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Publication numberUSRE28688 E
Publication typeGrant
Application numberUS 05/385,050
Publication dateJan 20, 1976
Filing dateAug 2, 1973
Priority dateOct 31, 1960
Publication number05385050, 385050, US RE28688 E, US RE28688E, US-E-RE28688, USRE28688 E, USRE28688E
InventorsPaul M. Cook
Original AssigneeRaychem Corporation
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Solid heat-flowable dispersed phase in a crosslinked elastomer
US RE28688 E
Abstract
.Iadd.Heat recoverable articles of manufacture made from organic polymeric compositions are described. The compositions comprise a mixture of a thermoplastic resin material, or other organic, normally solid heat-flowable material, in an elastomeric material. A heat recoverable article obtained from these compositions is elastomeric in both its heat-unstable and heat-stable states. .Iaddend.
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Claims(35)
I claim:
1. An article of manufacture composed of an organic polymeric composition comprising a cross-linked elastomeric component having incorporated therewith and substantially uniformly distributed therein an organic, normally solid heat-flowable constituent having a softening temperature having above about 140° F., said heat-flowable constituent being present in an amount sufficient to hold said elastomeric component in a stretched, elastically deformed condition, said article being elastomeric and having a Young's modulus determined in accordance with ASTM D-638 in the range of from about 50 to about 3000 p.s.i. at storage temperatures and at the softening temperature of said heat-flowable constituent and being in a dimensionally heat-unstable condition capable of altering its physical form upon application of heat alone to soften said heat-flowable constituent, said article upon application of such heat assuming a dimensionally heat-stable condition, the article in its altered, heat-stable form being elastomeric and having a Young's modulus determined in accordance with ASTM D-638 in the range of from about 50 to about 3000 p.s.i.
2. The article of claim 1 wherein the elastomeric component is a polychloroprene rubber.
3. The article of claim 1 wherein the organic, normally solid heat-flowable constitutent is a siloxane resin.
4. The article of claim 1 wherein the organic, normally solid heat-flowable constituent is a coumarine-indene resin.
5. The article of claim 1 wherein the organic, normally solid heat-flowable constituent is a polyester resin.
6. The article of claim 1 wherein the organic normally solid heat-flowable constituent is an epoxy resin.
7. The article of claim 1 wherein the organic, normally heat-flowable constituent is a chlorinated naphthalene.
8. The article of claim 1 wherein the organic, normally solid heat-flowable constituent is a wax.
9. The article of claim 1 wherein the organic, normally solid heat-flowable constituent is a polystyrene.
10. The article of claim 1 wherein the elastomeric component is natural rubber.
11. The article of claim 10 wherein the organic, normally solid heat-flowable constituent is polyethylene.
12. The article of claim 1 wherein the elastomeric component is a silicone rubber.
13. The article of claim 1 wherein the elastomeric component is a chlorosulfonated polyethylene.
14. The article of claim 1 wherein the elastomeric component is a butadiene styrene copolymer.
15. The article of claim 1 wherein the elastomeric component is a butadiene-acrylonitrile copolymer.
16. The article of claim 1 wherein said elastomeric component is cross-linked by means of a chemical cross-linking agent.
17. The article of claim 1 wherein said elastomeric component is cross-linked by means of high energy radiation.
18. The article of claim 2 wherein the non-elastomeric organic constituent is a butadiene-styrene copolymer containing a major amount of styrene.
19. An article of manufacture composed of an organic polymeric composition comprising a cross-linked elastomer having incorporated therewith a thermoplastic resinous material, said article being elastomeric and having a Young's modulus determined in accordance with ASTM D-638 in the range of from about 50 to about 3000 p.s.i. at storage temperatures, said thermoplastic resinous material being present in an amount sufficient to hold said article in a deformed heat-unstable condition, said article being in a dimensionally heat-unstable condition capable of altering its physical form upon application of heat alone to assume a dimensionally heat-stable condition, the article in its altered, heat-stable form being elastomeric and having a Young's modulus determined in accordance with ASTM D-638 in the range of from about 50 to about 3000 p.s.i.
20. The article of claim 19 wherein the thermoplastic material is polyvinyl chloride.
21. The article of claim 19 wherein the thermoplastic material is a polyolefin.
22. The article of claim 19 wherein the elastomer is a polychloroprene rubber and wherein the thermoplastic material is polyethylene.
23. The article of claim 19 wherein the elastomer is polychloroprene rubber and wherein the thermoplastic material is polyvinyl chloride.
24. The article of claim 19 wherein the elastomer is a silicon rubber and wherein the thermoplastic material is polyethylene.
25. The article of claim 19 wherein the elastomer is a silicon rubber and wherein the thermoplastic material is a siloxane resin.
26. The article of claim 19 wherein the elastomer is a silicon rubber and wherein the thermoplastic material is polyvinyl chloride.
27. The article of claim 19 wherein the elastomer is a chlorosulfonated polyethylene.
28. The article of claim 19 wherein the elastomer is a chlorosulfonated polyethylene and the thermoplastic material is polyvinyl chloride.
29. The article of claim 19 wherein the elastomer is a butadiene-styrene copolymer and wherein the thermoplastic material is polyethylene.
30. The article of claim 19 wherein the elastomer is a butadiene-styrene copolymer and wherein the thermoplastic material is polyvinyl chloride.
31. The article of claim 19 wherein the elastomer is a butadiene-acrylonitrile copolymer and the thermoplastic material is polyethylene.
32. The article of claim 18 wherein the elastomer is a chlorosulfonated polyethylene and wherein the thermoplastic material is polyethylene.
33. The article of claim 24 wherein the thermoplastic material includes a butadiene-styrene copolymer containing a major amount of styrene.
34. The article of claim 19 wherein the elastomer is a silicone rubber and wherein the thermoplastic material is polystyrene.
35. An article comprising a composition by weight of one hundred parts of silicon-rubber and 5-50 parts of polyethylene, said article being formed and cured to obtain original dimensions and said article being stretched at a temperature of 150° C. from said original dimensions to stretched dimensions, said stretched dimensions being stable at room temperature, said article substantially resuming said original dimensions upon being heated. .Iadd. 36. An article of manufacture composed of an organic polymeric composition comprising a cross-linked elastomeric component having incorporated therewith and substantially uniformly distributed therein an organic, normally solid heat-flowable constituent having a softening temperature above about 140° F., said heat-flowable constituent being present in an amount sufficient to hold said elastomeric component in a stretched, elastically deformed condition, said article being elastomeric at storage temperatures and at the softening temperature of said heat-flowable constituent and being in a dimensionally heat-unstable condition capable of altering its physical form upon application of heat alone to soften said heat-flowable constituent, said article upon application of such heat assuming a dimensionally heat-stable condition, the article in its altered, heat-stable form being elastomeric. .Iaddend..Iadd. 37. The article of claim 36 wherein the elastomeric component is a polychloroprene rubber. .Iaddend..Iadd. 38. The article of claim 36 wherein the organic, normally solid heat-flowable constituent is a siloxane resin. .Iaddend..Iadd. 39. The article of claim 36 wherein the organic, normally solid heat-flowable constituent is a coumarine-indene resin. .Iaddend..Iadd. 40. The article of claim 36 wherein the organic, normally solid heat-flowable constituent is a polyester resin. .Iaddend. .Iadd. 41. The article of claim 36 wherein the organic, normally solid heat-flowbale constituent is an epoxy resin. .Iaddend..Iadd. 42. The article of claim 36 wherein the organic, normally heat-flowable constituent is a chlorinated naphthalene. .Iaddend..Iadd. 43. The article of claim 36 wherein the organic, normally solid heat-flowable constituent is a wax. .Iaddend..Iadd. 44. The article of claim 36 wherein the organic, normally solid heat-flowable constituent is a polystyrene. .Iaddend..Iadd. 45. The article of claim 36 wherein the elastomeric component is natural rubber. .Iaddend..Iadd. 46. The article of claim 45 wherein the organic, normally solid heat-flowable constituent is polyethylene. .Iaddend..Iadd. 47. The article of claim 36 wherein the elastomeric component is a silicone rubber. .Iaddend..Iadd. 48. The article of claim 36 wherein the elastomeric component is a chlorosulfonated polyethylene. .Iaddend..Iadd. 49. The article of claim 36 wherein the elastomeric component is a butadiene-styrene copolymer. .Iaddend..Iadd. 50. The article of claim 36 wherein the elastomeric component is a butadiene-acrylonitrile copolymer. .Iaddend..Iadd. 51. The article of claim 36 wherein said elastomeric component is cross-linked by means of a chemical cross-linking agent. .Iaddend..Iadd. 52. The article of claim 36 wherein said elastomeric component is cross-linked by means of high energy radiation. .Iaddend. .Iadd. 53. The article of claim 37 wherein the non-elastomeric organic constituent is a butadiene-styrene copolymer containing a major amount of styrene. .Iaddend..Iadd. 54. An article of manufacture composed of an organic polymeric composition comprising a cross-linked elastomer having incorporated therewith a thermoplastic resinous material, said article being elastomeric at storage temperatures, said thermoplastic resinous material being present in an amount sufficient to hold said article in a deformed heat-unstable condition, said article being in a dimensionally heat-unstable condition capable of altering its physical form upon application of heat alone to assume a dimensionally heat-stable condition, the article in its altered, heat-stable form being elastomeric. .Iaddend..Iadd. 55. The article of claim 54 wherein the thermoplastic material is polyvinyl chloride. .Iaddend..Iadd. 56. The article of claim 54 wherein the thermoplastic material is a polyolefin. .Iaddend..Iadd. 57. The article of claim 54 wherein the elastomer is a polychloroprene rubber and wherein the thermoplastic material is polyethylene. .Iaddend..Iadd. 58. The article of claim 54 wherein the elastomer is polychloroprene rubber and wherein the thermoplastic material is polyvinyl chloride. .Iaddend..Iadd. 59. The article of claim 54 wherein the elastomer is a silicon rubber and wherein the thermoplastic material is polyethylene. .Iaddend. .Iadd. 60. The article of claim 54 wherein the elastomer is a silicon rubber and wherein the thermoplastic material is a siloxane resin. .Iaddend..Iadd. 61. The article of claim 54 wherein the elastomer is a silicon rubber and wherein the thermoplastic material is polyvinyl chloride. .Iaddend..Iadd. 62. The article of claim 54 wherein the elastomer is a chlorosulfonated polyethylene. .Iaddend..Iadd. 63. The article of claim 54 wherein the elastomer is a chlorosulfonated polyethylene and the thermoplastic material is polyvinyl chloride. .Iaddend..Iadd. 64. The article of claim 54 wherein the elastomer is a butadiene-styrene copolymer and wherein the thermoplastic material is polyethylene. .Iaddend..Iadd. 65. The article of claim 54 wherein the elastomer is a butadiene-styrene copolymer and wherein the thermoplastic material is polyvinyl chloride. .Iaddend..Iadd. 66. The article of claim 54 wherein the elastomer is a butadiene-acrylonitrile copolymer and the thermoplastic material is polyethylene. .Iaddend..Iadd. 67. The article of claim 53 wherein the elastomer is a chlorosulfonated polyethylene and wherein the thermoplastic material is polyethylene. .Iaddend..Iadd. 68. The article of claim 59 wherein the thermoplastic material includes a butadiene-styrene copolymer containing a major amount of styrene. .Iaddend..Iadd. 69. The article of claim 54 wherein the elastomer is a silicone rubber and wherein the thermoplastic material is polystyrene. .Iaddend. .Iadd. 70. An article of manufacture composed of an organic polymeric composition comprising a cross-linked elastomeric component having incorporated therewith and substantially uniformly distributed therein as a disperse phase an organic, normally solid heat-flowable constituent having a softening temperature above about 140° F., said heat-flowable constituent being present in an amount sufficient to hold said elastomeric component in a stretched, elastically deformed condition, said article being elastomeric at storage temperatures and at the softening temperature of said heat-flowable constituent and being in a dimensionally heat-unstable condition capable of altering its physical form upon application of heat alone to soften said heat-flowable constituent, said article upon application of such heat assuming a dimensionally heat-stable condition, the article in its altered, heat-stable form being elastomeric. .Iaddend..Iadd. 71. An article of manufacture composed of an organic polymeric composition comprising a cross-linked elastomer having incorporated therewith as a disperse phase a thermoplastic resinous material, said article being elastomeric at storage temperatures, said thermoplastic resinous material being present in an amount sufficient to hold said article in a deformed heat-unstable condition, said article being in a dimensionally heat-unstable condition capable of altering its physical form upon application of heat alone to assume a dimensionally heat-stable condition, the article in its altered, heat-stable form being elastomeric. .Iaddend..Iadd. 72. An article of manufacture composed of an organic polymeric composition comprising from about 50 to about 95 parts by weight of a cross-linked elastomeric component having incorporated therewith and substantially uniformly distributed therein from about 5 to about 50 parts by weight of an organic normally solid heat-flowable constituent having a softening temperature above about 140° F., said heat-flowable constituent being present in an amount sufficient to hold said elastomeric component in a stretched, elastically deformed condition, said article being elastomeric at storage temperatures and at the softening temperature of said heat-flowable constituent and being in a dimensionally heat-unstable condition capable of altering its physical form upon application of heat alone to soften said heat-flowable constituent, said article upon application of such heat assuming a dimensionally heat-stable condition, the article in its altered, heat-stable form being elastomeric. .Iaddend..Iadd. 73. An article of manufacture composed of an organic polymeric composition comprising from about 50 to about 95 parts by weight of a cross-linked elastomer having incorporated therewith from about 5 to about 50 parts by weight of a thermoplastic resinous material, said article being elastomeric at storage temperatures, said thermoplastic resinous material being present in an amount sufficient to hold said article in a deformed heat-unstable condition capable of altering its physical form upon application of heat alone to assume a dimensionally heat-stable condition, the article in its altered, heat-stable form being elastomeric.
Description

This invention relates to elastomeric materials and products and has particular reference to the production of elastomeric articles having heat-activated dimensional memory characteristics.

Elastomers or rubbers are important products being used in a very large number of applications for commercial uses and constituting a very large and important market. Elastomers are generally called rubbers. The word "rubber" is used in two different senses, originally being applied only to the natural product rubber. Recent use, however, has been the development of a very large number of synthetic rubbers having a wide variety of chemical constitutions, so that today the term rubber is commonly employed not to characterize the specific chemical substance obtained from the rubber tree, but to characterize a state of matter, i.e., any material comparable to natural rubber and possessing the physical property of elastic extensibility. Hence, an elastic material or rubber will stretch an amount directly proportional to the applied force and will recover upon the removal of the force.

The principal property of rubbers or elastomers which leads to their wide usage is the property of elastic deformation and the resulting flexibility and resilience of articles made of such materials. The most important commercial use of rubbers today is for the production of rubber tires for automobiles and other wheeled vehicles. The important factor in the use of rubber in this application is the property of elastic deformation, the ability to deform and recover quickly serving to cushion the blows from surface irregularities as the tire travels along the road. Although rubber materials in general have relatively poor toughness and abrasion resistance, the significant factor in terms of the long life of such materials in difficult physical environments is the fact that the application of wearing surfaces, such as sharp edges of stones or pebbles, will cause the rubber to deform and assume a new shape, wherein the applied stress is redistributed over a much wider area, thereby causing less wear and abrasion. Upon removal of the stress the rubber returns to its original vulcanized size and shape. On the other hand, a non-elastic thermoplastic material subjected to the same conditions would, because of a high unit pressure, deform by passing the yield point and thereby lead to a permanent deformation which is not recoverable.

A series of important commercial products have been developed over the past few years, based upon the property of plastic memory. Two different techniques are used for the production of such so-called dimensionally heat-unstable or perhaps more properly "heat-recoverable" thermoplastic materials, i.e., products which change their size and shape upon the application of heat without the necessity for the application of external forces. The first technique is that of imparting a considerable amount of built-in stresses during fabrication, followed by a cold temperature quench to hold the molecules in the stressed condition. Upon careful heating, this fabricated product will tend to reform or recover to the original configuration. However, upon slight over heating, or upon heating too long, such thermoplastic materials will melt and relax to a new size and shape. More recently, a series of cross-linked thermoplastic products have been fabricated wherein the memory characteristic of the plastic is obtained by a 3-dimensional network rather than built-in stresses in a 2-dimensional system. For example, a cross-linked polyethylene can be heated to above the crystalline melting temperature, at which point it behaves as an elastomer wherein the application of a force will lead to a deformation directly proportional to that force. If, while the cross-linked polyethylene is in the elastomeric state, a force is applied to cause deformation proportional to the force, and this is followed by a reduction in temperature, crystallization will take place which will maintain the cross-linked polyethylene in its deformed condition. Upon the subsequent application of heat sufficient to remelt the crystals (in the absence of a deforming force), the material will rapidly recover to the exact size and shape in which it has been cross-linked. However, such materials, being of crystalline thermoplastic nature, will exhibit normal thermoplastic properties while in the crystalline state, and will act as elastomers only at the elevated temperatures wherein the crystals are melted.

A very large variety of applications of commercial importance can be envisioned for elastomeric articles which are heat-recoverable, i.e., having the properties of changing shape and/or size upon the application of heat without the necessity of the application of external forces, but exhibiting essentially the elastomeric property of elastic deformation under stress. The commercial importance of such a series of products is believed to be clear to anyone familiar with rubber and rubber-like products.

Accordingly, it is a primary object of the present invention to provide novel elastomeric articles of manufacture capable of changing size and/or shape upon the application of heat.

A further object of the present invention is to provide novel elastomeric articles possessing dimensional memory characteristics and capable of returning to an original, predetermined, vulcanized or cross-linked configuration upon the application of heat.

Another object of this invention is to provide a novel process for the production of elastomeric articles.

Still another object of the present invention is to provide a novel process for the production of elastomeric articles having dimensional memory characteristics.

Other objects and advantages of this invention it is believed will be readily apparent from the following detailed description of preferred embodiment thereof.

Briefly, this invention comprehends within its scope the discovery that elastomer products can be made having the properties of elastic deformation substantially equal to true elastomers, and at the same time having the properties of changing shape and/or size merely upon the application of heat and recovering to the original, vulcanized or cross-linked shape and size. As used in the specification and claims herein, the term "elastomeric" and similar terms are intended to mean and include products or articles of any configuration having a Young's modulus in the range of from about 50 to 3,000 p.s.i. and exhibitng the characteristic rubber-like elastic deformability under the action of comparatively small stresses, .Iadd.and .Iaddend.returning substantially to the original size and shape upon the removal of the applied stress. The Young's modulus is measured at room temperature and determined in accordance with ASTM D638-58T. As will be more fully brought out below, an essential aspect of the present invention is that the elastomeric component of the articles of the present invention must be cross-linked. As used in the specification and claims herein, the term "cross-linked" and similar terms as applied to the articles of the present invention are intended to mean and comprehend a 3-dimensional molecular network having a modulus of elasticity of at least about 10 p.s.i., as measured at a temperature of 50° C. above the softening or flow temperature of the thermoplastic or resinous material component, as hereinafter defined. For the purpose of this definition, the modulus of elasticity is determined in accordance with the method of Black, R. M., The Electrical Manufacturer, October 1957, as is further described below. The softening or flow temperature is measured in accordance with ASTM D569-48.

The heat-recoverable elastomeric materials or articles of the present invention are produced by forming or fabricating into the desired configuration a composition comprising either (1) an uncured elastomer in which is incorporated a normally solid, heat-flowable material capable of being formed by the application of heat and an external force, e.g., a thermoplastic or non-elastic resinous material, or (2) a plasticized thermoplastic material having elastomeric properties as herein defined, such as a plasticized polyvinyl chloride; then vulcanizing or cross-linking the formed composition or article; heating it to a temperature at which the thermoplastic or resinous material loses the major portion of its strength, e.g., a temperature above the thermoplastic melting or softening point or range; then applying an external force or forces to deform the article to the desired heat-recoverable configuration; and then quenching or cooling the article to a temperature at which the thermoplastic or resinous material regains its strength, e.g., to a temperature below the thermoplastic melting or softening point or range. After such cooling, the external force or forces are released and the article remains in the heat-recoverable configuration, not returning to its original vulcanized or cross-linked configuration, as would be the case with a true elastomer. The non-elastic thermoplastic or resinous material in some manner holds the article in the heat-recoverable form until the article has been heated to or above the softening temperature as hereinabove defined, whereupon the unrestrained and heated article will return to the original as-formed, vulcanized or cross-linked configuration. The essential feature of the present invention resides in the fact that the cooled or quenched heat-recoverable article has resiliency and exhibits the property of elastic deformation upon the application of force.

More specifically, the squence of steps utilized in carrying out the process of the present invention is as follows.

(1) Intimately mixing the thermoplastic or resinous material with the elastomer or rubber gum in the uncured state, or mixing the plasticizer and cross-linkable thermoplastic material. The usual fillers, extenders, curing agents, accelerators and the like are included at this stage if desired, depending upon the desired properties of the final article.

(2) The composition formed in step 1 is then fabricated or formed into an article of predetermined configuration and cross-linked or vulcanized. The cross-linking or vulcanization may be accomplished by a chemical cross-linking technique wherein a vulcanizing agent or cross-linking agent is added, the subsequent application of heat and/or pressure bringing about the desired cure. Alternatively, the cross-linking may be brought about by exposure of the article to high energy radiation such as from an accelerated electrons, X-rays, gamma rays, alpha particles, beta particles, neutrons, etc., without the necessity for the addition of cross-linking or vulcanizing agents. Further, the cross-linking or vulcanization can be accomplished by a combination of these two techniques. The degree of chemical cross-linking or the radiation dosage are sufficient to produce at least the minimum high temperature modulus of elasticity of 10 p.s.i. referred to hereinabove. Generally, the minimum radiation dosage is of the order of 2×106 rads.

(3) The cross-linked and cured article is then heated to a temperature sufficiently high to soften the thermoplastic component, i.e., above the melting or softening point or range, and while the material is maintained at that temperature an external force or forces are applied to change the size and/or shape of the article to a more convenient configuration for later application and use.

(4) The deformed article is cooled or quenched while still under the external deforming stresses, whereupon the article will retain the deformed shape upon the release of the external stresses. The article is now in the heat-recoverable state but may be left for an indefinite period of time at room temperature without danger of its recovering back to its original size and shape.

The use of articles produced in accordance with the above process is simple and straight-forward. The article is simply put into the position for use and heat is applied to it, whereupon the article will recover quickly to its original vulcanized or cross-linked configuration. A particularly useful example of an article within the scope of the present invention is heat-recoverable elastomeric tubing. In producing such articles, the starting material, such as a mixture of rubber and thermoplastic or resinous material, is properly compounded and extruded into tubing form. The extruded tubing is cured by radiation or by the proper application of heat with a cross-linking or vulcanizing agent, resulting in a cured, rubber-like tough, strong tubing. This tubing is then heated to a temperature above the thermoplastic melting or softening point or range, followed by the application of a deformation force while the tubing is at the elevated temperature, as by the application of pressure upon the inside of the tubing or a reduction of pressure on the outside of the tubing, resulting in an expansion of the tubing. Quenching or cooling of the thus formed tubing while it is in the expanded state locks the tubing in that state. The tubing has a diameter greater than the original diameter of the extruded and cured tubing and it will remain in this increased diameter condition indefinitely while at room temperature. The tubing is thus available for application at any time. For example, the expanded tubing is placed over articles which are desired to be encapsulated, adequate clearance between the tubing and the articles being provided to permit easy application. The brief application of heat to the deformed tubing will cause it to shrink and attempt to return to its original vulcanized or cross-linked dimensions. This recovery permits the tubing to tightly clad and cover the article which had been inserted therein prior to application of the heat. Such an article and process finds great utility in the covering of a group of wires cabled together such as in wire harness and the like, the resulting rubber jacket providing the desired toughness abrasion resistance and other properties of rubber or elastomeric materials. This method of encapsulating cable wires and the like is far superior from the standpoint of expense and ease of application to the acepted techniques of application of air pressure to temporarily expand tubing during the application of the tubing to the cabled wires, or the difficult, cumbersome and expensive method of application of uncured rubber jackets followed by heat or radiation cure in place.

It will be readily apparent that heat-expandable rather than heat-shrinkable elastomers can be made in accordance with the present invention. Thus, for example, a heat-expandable elastomeric tubing can be made by the process described above, except that rather than expanding the tubing in the heated condition, it is longitudinally stretched while heated, resulting in a contraction of the tubing diametrically as well as extension in length. Quenching and cooling of the thus formed tubing while it is in the elongated, contracted state locks the tubing in that state, the tubing then being available for use. For example, the tubing can be placed inside of a pipe or tube, the brief application of heat causing it to expand and to attempt to return to its original vulcanized or cross-linked condition, this recovery permitting the tubing to tightly engage the inside of the pipe forming a lining thereof.

Another example of an article within the scope of the present invention is a molded covering for cable breakout legs, such article being Y-shaped or the like, adapted for application onto a cable breakout or transition and shrinking into place thereupon upon the application of heat.

Any elastomeric material may be used in carrying out the present invention, for example: nautral rubber; butadiene-styrene copolymers (GR-S); butadiene-acrylonitrile copolymers (Buna N); isoprene-isobutylene copolymers (Butyl); polyisoprene; polybutadiene; polysulfide (Thiokol); polychloroprene (neoprene); polysiloxane (silicone); fluorocarbon (viton A, etc.); chlorosulfonated polyethylene (Hypalon); plasticized polyvinyl chloride; polybutene.

For each elastomeric material, a wide range of thermoplastic or resinous materials, generally added in relatively small proportions, have been found which will produce the desired results in accordance with the present invention. Such thermoplastic or resinous materials include: acrylic plastics; polyethylene; polytetrafluoroethylene; polychlorotrifluoroethylene; polyvinyl formal; polyvinyl butyral; polyvinyl chloride; vinyl chloride-vinyl acetate copolymers; polyvinylidene chloride; polystyrene; polycarbonates; polyamides; cellulose acetate butyrate; cellulose acetate propionate; ethyl cellulose; polypropylene; ethylenepropylene copolymers; epoxy resins; polyester resins.

It has been found that from the standpoint of commercial practability, for each combination of each thermoplastic or resinous material and each elastomer, there is a narrow range of proportions of the thermoplastic or resinous materials which will accomplish the desired result. The addition of too small a quantity of the thermoplastic or resinous material will not produce the desired permanent deformation upon the subsequent cooling after deforming at elevated temperatures. The addition of too high an amount of the thermoplastic or resinous material will result in the article assuming properties more closely allied to the thermoplastic or resinous materials rather than retaining the properties of the elastomeric or rubber-like materials. Thus, it is evident that for each system under consideration, in order to obtain optimum properties a relatively narrow range of concentrations must be observed. However, it is possible to impart memory characteristics to elastomers within a range of concentrations of the thermoplastic or resinous material of from approximately 5 to 50% by weight, based upon the total weight of the thermoplastic or resinous material and elastomer. In general, the lower modulus elastomers require less thermoplastic or resinous material to accomplish the desired result, while the higher modulus elastomers require more thermoplastic or resinous material. Further, the nature of the memory additive itself is important and certain materials will impart greater memory characteristics than others. For example, high density, high molecular weight polyethylene is a better memory additive than is low density, low molecular polyethylene. A further restricted requirement in the practice of the present invention is the selection of suitable curing agents and/or the use of a composition susceptible to radiation vulcanization or cross-linking.

Those skilled in the art of rubber chemistry and the art of proper compounding of rubber-like materials, will understand that in the practice of this invention a very wide variety of properties are obtainable and that normal rubber compounding techniques will apply, modified only as required by the inclusion of the thermoplastic material.

As will be apparent from the above, the most important commercial applications for the articles of the present invention lie in applications or articles which permit the deformed configuration to be retained at room temperature and for it to be released upon the application of heat above room temperature. For convenience and practicality, it is important that the articles can be shipped in normal fashion without having to cool them to below room and weather temperature conditions. This permits standard, easy packaging and straight-forward commercial applications. In addition, a normal requirement is that the articles be able to withstand temperatures normally encountered in weather conditions around the world and still prevent premature recovery of the article to its predetermined size and shape. Thus, in the specific examples given below, materials have been compounded specifically to meet this requirement, and to not shrink or change in shape even upon the application of temperatures encountered in the tropics or in warehouses where temperatures as high as 140° F. are reached.

To simplify the practice of the present invention it is necessary to select thermoplastic or resinous materials for addition to each rubber which can be easily mixed and dispersed therewith. Although almost all thermoplastic materials can be used with each rubber, it is necessary for simplicity in commercially feasible practice, to pick material which can be mixed together and which are compatible, the quick and easy dispersion of the thermoplastic material in the rubber material being a necessary commercial consideration. Therefore, the selection of a thermoplastic or resinous material which is similar in chemical structure to the elastomer is preferred in carrying out the invention.

The specific examples set forth below are illustrative of the articles and processes of the present invention, but it is to be understood that the invention is not to be limited to the specific details thereof.

The following methods of sample preparation and test procedures were utilized in carrying out the specific examples:

Mixing technique

The method of incorporating the resin into the elastomer is important. If the resin is not dispersed thoroughly and completely throughout the elastomer, the properties of the compound are impaired. The preferred method used in the examples is as follows: A quantity of the resin is placed on a 2-roll mixer operating at a temperature sufficient to soften or melt the resin. The resin is milled until completely softened and then an equal amount of elastomer is slowly added to the resin. Mixing is continued until an homogeneous composition is secured. This is removed from the rolls and cooled. The balance of the mixture is done by placing a requisite amount of mixture on a cold 2-roll mill and adding the additional elastomer along with antioxidants, accelerators, fillers, plasticizers, etc., as required.

Molding technique

Molded slabs were prepared using a 6" × 6" × .062" rubber mold as described in ASTM D-15. The time-temperature cycles were varied depending upon the particular rubber-memory plastic system.

Irradiation technique

Samples were irradiated using a General Electric resonant transformer operating effectively at 850 kv. and 5 milliamps. The samples were cross-fired to insure uniform irradiation through the sample, and the irradiation dose was predetermined by Faraday cage measurements. A well-grounded thermocouple in contact with the sample served to measure the temperature of the sample.

Tensile strength, Young's modulus and elongation

All tests were run at room temperature using the variable speed automatic recording Instron tester. All samples were tested at a crosshead speed of 20+1 inch per minute.

The tensile strength and elongation were determined in accordance with ASTM D-412. .[.Young's modulus was determined in accordance with ASTM D-638..].

Determination of modulus of elasticity and ultimate strength

The basic technique for determining these values has been described by Black, R. M., The Electrical Manufacturer, October 1957.

For this investigation, a similar apparatus was used, consisting of a vertical glass tube with a glass jacket (similar to a Liebig condenser). The jacketed space was filled with boiling cyclohexanone and this kept the interior tube at a temperature of 150° C.

Strips of the cross-linked compound were prepared (.062" × .125" × 6"). Bench marks 1" apart were stamped in the middle portion of the sample. This strip was placed in the center tube and fastened securely at the top. Stress was applied to the sample by hanging weights on the bottom of the sample. Strain was measured by noting the increase in distance between the bench marks, the measurement being made at equilibrium after each addition of weight. The weights were increased until the sample broke.

From the stress-strain data obtained, a modulus chart was prepared. The slope of the line was determined as the M100 figure, or stress necessary to effect a strain of 100%. The breaking force was recorded as the Ultimate Strength or U.S.

Importance of modulus of elasticity-ultimate strength relationship

For memory devices the modified elastomer must have certain physical properties. The importance of tensile strength, elongation, cold bend, etc., for proper functions are well known to those skilled in the art and need not be expounded here.

However, for heat shrinkable devices, the M100-U.S. ratio is a vital one. For the best use of such devices, either tubing or molded items, they must be capable of a significant amount of stretching or expansion without splitting at elevated temperatures. The M100 figure expresses the stress necessary to effect a stretch of 100% at a temperature above the resin softening point. The Ultimate Strength (U.S.) is the stress at the breaking point. The elongation at the breaking point expressed in percent is ##EQU1## Thus the larger the ratio, the more a compound can be stretched without danger of breaking.

Description of plastic memory test

Strips of cross-linked compound, 1/8" × .062" × 6" were marked in the middle with 2 parallel ink impressions 1" apart. The strip was heated 1 minute in a 150° C. glycerine bath, stretched until the 1" lines were 3 inches apart (200% stretch) where possible, removed from the hot bath and plunged into cold water. Five minutes after the cooling, the distance between the marks was measured as the extended length. This distance was expressed a percent increase in length over the original 1" and recorded as the "Memory." Twenty-four hours later the extended strip was placed in the 150° C. glycerine bath for 1 minute and allowed to freely retract or shrink. It was then cooled and the distance measured between the marks as the retracted distance. The "Retraction," calculated as a percentage as follows, was recorded: ##EQU2##

Following is a glossary of trademarks identifying the various materials used in carrying out the specifc examples:

A 34:

alathon 34

A branched chain polyethylene

Density 0.93 g./ml.

Melt Index 3

Acrawax B:

A synthetic wax

Melting point 82° C.

Agerite Resin D:

Polymerized trimethyl dihydroquinoline

Antioxidant

Altax:

2,2' benzothiazyl disulfide

Rubber accelerator

Asrc 3105:

a butadiene-styrene copolymer

23% styrene

Atlac 382:

A polyester resin, a reaction product of bisphenol with fumaric or maleic anhydride

Chemigum N3:

A butadiene-acrylonitrile copolymer

50% acrylonitrile

Cumar S:

A coumarine-indene resin

Melting Point 90° C.

Cumate:

Copper dimethyldithiocarbamate

Rubber accelerator

Dotg:

accelerator

Di-o-tolyl-guanadine

Epon 1031: An epoxy resin

Flexol TOF:

Trioctyl phosphate

Plasticizer

Geon 101 EP: A general purpose polyvinyl chloride resin

Halowax 2141: A

A chlorinated naphthalene-approximately 50% chlorine

Melting point 131° C.

Hi-Fax 1400E:

A linear polyethylene

Density 0.947 g./ml.

Melt Index 0.3

Hypalon 40: A chlorosulfonated polyethylene Methyl Tuads:

Tetramethylthiuram disulfide

Rubber accelerator

Jzt:

antioxidant

N-n' diphenyl-p-phenylenediamine

Kadox 15:

A french process zinc oxide

Particle size 0.11 micron

0.01% acidity as SO3. Used as a free radical promoter in sulfur cross-linking reactions

Lectro 78:

Tetrabasic lead fumarate

Stabilizer or acid-acceptor for polyvinyl chloride

Maglite D:

Light calcined magnesium oxide

Particle size .09 micron. Used as an acid-acceptor in Neoprene Cures

Methyl Zimate:

Zinc di methyl dithiocarbamate

Rubber accelerator

Marbon 8000:

A butadiene-styrene copolymer

85% styrene

Neoprene W:

Elastomer

A stabilized polychloroprene

Contains no sulfur

Ottacide P:

Fungicide

Derivative of p-chloro meta xylanol

Resin R-4281: A low molecular weight siloxane polymer

Resin Z-6018; A low molecular weight siloxane resin

Silastic 82U:

A general purpose silicone rubber of approximately 80 Shore A durometer hardness

Non-catalyzed

Silastic 916U:

An extremely low temperature silicon rubber stock of approximately 50 Shore A durometer hardness

Non-catalyzed

Smoked sheet: Natural rubber-Commercial No. IX grade

Sterling S.O. Filler. Semi-reinforcing oil-type furnace black. Particle size 41 millimicrons.

Tetrone A:

Dipentamethylene thiuramtetrasulfide

Rubber accelerator

Processor oil:

Circo light process oil

A general purpose naphthenic-type softener and process aid

Stearite:

Single pressed, fish oil base stearic acid

Free radical promoter

Sterling V:

Filler

A semi reinforcing oil-type furnace black

Particle size 51 millimicrons

Styron 666: A general purpose polystyrene thermoplastic

Tenite 812:

A branched chain polyethylene

Density 0.915 g./ml.

Melt Index 200

Thermax:

A furnace type carbon black, nonreinforcing

Particle size 320-472 millimicrons

Thiate A: Thio hydropyrimidene, accelerator

Tube brand sulfur:

Commercial rubber makers grade

Conditioned with MgCO3 for long flowing

Vancide 51Z:

Fungicide

A mixture of zinc dimethyl dithiocarbamate and zinc 2-mercaptobenzothiazole

Varox: A peroxide cross-linking agent containing 2.5 bis

(tert-butyl peroxy), 2,5-dimethyl hexane coated onto

an inert mineral carrier

Zetaz:

Accelerator

Zinc salt of 2-mercaptobenzothiazole 6001 or DMD-6001 Polyethylene:

High density polyethylene

Density 0.95 g./ml. Melt Index 2.0

In the examples, the relative amounts set forth opposite the ingredients of the compositions are parts by weight, unless specifically indicated otherwise.

EXAMPLE I

In carrying out this example several specimens comprising polychloroprene elastomer and polyvinyl chloride were made and tested. As indicated by the data set forth below, as little as 10% of polyvinyl chloride, based on the total of the polyvinyl chloride and elastomer, imparts memory properties to the article in accordance with the invention. By increasing the amount of polyvinyl chloride the memory properties are progressively improved, excellent properties being obtained with as much as 40% polyvinyl chloride without sacrifice in tensile strength and with substantial retention of the elastomeric properties of the elastomer. The followinge compositions or mixes were press cured for 10 minutes at 350° F.:

______________________________________Mixes       1         2         3       4______________________________________Geon 101 EP 10        20        30      40Neoprene W  90        80        70      60JZF         2         2         2       2Stearic acid       1         1         1       1Vancide 51Z 1         1         1       1Maglite D   4         4         4       4Sterling V  15        15        15      15Flexol TOF  9.2       8.4       7.6     6.8ZnO         5         5         5       5______________________________________

______________________________________TENSILE AND ELONGATION______________________________________    Average    P.s.i.    Percent      .[.Young's              elongation   modulus                           (p.s.i.)______________________________________Specimen:1          1,151       533          1132          1,146       457          1783          1,094       407          3604          917         193          656.].______________________________________

______________________________________ELASTIC MODULUS AND ULTIMATESTRENGTH AT 150° C.     M100 (p.s.i.)                  U.S. (p.s.i.)______________________________________Specimen:1           79             1942           70             1873           68             2184           63             133______________________________________

______________________________________MEMORY CHARACTERISTICS        1      2        3        4______________________________________Memory, percent          40       80       130    200Retraction, percent          100      100      100    100______________________________________
EXAMPLE II

This example illustrates that a wide variety of thermoplastics, resins and waxes can be incorporated in polychloroprene compositions to produce articles within the scope of this invention. The basic formulation was as follows:

Effect of various memory plastics in heat shrinkable neoprene rubber

Compounds were prepared as described in mixing procedure.

______________________________________BASIC FORMULA______________________________________                  PartsMemory ingredient      35Neoprene W             65Stearic acid           1MgO                    4Sterling V             15Vancide 51Z            1Flexol TOF             5ZnO                    5JZF                    2______________________________________

Test specimen slabs made up using the memory ingredient indicated were press cured for 20 minutes at 340° F. and tested with the following results:

__________________________________________________________________________   Specimen No.   1   2  3    4   5   6  7    8    9   10 11   12  13__________________________________________________________________________   Memory ingredient   Sili-       Cu-         Hal-                       Acro-            Ala-                                           6001 Mar-   cone       mar          Atlac               Epon                   owax                       wax                          Styron                               Geon Tenite                                        thon                                           poly-                                                bon Hi-Fax   R 4281       S  382  1031                   2141                       B  666  101 EP                                    812 34 ethylene                                                8000                                                    1400__________________________________________________________________________Tensile strength (p.s.i.)   926 959          1,062               736 1,157                       384                          1,071                               1,479                                    770 826                                           985  1,206                                                    1,144Elongation (percent)   480 510          410  180 460 400                          420  317  200 230                                           252  518 338M100 (p.s.i.)   58  76 73   123 36  35 56   109  32  45 70   38  60U.S. (p.s.i.)   288 121          251  222 218 56 182  390  100 120                                           200  130 190Memory (percent)   180 190          200  150 70  190                          200  200  125 100                                           100  100 150Retraction (percent)   100 94 100  93  100 100                          95   100  86  100                                           100  82  100__________________________________________________________________________
EXAMPLE III

This example illustrates that the conventional polychloroprene rubber accelerators function as such in the compositions of the present invention. In carrying out this example the following compositions were press cured for 10 minutes at 350° F.:

______________________________________Specimen No    1      2      3    4    5    6______________________________________Geon 101 EP    40     40     40   40   40   40Neoprene W     60     60     60   60   60   60JZF            1      1      1    1    1    1Maglite D      4      4      4    4    4    4Stearic acid   1      1      1    1    1    1Flexol TOF     5      5      5    5    5    5Sterling V     15     15     15   15   15   15ZnO            5      5      5    5    5    5Ottacide P                   1    1    1    1Methyl zimate                1              0.5Zetax                             1         0.5Thiate A                               1Vancide 51Z           1______________________________________

Test results for the articles thus formed were as follows:

__________________________________________________________________________Specimen No   1    2    3    4    5    6__________________________________________________________________________Tensile strength (p.s.i.)         1,220              1,911                   1,806                        1,448                             2,410                                  1,709Elongation (percent)         253  230  273  297  203  320M100 (p.s.i.) 18   26   62   60   142  58U.S. (p.s.i.) 157  220  295  302  272  246Memory (percent)         200  200  200  200  200  200Retraction (percent)         100  100  100  100  100  100__________________________________________________________________________
EXAMPLE IV

To illustrate that by the inclusion of a suitable low-temperature plasticizer, heat-recoverable polychloroprene articles can be produced having low temperature flexibilities equivalent to those of conventional polychloroprene articles, and in fact having adequate flexibility at -55° C., the following compositions were prepared and press cured for 10 minutes at 350° F.:

______________________________________Specimen No      1         2          3______________________________________Geon 101 EP      35        35         35Neoprene W       65        65         64JZF              1         1          1Stearic acid     1         1          1MgO              4         4          4ZnO              5         5          5Sterling V       15        15         15Vancide 51Z      1         1          1Flexol TOF       2.5       5          10______________________________________

Cold Bend tests were performed in accordance with MIL-R-6855, as follows:

The test specimens were strips 51/2" × 1/4" × .062". The bending devices consisted of 2 parallel jaws 21/2" apart.

The ends of the strips were inserted into the jaws for a distance of 3/4" and fastened firmly with the middle portion of the strip forming a loop between the jaws. This assembly was conditioned in dry air at the indicated temperature for five hours. While still at this low temperature, the jaws were moved rapidly from the 21/2" to a 1" separation. Failure was denoted by cracking of the sample. The results were as follows:

______________________________________Specimen No      1         2         3______________________________________-40° C    OK        OK        OK-45° C    .sup.(1)  OK        OK-50° C              OK        OK-55° C              .sup.(1)  OKTensile strength (p.s.i.)            1,421     1,409     1,521Elongation (percent)            230       250       260M100 (p.s.i.)    71        75        77U.S. (p.s.i.)    276       308       299Memory (percent) 200       190       170Retraction (percent)            100       97        94______________________________________ .sup.(1) Broke.
EXAMPLE V

A number of heat-recoverable polychloroprene articles were prepared by press-curing the following compositions for 20 minutes at 340° F. to illustrate that the properties of the articles can be changed by varying the amounts and type of compounding ingredients:

______________________________________Mix No        1      2      3     4     5    6______________________________________Geon 101 EP   50     50     50    50    50   50Neoprene W    50     50     50    50    50   50Stearic acid  1      1      1     1     1    1JZF           2      2      2     2     2    2Vancide 51Z   1      1      1     1     1    1Flexol TOF    3      3      3     3     3    3MgO           4      4      4     4     4    4ZnO           5      5      21/2  21/2  5    21/2DOTG                        .5Sulfur                      .25Sterling V           15     15    15Thermax                                 5    5______________________________________

Following are the results of the physical tests:

__________________________________________________________________________Specimen No   1   2    3   4    5   6__________________________________________________________________________Tensile strength (p.s.i.)         827 1,088                  978 1,282                           846 810Elongation (percent)         133 103  113 80   133 140M100 (p.s.i.) 26  66   58  140  31  31U.S. (p.s.i.) 101 173  162 224  123 111Memory (percent)         120 160  140 200  170 140Retraction (percent)         96  100  100 100  97  92__________________________________________________________________________
EXAMPLE VI

A heat-shrinkable elastomeric tubing was produced by extruding the composition set forth below in a 11/2" Davis Standard extruder with a conventional thermoplastic screw. The tubing had a 0.250 I.D. and a 0.031" wall thickness. The tubing was vulcanized in a cylindrical steam vulcanizer at a pressure of 70 p.s.i. for 2 hours (Sample No. 1) and 3 hours (Sample No. 2).

FORMULA-EXAMPLE VI

                       Percent______________________________________Geon 101 EP vinyl resin  29.0Neoprene W               43.0JZF                      1.5Flexol TOF               7.5Maglite D                3.0Stearic acid             1.0Vancide 51Z              1.0Sterling S.O.            10.0Zinc oxide               4.0______________________________________

To produce the heat-shrinkable tubing, the samples were expanded using a hot glycerine bath and a heated mandrel to 100% and 200%. The tubing was then cooled while over the mandrel in cold water and removed. The tubing showed an initial shrinkage of 10%-15% and thereupon remained expanded until it was heated above the softening range of the polyvinyl chloride whereupon it shrank to its original dimension.

Test results were as follows:

ELASTIC MODULUS AND ULTIMATESTRENGTH AT 150° C.         M100          U.S.         (p.s.i.)      (p.s.i.)______________________________________Sample No.:1               29              1922               38              181______________________________________

TENSILE STRENGTH AND ELONGATION         Average      Percent         p.s.i.       elongation______________________________________Sample No.:1               1.077          2502               1.007          260______________________________________
EXAMPLE VII

Another form of heat-shrinkable article was made utilizing the following milled composition:

FORMULA

       Geon 101 EP      40  Neoprene W       60  JZF              1  Stearic acid     1  MgO              4  Vancide 51Z      1  Sterling V       15  Flexol TOF       10  ZnO              5

The milled material was molded in a compression type mold to form a hollow 3-finger splice cover for use in cable harnesses. The configuration was roughly T-shaped.

The parts were cured 15 minutes at 360° F. As molded, one of the hollow fingers had a .375" orifice. The parts were immersed in 150° C. glycerine for 1 minute and the specified finger orifice was mechanically expanded to 1.250", and the expanded part cooled in water.

The expanded hole was remeasured immediately after expansion and again after two weeks at room temperature. The parts were then placed in 150° C. glycerine for 1 minute, cooled and remeasured. Results on six samples were:Inches Immediately Original Expanded after Re-Sample OD to expansion 2 weeks covered______________________________________1 .375 1.250 .940 .905 .3902 .375 1.250 1.000 .940 .3853 .375 1.250 1.062 1.600 .3854 .375 1.250 .980 .900 .3905 .375 1.250 1.002 1.000 .3856 .375 1.250 1.062 1.010 .380______________________________________

In another test, a similar molding was made and expanded. However, it was held two weeks at 55° C. (131° F.) and then remeasured. Data obtained was:

Inches    Expanded Immediately  After  Re-Original OD    to-      after expansion                          2 weeks                                 covered______________________________________.375     1.250    1.170        .955   .385______________________________________
EXAMPLE VIII

This example illustrates the production of heat-recoverable silicone elastomeric articles in accordance with the present invention. Test specimens having the compositions set forth below were made as described above and irradiated at a dose level of 10 megarads with the following results:

(1)                  PercentSilastic 82U           906001 polyethylene      10Memory                 62Retraction             94(2)                  PercentSilastic 82U           90Styron 666             10Memory                 87Retraction             100
EXAMPLE IX

This example illustrates the production of heat-recoverable silicone elastomeric articles wherein the memory ingredient is a silicone resin. As is apparent from the test results, as little as 10% silicone resin is effective, excellent results being obtained with 30% of the silicone resin. The test specimens were prepared from the following compositions press cured for 10 minutes at 350° F.:

                 1      2       3______________________________________Silastic 82U       90       85      70Resin Z 6018       10       15      30Varox              2        2       2______________________________________              1        2       3______________________________________Tensile strength (p.s.i.)              742      616     515Elongation (percent)              397      283     250M100 (p.s.i.)      61       55      67U.S.(p.s.i.)       210      215     200Memory (percent)   120      150     200Retraction (percent)              100      100     100______________________________________
EXAMPLE X

In carrying out this example a shrinkable silicone rubber tubing having a 100-mil wall thickness was prepared as described in Example 6 utilizing the following extrusion compound:

Tenite 812A             16Marbon 8000A            4Agerite Resin D         1Silastic 916U           64Silastic 82U            16Varox                   2

These samples were prepared by vulcanizing the extruded tubing at 70 p.s.i. steam pressure in a cylindrical rubber vulcanizer for 60 minutes (Sample No. 1), 45 minutes (Sample No. 2) and 30 minutes (Sample No. 3).

The tubing was expanded 100% utilizing the process and apparatus described in Cook et al., U.S. patent application, Ser. No. 43,230, on Process and Apparatus for Producing Materials Having Plastic-Memory, now Pat. No. 3,086,242. The samples showed very little initial recovery (5% to 10%) and remained expanded until heated above the softening range of the polyethylene additive whereupon they shrunk to their original dimensions. Physical test results were as follows:

TENSILE STRENGTH AND ELONGATION         Average                Percent         p.s.i. elongation______________________________________1               887      3832               856      3933               836      390______________________________________

ELASTIC MODULUS AND ULTIMATESTRENGTH AT 150° C.   M100 (p.s.i.)              U.S. (p.s.i.)______________________________________1         93           1282         83           1023         84           150______________________________________
EXAMPLE XI

This example illustrates the production of heat-recoverable articles of cross-linked plasticized polyvinyl chloride. Sheets were molded from the several milled compositions set forth below in a 6" × 6" × 0.062" flask-type mold and samples were irradiation cross-linked at 5 and 10 megarads.

______________________________________Sample No     1      2      3     4   5     6______________________________________Molding compositions: Geon 101 EP  90     80     60   70   100   100 Lectro 78    2      2      2    2    1     1 Triallyl cyanurate         10     20     10   10   20    40 Flexol TOF                 30   20   60    40______________________________________

__________________________________________________________________________Sample No      1       2      3        4       5       6__________________________________________________________________________Irradiation dose (megarads)          5   10  5   10 5   10   5   10  5   10  5   10Tensile strength (p.s.i.)          Too brittle to test                         1,668                             2,037                                  2,579                                      2,791                                          2,071                                              2,400                                                  2,041                                                      2,582Elongation (percent)          220 200  170 120 320 250 330 200M100 (p.s.i.)                 22  61   44  87  33  85  20  123U.S. (p.s.i.)                 37  52   65  95  100 146 84  109Memory (percent)              185 1 Broke                                  100 100 190 100 180 175Retraction (percent)          100 --   100 100 90  100 100 100__________________________________________________________________________ 1 Sample ruptured in attempting to expand it 100%. A sample was then expanded 75% with 100% retraction.
EXAMPLE XII

This example illustrates the production of heat-recoverable articles utilizing polyvinyl chloride or polyethylene in various elastomers, cured by chemical cross-linking or by high energy radiation. In making the specimens, masterbatches were prepared by milling equal amounts of elastomer and resin on a hot mill. These were then incorporated into finished stock on a cold mill. Two types of masterbatches were made as follows:

Type I

                        GramsGeon 101 EP polyvinyl chloride                   100Elastomer               100Flexol TOF              5JZF                     2
Type II

6001 polyethylene       100Elastomer               100JZF                     2

The cross-linking was carried out as follows:

TYPE I MIXES

1           Cured 20 minutes at 307°F.1A          Irradiated 20 megarads3           Cured 20 minutes at 287°F.3A          Irradiated 20 megarads
TYPE II MIXES

2           Cured 10 minutes at 307°F.2A          Irradiated 20 megarads4           Cured 20 minutes at 307°F.4A          Irradiated 20 megarads5           Cured 15 minutes at 287°F.5A          Irradiated 15 megarads6           Cured 20 minutes at 287°F.6A          Irradiated 20 megarads

The following are the specific mixes which were prepared:

TYPE I, NO. 1

Geon 101 EP           30Hypalon 40            70Litharge              25Sterling V            15Process oil           5Tetrone A             2Altax                 0.5
TYPE I, NO. 1A

Geon 101 EP           30Hypalon 40            70Litharge              25Sterling V            15Process oil           5
TYPE II, NO. 2

6001 polyethylene      30Chemigum N3            70Stearic acid           1ZnO                    5Flexol TOF             5Sterling V             15Altax                  1.5Methyl Tuads           0.1Sulfur                 1
TYPE II, NO. 2A

6001 polyethylene      30Chemigum N3            70Stearic acid           1ZnO                    5Flexol TOF             5Sterling V             15
TYPE I, NO. 3

Geon 101 EP            30ASRC 3105              70Stearic acid           1ZnO                    5Sterling V             15Process oil            5Altax                  1Cumate                 0.1Sulfur                 1.5
TYPE I, NO. 3A

Geon 101 EP              30ASRC 3105                70Stearic acid             1ZnO                      5Sterling V               15Process oil              5
TYPE II, NO. 4

6001 polyethylene       30Hypalon 40              70Litharge                25Sterling V              15Process oil             5Tetrone A               2Altax                   0.5
TYPE II, NO. 4A

6001 polyethylene        30Hypalon 40               70Litharge                 25Sterling V               15Process oil              5
TYPE II, NO. 5

6001 polyethylene       30Smoked sheet            70Stearic acid            1ZnO                     5Process oil             5Sterling V              15Altax                   1Methyl Tuads            0.1Sulfur                  1
TYPE II, NO. 5A

6001 polyethylene        30Smoked sheet             70Stearic acid             1ZnO                      5Process oil              5Sterling V               15
TYPE II, NO. 6

6001 polyethylene       30ASRC 3105               70Stearic acid            1ZnO                     5Sterling V              15Process oil             5Altax                   1Cumate                  0.1Sulfur                  1.5
TYPE II, NO. 6A

6001 polyethylene        30ASRC 3105                70Stearic acid             1ZnO                      5Sterling V               15Process oil              5

Test results were as follows:

MODULUS OF ELASTICITY AND ULTIMATESTRENGTH AT 150° C.______________________________________     M100 (p.s.i.)                  U.S. (p.s.i.)______________________________________Specimen:1           228            3222           170            943           150            914           132            1175           81             2566           73             178 1A         139            156 2A         246            147 3A         65             75 4A         124            165 5A         18             251 6A         66             126.58______________________________________

PLASTIC MEMORY______________________________________        Memory,   Retraction,        percent   percent______________________________________Specimen:1              70          1002              80          1003              30          1004              95          1005              100         1006              100         100______________________________________          Memory,     Retraction,          percent     percent______________________________________Specimen:1A             80          1002A             40          1003A             50          1004A             100         1005A             90          1006A             100         100______________________________________

TENSILE AND ELONGATION______________________________________    Average    P.s.i.    Percent      .[.Young's              elongation   modulus                           (p.s.i.)______________________________________Specimen:1          2,596       200          4872          575         253          3323          553         407          2414          1,762       147          1,6445          2,470       483          5766          872         527          503 1A        1,771       250          841 2A        766         93           761 3A        368         340          167 4A        1,507       130          1,368 5A        1,168       350          423 6A        981         480          533.].______________________________________

Having fully described my invention, it is to be understood that I do not wish to be limited to the details set forth, but my invention is of the full scope of the appended claims.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2194579 *Oct 13, 1934Mar 26, 1940B B Chem CoPlastic composition and method of molding the same
US2342977 *Aug 2, 1940Feb 29, 1944Wingfoot CorpPackaging
US2458152 *Apr 3, 1945Jan 4, 1949Us Rubber CoPlastic rivet and method of making same
US2549122 *Apr 3, 1948Apr 17, 1951Wingfoot CorpPackaging in stretched film
US2603838 *Aug 1, 1949Jul 22, 1952Dow Chemical CoMethod for preshrinking crystalline vinylidene chloride copolymer film
US2769789 *Jan 7, 1953Nov 6, 1956Dunlop Tire & Rubber CorpRubber reinforcing agents and compositions containing such agents
US2821155 *Dec 11, 1953Jan 28, 1958Richard A FischProcess of applying protective coatings
US2989515 *Aug 13, 1956Jun 20, 1961Du PontProcess of copolymerizing aromatic dienes and monoolefins with catalyst of metal halide and organometal compound
US3042652 *Jul 31, 1959Jul 3, 1962Du PontElastomeric compositon comprising a benzene-soluble chloroprene polymer and a benzene-insoluble radiation cross-linked chloroprene polymer
US3056171 *May 17, 1960Oct 2, 1962Mimx CorpInhibitor and thermal insulation liner for propellant grains
US3086242 *Jul 15, 1960Apr 23, 1963Raychem CorpProcess and apparatus for producing materials having plastic memory
US3139468 *Jun 20, 1960Jun 30, 1964Phillips Petroleum CoAltering dimension of vulcanized transpolybutadiene and heating to cause same to appoach original shape
Non-Patent Citations
Reference
1 *Einfuhrung in de Chemie & Technologie dor Runststoffe, Berlin, 1952, p. 48, F. Runge.
2 *Kunststoffe, 50, (1960), p. 480.
3 *Merrett & Wood, Proceedings of the Institution of the Rubber Industry, Vol. 3, (1956), pp. 36-37.
4 *Plastics, Vol. 21, (October 1956), p. 273.
5 *Plastuarlden, Vol. 4, (1954), p. 125.
6 *Schmidt et al., Principles of High Polymer Theory & Practice; N.Y., 1948, pp. 302, 303 & 308.
Referenced by
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US4910085 *Oct 11, 1988Mar 20, 1990American National Can CompanyMultiple layer packaging films and packages formed thereof
US4966795 *May 5, 1988Oct 30, 1990American National Can CompanyMultiple layer sheet structures and package
US5011719 *Jul 27, 1987Apr 30, 1991American National Can CompanyPolymeric compositions and films
US5043383 *Nov 17, 1989Aug 27, 1991Minnestoa Mining And Manufacturing CompanyHeat-shrinkable film having high shrinkage upon brief exposure to low activation temperatures
US5071686 *Nov 29, 1985Dec 10, 1991Genske Roger PFilms of polypropylene blends and polyethylene blends and articles made therewith
US5073599 *Jun 13, 1988Dec 17, 1991American National Can CompanyFilms using blends of polypropylene and polyisobutylene
US5120138 *Feb 15, 1991Jun 9, 1992Minnesota Mining And Manufacturing CompanyFlexible bag closure system
US5501679 *Mar 30, 1990Mar 26, 1996Minnesota Mining And Manufacturing CompanyElastomeric laminates with microtextured skin layers
US5567757 *Jul 18, 1995Oct 22, 1996Rjf International CorporationLow specific gravity binder for magnets
US5691034 *May 16, 1995Nov 25, 1997Krueger; Dennis L.Elastomeric laminates with microtextured skin layers
US5843068 *Sep 12, 1997Dec 1, 1998J&M Laboratories, Inc.Disposable diaper having elastic side panels
US6419798Dec 15, 2000Jul 16, 2002Kimberly-Clark Worldwide, Inc.Methods of making disposable products having materials having shape-memory
US6436529Jul 18, 1997Aug 20, 20023M Innovative Properties CompanyElatomeric laminates and composites
US6533987Dec 15, 2000Mar 18, 2003Kimberly-Clark Worldwide, Inc.Methods of making materials having shape-memory
US6550481 *Sep 22, 2000Apr 22, 2003Thämert Orthopädische Hilfsmittel GmbH & Co. KGMethod for producing an orthopedic cushion having a soft elastic region
US6627673Jul 24, 2001Sep 30, 2003Kimberly-Clark Worldwide, Inc.Methods of making humidity activated materials having shape-memory
US6664436Jul 24, 2001Dec 16, 2003Kimberly-Clark Worldwide, Inc.Disposable products having humidity activated materials with shape-memory
US6933421Jul 24, 2001Aug 23, 2005Kimberly-Clark Worldwide Inc.Methods of making disposable products having humidity activated materials with shape-memory
US6994469Nov 13, 2002Feb 7, 2006The Glad Products CompanyShirred elastic sheet material
US7074484Dec 15, 2000Jul 11, 2006Kimberly-Clark Worldwide, Inc.Materials having shape-memory
US7300395Sep 9, 2005Nov 27, 2007The Glad Products CompanyMethod for manufacturing a bag
US7459191Sep 9, 2005Dec 2, 2008The Glad Products CompanyShirred elastic sheet material
US7582178Nov 22, 2006Sep 1, 2009Kimberly-Clark Worldwide, Inc.Nonwoven-film composite with latent elasticity
US7585382Oct 31, 2006Sep 8, 2009Kimberly-Clark Worldwide, Inc.Latent elastic nonwoven composite
US7717893Jun 3, 2005May 18, 2010The Procter & Gamble CompanyAbsorbent articles comprising a slow recovery elastomer
US7905872Jun 3, 2005Mar 15, 2011The Procter & Gamble CompanyAbsorbent articles comprising a slow recovery stretch laminate
US7910795Mar 9, 2007Mar 22, 2011Kimberly-Clark Worldwide, Inc.Absorbent article containing a crosslinked elastic film
US7938921Nov 22, 2006May 10, 2011Kimberly-Clark Worldwide, Inc.Strand composite having latent elasticity
US7946765Jun 28, 2007May 24, 2011The Glad Products CompanyShirred elastic sheet material
US8029488Jan 26, 2006Oct 4, 2011The Procter & Gamble CompanyDisposable pull-on diaper having a low force, slow recovery elastic waist
US8323257Nov 20, 2008Dec 4, 2012The Procter & Gamble CompanyAbsorbent articles comprising a slow recovery stretch laminate and method for making the same
US8419701Jun 3, 2005Apr 16, 2013The Procter & Gamble CompanyAbsorbent articles with stretch zones comprising slow recovery elastic materials
WO1993002137A1 *Jul 22, 1991Feb 4, 1993Dow Chemical CoCompositions of vinylaromatic polymers and vinylidene chloride polymers
Classifications
U.S. Classification523/300, 525/281, 525/233, 524/572, 525/177, 524/467, 522/112, 264/230, 525/121, 524/575, 525/239, 524/545, 524/552, 525/106, 525/232, 525/215, 525/206, 522/111, 524/565, 524/588, 524/574, 525/104, 524/569, 524/579
International ClassificationC08L23/02, C08L101/00, C08L23/34, C08L83/04, C08L21/00, C08L19/00, C08J3/24
Cooperative ClassificationC08L21/00, C08J3/24, C08L91/06, C08L25/06, C08L23/06, C08L27/06, C08L83/00, C08L23/02, C08L19/003, C08L2312/00, C08L2310/00, C08L53/02, C08L83/04, C08L45/02, C08L23/0815, C08L9/02, C08L2205/02, C08G77/442, C08L63/00, C08L2205/035, C08L101/00, C08L91/00, C08L9/06, C08K5/14, C08G77/24, C08L2207/07, C08L23/34, C08L67/00, C08K3/22, C08L55/02, C08L11/00, C08G77/04
European ClassificationC08L83/04, C08L19/00B, C08L83/00, C08L21/00, C08L9/06, C08L9/02, C08L23/02, C08L23/34, C08L27/06, C08L67/00, C08L53/02, C08L11/00, C08L55/02, C08L101/00, C08J3/24