阅读说明：本技术 聚酰胺泡沫的制备 (Preparation of Polyamide foams ) 是由 严金良 R·T·H·周 K·豪斯曼 王钟瑜 于 2018-09-28 设计创作，主要内容包括：本文公开了一种发泡组合物,其包含55至98重量％聚酰胺和2至45重量％的包含经锌中和的乙烯酸共聚物的离聚物。经锌中和的乙烯酸共聚物是乙烯单体、单羧酸单体和不饱和二羧酸单体的聚合反应产物,并且离聚物的总酸单元的30至70摩尔百分比被中和。(Disclosed herein is a foaming composition comprising 55 to 98 weight percent polyamide and 2 to 45 weight percent ionomer comprising zinc neutralized ethylene acid copolymer. The zinc neutralized ethylene acid copolymer is the polymerization reaction product of ethylene monomers, monocarboxylic acid monomers, and unsaturated dicarboxylic acid monomers, and 30 to 70 mole percent of the total acid units of the ionomer are neutralized.)

1. A foam, comprising:

55 to 98 weight percent polyamide; and

2 to 45 weight percent of an ionomer comprising a zinc neutralized ethylene acid copolymer,

wherein the zinc neutralized ethylene acid copolymer is the polymerization reaction product of ethylene monomers, monocarboxylic acid monomers, and unsaturated dicarboxylic acid monomers, and

wherein 30 to 70 mole percent of the total acid units of the ionomer are neutralized.

2. The foam of any preceding claim, wherein the foam has a density of from 0.03 to 0.5 g/cc.

3. The foam of any preceding claim, wherein the foam has an expansion ratio of at least 1500%.

4. The foam of any preceding claim, wherein the foam is free of polyurethane.

5. The foam of any preceding claim, wherein the foam comprises 75 to 97 wt.% polyamide.

6. The foam of any preceding claim, wherein the polyamide comprises an aliphatic polyamide.

7. The foam of any preceding claim, wherein the polyamide comprises PA6, PA11, PA12, or a combination thereof.

8. The foam of any preceding claim, wherein the foam comprises from 3 to 20 wt% ionomer.

9. The foam of any preceding claim, wherein the zinc neutralized ethylene acid copolymer comprises at least 50% ethylene monomer based on the total weight of the monomers present in the zinc neutralized ethylene acid copolymer.

10. The foam of any preceding claim, wherein the zinc neutralized ethylene acid copolymer comprises at least 5 to 25 weight percent monocarboxylic acid monomer based on the total weight of the monomers present in the zinc neutralized ethylene acid copolymer.

11. The foam of any preceding claim, wherein the zinc neutralized ethylene acid copolymer comprises 2 to 20 weight percent unsaturated dicarboxylic acid monomer based on the total weight of the monomers present in the zinc neutralized ethylene acid copolymer.

12. The foam of any preceding claim, wherein the unsaturated dicarboxylic acid monomer comprises maleic anhydride, monomethyl maleic anhydride, monoethyl maleic anhydride, monopropyl maleic anhydride, monobutyl maleic anhydride, or a combination thereof.

13. The foam of any preceding claim, wherein the monocarboxylic acid monomer comprises one or more of methacrylic acid, acrylic acid, or a combination thereof.

14. A method of producing a foam comprising:

introducing CO₂、N₂Or a combination of both, wherein the container is at a pressure and temperature that is higher than the supercritical temperature and pressure of the blowing agent, and wherein the foam precursor mixture comprises 55 to 98 weight percent polyamide; and 2 to 45 weight percent of an ionomer comprising a zinc neutralized ethylene acid copolymer,

wherein the zinc neutralized ethylene acid copolymer is the polymerization reaction product of ethylene monomers, monocarboxylic acid monomers, and unsaturated dicarboxylic acid monomers, and

wherein 30 to 70 mole percent of the total acid units of the ionomer are neutralized;

the foam is produced by reducing the pressure below the pressure of the supercritical blowing agent.

Technical Field

Embodiments of the present disclosure generally relate to foams and, more particularly, to foams comprising blends of polyamides and ionomers.

Background

Foams continue to be a product of significant interest due to their suitability for use in various industrial applications. One interesting foam is polyamide foam; however, the melt viscosity of polyamides is generally too low for foaming applications. Accordingly, there is a continuing need for improved polyamide foams having improved melt viscosities.

Disclosure of Invention

Embodiments of the present disclosure address this need by blending polyamides with ionomers to increase melt viscosity.

According to one foam embodiment, the foam comprises 55 to 98 weight percent polyamide and 2 to 45 weight percent ionomer comprising zinc neutralized ethylene acid copolymer. The zinc neutralized ethylene acid copolymer is the polymerization reaction product of ethylene monomers, monocarboxylic acid monomers, and unsaturated dicarboxylic acid monomers. In addition, 30 to 70 mole percent of the total acid units of the ionomer are neutralized.

According to another embodiment, a method of producing a foam comprises introducing CO₂、N₂Or a combination of both, wherein the container is at a pressure and temperature that is higher than the supercritical temperature and pressure of the blowing agent, and wherein the foam precursor mixture comprises 55 to 98 weight percent polyamide; and 2 to 45 weight percent of an ionomer comprising a zinc neutralized ethylene acid copolymer. The zinc neutralized ethylene acid copolymer is the polymerization reaction product of ethylene monomers, monocarboxylic acid monomers, and unsaturated dicarboxylic acid monomers, and 30 to 70 mole percent of the total acid units of the ionomer are neutralized. Finally, the method comprises generating the foam by reducing the pressure to a pressure below that of the supercritical blowing agent.

Detailed Description

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In case of conflict, the present specification, including definitions, will control.

Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of various embodiments, suitable methods and materials are described herein.

All percentages, parts, ratios, etc., are by weight unless otherwise indicated. When an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of lower preferable values and higher preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any lower limit or lower preferable value and any upper limit or higher preferable value for the range, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. When defining a range, it is not intended that the scope of the invention be limited to the specific values recited.

When the term "about" is used to describe a value or range endpoint, the disclosure should be understood to include the specific value or endpoint referred to.

As used herein, the terms "comprises," "comprising," "includes," "including," "contains," "characterized by," "has/having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements, and may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" means an inclusive or and not an exclusive or.

The transitional phrase "consisting essentially of … …" limits the scope of the claims to the specified materials or steps and those materials or steps that do not materially affect one or more of the basic and novel features of the disclosure. Where applicants have defined an embodiment, or a portion thereof, using open-ended terms such as "comprising," the description should be construed as also using the term "consisting essentially of … … to describe such embodiment, unless otherwise noted.

The use of "a" or "an" is employed to describe elements and components of various embodiments. This is for convenience only and to give a general sense of the various embodiments. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

When materials, methods, or machinery are described herein with the term "known to those of skill in the art," "conventional," or a synonym or phrase, the term means that the materials, methods, and machinery that are conventional at the time of filing the present application are encompassed by the present embodiments.

The term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term polymer thus embraces the terms "homopolymer" and "copolymer". The term "homopolymer" refers to a polymer prepared from only one type of monomer. The term "copolymer" refers to a polymer prepared from two or more different monomers, and for purposes of this disclosure, may include "terpolymers" and "interpolymers".

The term "monocarboxylic acid monomer" means a molecule having a reactive moiety (e.g., a vinyl or vinylidene group) that can bond to other monomers to form a polymer and carboxylic acid (-c (o) OH) moieties not included in the reactive moiety. For example, (meth) acrylic acid is a monocarboxylic acid monomer in which a vinylidene group is the reactive moiety and a carboxylic acid is present. The term "(meth) acrylic" includes methacrylic and/or acrylic, and "(meth) acrylate" includes methacrylate, acrylate, or a combination of methacrylate and acrylate.

The term "unsaturated dicarboxylic acid monomer" as used in this disclosure means a molecule having a reactive moiety (such as a vinyl or vinylidene group) that can bond to other monomers to form a polymer and two carboxylic acid (-c (o) OH) groups that are not included in the reactive moiety. In addition, "unsaturated dicarboxylic acid monomer" includes unsaturated dicarboxylic acid derivative monomers (half esters and anhydrides).

As used herein, "melt viscosity" can also be considered shear viscosity, which is the resistance of a polymer composition to shear flow. The present disclosure reports shear viscosity data at a shear rate of 100 radians/sec; however, other shear rates are contemplated in capillary rheometers.

Embodiments of the present disclosure are directed to foams having increased melt viscosity by blending polyamides with ionomers. According to one embodiment of the foam of the present invention, the foam comprises 55 to 98 wt.% polyamide and 2 to 45 wt.% ionomer. The ionomer comprises a zinc neutralized ethylene acid copolymer that is the polymerization reaction product of ethylene monomers, monocarboxylic acid monomers, and unsaturated dicarboxylic acid monomers. In addition, 30 to 70 mole percent of the total acid units of the ionomer are neutralized.

Polyamide

For polyamides, various compositions are contemplated, such as aliphatic or aromatic polyamides. In one or more embodiments, the polyamide is an aliphatic polyamide selected from the group of polyamides derived from lactams or amino acids (e.g., polyepsiloncaprolactam (PA6) or PA11), or from the condensation of a diamine (e.g., hexamethylene diamine) with a dibasic acid (e.g., succinic acid, adipic acid, or sebacic acid). Copolymers and terpolymers of these polyamides are also included. In other embodiments, the aliphatic polyamide may be selected from poly epsilon caprolactam (PA 6); polyhexamethylene adipamide (PA6, 6); PA 11; PA 12; PA12,12 and copolymers and terpolymers, e.g. PA6/6, 6; PA6, 10; PA6, 12; PA6, 6/12; PA6/6,6/6,10 and PA 6/6T. In particular embodiments, the polyamide may comprise PA6, PA12, or a combination thereof. It is contemplated that the foam may comprise a plurality of polyamides from the above list. In another embodiment, the foam may be free of polyurethane.

The polyamide may have a density greater than 1.0g/cc, or greater than 1.1g/cc, prior to blending with the ionomer. In other words, the polyamide foam may have a density of 1.0g/cc to 1.5g/cc, 1.1 to 1.2g/cc, prior to blending with the ionomer.

Various amounts of polyamide are contemplated within the foam. For example, the foam may comprise 55 to 98 weight percent polyamide, 60 to 97 weight percent polyamide, 75 to 97 weight percent polyamide, or 80 to 90 weight percent polyamide.

Ionomer

To increase the melt shear viscosity, the polyamide is blended with an ionomer comprising a zinc neutralized ethylene acid copolymer as described above. Various amounts of ionomers are contemplated. In one or more embodiments, the foam comprises 2 to 45 weight percent ionomer, 3 to 20 weight percent ionomer, or 10 to 20 weight percent ionomer.

As previously mentioned, the zinc neutralized ethylene acid copolymer can be a terpolymer product of ethylene monomers, monocarboxylic acid monomers, and unsaturated dicarboxylic acid monomers. The zinc neutralized ethylene acid copolymer can comprise at least 50% ethylene monomer, based on the total weight% of monomers present in the zinc neutralized ethylene acid copolymer. In further embodiments, the zinc neutralized ethylene acid copolymer comprises at least 60% ethylene monomer, at least 70% ethylene monomer, or at least 80% ethylene monomer.

In addition, the zinc neutralized ethylene acid copolymer can comprise at least 5 to 25 weight percent monocarboxylic acid monomer based on the total weight percent of monomers present in the zinc neutralized ethylene acid copolymer. In further embodiments, the zinc neutralized ethylene acid copolymer comprises 8 to 20 weight percent monocarboxylic acid monomer, or 10 to 15 weight percent monocarboxylic acid monomer. The monocarboxylic acid monomer may comprise methacrylic acid, acrylic acid, or a combination thereof. In a particular embodiment, the monocarboxylic acid monomer comprises methacrylic acid.

In addition, the zinc neutralized ethylene acid copolymer comprises 2 to 20 weight percent of unsaturated dicarboxylic acid monomers based on the total weight percent of monomers present in the zinc neutralized ethylene acid copolymer. In further embodiments, the zinc neutralized ethylene acid copolymer comprises from 3 to 15 weight percent of unsaturated dicarboxylic acid monomer, or from 5 to 10 weight percent of unsaturated dicarboxylic acid monomer. The unsaturated dicarboxylic acid monomer may comprise maleic anhydride, monomethyl maleic anhydride, monoethyl maleic anhydride, monopropyl maleic anhydride, monobutyl maleic anhydride, or combinations thereof. In a particular embodiment, the monocarboxylic acid monomer comprises monomethyl maleate.

The carboxylic acid functional groups present in the ionomer are at least partially neutralized by zinc and optionally one or more alkali metal, transition metal or alkaline earth metal cations (e.g., sodium, lithium, magnesium and calcium). The carboxylic acid functional groups may be at least partially neutralized 30 to 70 mole% or 40 to 60 mole%. The ionomers of the present disclosure can be prepared by standard neutralization techniques, as disclosed in U.S. Pat. No. 3,264,272 (Rees), which is incorporated herein by reference.

In further embodiments, the zinc neutralized ethylene acid copolymer can have a density of at least 0.95 g/cc. The zinc neutralized ethylene acid copolymer can also have a Melt Index (MI) of from 0.1 to 20g/10min or from 0.5 to 10g/10min when measured at 210 ℃ at 2.16kg according to ASTM D-1238.

In addition, the zinc neutralized ethylene acid copolymer can have a melting point of at least 80 ℃ as measured by Differential Scanning Calorimetry (DSC). In further embodiments, the zinc neutralized ethylene acid copolymer can have a melting point of at least 85 ℃ or at least 90 ℃.

Additional additives

The foam composition may optionally comprise from about 0.0001 to about 50 weight percent (based on the total weight of the composition) of conventional additives for polymeric materials, including: plasticizers, stabilizers, antioxidants, ultraviolet light absorbers, hydrolytic stabilizers, antistatic agents, dyes or pigments, fillers, flame retardants, lubricants, reinforcing agents (such as glass fibers and flakes), processing aids, antiblock agents, mold release agents, nucleating agents, and/or mixtures thereof. In one embodiment, the foam composition comprises 0.01 to 1 weight percent antioxidant.

Foam

The shear viscosity (v) of the foam composition of the present invention at a shear rate of 100 rad/sec₁₀₀) May be greater than 500Pa s, greater than 750Pa s at a shear rate of 100 rad/sec, greater than 1000Pa s at a shear rate of 100 rad/sec, greater than 1500Pa s at a shear rate of 100 rad/sec, or greater than 2000Pa s at a shear rate of 100 rad/sec.

Further, the foam may have an expansion ratio of at least 200%, at least 500%, at least 750%, at least 1000%, at least 1250%, at least 1500%, or at least 2000%. Further, the foam can have a density of 0.02 to 0.5g/cc, or 0.03 to 0.1 g/cc. As described in detail below, these low density foams can be achieved by utilizing a physical foaming process.

The polyamide foams of the present invention are useful in a variety of applications and articles. In various embodiments, the resulting polymer foam compositions can be used in lightweight/high temperature resistant parts for the automotive industry, thermal insulation for construction and packaging, rigid core materials for composites, and the like.

Manufacturing method

Various methods are contemplated as being suitable for mixing the polyamide and ionomer. For example, the polyamide and ionomer may be fed in solid form, for example in pellet form, to a suitable mixing device for blending.

Suitable mixing devices can be selected among twin-screw extruders with mixing screws, Brabender-type mixers (Brabender-type mixers), internal mixers, Farrell continuous mixers (Farrell continuous mixers) or Buss Ko kneaders. In a particular embodiment, the mixing device is a twin screw extruder.

During the mixing step, the ionomer can be dispersed in the polyamide (which forms the continuous phase) in the form of very fine particles having a very narrow particle size distribution. After melt mixing, the blend is passed through the die of an extruder and then cut to give solid particles, e.g., pellets, of the polyamide/ionomer blend.

Foams can be produced by a variety of methods, such as compression molding, injection molding, and a mixture of extrusion and molding. The method may include mixing the components of the foam composition under heat to form a melt. The components may be mixed and blended using any technique known and used in the art, including Banbury (Banbury) machines, intensive mixers, twin roll mills, and extruders. The time, temperature and shear rate can be adjusted to ensure dispersion without premature crosslinking or foaming.

For making foamsThe blowing agent (also referred to as a blowing agent) of (a) may be a physical blowing agent or a chemical blowing agent. As used herein, a "physical blowing agent" is a low boiling liquid that volatilizes under curing conditions to form a blowing gas. Exemplary physical blowing agents include hydrocarbons, fluorocarbons, hydrofluorocarbons, hydrofluoroolefins, hydrochlorofluoroolefins, and other halogenated compounds. In one or more embodiments, it can include the inclusion of CO₂、N₂Or a combination of both. In one embodiment, supercritical CO may be utilized₂A blowing agent. As used herein, supercritical means at a temperature and pressure higher than the supercritical temperature and pressure of the blowing agent. For example, supercritical CO₂The blowing agent is above about 31 ℃ and above about 7.4 MPa.

In chemical foaming, a chemical blowing agent (such as azodicarbonamide) is first mixed and dispersed in the molten polymer. The chemical blowing agent then decomposes at elevated pressure and temperature to release a gas, such as N₂And CO₂And the azodicarbonamide shell acts as a blowing agent. However, for chemical blowing agents, other by-products are produced in addition to the blowing agent gas. Without being bound by theory, chemical blowing agents may in some cases be unsuitable for producing low density foams, e.g., foams less than 0.1 g/cc.

In contrast to chemical blowing agents, physical blowing agents at high pressure are metered directly into the plastic melt during foam extrusion or injection molding foaming. These physical blowing agents do not have the byproduct problems associated with chemical blowing. Physical blowing agents may have the advantage of forming a more uniform foam structure while being less costly and more environmentally sustainable, particularly for inorganic gas blowing agents such as N₂And CO₂. In addition, physical blowing agents may be more preferred for producing lower density foams.

The following are example methods for adding physical blowing agents during extrusion foaming. Here, the precompounded polyamide and ionomer dope were introduced into a hopper, flowed through the barrel and began to melt. Extracting physical foaming agent (e.g. CO) from cylinder₂) And directly injected into the polymer meltTo form a single phase gas/polymer solution. The solution may then be transferred to a heat exchanger that provides cooling to inhibit cell coalescence. Finally, the gas/polymer melt enters the extrusion die and foaming occurs due to the sudden pressure drop.

Without being limited by theory, a sudden pressure drop induces phase separation of the gas from the polymer melt, thereby forming a foam structure. In some cases, this may be a rapid pressure drop, for example 15 to 30 MPa/sec.

The foam composition may further include a free radical initiator or cross-linking agent, a co-curing agent, an activator, and any other type of additive typically used in similar compositions, including but not limited to pigments, adhesion promoters, fillers, nucleating agents, rubbers, stabilizers, and processing aids.

The free radical initiator or crosslinking agent may include, for example, but is not limited to, organic peroxides, such as dialkyl organic peroxides. Suitable example organic peroxides include 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane, tert-butylcumyl peroxide, dicumyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butyl-peroxy) hexane, 1, 3-bis (tert-butyl-peroxy-isopropyl) benzene, or a combination of two or more thereof.

The co-curing agent comprises trimethylpropane triacrylate (and similar compounds), N-m-phenylene bismaleimide (N, N-m-phenylene bismaleimide), triallyl cyanurate, or a combination of two or more thereof.

The activator may comprise an activator for the blowing agent and may comprise one or more metal oxides, metal salts or organometallic complexes. Examples include ZnO, zinc stearate, MgO, or a combination of two or more thereof.

Test method

Density of ionomer

Density measurements were made according to ASTM D792, method B.

₂Melt index (I) of the ionomer

Melt Index (MI) was measured according to ASTM D-1238 at 190 ℃ or at 210 ℃ at 2.16 kg. Values are reported in g/10min, which corresponds to grams eluted every 10 minutes.

Shear viscosity

The shear viscosity of the foam was characterized using a capillary rheometer at a temperature of 270 ℃ and a shear rate of 100 rad/sec.

Density of foam

Foam density was measured according to ASTM D792.

Expansion ratio

To accurately calculate the expansion ratio, the density before and after foaming can be measured. Expansion ratio-plastic density (unfoamed)/density (after foaming).

Compressive strength (MPa)

Compressive strength was measured at a compression rate of 1mm/min according to ASTM D1621. The compressive strength in MPa is the stress required to produce a compressive strain of up to 15%.

Examples of the invention

The following examples are provided to illustrate various embodiments and are not intended to limit the scope of the claims. All parts and percentages are by weight unless otherwise indicated. The following provides approximate characteristics, features, parameters, and the like with respect to various working examples, comparative examples, and substances used in the working and comparative examples.

Further, descriptions of raw materials used in the examples are listed in table 1 below.

TABLE 1

Measurement at 210 ℃ and measurement at 190 ℃

Referring to table 1, the ionomers of the present invention are Zn ionomers of an ethylene/methacrylic acid/monoethyl maleate (E/MAA/MAME) (83/11/6 wt%) terpolymer, having a Melt Index (MI) of 1.1, as measured at 210 ℃, with 50 mole% of the acid moiety neutralized with Zn cations. The comparative ionomer was a Zn ionomer of an ethylene/n-butyl acrylate/methacrylic acid (68/23/9 wt%) terpolymer having an MI of 0.8, as measured at 190 ℃, with 50 mol% of the acid moieties neutralized with Zn cations.

Mixing and blending

For inventive examples 1-5 set forth in Table 2 below, the following will beB33L PA6 (from BASF) was reacted at room temperature with the ionomers of the present invention and1098 phenolic antioxidants (produced by BASF) were dry blended and then compounded at 240 ℃ and 250 ℃ using a Brabender twin screw extruder, followed by pelletization in a separate pelletizing unit. Dry blending was performed using a separate super flotation machine. The Brabender twin screw extruder having a temperature range of 240 ℃ and 250 ℃ comprises a continuous temperature zone of 240 ℃/245 ℃/245 ℃/245 ℃/245 ℃/245 ℃.

Comparative examples B and C were prepared similarly. However, a comparative ionomer was used instead of the inventive ionomer. Comparative example A is a composition comprisingB33L PA6 and no ionomer reference material.

Injection moulding

Pellets comprising the compositions of examples 1-5 of the present invention and comparative examples A-C were injected into plaques (7.5 mm. times.15 mm. times.5 mm) using an Arburg 520C injection molding machine. The injection molding process was performed under the following process parameters: the polymer melt temperature was 250 ℃; the temperature of the die is 70 ℃; the pressure is 80 MPa; and the injection speed was 5 mm/s.

Batch foaming

The batch foaming process is carried out in a high pressure vessel. Place the injection molded plate in a container, and then place the CO₂And injecting into the container. Temperature and pressure of the vessel230 ℃ and 15MPa respectively, and held for 30 minutes to saturate the sample with supercritical fluid CO₂. The foam structure is formed by a sudden pressure drop that occurs in less than one second through a pressure cell having a diameter of 3 mm.

Characterization of

Tables 2 and 3 below provide characteristic data for the foams produced.

Table 2: PA/ionomer blends

TABLE 3

As shown in Table 2, inventive examples 1-5 took 100s^-1Both have a shear viscosity of more than 500Pa s, while comparative examples a and B have a shear viscosity of 100s^-1All lower values are less than 500Pa s. Although inventive example 1 and comparative example C have comparable shear viscosity values as shown in table 2, the compressive strength of inventive example 1 is at least 4 times that of comparative example C as shown in table 3.

Finally, referring to table 2, inventive examples 2-4 exhibited much higher shear viscosity values and lower density values than comparative examples.

Further, comparative example a including only PA6 achieved only an expansion ratio much lower than 100%. However, much higher expansion ratios were achieved after blending with ionomers.

It should be apparent to those skilled in the art that various modifications to the described embodiments can be made without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the present specification cover the modifications and variations of the described embodiments provided they come within the scope of the appended claims and their equivalents.