CA1141558A - Controlled release of trace nutrients - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Compositions of an a method for pre-paring polymeric formulations that gradually, con-tinuously and uniformly release various compounds over a long period of time in ionic form that are well recognized as essential to the growth of agri-cultural commodities. The compounds, such as inor-ganic salts of varying water solubilities, are mono-lithically incorporated in a thermoplastic polymeric matrix usually of two thermoplastic polymers, for example, a copolymer of poly(ethylene-vinyl acetate) or a copolymer of ethylene and propylene. Release is generally conditioned upon the presence of moisture and is proportional to the moisture content of soil treated with the subject invention. Release rate is tailored to a given desirable condition by regulation of the free volume and/or polarity within the polymer matrix and through dispenser geometry. Free volume is maintained at the level conducive to agent release such as through the use of free volume modifying secondary thermoplastic additives such as low density polyethylene; and porosity is controlled through the use of porosity enhancing agents appropriately termed porosigens. Said porosigens can be the low or moderate soluble salts such as the carbonates, bicarbonates, sulfates, phosphates, nitrates, etc.; of the alkali metals, the alkaline earths, or ammonium. Upon exposure to moisture, water ingress into the dispens-ing pellet removes said porosigen through dissolution.

processes thus creating a porous network permitting water contact with the incorporated nutrient mole-cules and their gradual egress in said water over a period of time such as for about a couple months to four years, or longer.

Description

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BACKGROUND OT THE INVENTION

The present invention relates to the in-corporation of the soluble or sparingly soluble com-pounds of various elements recognized as essential to plant health and growth in a modified thermoplastic dispensing pellet, powder, granule, or other con-venient dispensing form. Such compounds are salts or oxides of well recognized trace elements vital to plant nutrition. Said salts or oxides upon contact with water release zinc, iron, copper, boron, manga-nese, molybdenum, magnesium, cobalt and selenium in an ionic form as a water solution. Said plants, through natural processes, absorb the trace nutrient during uptake of the nutrient enriched water. Re-114~SSI~
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lease, being largely moisture dependent, is self-regulatory. During the growing season, wherein soil moisture is readily available, trace nutrlent release is continuous and uniform. When moisture is not presen., the plants generally do not grow and said nutrients are not released, thus avoiding loss of nutrient.
Heretofore, agronomists and nutritionists have recognized the vital and essential function of various elements needed in minute quantities by growing plants. Such elements have been termed "trace nutrients." Their functions vary, some being essential to the photosynthetic process or being a critical component in various enzyme systems. In general, the complete lack of a given trace element precludes plant growth For instance, Western Australia would not support agricultural field crops prior to the introduction of zinc into the soil. In most instances where trace nutrients are utilized, the normal soil content is too low for proper nutri-tion and plants cultivated in said soils are gener-ally more susceptible to disease, show poor growth characteristics and consequently crop yields are low.
It is common practice to supplement trace element poor soils by adding the needful material directly or as an additive in bulk nutrient applica-tions containing those substances classified as "fertilizers", i.e., nitrogen, potassium and phos-phorus. Most agricultural commodities require trace element soil supplement for optimum growth and thus ~415~

maximum yield. Such agricultural commodities include field crops such as wheatt alfalfa, potatoes, clover, tobacco, pineapple, soy beans, sugar, beets, cotton, corn, barley, oats, rice, and the like; citrus fruits;
nuts, such as pecans peanuts, coffee, cocoa, walnut, almond; fruits such as apples, pears, cherries, plums, peaches; vegetables, such as beans, peas, cauliflower, carrots, lettuce, tomatoes, cabbage, and the like;
and, forestry commodities such as pine trees, and pasture grasses. In the latter case, elementc es-sential to animal growth such as zinc, iron, copper and selenium are ingested by domestic animals con-suming said pasture grasses as forage. Lack of trace amounts of critical elements in the cow, sheep, goat and swine lead to deficiency diseases and thus de-creased output of meat, milk and wool.
It is probable that lack of application of trace nutrients in U. S. agricultural activities could lead to substantial declines in food production~
It is also likely that proper use of trace elements in soils lacking adequate quantities of said mater-ials, such as in vast reaches of Africa, would lead to a dramatic increase in agricultural productivit~.
Heretofore, in a typical utilization system, relatively high dosages of trace nutrients are added periodically to the soil. A number of disadvantages, ameliorated by this invention, occur. Said nutrients are of necessity water soluble salts or oxides else the treated plant cannot absorb them. ~eing water soluble, a large proportion of material applied, '''` ll~lSS~

perhaps 80 percent or more, is lost from the root zone via natural processes such as percolation in the vertical direction to earth strata below the effec-tive range of the root structure or washed beyond said root range through the movement of ground waters in the horizontal direction. In addition, the type of soil plays a profound role in the trace nutrient contact and ingestion processes. Alkaline soils and/or clay type soils generally complex the added nutrient chemical thus creating insoluble ligands of no value to the nutrient deficient plant. The rate of soil intervention in the nutrition process varies with p~ and type, but is an extremely important negative factor.
Relatively massive amounts of the trace elements must thus be applied to overcome natural loss processes and mechanisms. This leads to two distinct and severe disadvantages. In general, treatment must be afforded before each growing season and sometimes followed by one or more retreatments during that season. It is unusual for one treatment to last over any great length of time and consequent-ly, effort is expended and chemicals are purchased repeatedly by the agriculturist at frequent intervals with a concommitant economic factor increasing the cost of foodstuff production. Probably of even great-er significance is that massive treatment early in the season leads to luxurious consumption (i.e., consumption beyond real plant needs) early in the growing season with rapidly depleting chemical availa-~14~5S~

bility during the middle and late growing season. It i~ generally recognized that the uniorm availability of the trace nutrient in appropriate day-by-day quantities optimizes yield.
The use of controlled-release trace nutrients - of the present invention will overcome the luxury consumption, inadequate consumption cycle thus giving greater crop yield, will reduce the total amount of trace nutrient needed, and will also greatly extend between treatment times, from one to two, three, or more years, possibly five or ten years, depending on agricultural practices and natural circumstances (crop rotation and so on).
It is well known that biocid~l materials can be incorporated in a polymeric matrix and caused to release at a rate efficacious with pest destruc-tion. U. S. Patent No. 3,417,181 teaches that organo-tin toxicants can be dissolved in an elastomer-type matrix and caused to release through a diffusion-dissolution mechanism when exposed to water. The crux of this seminal invention was keyed to the necessity of the agent being soluble in the polymer.
Similarly, U. S. Patents 3,590,119; 3,426,473;
3,851,053; and 3,639,5~3 extend the scope of the art to embrace new formulations encompassing different elastomers, specific release regulants that effect the diffusion path length and the like, but again the key concept is the necessity of agent solubility in the elastomer. Agents incorporated are oryanic pesticides and the generic matrix type is elastomers `" 114~5~

such as natural rubber, styrene-butadiene rubber, and t~.e like. In contrast, U. S. Patent No. 4,012,221 teaches that inorganic copper salts capable of being released into water are incorporated in a moderately crosslinked elastomer in which the copper salts are insoluble.
It is well known to the compounding art that agents not soluble within a polymeric matrix will not move at an efficacious rate through said matrix to said matrix surface and thus enter the ambient environment.
Almost all organic pesticidal agents lack solubility in thermoplastic matrixes. Similarly, inorganic pesticidal agents are likewise insoluble in known thermoplastic or thermosetting polymers.
One method of causing an insoluble organic agent to emit from a plastic dispensing unit is to use a third phase material that is (1) soluble in some extent in said plastic and (2) will carry said organic agent in solution or serve as a migratory pathway for said agent to reach the surface of said dispenser. It is, of course, recognized that the incorporated agent must reach the plastic/external environment interface to have any effect on organisms inhibiting the external environment. ~. S. Patents

2,956,073 and 3,116,201 describe the use of plasti-cizers as carrier elements. In an improvement on such patents, U. S. Patents 3,705,938 and 3,864,468 teach that surface loss from a plasticized ma-trix is subject to control through the use of a regulating membrane at said surface.

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The controlled-release art has been gener-ally confined to the incorporation and release of insecticides, bactericides, molluscicides and other toxic materials of an organic nature from an elasto-mer, wherein solubility is essential or a plastic, wherein an additive carrier material is critical.
~icroencapsulation processes wherein an inner core of the toxic agent is surrounded by a polymeric matrix is well known to the pest control art. In general, release is effected by the rupture of the enveloping membrane and/or the passage of water through the porous membrane structure, said water path er~ing as a means of egress for said pesticide which reaches in this manner the external environment.
Little work has been hitherto performed in the development of efficacious long lasting fertilizing systems, U. S. Patent 3,748,115 teaches that plant nutrients can be bound in a matrix of synthetic rub-ber, waxes, asphalt, and the like. In this work, four critical elements of the invention are set forth.
The fertilizer, emphasizing bulk materials and not trace nutrient, must be uniformly dispensed in a hydrophobic binding element. The dispensing unit must be cylindrical in shape. Said cylinder must be partially coated with a water-insoluble, water-permea-ble exterior membran~. A portion of the cylinder must be non-coated with said membrane. tJ. S. Patent

3,520,651 extends this art to teach that more than one nutrient can be incorporated in similar dis-pensing co~nodities.

~l4~5515 In contrast, the subject invention is re-lated to trace nutrient elements, the binding matrix need not be hydrophobic, the dispenser can take any shape although the granule or pellet is preferred, and no exterior membrane is utiliæed.
Of course, fertilizing materials have long been compounded with various binders to facilitate dispersal and, in some cases, to prolong availability by slowing the rate of solution in water through pre-cludin~ immediate nutrient element contact with water.
U. S. Patent 3,336,129 teaches that the use of small amounts of water insoluble copolymers and terpolymers o~ ethers, substituted ethers, ethylene oxide and the like will serve as carriers for fertilizing materi-als, said copolymers and terpol~mers must be cross-linked. Materials are comprised of polymer + ferti-li~er + water + soil components and the plant is grown within this medium.
Also, fertilizers such as urea can be coated in a granular form as taught in U. S. Patent 3,336,155 thus retarding solution in ground waters. U. S.
Patent 3,276,857 teaches that a fertilizer can be encapsulated with asphalt or various waxes and thus emission into the environment is slowed.

SUMM~RY OF THE INVENTION

Accordingly, it is an object of the present invention to provide for the slow release of plant trace nu~rients.

~415~3 _g_ It is another object of the present inven-tion to provide for the slow release of trace nutrients, as above, wherein said trace nutrients are contained in a polymer matrix.
It is a further object of the present invention to provide for the slow release of trace nutrients, as above, wherein said trace nutrients include zinc, iron, copper, boron, manganese, molyb-denum, magnesium, cobalt, and selenium.
It is an additional o~ject of the present invention to provide for the slow release of trace nutrients, as above, wherein said trace nutrients, when applied to $oil and through water dissolution, is readily available to various plants such as crops, citrus fruits, nuts, vegetables, pasture grasses, trees, and the like through natural processes such as absorption of the trace nutrient during uptake of the nutrient-enriched water.
It is still another object of the present invention to provid~ for the slow release of trace nutrients, as above, wherein said polymer matxix is made from a copolymer of ethylene-vinyl acetate, a copolymer of ethylene-propylene, a low density poly-ethylene, and combinations thereof.
It is a still further object of the presen-t invention to provide for the slow release of trace nutrients, as above, wherein said polymer matrix is made from a copolymer of ethylene-vinyl acetate, a copolymer of ethylene-propylene, and combinations thereof.

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It it yet another object of the present in~ention to provide for the slow release of trace nutrients, as a~oYe, wherein said polymer ~atrix con-tains a porosigen compound(.
It is yet another object of the present invention to provide for the slow release of trace nutri~ents, as above, wherein said porosigen desirably is soluble or sparingly soluble in water such that said trace nutrient is released over a time period from a few ~onths to a few years.
These and other objects of the present nven~i`on will become apparent from the speciication.
In general, a controlled release plant nutrient dispenser, which is characterized by: a uni-formly dispersed admixture of a plant nutrient, a porosigen, and 100 parts by weight of a polymer matrix;
said polymer matrix made from a co~ound selected from the class consisting of an ethylene-vinyl acetate copolymer, an ethylene-propylene copolymer, a low density polyethylene, and combinations thereof; the amount by weight of said ethylene constituent in said ethylene-vinyl acetate copolymer ranging from about 60 percent to about 95 percent, the weight average mo-lecular wei~ht of said ethylene-vinyl acetate copoly-mer ranging from about 40,000 to about 400,000; the amount by weight of said ethylene constituent in said ethylene-propylene copolymer ranging from about 30 percent to about 75 percent, the weight average molecular weight of said ethylene-propylene copolymer ranging from about 50,000 to about 250,000; said plant nutrient being a trace nutrient which is required in minute amounts by a plant, the amount o:E said plant nutrient ranging from about 10 to about 160 I)arts by weight per 100 parts of said polymer matrix; the amount of said porosigen ranging from about 0.1 to about 70 parts by weight per 100 parts oE said polymer matrix, .~ i .~

said porosi~en Ila~ing a solubil~ty of less ~han 100 gxa~s per 100 gra~s of water so that upon contact of said dispenser with 50il moisture, the plant nutrient is released at a rate req-ulred by the plant to stimu-late growth; the total weight o~ said plan-t nutrient, said poros~gen, and said polymer matrix ranging from about 110.1 parts to about 330 parts.

DE~SCRIPTION OF THE PREFERRED F.~IBODI~ENTS
According to the concepts of the present invention, trace nutrients are slowly and controlla-bly released to soil to improve plant growth and yield over an extended period of time. This result is obtained by incorporating the trace nutrient into a polymer matrix. Additionally, the matrix can con-tain soluble or sparingly soluble porosigen compounds therein.
-My invention relates to the sustained release of various pesticides, from a polymer matrix, against such aquatic pests such as mosquito larva, the aquatic larya form of parasites, molluscan hosts of trematode parasites, and the like. The pesticide such as an organotin compound, and the like, could be contained in a polymer matrix which ei-ther sank or floatedO
The exact nature of the various pesticides and porosi-~en~ contained within the polymer matrix, as well as the concepts of the inventions therein, are set forth herein.

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Now it has been found that trace nutrients can slowly be released when contacted by an aquatic environment or moisture, such as rain or moisture in the soil, often times by only the copolymer matrix when the trace nutrient itself is a porosigen, and most always released when using the porosigen compounds set forth below. A polymer matrix binder of the present invention is an ethylene-vinyl acetate copolymer.
Such a copolymer is readily available in commerce and the amount by weight of the ethylene units, based upon the total weight of the copolymer, ranges from about 60 percent to about 95 percent with a range of from about 80 percent to about 93 percent being preferred.
The weight average molecular weight of the copolymer generally ranges from about 40,000 to about 400,000 and preferably from about 75,000 to about 300,000.
Desirably, the copolymer has an ASTM Test ~Dl238 melt flow index of from about 6 to about 12 and preferably from about 7 to about 11 and a Vicat softening point of from about 70C to about 95C. Since, apparently, the ethylene repeating units in the copolymer act as a regulator with regard to pore size, higher amounts of the ethylene constituent will result in slower release times.
Additionally, another polymer matrix or binding agent of the present invention which can be utilized alone or in combination with said ethylene-vinyl acetate copolymer, that is from l percent to 99 percent and preferably from about 35 percent to about 60 percent is an ethylene-propylene copolymer having a weight average molecular weight of from about 50,000 to about 250,000 with a preferred range of from about 100,000 to about 200,000. The percent by weight of the ethylene units can generally vary from about 30 percent to about 75 percent, and preferably from about 45 to about 75 percent by weight, based upon the total weight of the copolymer.
The melt flow index of the ethylene-propylene co-polymer can generally range from about 15 to about 45, and preferably from about 20 to about 32 accord-ing to ASTM Test #D1238 at 190, 21600 gm,gm/10 minutes.
Additionally, it has been found that low density polyethylene can be used by itself as a polymer matrix. Preferably, the polyethylene matrix has been found useful to provide a long release deviation when blended with the ethylene-vinyl acetate copolymer or the ethylene-propylene copolymer, or combinations thereof. By low density polyethylene, it is meant a polyethylene having a density of from about 0.90 to 0.94 g/cc and a weight average molecu-lar weight of from about 100,000 to about 400,000.
The melt flow index of the low density polyethylene may be similar to said ethylene-vinyl acetate copoly-mer, that is from about 5 to about 14, and preferably from about 7 to about 11, as in Microthene ~ 718, (a trademark manufactured by U.S.I. Chemicals). Melt flow = 8.5 g/10 minutes according to ASTM Test ~D 1238. Although generally a lower release rate is obtained, the melt flow index of the low density poly-ethylene may be low, that is from about 1.0 to about 5.0 as when Microthene MN 703 is utilized (a low density polyethylene manufactured by U.S.I. Chemicals) ~.4~55~

having a melt index of 1.2 g/10 minutes according to ASTM Test #D1238. Similarly, a low density poly-ethylene having a high melt flow index such as from about 11 to 25 may be utilized and results in a greater release rate. Thus, depending upon the rate of release, various amounts of low density polyethy-lene may be utilized, as from 1 percent to 99.9 percent. ~enerally, to obtain desirable release rates, the amount of homopolyethylene utilized may range from about 30 percent to about 75 percent and, preferably, from about 40 percent to about 60 pe~cent by weight based upon the total weight of the polymer matrix blend, that is the weight of the ethylene-vinyl acetrate copolymer and/or the weight of the ethylene-propylene copolymer with the low density polyethylene.
The various trace elements utilized are generally in the foxm of salts or oxides, which are readily available, desirably low in cost, and are not highly deliquescent. It is noted that the term "salts" includes the various hydratcs thereof, that is the mono-, the di-, the tri-, the tetra-, the penta-, the hexa-, the hepta-, etc. Should the salt not exist in a non-hydrate form, the most common forms are meant. With xegard to zinc-contain-ing compounds which may be utilized as trace nutrients, they include the following: zinc sulfate, sinc chloride, zinc carbonate, zinc oxide, zinc phosphate, zinc chlorate, zinc nitrate, the various existing hydrates thereof, and the like. rrypical copper trace nutrient compounds include copper sulfate, copper carbonate, copper oxide, copper ~14~5~

oxychloride, copper nitrate, copper phosphate; various copper complexes such as tetramines, diamines; the various existing hydrates thereof, and the like.
Typical iron trace nutrient compounds include iron chloride, iron sulfate, iron oxide, the various exist-ing hydrates thereof, and the like. Typical manganese trace nutrient compounds include manganese oxide, manganese sulfate, manganese chloride, manganese ni-trate; the various existing hydrates thereof, and the like. Typical boron trace nutrient compounds include boric ~cid, sodium biborate; the various existing hydrates thereof, and the like. Typical molybdenum trace nutrient compounds include molybdenum oxide, sodium molybdate, potassium molybdate, the various existing hydrates thereof, and the like. Typical cobalt trace nutrient compounds include cobalt sulfate, cobalt chlorate, cobalt nitrate; the various existing hydrates thereof, and the like. Typical selenium trace nutrient compounds include sodium selenate, selenium dioxide, selenium trioxide, selenium oxy-chloride, selenium disulfide, selenium sulfur oxide, and the like. Typical magnesium compounds include magnesium carbonate, magnesium sulfate, magnesium ni-trate, magnesium acetate, magnesium oxide, magnesium chloride, magnesium ammonium chloride, magnesium phosphate, magnesium sulfite; the various existing hydrates thereof, and the like.
Desirably, the amount of trace nutrient released by the polymer matrix is such to make the plant grow or to supplement the environment. That is, ~4~S~15 the soil is supplemented such that the plant's intake is supplemented, preferably to an extent of its normal amount of the particular trace nutrient required.
Naturally, the exact amount will vary depending upon several factors such as the lack of the specific trace nutrient in the soil, the various types of soil, the intake requirement of a particular trace nutrient for a specific plant or crop. Thus, the actual amount will vary from site to site, depending upon soil characteristics and the plant species in-volved. Accordingly, the exact demands for a parti-cular trace nutrient of the present invention will naturally and inherently vary greatly. In order to achieve a desirable amount of trace nutrient required for a particular or specific soil and type of plant, several methods may be utilized. For example, a much larger amount of the polymer matrixes containin~
the particular trace nutrient or nutrients may be released, i.e., a larger number of pounds per acre.
Another method i5 simply to utilize a formulation having a higher release rate of a particular trace nutrient. Still another method is to use a formula-tion having a higher amount of trace nutrient content therein. Yet another method relates to utilizing larger particles, that is, granules or chips. Addi-tionally, other variations may also be utilized. As an approximate rule of thumb, the formulation can contain from about 1 percent to about 60 percent by weight of a particular trace nutrient ion, based upon the total weight of the formulation. A desirable 1~4~S51~

amount is from about 2 percént to about 50 percent, with a more desirable amount being from about 4 per-cent to about 40 percent. The amount of trace nutrient compound which usually exists as a salt or oxide ranges from about 10 to about 160 parts by weight based upon 100 parts by weight of the polymer, desira-bly from about 25 to about 125 parts, and preferably from about 50 to about 100 parts by weight.
Generally, a particular soil is usually deficient in one or two trace nutrients. However, in some instances, it may require a few or even several trace nutrier.ts. According to the present invention, a plurality of trace nutrients can be contained within a particular polymer matrix in various amounts suitable to meet the demands of the particular crop or plant desired. Thus, a so-called "one-shot approach" may be utilized instead of apply-ing several applications of polymer matrixes, each containing a different trace nutrient.
Release of the trace nutrient is generally confined to the soil environment. However, the plants allowed to assimilate the trace nutrients will not grow unless the soil contains some degree of moisture.
Thus, moisture is utilized as a transporting material in dispensing the trace nutrient. Therefore, it is essential that the formed polymer matrix be amenable to water egress and ingress. Thus, the porosity of the polymer matrix becomes important to the slow release process. It is generally believed that the enhancement of microporosity (free volume~ as well as ` 1141S~
-18- ' macroporosity of the polymer matrix is important to the present invention. Porosity can be imparted by various chemical compounds termed porosity enhancing agents or "porosigens." However, depending upon the type of polymer utilized as well as the type of compound utilized as a trace nutrient which, itself, often times serves as a porosity agent, it is thus not always necessary to utilize such an agent.
For example, trace nutrient compounds such as a chloride, copper sulfate, iron sulfate, iron chloride, manganese sulfate, manganese oxide, manganese chloride, boric acid, sodium biborate, sodium molybdate, cobalt sulfake and sodium selenate can be utilized without the aid of a porosigen. Of course, a co-porosigen of a low water solubility would increase the rate released and a co-porosigen having a higher water solubility would increase the rate even more.
Generally, the amount of trace nutrient and the optional porosigen is such that release occurs over a period in excess of one month to a couple, a few, and even several years. Although largely dependent upon soil conditions and plant intake required, an amount of porosigen is utilized such that the daily release rate of the trace nutrient varies from about 0.001 to about 4 percent by weight per day based upon the total weight of the trace ion available in a particular matrix. A desired daily release rate is from about 0.001 or, more desirably, 0.01 percent to about 3 percent of the total amount of trace nutrient ion available, and ~ 4~.S~

more desirably from about 0.90 percent to about 1.6 percent per day, and preferably from about .30 percent to about 1.1 percent per day.
As noted above, the type of porosigen will vary depending upon t~e desired release rate sought. Should a relatively low increase rate be sought over the release rate level effected by only the polymer and the trace nutrient, a number of moderate or low solubility compounds can be utilized as a porosity-inducing agent. By moderate solubility, it is meant that the solubility is approximately 0.1 grams or less per 100 grams of water, whereas by a low solubility compound, it is meant that it has a solubility of approximately 0.01 grams or less per 100 grams of water.
Generally, any compound which is inert with respect to the polymer matrix and the trace nutrient can be utilized, as a porosigen. By inert, it is meant that the porosigen does not chemically react with the polymer or the trace nutrient. Addi-tionally, the porosigen is also not damaging or harm-ful to the environment in terms of toxicity. Thus, the porosigen can be any compound which meets the above requirements with regard to solubility and non-harmful to the environment.
A suitable class oÇ an inert porosigen com-pound includes the inorganic salts or the hy-drates thereof, or oxides. The cation of such a , .

` 114~55~3 --~o--salt may generally be any of the alkaline metals and preferably any of the non-toxic alkaline earth metals, Column lA and 2A, respectively, of the Perio-dic Table. Additionally, various other metals may be utilized such as iron, nickel, zinc, tin, silver and the like. The anion portion of the salt may generally be any ne~ative charge entity, as the various carbo-nates, the various bicarbonates, the various nitrates, nitrites, or nitrides, the various sulfates, sulfites, or sulfides, the various phosphates, phosphites, or phosphides, including the ortho, pyro, hypo, varia-tions thereof, and the like. Generally, the sulfates, sulfites and sulfides are preferred as anions, with carbonates being hig~ly preferred. Moreover, as noted above, the anion may be an oxide of the metal. Spe-cific examples of coleachants include magnesium carbo-nate, magnesium sulfide, magnesium phosphide, magne-sium oxide, calcium carbonate, calcium bicarbonate, calcium nitride, calcium oxide, calcium phosphate, calcium phosphite, calcium sulfide, calcium sulfite, iron carbonate, iron sulfate, iron sulfide, iron sulfite, nickel carbonate, nickel sulfide, zinc carbo-nate, zinc oxide, zinc sulfide, zinc sulfite, tin sulfide, tin oxide, silver carbonate, silver oxide, silver sulfide, silver sulfite, sodium bicarbonate, lithium phosphate, beryllium oxide, strontium carbo-nate, strontium sulfate, and strontium sulfite. Addi-tionally, silicon dioxide may also be utilized.
Magnesium carbonate, strontium carbonate, ammonium carbonate, and barium carbonate are preferred, with s~

calcium carbonate Being highly pre~e~Yed.
W~en it is desi-rable to ~se a po~osigen c~mpound having a sparingly soluble or solubility poros~gen, that is a ~oluBility greater than 0.1 grams per laO g~ants of water, generally any inert and non-en~ironntental ~armful compound can Be utilized which ~as a sol~BIlity of from about 0.1 to about lo O ~ram and desira~ly from about 1.0 to about 100 gram~ per lOa grams of water. Specific examples include sodium carbonate and sodium ~icarbonate.
~ enerally, the halogen salts of the alkalin metals and the alkalin earth metals, Column lA and 2A, respecti~ely, of the Periodic TaBle, as well as of n~c~el,`i~on, zinc, tin and silver, which have a sol~Bi~lity of at lea~t Ool grams/100 grams of water, and pre~eraBly the cfiloride salts thereof can also be ~ttil~zed. Additionally, ammonia as a cation consti-tutes another cla5~ of salts with specific examples b-eing anmoni~m Bromide, am~toniuml~carbonate, ammonium 2Q bicarBonate, ammonium c~lorate, ammonium chlorite, anmonium chloride, ammonium fluoride, ammonium sulfate, and the like. Additionally, sodium silicate can also be used. Of t~is group, sodium bicarbonate, B

114~558 sodium carbonate, silicon dioxide, sodium silicate, and ammonium sulfate are preferred. Moreovert inert li~uids compatible with and dispersible in the polymer matrix such as the lower and glycerol glycols may be utilized, especially ethylene glycol.
Generally, suitable amounts of a porosigen range from 0.1 to 70 parts by weight based upon lO0 parts by weight of polymer matrix, desirably from about l.0 parts to about 30 parts, and preferably from about 2.0 parts to about 12 parts.
The slow release trace nutrient composition or formulation can contain, in addition to the above-mentioned components, various well known and conven-tional additives to enhance dispersion, add color, aid in processing, or to alter density. For example, zinc stearate may be utilized as a dispersant in suitable amounts as from 0.2 parts to about 5 or lO parts by weight per 100 parts by weight of polymer ~ith about l or 2 parts being preferred.
The composition can also contain suitable amounts of an attractant-porosigen such as from about 2 to about 25 parts of soy oil or lecithin when it is desired that a particular type of animal eat the nutrient, e.g., cattle, with 4 to 16 parts being desira-ble. Additionally, various amounts, i.e., l to 30 or 2 to 12 parts of carbon black may be utilized as a regulant.
In order to form a suitable thermoplastic dispenser which releases suitable amounts of the trace nutrient, it is desirable that the particle sizes of the various components be relatively small.
For example, it is desirable that the various trace 114~558 nutrients have a Tyler mesh size of rou~hly 100 or ~reater (i.e., a particle size smaller than 100 mesh) and preferably smaller than 200 mesh. Accord-ingly, a particle size range for the porosigen is generally the same. The particle size of the ethylene-vinyl acetate copolymer, the polyethylene, and the ethylene-vinyl acetate copolymer is roughly about 50 to 200 Tyler mesh. Since the composition is made by heating and melting the polymer, the polymer size prior to formation of the matrix is not very important.
The slow release trace nutrient composition is prepared by mixing the trace nutrient with the copolymer and/or the low density polyethylene either alone or with the porosigen in suitable proportions as indicated above in any conventional mixing appara-tus along with various additives such as colorants, dispersants, and the like. The mixture is then coalesced by heating at least above the softening point and preferably above the melting point of the copolymer and partitioned for use in any suitable size or shape, for example, chip, pellet, etc. Thus, the mixture may be added to a conventional extruder where it is molded at from about 120C to about 220C
in a suitable form such as a ribbon which can be cut into pellets, etc.
Before numerous examples are presented to disclose various embodiments and best mode of the invention, a few general rules are noted with regard to determining the effect of any formulation with regard to release of a trace nutrient. In general, 114~551~il the incorporation of a porosigen agent will cause *he release of more trace nutrient on a daily basis.
Conversely, the incorporation of a low density poly-ethylene will moderate or reduce the daily release, especially if the polyethylene has a low melt flow index tfor example, 5.0 or less). If the trace nutrient is fairly soluble in water, for example, 1.0 or greater, or if a very low release rate is desired and the polymer is either the ethylene-propylene copolymer or the ethylene-vinyl acetate copolymer, a porosigen is not required. Additionally, the ethylene-vinyl acetate copolymer gives better release than the ethylene-propylene copolymer. As well appreciated by one skilled in the art, many factors can effect the results such as the actual particle or chip size of the polymer matrix, surface area of the polymer matrix or chip, and the like, so that the general rules are just that, general rules.
The invention will be better understood by reference to the following examples.
Typical formulations for the controlled release of zinc ions are set forth hereinbelow.

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1~4~558 -2~-The materials in Table I were immersed in mineral free distilled water. Said water was analyzed at periodic intervals for zinc ion in accordance with the standard diphenylthiocarbazone method (ASTM 25.077).
After each zinc determination, immersion water was discarded and zinc free water added to the test containers in order to forstall the development of solution equilibrium. Analyses were performed at 1, 2, 7, 14, 21 and 30-day intervals and once monthly thereafter for 4 to 12 months.
Steady state conditions typified by a continuous emission rate were achieved, usually by the seventh day past immersion. After initial addition to water, a preliminary high emission is observed as the zinc sulfate molecules on or very close to the surface are dissolved by and lost into the surrounding waters.
The following steady state emission rates were determined:
EMISSION RATE
FORMULATIONS % AGENT LOSS PER DAY
l-A 0-04 l-B 0.08 l-C 0.83 l-D 0.38 l-E 0-34 l-F 0.76 l-G 0.37 l-H 0 0 l-I 0.13 l-J 0.37 l-K 1.2 1~.4~55~

Several salient features underlying the uniqueness of this invention can be noted. (1) Other factors being constant, comparison of l-G using ethylene-vinyl acetate alone as the matrix element (0.37 percent per day emission) with formulation l-H
using low density polyethylene (melt index 8.5) as the sole matrix element (0.0 percent per day emission) and formulation l-I using only low density polyethylene (melt index 1.2) indicates that polyethylene alone provides a lower and, in an agricultural context, inferior loss rate.
It is evident that the use of a porosity-enhancing agent such as ammonium sulfate and sodium bicarbonate, among others, greatly increases emission rate.
Ethylene glycol in conjunction with ammonium sulfate greatly enhances porosity growth and hence increased emission. In contrast, ethylene glycol alone provides only a small degree of porosity enhance-ment.
Under the test conditions used, specifically the fact that immersion water was of slightly acidic pH, the use of sodium bicarbonate as the porosigen provided considerably higher emission rates. Compare formulation l-J having approximately 3 percent porosi-gen (0.37 percent per day e~ission) with l-K having approximately 6 percent porosigen (1.2 percent per day emission).

EXAMPLE II - ZINC OXID~: FORMULATIONS
The low water solubility of zinc oxide results in much lower omission rates as compared with the 114~5~

highly water soluble zinc sulfate material of the previous example.
A few formulations are depicted below:

TABLE II
Ingredient FOP~ULATION (parts~

LDPE 703 -- -- ~~ ~~ 40 Zinc Stearate 2 2 2 2 2 Zinc Oxide 80 80 80 80 80 Ammonium Sulfate -- 5 -- -- 5 Sodium Bicarbonate -- -- 5 -- --Periodic zinc analysis using the procedure previously described provided the following results:
EMISSION RATE
FORMULATION % AGENT LOSS PER DAY
2-A0.005 percent 2-B0.014 percent 2-C0.017 percent 2-D0.017 percent 2-E0.018 percent Comparing 2-A (no porosigen) to 2-B (3 percent ammonium sulfate) again indicates the enhance-ment of porosity, and hence emission, observed by the use of such additives. Also comparing 2-D (using ethylene-vinyl acetate copolymer alone) having a 0.017 percent per day emission with 2-A, wherein ethylene-vinyl acetate copolymer is modified with polyethylene, indicates the moderating effect of said 55~

polyethylene. Importantly, it is observed that when ethylene-vinyl acetate copolymer ~melt index 9.0) is modified with polyethylene of melt index 8.5 (MN 718), emission is present.

EXAMPLE III ~ ZINC CHLORIDE FORMULATIONS
Several formulations using highly water soluble zinc chloride salt (432 g/100 g H20 compared to 100 g/lOOg H20 zinc sulfate soluble) were simi-larly prepared and evaluated for zinc emission rate.Formulations and emission rates are shown below.

TABLE III

15Ingredient FORMULATION (parts) Zinc Stearate 2 2 2 Zinc Chloride 80 80 80 Ammonium Sulfate5 -- --Emission Rate % 2.1% 0.18% 0.90%
loss per day In this instance, the extreme water solu-bility of zinc chloride is such that it, in essence, acts as its own porosigen, porosity growth arising as the zinc ion is rapidly dissolved into the surrounding water. Although the highest emission is ~L14155~3 is from ethylene-vinyl acetate copolymer as expected, polyethylene will also bind and emit, though at a much reduced rate.
EXAMPLE IV - ZINC CARBONATE FORMULATIONS
Under practical use conditions, the very low emission observed with zinc oxide materials and the high rates expected with zinc chloride may not be optimal in many instances. Likewise, zinc sulfate having considerable water solubility may not be accept-able in an agricultural situation of high rainfall and/or prolonged heavy ground moisture, rice paddy for instance. Thus, a relatively low solubility of controlled-release zinc carbonate might be of greater utility. Formulations and emission rates are depicted in the following table:
TABLE IV
Ingredient FORMULATION (Parts)

4-A 4-B 4-C 4-D 4-E

~U 718 40 40 40 -- --Zinc Stearate 2 2 2 -- 2 Zinc Carbonate50 80 80 80 80 Ethylene Glycol 25 -- -- -- --Sodium Bicarbonate -- -- -- -- --Amrnonium Sulfate -- -- 5 -~ --Emission Rate 0.0% 0.014% 0.038%0.029% 0.040 % Loss per day It is observed that even large amounts of ethylene glycol without another porosigen also present does not enhance porosity. Comparing 4-D using MU 763 only as the binding matrix without a porosigen to essentially the same material with about 3 percent ammonium sulfate (4-C), the porosity enhancement in the latter case leads to a hic~her ernission rate.

1~4155~

BIOASSAY EVALUATION
-Due to the high variability of composition and nature of soils, and the lack of a standard soil type, the tests described herein as typifying the invention have been performed in water since standard-ization is possible. It is recognized that (1) the end use of the formulations of this invention are in application to soil for (2) the increase in the yield of specific agxicultural commodities. In this respect, a fast emission zinc sulfate formulation and a slow emission zinc carbonate formulation were evaluated in zinc poor soil as a means of ascertaining merit therein. Soy bean plants were grown in seven inch diameter pots in the laboratoryt said pots each con-taining 1, 300 grams of soil. Two hundred milliliters of water were added once daily. Results are shown below:
GROWTH RATE OF SOY BEANS IN ZIMC POOR
SOIL TREATED WITH CONTRO~LED R~LEASE ZINC FO~ULATIONS

POTAVERAGE POST ZINC CONTENT
COMPOUND DOSAGE GERMINATION STEM GROWTH ~Leaehate) -Dl 1 g2.75 em/day 0.0015 ppm/day 0.5 g1.94 cm/day 0.0011 ppm/day 0.2 g1. 40 em/dayn . 0007 ppm/day 0.1 g1.14 em/day 0.0002 ppm/day Control o.o gl.os em/day 0.00008 ppm/day 4-E 1 g3.13 cm/day 0.0003 ppm/day 0.5 g2.20 em/day 0 0004 ppm/day o. 2 g 2.14 em/day 0. 0002 ppm/day 0.1 g1.95 em/day 0. 0002 ppm/day Control o.o g1.07 em/day 0.00008 ppm/day As can be observed in examininc~ the bioassay data, a definite enhancement in soy bean growth is present due to the use of controlled release zinc 114~55~

formulations. It is further noted that in this in-stance the zinc carbonate material gave better growth characteristics in that less of the emitted agent was lost through leaching. To further illustrate the im-portance of the dis-tinction bet~een fast and slow emission formulations~ zinc analy-sis was performed on plant tissue and soil after 56 days of growth. Results are shown below:
Zn+~ Zn~+ Zn~+

FORM~LATION DOSAGE (Soil) (Leaf) (Root)_ l-D 1.0 g 0.075 ppm 0.03 ppm 0.10 ppm 0.5 g 0.060 ppm 0.05 ppm 0.09 ppm 0.2 g 0.050 ppm 0.03 ppm 0.08 ppm 0.1 g 0.050 ppm 0.04 ppm 0.07 ppm 15 Control 0.0 0.00 0.05 ppm 0.04 ppm 4-E 1.0 g 0.01 ppm 0.08 ppm 0.05 ppm 0.5 g 0.01 ppm 0.05 ppm 0.03 ppm 0.2 g 0.04 ppm 0.08 ppm 0.02 ppm 0.1 g 0.02 ppm 0.08 ppm 0.01 ppm 20 Control 0.0 0.005 ppm 0.05 ppm 0.01 ppm Whereas the higher emission rate of l-D leads to a greater soil concentration at any given instant than that seen with 4-E; the leaf content is greater and hence plant growth, in the latter instance. Under differing moisture conditions, the values might well reverse.
43 percent zinc sulfate and 6 percent porosigens rapid release.

44 percent zinc carbonate and no porosigen providing a very slow release.

EXAMPLE Y - COP~PE~ E~iISSIOI~

Se~eral copper salts and o,xides were in-corporated in plastic matrices and the release rates measured in de~ineralized water using the procedure previously described. The ~icinchoninate method of determining copper ion content was used.
COPPE~'SULTATE ~ONOHYDRATE MATERIALS (CuSo~-H~0~
A num~er of formulations containing copper sulate-monohydrate were prepared in accordance with the following recipes. Unlike zinc formulations, it was discovered that an ethylene-propylene thermoplastic (Vistalon 702, a trademark, melt index 27, product of Exxon Ch~m~cal Co.), when ~odiied by a low density polyethylene, pro~ided a superior release rate.
TABLE V

Ingred~ent Formulation EPM 702 100 ~ 50 E~A 763 -- -- 50100 50 --Zinc Stearate 2 2 2 2 2 2 Copper sulfate ,Monohydrate 80 80 80 80 80 80 Ammon~um Sulfate5 5 -- 5 -- --In~redient _ _ _ Zinc Stearate 2 2 2 Copper Sulfate Monohydrate 80 80 100 Ammonium Sulfate -- -- 5 114~558 Copper release rate in water was found to be as follows:
Release Rate Formulation (% copper lon/day) Remarks

5-A 0.19 % EPM 702, with (NH4~2SO4 additive as a porosi-gen 5-B 0.19 % LDPE 718, with (NH4)2SO4 additive as a porosigen 5-C 0.026 % EVA 763/LDPE 718, no porosigen S-D 0.15 % EVA 763 with (NH4)2SO4 additive as a porosigen 5-E 0.37 % E~A 763/LDPE 703, no porosigen 5-F 0.28 % EPM 702/LDPE 718, no porosigen 5-G 0.002% EPM 702, no porosigen 5-H 0.0021% LDPE 718, no porosigen 5-I 0.31 % EPM 702/LDPE 718 with (NH4)2SO4 additives as the porosigen It is evident that the addition of a porosi-ty enhancing agent, ammonium sulfate, greatly increases the loss rate of copper ion. When a LDPE is used, whose melt index varies greatly from that of EVA, enhanced release is obtained, for example, EVA 763 of a melt index 9.0 modified with LDPE 718 of melt index 8.5, as with compound 5-C displays a very slow copper ion emission, whereas EVA 763 of melt index 9.0 modified with LDPE 703 of melt index 1.2, as with compound 5-E has a much higher emission rate.

EXAMPLE VI - COPPER CARBONATE EMITTING FORMULATIONS

Formulations were prepared containing very low solubility copper carbonate as the copper ion source. Recipes are shown below:

TABLE VI
Ingredient E`ormulation

6-A 6-~ 6-C 6-D

Zinc Stearate2 2 2 2 Copper Carbonate 80 80 80 80 Ammonium Sulfate -- -- -- -~
Measured loss rates over a 120-day period are shown below with other pertinent information:
Loss Rate % Melt Formulation Cu++~day Matrix Indices Poroslgen 6-A 0,0021% EPM 702/27/8.5 r.one 6-B 0.0033% EPM 702 27 none 6-C 0.0042% EVA 763 9.0 none 6-D 0.0017% EVA 763/9.0/1,2 none It is again noted that the use of a low density polyethylene modifier lowers the copper emission rate.
EXAMPLE VII - COPPER OXYCHLORIDE FORMUIATIONS
Several controlled-release copper formula-tions were prepared utilizing Cu2(OH)3C1 as the copper 5~

source. It was discovered that the principles pre-viously enumerated similarly held for this material incorporated in thermoplastics. Note the following recipe comparison.
TABLE VII

; Ingredient 7-A _ 7-B
LDPE 718 (M.I. = 8.5) 50 --EPM 702 (M.I. = 27) 50 100 10 Zinc Stearate 2 2 Cu2(OH)3C1 80 80 Ammonium Sulfate 5 5 Loss Rate % Cu++/day 0.021%0.0057%

s~ 15 It is again observed that emission rate is enhanced when LDPE is used to modify the EPM matrix.
!

EXAMPLE VIII - CUPROUS OXIDE FORMULATIONS

Cuprous oxide having extremely low water solubility was incorporated in thermoplastic matrices and loss rate measured as depicted below.

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:114~55~3 It is duly noted that emission rate of copper ion from the aforementioned formulations is temperature dependent. When soil conditions are cold and plant growth absent, the wasteful emission of copper is drastically reduced, while as the growing season pro~
gresses with warming weather, copper release increases to fully satisfy, when appropriate dosages are used, the needs of the crops. The following data taken as water emission rate at several temperatures exempli fies this phenomenon.

RELEASE OF Cu++ FROM 5-I
(Accumulative % Release, average of replicates) Time (da~s) _ 90F 72 40F
1 6.~% 5.5% 4.6%
14.0% 7.5% 6.3%
14.9% 9.9% 6.35%
17.5% 12.5% 6.65%
2031 26.9% 13.2% 7.1%
31.4% 15.5% 7.55~, 32.4% 18.6% 7.6%
87 38.7% 23.8% 7.7%
118 41.75% -- 8.1%
25158 45.6% __ 8.4%
EXAMPLE IX - IRON EMISSION
Various water soluble or sparingly water iron salts or oxides can be incorporated in ethylene vinyl acetate copolymers and low density polyethylene and blends thereof, and upon exposure to moisture ~14~55~

caused to release iron ion at a controllable rate. Iron bearing chemicals utilizable include ferric chloride/
ferrous sulfate, ferric oxide, ferxic ammonium citrate, ferrous oxide, and the like, excepting those materials that decompose at extrusion temperatures such as ferric nitrate and ferric ammonium sulfate. Recipes for several formulations are shown below with extru-sion conditions.

TABLE IX
Ingredient 9-~ 9-B 9-C 9-D 9-E

Zinc Stearate1 1 1 2 2 FeC13-6H20 25 -- -- __ __ FeS04-7H 0 -- 50 50 -- --2 3 -- __ 80 80 Ammonium Sulfate -- -- -- 5 --20Extrusion Barrel Temp. 400F 420F400F 370F 390F
Die Temp. 400F 400F400F 390F 410F

Loss rate is demineralized water averaged 25 over the post immersion period from day 8 to day 151 i6 as follows:
9-A 0.052% Fe release per day 9-B 0.17% Fe release per day 9-C 0.216% Fe release per day 9-D 0.0017% Fe release per day 9-E 0.0010% E'e release per day Iron content in water is determined by the ferrozine method, L.L. Stookey, Anal. Chem. 42(7), 779, 1970.

1~4~558 EXAMPLE x - MANGANESE EORMULATIONS

Controlled-release manganese emittors were prepared in accordance with the principles outlined herein. Manganese chloride, manganese sulfate and manganese dioxide were used as the agents. Several illustrative recipes are presented ~elow:

TABLE X
Ingredient 10-A 10-B 10-C 10-D
(parts by weight _ LDPE 703 -- ~~ ~~ ~~

Zinc Stearate Manganese Sulfatel -- 51 51 50 Manganese Chloride2 -- -- -- --Manganese Dioxide 80 -- -- --Ammonium Sulfate -- -- -- 5 -Zinc Stearate Manganese Sulfatel 60 -- -- --Manganese Chloride2 -- 25 30 30 Manganese Dioxide -- -- -- --; Ammonium Sulfate -- -- -- --MgS04 H20 MgC 2 2 55~

Said formulations were immersed in water and manganese release determinedl periodically as depicted below. It is noted that manganese dioxide having a very low solubility possesses a correspondingly low release rate - approximately 0.001 percent total manganese per day.
Release Rate of Manganese Compounds in Water Initial Mn Loss Rate; % Loss/Day FormulationLoss C30 days) Day 31 to Day 122 10-B 48.2% 0.18%
10-C 52.2% 0.27%
10-D 43.0% 0 35%
10-E 52.9% 0.27%
10-F 46.9~ 0.085%
10-G 54.2% 0.06~
10-H 21.6% 0.047%
Both manganese sulfate and manganese chloride formulations show high initial loss over the first 30 days or so immersion. After that time, a steady state situation is reached. It is noted that the manganese sulfate emitting materials show a higher loss rate due to the greater water solubility of this agent. Formulation 10-D, an ethylene vinyl acetate copolymer matrix using ammonium sulfate as a porosigen exhibits the greatest degree of release.

EXAMPLE XI - CONTROLLED_RELEASE BORON MATERIALS
Boron emitting materials were prepared Manganese in water is determined by the tetraphenyl arsonium chloride method. The Analyst 87, 435, June 1962.

_ __ 1~4~55~

in accordance with the principles outlined herein.
Several such compounds are depicted below. Boric acid and sodium biborate, both being highly water soluble are preferred over other boron salts. Sodium bicarbonate was used as the porosigen.

TABLE XI
Ingredient Formulation ll-A ll-B ll-C ll-D
Vistalon 703 60 100 -- --Zinc Stearate Boric Acid (Na2B407) 50 50 50 50 Sodium Bicarbonate -- -- -- 2 ll-E ll-F
Vistalon 702 -- --Zinc Stearate 1 2 Boric Acid (Na2s407)50 75 Sodium Bicarbonate -- ---Ingredient Formulation ll-C ll-H ll-J ll-Kll-L
-Vistalon 702 60 100 -- -- --Zinc Stearate 1 1 1 1 2 Na2B407 50 50 50 50 75 NaHCO8 -- -- 2 -_ __ 5~8 Immersion in ~ater indicated the following release rates.

BORIC ACID GROUP
Formùlation Release Rate (%/Day) Remarks ll-B 0.130~ Vistalon 702 matrix ll-A 0.135% ~istalon 702 modified with low density polyethylene ll-F 0.321~ EVA 763 matrix ll-D 0.321% EVA 763 with NaHCO3 as a porosigen (no effect) 5.78%
boron content ll-C 0.378% EVA 763 containing 5.85% boron content ll-E 0.722~ EVA 763 modified with low density polyethy-lene to provide much higher release rate 6.27% boron content SODIUM BIBORATE GROUP
ll-L 0.390% EVA 763, no modifi-cation, contains 9.22~ boron.
ll-K 0.552% EVA 763, modified with low density polyethylene, con-tains 7.72~ boron ll-J 0.765% EVA 763 with a poro-sigen, contains

7.14% boron ll-G 0.63% Ethylene-propylene copolymer modified with low density polyethylene, with 7.12% boron ll-H 0.66% Ethylene-propylene copolymer with no modification, with 7.21~ boron 5~1~

Boron in water was determined by the method described in APHA Standard Methods 13 Ed. p. 72, 1971.

EXAMPLE XII - CONTROLLED RELEASE MOLYBDENUM MATERIALS
.
Controlled release molybdenum formulations were prepared in accordance with the recipes shown below:

TABLE XII
_ Formulation No.
Ingredient 12-A 12-B12-C 12-D 12-E12-F
Vistalon 702 50 -- -- -- -- --Zinc Stearate 2 2 1 1 1 2 MoO3 75 75 75 50 50 --2 4 ~~ ~~ ~~ ~- - 75 Formulation ~o.
~redient 12-G 12-H12-I 12-J 12-K
Vistalon 702 100100 50 5050 Zinc Stearate 1 2 1 2 2 Na2MoO4 50 75 50 75 75 (NH4)2SO4 3 3 ~~ ~~ ~~ - 3 Initial 24-hour release and average daily release after release is shown below. Molybdenum content in water was determined using the technique in Analytical Chemistry 25(9), 1363, 1953.

5~1~

Mo. Initial Daily Release Rate Formulation Content 24-Hour CDay 7 through (1%) Release Day 30) 12-A 28.2 0.38% 0.06%
12-B 28.2 0.63% 0.09%
12-C 28.2 0.80% 0.0~%
12-D 22.0 0.69% 0.04~
12-E 26.4 0.67% 0.03%
12-F 19.8 1.26% 0.09%
12-G 15.4 15.9~ 1.00 12-H 19.7 20.3~ 1.18~
12-I 15.4 17.8% 1.81%
12-J 19.4 33.8% 1.45~
12-K 19.4 34.5% 1.63%
The effects of lower water solubility of MoO3, (O.lg/lOOg cold water), as compared to Na2MoO4, (44g/lOOg cold water) can readily be seen through comparing compounds 12-A through 12-E containing MoO3 with compounds 12-F through 12-K wherein Na2MoO4 in LDPE shows the relatively small initial loss rate in comparison with formulations 12-G through 12-K uti-lizing an ethylene-propylene matrix with or without an LDPE modifier. Examining of 12-H (19.7% Na2MoO4) and 12-G (15.4~ Na2MoO4) it is seen that the loss rate is partially dependent upon the total agent loading.
Comparison of compounds 12-C (28.2% MoO3) and 12-D
(22.0% MoO3) one notes the same effect. Whereas 12-G
(15.4% Na2MoO4 in Vistalon 702) provides a 1.00~ per day release in water, 12-I (15.4% Na2MoO4) wherein Vistalon 702 is modified with LDPE 718 a much higher, 1.81~ per day, loss rate is indicated. Interestingly, compounds 12-J and 12-K, both using a porosigen addi-114~55~

tive, show extremely high initial loss rate of 33.8% and 34.5% for the first 24 hours post immersion, respectively. In this instance, the use of a porosi-gen is contraindicated.

EXAMPLE XIII - CONTROLLED RELEASE COBAL~ MATERIALS
Controlled release cobalt formulations, using cobalt sulfate as the agent, were prepared in accordance with the recipes shown below.

TABLE XIII
Formulation No.
Ingredient 13-A 13-B13-C 13-D 13-E _ Vistalon 702 60 60 -- -- --Zinc Stearate CS4~7H2 50 ~NH4) SO4 __ __ __ __ __ 3 ~~ -- --Carbon Black -- -- -- -- --Formulation No.
13-F 13-G13-~ 13-T
Vistalon 702 -- -- -- --Zinc Stearate CoS~4~7H20 75 50 50 50 (NH4)2SO4 -- 5 -- -~
NaHCO3 __ __ 5 __ Carbon Black -- -- -- 5 1~4~5~3 Cobalt loss from an immersed pellet into demineralized water was measured in accordance with the technique prescribed by Pyatnitskii ("Analytical Chemistry of the Elements," p. 130, Humphrey Science Pub. Co., Ann Arbor, Mich. 1969). Emission rate over the immersion period from day 7 to day 30 and other pertinent data is shown below:
Formulation No. Emission Rate Remarks ___ (per day~
13-E 0.13% Low density polyethylene (703) matrix, no porosigen, 12~2% total cobalt content (W/W~
13-C 0.29% Low density polyethylene (718) matrix, no porosi-gen 14.4% total cobalt content (W/W) 13-A 0.24% Vistalon 702 EPM matrix modified with LDPE 718.
Only 5.9% total cobalt content (W/W) No porosi-gen.
13-B 0.39~ Vistalon 702 EPM matrix modified with LDPE 718, but with a higher (12.3%) total cobalt content. No porosigen.
13-D 0.53% EVA 763 matrix, no por-osigen. Total cobalt content 10.4%(W/W).
13-F 0.69~ EVA 763 matrix, no porosigen. Higher total cobalt content, 12.1%
(W/W ) .
13-I 0.90% EVA 763 matrix with carbon black as an addi-tive to increase free volume.

s~

Formulation No. Emission Rate Remarks (~er day) 13-G 0.95% EVA 763 matrix with ammonium sulfate addi-tive as a porosigen.
13-H 1.05~ E~A 763 matrix with sodium bicarbonate as a porislgen.
Cobalt sulfate is a highly soluble material (60.4g/lOOg cold water) and thus essentially serves a porosigenic function in L~PE so that emission is possible.

EXAM_LE XIV - CONTROLLED RELEASE SELENI~M MATERIALS
The following controlled release materials, using sodium ~elenate as the agent, were prepared and immersed in dimineralized water.
TABLE XIV
Ingredient Formuiation No.
14-A 14-B14-C_ _ 14-D

Vistalon 702 25 -- 25 --Zinc Stearate Na2SeO4 25 25 25 25 (NH4)2S04 -- -- 2 __ NaHCO -- ~- -- 2 In accordance with agricultural needs, release rates are very low as measured o~Jer a 120-day period in demineralized water.
14-A 0.0071% Se emission per day 14-B 0.0066~ Se emission per day 14-C 0.0053% Se emission per day 14-D 0.0055% Se emission per day 5S~3 EXAMPLES XV - CONTROLLED RELEASE MAGNESIUM FORMULATIONS
Recipes for several typical magnesium emitters are shown below:
TABLE XV
Ingredient Fonmulation No.

. . . _ _ .
Vistalon 702 25 -- 25 Zinc Stearate 10Mg CO3 15 15 ~_ Mg SO4 -- __ 15 Release in demineralized water was measured periodically and a rate of 0.15%/day (15-A), 0.09~/day (15~B), and 0.48%/day (15-C) noted. Magnesium analysis was performed by the method described in Flaschka, H.A., et al., ~uantitative Analytical Chemistry, Vol. II, p. 140, Harper and Row, pub. Inc.
N.Y., 1969.
EX~MPLE_XVI - MULTIPLE ELEMENT RELEASE
With proper compounding, it is possible -to release two or more elements simultaneously from the same matrix. In treating.soil, that is cobal-t poor~
and which also requires a small supplement of zinc 25 and iron formulation (16), shown below, can be utilized.
TABLE XVI
Ingredie t Recipe Zinc Stearate Cobalt Sulfate* 25 Iron Oxide** 25 Zinc Oxide*** 10 4 H20 ** Fe203 *** ZnO

s~

A daily loss rate of 0.25%/day cobalt, 0.002%/day iron and 0.01%/day zinc was measured.
Multiple emission rom one matrix can thus be accomplished and a material tailored to meet specific soil needs in some instances. It is, however, more likely that a given trace element's need can be met by appropriately mixing the proper proportion of different emitters (i.e. different matrices~ during application to a given soil.
While in accordance with the patent statutes, only the preferred embodiments of the invention have been described in detail,therefore, for the true scope of the invention, reference should be had to the appended claims.

Claims (25)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A controlled release plant nutrient dis-penser, which is characterized by: a uniformly dis-persed admixture of a plant nutrient, a porosigen, and 100 parts by weight of a polymer matrix, said polymer matrix made from a compound selected from the class consisting of an ethylene-vinyl acetate copolymer, an ethylene-propylene copoly-mer, a low density polyethylene, and combinations thereof;
the amount by weight of the ethylene con-stituent in said ethylene-vinyl acetate copolymer ranging from about 60 percent to about 95 percent, the weight average molecular weight of said ethylene-vinyl acetate copolymer ranging from about 40,000 to about 400,000;
the amount by weight of the ethylene con-stituent in said ethylene-propylene copolymer rang-ing from about 30 percent to about 75 percent, the weight average molecular weight of said ethylene-propylene copolymer ranging from about 50,000 to about 250,000;
said plant nutrient being a trace nutrient which is required in minute amounts by a plant, the amount of said plant nutrient ranging from about 10 to about 160 parts by weight per 100 parts of said polymer matrix;
the amount of said porosigen ranging from about 0.1 to about 70 parts by weight per 100 parts of said polymer matrix, said porosigen having a solu-bility of less than 100 grams per 100 grams of water so that upon contact of said dispenser with soil moisture, the plant nutrient is released at a rate required by the plant to stimulate growth, -51a-the total weight of said plant nutrient, said porosigen, and said polymer matrix ranging from about 110.1 parts to about 330 parts.

2. A controlled release plant nutrient dis-penser, according to Claim 1, said plant nutrient selected from the group consisting of zinc, copper, iron, manganese, boron, molybdenum, cobalt, selenium, magnesium, and combinations thereof.

A controlled release plant nutrient dispenser according to Claim 2, wherein said ethylene-propylene copolymer has a melt flow index of from about 15 to about 45, wherein said ethylene-vinyl acetate has a melt flow index of from about 6 to about 12, and wherein said low density polyethylene has a melt flow index of from about 1 to about 250

4. A controlled release plant nutrient dis-penser according to Claim 2, wherein the amount of said plant nutrient compound ranges from about 25 parts to about 125 parts.

5. A controlled release plant nutrient dis-penser according to Claim 4, wherein the amount of said porosigen ranges from about 1.0 to about 30 parts by weight.

6. A controlled release plant nutrient dis-penser according to Claim 5, wherein the amount of ethylene by weight in said ethylene-vinyl acetate co-polymer ranges from about 80 percent to about 93 per-cent, wherein the amount of ethylene in said ethylene-propylene copolymer ranges from about 45 to about 75 percent by weight.

7. A controlled release plant nutrient dis-penser according to Claim 5, wherein the amount of said plant nutrient compound ranges from about 50 parts to about 100 parts, and wherein the amount of porosigen ranges from about 2.0 to about 12 parts by weight.

8. A controlled release plant nutrient according to Claim 2, wherein said porosigen has a solubility of less than 0.1 grams per 100 grams of water and is a compound and the various hydrates thereof having said solubility wherein the cation of said compound is selected from the group consist-ing of the alkaline metals, the alkaline earth metals, nickel, iron, zinc, silver, and tin, and wherein said compound has an anion selected from the group consisting of an oxide, a carbonate, bicarbonate, nitrate, nitrite, nitride, phosphate, phosphite, phos-phide, sulfate, sulfite, sulfide, and combinations thereof.

9. A slow release plant nutrient composi-tion according to Claim 2, wherein said porosigen has a solubility of from about 0.1 to about 100 grams per 100 grams of water and is a compound and the various hydrates thereof having such a solubility selected from the group consisting of the halogenated alkaline metals, the halogenated alkaline earth metals, halogenated nickel, halogenated tin, halo-genated silver, ammonium bromide, ammonium carbonate, ammonium bicarbonate, ammonium chlorate, ammonium chlorite, ammonium chloride, ammonium fluoride, ammonium sulfate, sodium carbonate, sodium bicarbonate, sodium silicate, and silicon dioxide.

10. A controlled release plant nutrient according to Claim 8, wherein said trace nutrient is a compound selected from the group consisting of zinc sulfate, zinc chloride, zinc carbonate, zinc oxide, zinc phosphate, zinc chlorate, zinc nitrate, the various hydrates of said zinc compounds, copper sulfate, copper carbonate, copper oxide, copper oxychloride, copper nitrate, copper phosphate, the. various hydrates of said copper compounds, iron chloride, iron sulfate, iron oxide, the various hydrates of said iron compounds, manganese oxide, manganese sulfate, manganese chloride, manganese nitrate, the various hydrates of said manga-nese compounds, boric acid, sodium biborate, the various hydrates of said boron compounds, molybdenum oxide, sodium molybdate, potassium molybdate, the various hydrates of said molybdenum compounds, cobalt sulfate, cobalt chlorate, cobalt nitrate, the various hydrates of said cobalt compounds, sodium selenate, selenium dioxide, selenium trioxide, selenium oxychloride, selenium disulfide, selenium sulfur oxide, magnesium carbonate, magnesium sulfate, magnesium nitrate, magnesium acetate, magnesium oxide, magnesium phos-phate, magnesium sulfite, and the various hydrates of said magnesium compounds, and combinations thereof,

11. A controlled release plant nutrient according to Claim 9, wherein said trace nutrient is a compound selected from the group consisting of zinc sulfate, zinc chloride, zinc carbonate, zinc oxide, zinc phosphate, zinc chlorate, zinc nitrate, the various hydrates of said zinc compounds, copper sulfate, copper carbonate, copper oxide, copper oxychloride, copper nitrate, copper phosphate, the various hydrates of said copper compounds, iron chloride, iron sulfate, iron oxide, the various hydrates of said iron compounds, manganese oxide, manganese sulfate, manganese chloride, manganese nitrate, the various hydrates of said manga-nese compounds, boric acid, sodium biborate, the various hydrates of said boron compounds, molybdenum oxide, sodium molybdate, potassium molybdate, the various hydrates of said-molybdenum compounds, cobalt sulfate, cobalt chlorate, cobalt nitrate, the various hydrates of said cobalt compounds, sodium selenate, selenium dioxide, selenium trioxide, selenium oxychloride, selenium disulfide, selenium sulfur oxide, magnesium carbonate, magnesium sulfate, magnesium nitrate, magnesium acetate, magnesium oxide, magnesium phos-phate, magnesium sulfite, and the various hydrates of said magnesium compounds, and combinations thereof.

12. A controlled-release plant nutrient according to Claim 10, wherein said trace nutrient is a compound selected from the group consisting of zinc sulfate, zinc chloride, zinc carbonate, zinc oxide, copper sulfate, copper carbonate, copper oxide, copper oxychloride, iron chloride, iron sulfate, iron oxide, manganese oxide, manganese sulfate, manganese chloride, boric acid, sodium biborate, molybdenum oxide, sodium molybdate, cobalt sulfate, sodium selenate, magnesium carbonate, magnesium sulfate, and combinations thereof.

13. A controlled release plant nutrient according to Claim 11, wherein said trace nutrient is a compound selected from the group consisting of zinc sulfate, zinc chloride, zinc carbonate, zinc oxide, copper sulfate, copper carbonate, copper oxide, copper oxychloride, iron chloride, iron sulfate, iron oxide, manganese oxide, manganese sulfate, manganese chloride, boric acid, sodium biborate, molybdenum oxide, sodium molybdate, cobalt sulfate, sodium selenate, magnesium carbonate, magnesium sulfate, and combinations thereof.

14. A controlled release plant nutrient according to Claim 12, wherein said porosigen is calcium carbonate.

15. A controlled release plant nutrient according to Claim 13, wherein said porosigen is selected from the group consisting of ammonium sul-fate, sodium bicarbonate, sodium carbonate, and sodium silicate.

16. A controlled release plant nutrient mix-ture according to Claim 9, wherein moisture removes said porosigen through dissolution and creates a porous network so that a plant nutrient within said mixture is released.

17. A controlled release plant nutrient mix-ture according to Claim 8, wherein said moisture slowly removes said porosigen through dissolution and creates a porous network so that a plant nutrient within said mixture is released.

18. A controlled release plant nutrient mix-ture according to Claim 14, wherein said moisture slowly removes said porosigen through dissolution and creates a porous network so that a plant nutrient within said mixture is released.

19. A controlled release plant nutrient mix-ture according to Claim 15, wherein said moisture slowly removes said porosigen through dissolution and creates a porous network so that a plant nutrient within said mixture is released.

20. A process of adding a controlled release plant nutrient mixture to a soil, which is characterized by applying the controlled release plant nutrient mix-ture of Claim 1 to the moist soil.

21. A process of adding a controlled release plant nutrient mixture to a soil, which is characterized by applying the controlled release plant nutrient mix-ture of Claim 2 to the moist soil.

22. A process of adding a controlled release plant nutrient mixture to a soil, which is characterized in applying the controlled release plant nutrient mix-ture of Claim 8 to the moist soil.

23. A process of adding a controlled release plant nutrient mixture to a soil, which is characterized in applying the controlled release plant nutrient mix-ture of Claim 9 to the moist soil.

24. A process of adding a controlled release plant nutrient mixture to a soil, which is characterized in applying the controlled release plant nutrient mix-ture of Claim 11 to the moist soil.

25. A process of adding a controlled re-lease plant nutrient mixture to a soil, which is characterized in applying the controlled release plant nutrient mixture of Claim 10 to the moist soil.