the same as those in Example l except that the pressure at the die was 1200 psi. After drying and sizing, the produ~t was stored at 100F and then tested for stability~ with the following results:' TABLE VI

Length of Storage of the Carbohydrate Extru- % Essential Oil date Containing Oil of Content on Storage Sa~e at 100F
.. ...
0 Days 3.86 4 Days 3.71 14 Days 3.82 2'6 ~ 1~3~9~;

The oil recovery on the extruded product was 96%
of the "theoretical".
The unexpanded, glassy carbohydrate products of the invention are dense and physically more defined than explosion puffed pxoteinace~us products of thé prior art. Typ~al den~
sity values, determined by the sand method, as described in U.S. Patent No. 3,904,769 at column 11 and 12 are set forth in Table VII below. The densities of the products of the invention cover a range of from about 0.9 to about 1.5 g/cc as contrasted with, for example, a density of about 0.5 gram/cc for the expanded product of Katzen U. S. Patent No.3,786,123.

TABLE VII

Density Product Gm/cc lbs./cu.ft.
_. _ Corn Starch Glass 1.28 79.9 Potato Starch.Glass 1.39 86.7 :
Waxy Maize Starch G-lass ~ 1.47 89.4 `Hard Wheat Flour Glass 1.29 80.5 Yellow Corn Flour Glass 1.30 81.1 Green Bell Pepper Flakes 0.94 58.7 (36% Hard ~heat Flour) (14% ~dditives) An important featur~e of the present invention is the utilization of a minimal guantity of water in the encasement process. This technique is in marked and significant contrast with.those prior art procedures commonly known as spray drying.
The method of the present inv~ntion effects important economies in that the costly evaporation of excessive quantitie~ of water is obviated. It is a practical feature of the invention that its improved method may be applied to effecting the encasement of essential oils and other substances in gums and related materials to provide useful products which, hereto~ore, have been produced only through the more costly spray drying pro-cedures.

. -27 .

-~ 163~9~

- In accordance with the present invention it has been discovered that it is no~ necessary to put a gum such as gum acacia completely into solution in order to carry out the en-capsulation of a flavoring agent or a fixed fat. That is, it has been discovered by adding only about 0.1 psund of water to each pound of gum acacia, along with the flavoring, it is possible to produce, under the extrusion conditions a glass.
The broad versatility of the invention is important in that for certain food or other applications an encapsula~ing or encasement agent such as gum acacia is to be preferred over starches or cereals. Specifically, the gum encasement matrix is soluble in water and the addition o such products ko a water system yields a solution which is clearer than are the solu-tions obtained upon dissolution of the starch-encased products.
The gum encased preparations produced utilizing the process of the invention contains markedly reduced moisture levels as discharged from the reactor, and the non-expanded gum encased products, which are translucent, can be shaped and dried to provide products exhibiting good encapsulation recoveries and sta~ilities.

Exam~le 8 Gum as an Encapsulating Medium,,~
Using Limited ~ater __ ___ _ The formulation was as follows:

Gum Acacia 475 Grams Water 47.5 ml.~9~) Essential Oil (Orange Terpenes) 25 ml.(5~) The water was dispersed on the gum acacia ancl the latter chopped into very small pieces followed by the blending in of ~he essen-tial oil to ~orm a semi-solid mass.

The mass was passed through the Brabender Extruder, Model 100, -2~-~ ~3~9~

under conditions as indicated below:

Screw 1:1 Transfer ~PM 100 Barrel Temperature 140F.
Die Temperature 194F.
Extension 7" Flattened to 1/8"
Extension Cooling 20 psi The pressure measured at the end of the extruder prior to the extension was 3~000 psi. The produc~ extruded in the form of a clear translucent glass with essentially no expansion.
On cooling, the glass became quite brittle and the glass strips were dried for 1 hour in an air'oven at 140F.
The e,ss~ntial oil content of the mix on a dry basis was 5.8%. The dried glass strips ground to pass a 20 mesh screen had an essential oil content of 4.5% indicating a 77%
recovery. In this example only 10% of water was required based on the weight o the gum acacia blend, a markedly lower moisture level than required in conventional spray-drying encapsulation~
~, ~xample 9 Encapsulation of Beef Extract ` Beef extract is a v~ry ~iscous~ difficult to use pas~e.' By utilizing the techniques of the subject invention, it is possible to convert 33% of beef extract into a free-~owing, easy to use particulate product. 200 grams of bee~
extract ~85 ~ solids) and 400 grams of Capsul brand dextrin were mixed and extruded through a Brabender extruder at a barrel temperature of 194F and a die temperature of 300F. with a 1:1 transfer screw. An extension to the Brabender was cooled to obviate expansion of the extruded product., The extrudate was discharged as a soft smooth strip which hardened on cooling.

The product was ground through a Cometrol using a 0.240 cutter and then dried for 2 1/2 hours at 140F. Ground to pass a 40 ~'-r ~ -29~

1 ~ 6 ~

mesh screen the end produc~ was free flowing and most useful in blending operations. The concentrate was found completel~
suitable for incorporation in many food preparations, con-centrations in the range of up to 10~ or 15% being employed in particular applications.
The products of the invention and tbe methods of producing the same are typified by, additional specific examples set forth below, provided for illustration only, and not in an~
limiting sens~.
Oil of sage was used to prepare a series:of ~omposi-tions in which the oil was encased as a microdispersion in a proteinaceous glass produced as an essentially unpuffed ex-trudate.
In Example 10, a solvent-extracted soy flour, having an NSI of 70% and a protein content of 52% on a dry weight basis, was used. Soy flour was also used in the microencapsu-lation of sage oil at a higher level, in Example ll. In Example ~2, soy protein concentrate was utilized as the protein base, :
and in Example 13, casein was used.
20 The proteins were added to a mixer such as a Hobart Model A-200, and, with agitation, the water was added with the addition of the oil of sage to develop a ~riable mass which could then be fed to the extruder.
~he mixtures were extruded through a Bxabender pilot plant extruder, the barre~ of which was heated to a temperature of about 80 to 90C., the barxel being ~itted with a die adapter which was heated to about 170C. At the exit of the ~rabender an extension was fitted, approximating 8 inches in length, which which was flattened at the end to an opening of approximately 1/8 inch. Suitable air cooling could be applied to the exten~

-3n-sion~ The extrudate left the Brabender in translucent un-expanded sheets and the final product had a density greater - than water.
The strips of extrudate were cut to approximately 1/4 inch lengths and the vitreous "glass" was then dried in an oven at 100C. for 1 hour followed by grinding in a Fitz Mill to the desired mesh.
The dried, ground products were steam distilled to determine the essential oil content to provide a measure of the conversion o~ essential oil after extrusion, drying, and ~rinding. A portion of the ~inal product was placed in open dishes for 4 weeks at room temperature to determine the "stability" o~ the produots. Perfect stability would mean no loss in essential oil on storage.
The results of these tests are shown in TABLE VIII:

TABLE VIII

Microencapsul ~

Soy Flour ~lbs~) 10 - 10 - -20 Soy Protein Concentrate(lbs.) - - 10 Casein (lbs.) - ~ - 10 Water (lbs.) 4 4 4 3.7 Water in the Mix (%) 28 28 28 28 50~ Sodium Hydroxide (ozs.) - - - 3.2 Oil of Sage (gms.) 90 185 18S 204 (2%) (4~) (4%) (4-1/2%j Stability After 4 wee~s 90 90 95 Storage at Room Temperature ~ ~M, 1 163~9~i The level of oil of sage used ranged from 2 to 4.3~
in the blends and the encapsulatio~ was excellent demonstrati~g that with as little as o~e part oi water to 2.5 parts of protein a suitable microdispersion can be foxmed which gives excellent conversion and stability, equivalent, if not better, to what can be obtained by conventional emulsification where the level oi water exceeds substantially, the quantity of protein.
In Ex~mple 14, 4 pounds of water was blended with 10 pounds of soy ~flour and 235 grams of oil of nutmeg (5~) wa~

added There was excellent conversion and stabillty.
In Example 15, 4 pounds of waker was added to 10 pounds of soy flour along with 185 grams of oil of ~age (4~).
Af~er extrusion and drying, the produc~ was ground into ~ractions as follows:
a) Through a 5 and on a 20 U.S.Standard Screen.
b) Through a 20 and on a 60 U.S.Standard Screen.
.

TABLE_ IX

Extraction of Oil of Sage from Extrudate, _by Use of Carbon Tetrachloride ~raction Through 5-Mesh Fraction Through 20-Mesh Screen and on 20-Mesh Screen Screen and on 60-Mesh Sc_een Mg.of Oil of Sage Percent of Mg. of Oil of Sage Percent of Solubility Extracted per Gram Oil of Sage Extracted per Gram Oil of Sage Procedure of Extrudaee* Extractedof Extrudate** __ Ex~racted A O Mg. 0% 0 Mg. 0%

B 7 Mg. 32%10 Mg~ 50%

C 19.5 Mg. 83%21 Mg. 105%

* Orig. concentration of oil of sage** Original concentration oE
2 23. mg./gram of extrudateoil of sage - 20 mg./gram of extrudate ~ ~3496 With the high shear developed forming the protein glass, the oil of sage is microdispersed to particle sizes in the xange,of from several microns to 1/2 micron or less.
As a result, the finished product may be coarsely ground or ground fine with excellent conversion and retention of the oil in excess of 9o% of theoretical. The fractionæ, when stored at 100F. for even 16 week~ showed remarkable stability in-dicating that the enveloping protein film or matrix provides excellent protection. The oil of sage locked in the protein matrix is "unavailable" for solvent extraction. This can be demonstrated by the followin~ experiments.
1) In Test A, the ground material was added directly to the carbon tetrachloride and the extent of 501u-bility was ~etermined by an ultraviolet photo~
metric procedure.
2) In Test B, the two fractions were dispersed i~
water for a period of 1 hour and the slurry was then extracted with carbon tetrachloride~

3) In Test C, the two fractions were dispersed in water and the product was then added to a Waring Blender where the high shear of the blades broke down the particles to a fine suspension. This product was then extracted with carbon tetrachloride.
The results are shown in Table IX. It can be seen that the stability of the two ground products is excelIent as evidenced by a zero extraction with carbon tetrachloride in the dry state (Test A). Even after substantial time allowed for hydration, the bulk of the oil of sage was still locked in the protein matrix (Test B). O~ly after complete disintegration .

~ ~63~

using a Waring Blender, was it possible to recover the oil of sage in carbon tetrachloride (Test C).
The data establish that an essential oil, normally soluble in carbon ~etrachloride, is protectively encased in a protain matrix in accordance with the practice of the present invention, it being necessary either mechanically to disrupt the protective coating or to solubilize it before the oil is releasable.
In additional tests the extrusion molten glass pro-cedure was used for the purpose of enrobing Vitamin C andferrous sulfate. Vitamin C can readily be oxidized on exposure to air or in the presence of moisture and is especially labile under heat processing conditions.. The iron present in ferrous sulfate has excellent nutritional qualities but the ferrous ion acts.as a pxo-oxidant. There was interest in learning whether the enrobing of the ferrous sulfate in a protein matrix would encase the ferrous sulfate.and make it unavailable as a pro-oxidant in food systems. The product compositions are given in TABLE X.
' TABLE X
ENROBING OF VITAMIN C AND EERROUS SULFATE

Casein (lbs.) 1.6 1.6 Water (lbs.) 0.45 0.45 Water (~) 21 21 Vitamin C (Gms.) 80 Vitamin C in the Mix (%) 10 Ferrous Sulfate ~Gms.) - 80 Ferrous Sulfate in the Mix (%) - 10 1 1~3~(~6 The two products were extruded using the pilot plant extruder and the glass s~rips were cut to a length of 1/4 inch and dried a~ 160~F. followed by grinding with the Fitz Mill through a 20 mesh screen. The slow release of Vitamin C Q~-tained through the microdispersion in the protein melt can be demonstrated through solubility tests. When 1 gram of the mechanical mix corresponding to the composi~ion of Example 16, but not extruded, was added to 100 ml. o water containing 15%
.by weight of sodium chloride, it was found that the entire theoretical amount of Vitamin C originally present dissolved in the aqueous pha~e in less than 1 minute. The results ob-tained on using the extruded product of Example 16, are shown in TABLE XI.
TABLE XI
SOLUBIL

Length of Stirring of 1 ~ of the Gram of Extrudate per Vitamin C
100 ml. of Salt Solution Extract_d 1 Minute 24.8 2 Minutes 30.9

4 Minutes 41.2 7 Minutes 53.4 10 Minutes 64.6 15 Minutes . 75.2 20 Minutes 83~5 Only 24.8~ of the Vitamin C is rendered soluble after 1 minute of extraction, showing the effect of the protective proteinaceous matrix which slows down the release of the Vitamin C. After 4 minutes of agitation more than half of the Vitamin C is still locked in the protein matrix.

-3~-.

1 1~349B

Experiments caxried out with the product of Example 17 provide still further proof of the efectiveness of the encasement or enrobing technique of the invention as a msans to protect or otherwise to isolate an encased material in a pxoteinaceous matrix. The material used in this study was ground extrudate consisting of 10% by weight of ferrous sulfate enrobed in casein.
The tests described are based upon the ~act that metals such as ferrous iron greatly accelerate peroxide for-mation in fa~s. In order ~o evaluate the pro-oxidant ~ffect o iron present, five gms~ of lard, containing no antioxidant, was melted and blended uniformly with 85 gms~ of wheat flour, and 10 gms. of the extrudate was then blend~ in. The sample (Sample:l?,thus prepared, was compaxed with two control samples prepared as follows:
In the first control sample (Sample 2~, 5 yms. of the same lard product was melted and blended uniformly with 85 gms. of the same wheat flour product. One gram of ~errous sulfate and 9 gms. of casein were uniformly blended with the lard and the wheat flour to form a control sample.
In the second control sample (Sample 3)~ 5 gms. of lard was melted and blended uniformly with 85 gms. of wheat flour. This was blended with 10 gms. of casein to provide a control sample containing no ferrous sulfate.
One batch of each of the three blends was filled to a depth of about 1/2 inch in each of separate, open 5-inch by 7-inch aluminum trays, and the trays stored for periods of 4, 6, 10, and 26 days in an incubator at 100F. At each of the indicated time intervals, a 25 gm. sample of each blend 1 ~3~96 was extractea with chloroform and the peroxide value of the extracted fat determined (A.O.A.C. 28.022, 12th Edition,1975;
meq. peroxide/kg. oil or fat). The peroxide values found are shown in TABLE XII. The samples were also examined for odor as an indication o~ the development of rancidity in the fat.
The results of these olfactory tests are recorded in T~BLE XII.
It was found that the control blend of ferrous sulfate (Sample 2) had already developed a rancid note after only ~ days of storage, the odor becoming more evident after 10 days of 10 storage and being very marked after 26 days of storage~ The ground extrudate glass (Sample 1~ showed only a low level of peroxide formation after 10 days of storage and the sample still had a good odsr and showed no evidence of rancidity after 26 days.
In a second series of runs, a portion of each of the same three blends was seal d in each of separate pint ~ars and the jars stored in an incubator at 100F. After 4 days, the control blend, without ferrous sulfate (Sample 3), had a perox-ide value of 3.4. The same peroxide value was obtained f~x the blend made with the extrudate (Sample 1~ The control blend, which contained ferrous sulfate (Sample 2) had a peroxide val~e of 18.8 after 10 days storage and had a marked rancid odor.
The above data esta~lish conclusively that the ex-trudate concentrate prepared in accordance with the practice of the lnvèntion possesses enhanced stability chaxacteristics.
The pieces were dried for 1 hour at 100F. and the product then ground to pass a U.S. 40 mesh screen. The product, when added to water, is not wetted and remains essentially in a pro-tected non-hydrated form indefinitely. In use, it was found 1 ~3~6 that during processing of the breakfast cereal to which the encapsulated minerals had been added, the matrix o water-insoluble vital wheat gluten protectively encased the mineral elements.

TABLE XII

PEROXIDE VALUE OF EXTR~CTED FAT
(1) - (2) ~3) Length of Blend Having Protein- Control Blend Control Blend Storage at aceous Extrudate with wlth Ferrous ~ithout Ferruus 10 100F. Ferrous Sulfate Therein Sulfate _ _ Sulfate 4 Day~ 3.4. 13.7 3.4 6 Day~ 3.3 14.2 10 Days- 5.2 18.8 0 26 Day~ Sweet Odor Very Rancid Odor Sweet Odor ' -Example 18 Encapsulation of Minerals The food Lndustry has long sought an effective way of encapsulating iron and other minerals for use in cereals which are subject to processing. The problem has been that any protective coatings used have either dissolved or have otherwise been rendered ineffective by the processing step.
As a result, the cereal itself is subject to premature rancidity.
The present invention solves the problem by providing an en~
capsulating medium which withstands the stresses of processing~
The example described below shows the importance o "special~' encapsulating materials for specific uses, in accordance with the present invention. In order to supply 25% o-E the RDA of iron and zinc, a premix was prepared in the ratio of 153 grams of zinc oxide and 147 grams of reduced iron.
The following material~ were combined in the concen-trations indicated.

1 ~3'1 96 Mineral mix, consisting of reduced 17.5 lbs.
iron and zinc salts Zinc Stearate 10 lbs.
,Whea~ Gluten (vital) 72.5 lbs, Water 14.5 lbs.
The zinc stearate serves as an additional '~water-proofing" agent.
A blend of the above was extruded through a laboratory Brabender extruder using a die temperature o 356F and a barrel temperature of 194F. wi~h a maximum speed and with a 1:3 com~
pression screw. A 5/8" stainless steel tube 8" long and ~lat-tened to give an opening of 1/8" was a~tached to the end of the extrusion die and cooling air at approximately 40 psi was directed onto the extension. The product extruded as a dense unexpanded glassy strip which was ground in a Comitrol through a 0.06 cutter.
The following is an example o how the extrusion pro-cess may be used to make an onion flavor concentrate with seven times the strength of onion powder.

Exam ~
NU-SPICE~ ONIO~ ?X
The formula used was as follows:
Soy Flour (defatted) 10 lbs.
Water 1800 ml. (28%3 Oil of Onion l oz. (0.6%) The product extrud~d, using`the pilot plant Brabender, a~ a good translucent glass. ~he extrudate was cut into lengths of 1~4 inch and was dried for 45 minutes at 200F. and then ground in the Fitz Mill to pass a 40-mesh scxeen.
Flavor evaluations demonstratPd that this product had sevenfold the flavor of good ~uality ground onion powder.

~163~

Storage tests over a lengthy period showed no loss of flavor.
Extended shelf studies in c~sserole dishes showed that the protein matrix film protected the aro~a and fl~vor of the onion to yield excellent spice concentrates. The onion concentrate may be used at a level of 1/8 to 1/2 oz. per 100 pounds of food product.
The following examples demonstrate the utility of the extrusion encasement process o~ the invention for preparing - spice products that simulate their natural counterparts in size and shape. But in contrast ~o the natural spice, the vola-tile flavor is protected from loss, by the protein matrix.

Example 20_ NU-SPICE(9 COARSE OREGANO
The formulation was as follows:
Soy Flour (defatted) 10 lbs.
Water 1800 ml. (28~) Oil of Oregano - 215 ml. (4~) Color The blend was extruded in the Brabender using a barrel temperature of 90C. and a die temperature of 150C.
A 1:3 transfer screw was used and the RPM was maximumO The extension at the end of the extruder was 10 inches long flat-tened to a 1/8 inch opening. 25 pounds of air pressure was used on the extension for cooling. The extrudate was cut to 1/4 inch lengths and dried for 45 minutes at 200F. and was then cracked in a Fitz Mill.
In order to produce the appearance of a coarse ore-gano one must modify the color syst~ms to have both a green component and a brown component and then blend these two pro-~ ~63~

ducts~ The mesh of the finished product for a coarse oregano was as follows~
On a 10 Zero On a 20 64%
Through a 30 6~
The essential oil content of the finished cracked product was 3.9~ showing excellent recovery and the product was stored for 8 days at 100F~ to check on stability. The essential oil content was 4.05%, showing no loss In similar tests made with the natural spice (ground oregano~, at leas~
503 of the essential oil was lost in 8 days' s~orage a~ 100F.
Also, in ground oreyano, which is a typical herb, seriou-~.
problems are always involved in freein~ the herb o~ ~LU~t frag-ments.and other contaminants.
. The product."NU-SPICE" Oregano, for practical pur-poses, looks like oregano and has the virtues of cleanliness, freedom from bacteria, stability of flavor, and other advantages. ~
It may be used at a range of 1/2 to about 4 ozs.~per 100 pounds of food.
20 . xample 21 NU-SPICEt9 FENNEL SEEI) . . _ . _ , - Pro~lems involved with ennel seed, in relation to its use in foods, probably are more involved than any of the other spices~ The shape and size of a.fennel seed is comparabl~
to that many natural contaminants, making it d:ifficult to clean.the spice.
A fennel seed was prepared as ~ollows:
Soy Flour (defatted) 10 lbs.
Water 1800 ml. (28%) 30 Oil of Fennel 172 ml. (3.6 pts.to 100 lbs.) ~3~S~) Color 9 ~ .

The blend Was extruded using ~the Brabender but in this case the die extension was fitted with six transverse stainless steel wires which sliced the extruded product to a thickness of 1/2 inch. The extrudate was dried for 15 minutes at 200F. and was then cut into 1/8 inch lengths.
The finished product had the color of ~ennel seed, had very much the shape and appearance of fennel seed, and the flavor was good.
The conversion recover~ of essential oil was 86% and the stability was excellent.

Exam~le 22 NU-SPICE~ BLACK PEPPER
The formula was as follows:

Soy Flour (defatted~ . 10 lbs.
Water 1800 ml. (28%) Oleoresin Black Pepper- 270 gms.(5~) . . .
Oleoresin Capsicum 28~5 gms.(0.6~) The blend was extruded usin~ the Brabender and cut to 1/4 inch lengths and dried in the oven for 35 minutes at 200F. The product was ground with a Ra~mond Mill to pass through a 40-mesh screen and 30% went through an ~0-mesh screen. The product ~as tasted against the natural spice and found to be comparable to the natural spice both in flavor and pungency. Use 1/2 to about 4 ozs. per 100 pounds of food.

Example 23 . ~ .
NU-SPICE~ BLACK PEPPER CONCENTRATE
A "Nu-Spice" Black Pepper product was pxepared with threefold the flavor strength of conventional soluble black peppers. The form~lation used was as follows:

--q2--. .
.

~ ~3'i96 Soy Flour (,defatted) ~4 lbs.
Oleoresin Black Pepper 16 lbs. (16~; 3~ es$ential oil) Water 33.6 lbs. (28%) The blend was extruded and the glass extrudate was cut into 1~4 inch pieces and dried for 35 minutes a~ 200F.
The product was then ground in the laboratory Raymond Mill to pass a 40-mesh screen. The finished product, on flavor evalu-ation, was found to have at least three times the black pepper flavor strength of a soluble seasoning.
If one were ~o blend 16 pounds of oleoresin black pepper with salt or sugar, the normal vehicles used for soluble seasonings, a thick viscous paste would result. This material would not be commercially acceptable. By utilizing the extru-sion encasement process of the present invention a product is obtained which is'very free flowing. The process is simplicity itself and makes it possible to produce concentrates which offer many advantages o~er soluble seasonings, including re-duced freight costs, lesser demands for storage space, and with the further advantage of flavor stability even at very high concentrational levels.

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Claims (5)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An encapsulated product in the form of spice concentrates and simulated spices, comprising from about one-half to about forty percent by weight of an agent selected from the group consisting of essential oils, oleoresins, and mixtures thereof, said agent being dispersed throughout and encased within but recoverable from an enveloping matrix comprising a fused encapsulating material selected from the group consisting of starches, cereal flour, modified starches, gums, proteins, and mixtures thereof, said agent being distributed throughout said encapsu-lating material as a micro dispersion of from about five microns to submicron in size, and said encapsulated product having a density in the range of from about fifty-five to about ninety pounds per cubic foot;
said encapsulated product containing said micro dispersion being the product obtained by blending said encapsu-lating material, said agent, and from about ten to about forty percent by weight of water based on the total weight of en-capsulating material and water to provide a friable blend, subjecting said blend through extrusion to pressure and to heat to form a glasseous melt, and extruding said melt under non-puffing conditions, the resulting said product constituting a substantially homogeneous, dense, essentially unexpanded, translucent-to-glassy extrudate, each said encapsulated product exhibiting excellent stability on long-tern storage, and being suitable for adding to foods as a flavoring therefor.

2. The product as set forth in claim 1 wherein said product is in a particulate form and comprises particles of a size to pass through a 5-mesh and to be retained on a 100-mesh U.S. standard screen.

3. The product as set forth in claim 1 wherein said product is in particulate form and comprises particles of a size to pass through a 100-mesh and to be retained on a 200-mesh &.S. standard screen.

4. The product as set forth in claim 2 wherein said product is of controlled size, shape and thickness to simulate the visual appearance of a natural spice product.

5. The method of flavoring and of enhancing the nutritional value of a food product, said method comprising the steps of . preparing a storage-stable, dense, glassy concentrate of an encapsulated agent selected from the group consisting of essential oils, oleoresins, vitamins, minerals, and mix-tures thereof, said encapsulated agent being dispersed throughout and encased within but recoverable from an enveloping matrix comprising a fused encapsulating material selected from the group consisting of starches, cereal flour, modified starches gums, proteins, and mixtures thereof, . said concentrate comprising from about 1/2 to about 20% by weight of said encapsulated agent distributed as a micro-dispersion throughout said encapsulating material, . said concentrate containing said micro-dispersion being prepared by blending said encapsulating ma-teri~l, said encapsulated agent, and from about 10 to about 40% by weight of water based on the total weight of encapsulating material and water, to provide a friable blend, subjecting said blend through extrusion to pressure and to heat to form a glasseous melt, and extruding said melt under non-pufflng conditions, thereby to yield a substantially homogeneous, dense, essentially unexpanded, translucent-to-glassy extrudate having a density in the range of from about 55 to about 90 pounds per cubic foot, said encapsulated agent being distributed substanti-ally uniformly throughout said extradate as a dispersed phase of micro particles of from about 5 microns to sub-micron in size in an enveloping matrix of said encapsulating material to provide a concentrate of said encapsulated agent in which said encapsulated agent is stable against loss and deterioration, and incorporating up to about 1/2 percent by weight of said concentrate in a food product.