Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method for high molecular weight polyethylene fiber by melt spinning, which has the advantages of obviously improving the flow property of melt, obviously improving the production rate, reducing the recovery cost and the like, and solves the technical problem of great preparation difficulty caused by high entanglement of molecular chains, extremely high melt viscosity and extremely low melt flow rate of the main raw material high molecular weight polyethylene for preparing the high molecular weight polyethylene fiber.
(II) technical scheme
In order to achieve the purposes of obviously improving the flow property of the melt, obviously improving the production rate and reducing the recovery cost, the invention provides the following technical scheme:
a method for preparing high molecular weight polyethylene fibers by melt spinning comprises the following steps:
1) preparation of modified kaolin
(1) Adding 5-10 parts by mass of kaolin crude ore and 100-200 parts by mass of deionized water into a stirring barrel, fully stirring, standing for 10-30min, siphoning out a part of suspension liquid with the upper part of 40-100mm, adding deionized water with the same volume as the sucked suspension liquid into the stirring barrel, stirring, settling and extracting, repeating the steps for multiple times until the suspension liquid with the upper part of 40-100mm is not turbid any more after adding deionized water and stirring for 10-30min, and filtering and drying the obtained kaolin pulp to obtain purified kaolin;
(2) adding 3-7.5 parts by mass of the purified kaolin prepared in the step (1) and 20-50 parts by mass of deionized water into an electric stirrer, stirring and dispersing for 2-5h by using the electric stirrer at room temperature, adding 5-10 parts by mass of a sodium hydroxide solution with the mass fraction of 4% into the electric stirrer, continuously stirring for 2-4h at room temperature, centrifuging, washing until the upper layer centrifugal liquid is neutral, drying at 70-90 ℃, and grinding to 200 meshes after drying to prepare micron-sized modified kaolin;
2) preparation of modified high molecular weight polyethylene
(1) Adding 1-2 parts by mass of the modified kaolin prepared in the step 1) into 20-40 parts by mass of deionized water, and stirring and mixing at a high speed to prepare a high-dispersion modified kaolin suspension;
(2) adding 4-8 parts by mass of methacryloyloxyethyl trimethyl ammonium chloride into 40-80 parts by mass of deionized water, and fully stirring and mixing to obtain a DMC aqueous solution;
(3) mixing the modified kaolin suspension prepared in the step (1) and the DMC aqueous solution prepared in the step (2), adding the mixture into an electric stirrer, stirring at a high speed for 12-16h at 50-80 ℃, naturally cooling to room temperature, carrying out suction filtration on a reaction solution to obtain a white precipitate, washing the white precipitate with deionized water until no chloride ion exists, then placing the white precipitate into a vacuum drying oven, drying the white precipitate for 18-24h at 70-90 ℃, grinding the white precipitate through a 200-mesh sieve, and carrying out sealed storage to obtain a modifier;
(4) adding 3-8 parts by mass of the modifier prepared in the step (3) and 0.2-0.5 part by mass of dibenzoyl peroxide into 5-10 parts by mass of absolute ethyl alcohol, and stirring for 10-30min to prepare a mixed solution;
(5) adding the mixed solution prepared in the step (4) and 40-60 parts by mass of high molecular weight polyethylene into an electric stirrer, stirring and mixing at high speed for 1-3h, and granulating by adopting a granulation auxiliary machine to prepare modified high molecular weight polyethylene particles;
3) placing the modified high molecular weight polyethylene particles prepared in the step 2) in a vacuum drying box, drying for 4-8h at the temperature of 100-;
4) allowing the nascent fiber prepared in the step 3) to pass through a normal-temperature nitrogen air gap with the length of 40-80mm, and cooling with chilled water at the temperature of 8-15 ℃ to prepare gel fiber;
5) drying the gel fiber prepared in the step 4), entering a three-stage hot oven, and carrying out hot stretching in three stages, wherein the first-stage hot stretching temperature is 102-110 ℃, the multiple is 2-4, the second-stage hot stretching temperature is 110-118 ℃, the multiple is 3-5, the third-stage hot stretching temperature is 118-126 ℃, the multiple is 4-6, and after the third-stage hot stretching, carrying out hot setting, curling, false twisting and the like, thus preparing the high molecular weight polyethylene fiber.
Preferably, the suspension of the kaolin crude ore and the deionized water in the step 1) is kept still for 20min, and the suspension of the upper 75mm part is siphoned out.
Preferably, the modified kaolin suspension in the step 2) is mixed with the DMC aqueous solution, added into an electric stirrer and stirred at a high speed for 14 hours at 60 ℃.
Preferably, the first zone temperature of the extruder in the step 3) is 168 ℃, the second zone temperature is 200 ℃, the third zone temperature is 245 ℃, the fourth zone temperature is 250 ℃, and the rotating speed of the screw of the extruder is 3.5 r/min.
Preferably, the tractor in the step 3) is pre-drawn at 80 r/min.
Preferably, the nascent fiber in the step 4) is cooled in paraffin oil at the temperature of 12 ℃ after passing through a normal-temperature nitrogen air gap with the length of 60 mm.
Preferably, the first-stage hot stretching temperature in the step 5) is 103 ℃ and the multiple is 3, the second-stage hot stretching temperature is 112 ℃ and the multiple is 4, and the third-stage hot stretching temperature is 118 ℃ and the multiple is 5.
(III) advantageous effects
Compared with the prior art, the invention provides a preparation method for high molecular weight polyethylene fiber by melt spinning, which has the following beneficial effects:
1. the melt spinning preparation method comprises the steps of carrying out ion exchange on micron-sized kaolin by adopting a cationic monomer of methacryloyloxyethyl trimethyl ammonium chloride to prepare organic kaolin, blending the organic kaolin with an initiator of dibenzoyl peroxide and high molecular weight polyethylene, granulating in a granulation auxiliary machine to prepare modified high molecular weight polyethylene particles, carrying out melt extrusion on the modified high molecular weight polyethylene particles in a screw extruder to prepare primary fibers, carrying out hot stretching after cooling and drying the primary fibers, carrying out heat setting, curling and false twisting after stretching to prepare the high molecular weight polyethylene fibers, wherein the lamellar kaolin has weak bonding force among lamellar layers, small friction coefficient, compact internal structure and high rigidity, and can remarkably improve the melt flow property of the high molecular weight polyethylene by utilizing the sliding among the lamellar layers without changing the main property of the high molecular weight polyethylene, the high molecular weight polyethylene can be prepared by adopting a common extruder in an extrusion manner, and the technical problem of great preparation difficulty caused by high entanglement of molecular chains, extremely high melt viscosity and extremely low melt flow rate of the main raw material high molecular weight polyethylene for preparing the high molecular weight polyethylene fiber is solved.
2. Compared with the traditional gel spinning preparation method, the melt spinning preparation method not only omits the steps of dissolution, extraction and the like in the gel spinning method, but also does not need to recover the solvent, and is more environment-friendly, so that the melt spinning preparation method is simpler and more convenient, and the production rate of the high molecular weight polyethylene fiber can be obviously improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
(1) adding 5 parts by mass of kaolin crude ore and 100 parts by mass of deionized water into a stirring barrel, fully stirring, standing for 10min, siphoning out a suspension liquid with the upper part of 40mm, adding deionized water with the same volume as the sucked suspension liquid into the stirring barrel, stirring, settling and extracting for many times, repeating the steps until the suspension liquid with the upper part of 40mm in the stirring barrel is not turbid after adding the deionized water and stirring for 10min, and filtering and drying the obtained kaolin pulp to obtain purified kaolin;
(2) adding 3 parts by mass of the purified kaolin prepared in the step (1) and 20 parts by mass of deionized water into an electric stirrer, stirring and dispersing for 2 hours by using the electric stirrer at room temperature, adding 5 parts by mass of a sodium hydroxide solution with the mass fraction of 4% into the electric stirrer, continuously stirring for 2 hours at room temperature, centrifuging and washing until the upper layer centrifugate is neutral, drying at 70 ℃, and grinding to 200 meshes after drying to prepare micron-sized modified kaolin;
(3) adding 1 part by mass of the modified kaolin prepared in the step (2) into 20 parts by mass of deionized water, and stirring and mixing at a high speed to prepare a high-dispersion modified kaolin suspension;
(4) adding 4 parts by mass of methacryloyloxyethyl trimethyl ammonium chloride into 40 parts by mass of deionized water, and fully stirring and mixing to prepare a DMC aqueous solution;
(5) mixing the modified kaolin suspension prepared in the step (3) and the DMC aqueous solution prepared in the step (4), adding the mixture into an electric stirrer, stirring at a high speed for 12 hours at 50 ℃, naturally cooling to room temperature, carrying out suction filtration on the reaction solution to obtain a white precipitate, washing the white precipitate with deionized water until no chloride ion exists, then placing the white precipitate in a vacuum drying oven, drying the white precipitate for 18 hours at 70 ℃, grinding the white precipitate, sieving the white precipitate with a 200-mesh sieve, and carrying out sealed storage to obtain a modifier;
(6) adding 3 parts by mass of the modifier prepared in the step (5) and 0.2 part by mass of dibenzoyl peroxide into 5 parts by mass of absolute ethyl alcohol, and stirring for 10min to prepare a mixed solution;
(7) adding the mixed solution prepared in the step (6) and 40 parts by mass of high molecular weight polyethylene into an electric stirrer, stirring and mixing at a high speed for 1h, and granulating by adopting a granulation auxiliary machine to prepare modified high molecular weight polyethylene particles;
(8) placing the modified high molecular weight polyethylene particles prepared in the step (7) in a vacuum drying oven, drying for 4h at 100 ℃, taking out, adding into a screw extruder, wherein the temperature of a first zone of the extruder is 165 ℃, the temperature of a second zone of the extruder is 175 ℃, the temperature of a third zone of the extruder is 230 ℃, the temperature of a fourth zone of the extruder is 245 ℃, the rotating speed of a screw of the extruder is 3r/min, the high molecular weight polyethylene particles are melted in the screw extruder, and are extruded from a monofilament machine head with the diameter of 1mm, and simultaneously, pre-traction is carried out by a tractor at 75r/min to prepare nascent fibers;
(9) allowing the nascent fiber prepared in the step (8) to pass through a normal-temperature nitrogen air gap with the length of 40mm, and cooling with chilled water at the temperature of 8 ℃ to prepare gel fiber;
(10) and (3) drying the gel fiber prepared in the step (9), then, entering a three-stage hot oven to carry out hot stretching in three stages, wherein the first-stage hot stretching temperature is 103 ℃, and the multiple is 2, the second-stage hot stretching temperature is 112 ℃, and the multiple is 3, the third-stage hot stretching temperature is 118 ℃, and the multiple is 4, and after the third-stage hot stretching, carrying out hot setting, curling and false twisting to obtain the high molecular weight polyethylene fiber.
Example two:
(1) adding 8 parts by mass of kaolin crude ore and 150 parts by mass of deionized water into a stirring barrel, fully stirring, standing for 20min, siphoning out suspension liquid with the upper part of 75mm, adding deionized water with the same volume as the sucked suspension liquid into the stirring barrel, stirring, settling and extracting for many times, repeating the steps until the suspension liquid with the upper part of 75mm in the stirring barrel is not turbid after adding the deionized water and stirring for 20min, and filtering and drying the obtained kaolin pulp to obtain purified kaolin;
(2) adding 5 parts by mass of the purified kaolin prepared in the step (1) and 30 parts by mass of deionized water into an electric stirrer, stirring and dispersing for 4 hours by using the electric stirrer at room temperature, adding 8 parts by mass of a sodium hydroxide solution with the mass fraction of 4% into the electric stirrer, continuously stirring for 3 hours at room temperature, centrifuging and washing until the upper layer centrifugate is neutral, drying at 80 ℃, and grinding to 200 meshes after drying to prepare micron-sized modified kaolin;
(3) adding 1.5 parts by mass of the modified kaolin prepared in the step (2) into 30 parts by mass of deionized water, and stirring and mixing at a high speed to prepare a high-dispersion modified kaolin suspension;
(4) adding 6 parts by mass of methacryloyloxyethyl trimethyl ammonium chloride into 60 parts by mass of deionized water, and fully stirring and mixing to prepare a DMC aqueous solution;
(5) mixing the modified kaolin suspension prepared in the step (3) and the DMC aqueous solution prepared in the step (4), adding the mixture into an electric stirrer, stirring at a high speed for 14 hours at the temperature of 60 ℃, naturally cooling to room temperature, carrying out suction filtration on the reaction solution to obtain a white precipitate, washing the white precipitate with deionized water until no chloride ion exists, then placing the white precipitate in a vacuum drying oven, drying the white precipitate for 21 hours at the temperature of 80 ℃, grinding the white precipitate, sieving the white precipitate with a 200-mesh sieve, and carrying out sealed storage to obtain a modifier;
(6) adding 6 parts by mass of the modifier prepared in the step (5) and 0.4 part by mass of dibenzoyl peroxide into 8 parts by mass of absolute ethyl alcohol, and stirring for 20min to prepare a mixed solution;
(7) adding the mixed solution prepared in the step (6) and 50 parts by mass of high molecular weight polyethylene into an electric stirrer, stirring and mixing at a high speed for 2 hours, and granulating by adopting a granulation auxiliary machine to prepare modified high molecular weight polyethylene particles;
(8) placing the modified high molecular weight polyethylene particles prepared in the step (7) in a vacuum drying oven, drying for 6h at 102 ℃, taking out, adding into a screw extruder, wherein the temperature of a first zone of the extruder is 168 ℃, the temperature of a second zone of the extruder is 200 ℃, the temperature of a third zone of the extruder is 245 ℃, the temperature of a fourth zone of the extruder is 250 ℃, the rotating speed of a screw of the extruder is 3.5r/min, the high molecular weight polyethylene particles are melted in the screw extruder and extruded from a monofilament machine head with the diameter of 2mm, and simultaneously, pre-drawing by a tractor at 80r/min to prepare nascent fibers;
(9) allowing the nascent fiber prepared in the step (8) to pass through a normal-temperature nitrogen air gap with the length of 60mm, and cooling with chilled water at the temperature of 12 ℃ to prepare gel fiber;
(10) and (3) drying the gel fiber prepared in the step (9), then, entering a three-stage hot oven to carry out hot stretching in three stages, wherein the first-stage hot stretching temperature is 106 ℃, the multiple is 3, the second-stage hot stretching temperature is 115 ℃, the multiple is 4, the third-stage hot stretching temperature is 121 ℃, the multiple is 5, and after the third-stage hot stretching, the high molecular weight polyethylene fiber is subjected to heat setting, curling and false twisting to obtain the high molecular weight polyethylene fiber.
Example three:
(1) adding 10 parts by mass of kaolin crude ore and 200 parts by mass of deionized water into a stirring barrel, fully stirring, standing for 30min, siphoning out a suspension with the upper part of 100mm, adding deionized water with the same volume as the sucked suspension into the stirring barrel, stirring, settling and extracting, repeating the steps for many times until the suspension in the range of 100mm above the stirring barrel is not turbid after adding the deionized water and stirring for 30min, and filtering and drying the obtained kaolin pulp to obtain purified kaolin;
(2) adding 7.5 parts by mass of the purified kaolin prepared in the step (1) and 50 parts by mass of deionized water into an electric stirrer, stirring and dispersing for 5 hours by using the electric stirrer at room temperature, adding 10 parts by mass of a sodium hydroxide solution with the mass fraction of 4% into the electric stirrer, continuously stirring for 4 hours at room temperature, centrifuging and washing until the upper layer centrifugate is neutral, drying at 90 ℃, and grinding into powder of 200 meshes after drying to prepare micron-sized modified kaolin;
(3) adding 2 parts by mass of the modified kaolin prepared in the step (2) into 40 parts by mass of deionized water, and stirring and mixing at a high speed to prepare a high-dispersion modified kaolin suspension;
(4) adding 8 parts by mass of methacryloyloxyethyl trimethyl ammonium chloride into 80 parts by mass of deionized water, and fully stirring and mixing to prepare a DMC aqueous solution;
(5) mixing the modified kaolin suspension prepared in the step (3) and the DMC aqueous solution prepared in the step (4), adding the mixture into an electric stirrer, stirring at a high speed for 16h at the temperature of 80 ℃, naturally cooling to room temperature, carrying out suction filtration on the reaction solution to obtain a white precipitate, washing the white precipitate with deionized water until no chloride ion exists, then placing the white precipitate in a vacuum drying oven, drying the white precipitate for 24h at the temperature of 90 ℃, grinding the white precipitate, sieving the white precipitate with a 200-mesh sieve, and carrying out sealed storage to obtain a modifier;
(6) adding 8 parts by mass of the modifier prepared in the step (5) and 0.5 part by mass of dibenzoyl peroxide into 10 parts by mass of absolute ethyl alcohol, and stirring for 30min to prepare a mixed solution;
(7) adding the mixed solution prepared in the step (6) and 60 parts by mass of high molecular weight polyethylene into an electric stirrer, stirring and mixing at a high speed for 3 hours, and granulating by adopting a granulation auxiliary machine to prepare modified high molecular weight polyethylene particles;
(8) placing the modified high molecular weight polyethylene particles prepared in the step (7) in a vacuum drying oven, drying for 8h at 104 ℃, taking out, adding into a screw extruder, wherein the temperature of a first zone of the extruder is 170 ℃, the temperature of a second zone of the extruder is 225 ℃, the temperature of a third zone of the extruder is 265 ℃, the temperature of a fourth zone of the extruder is 255 ℃, the rotating speed of a screw of the extruder is 3-5r/min, melting the high molecular weight polyethylene particles in the screw extruder, extruding from a monofilament machine head with the diameter of 3mm, and pre-drawing at 85r/min by adopting a tractor to prepare nascent fibers;
(9) allowing the nascent fiber prepared in the step (8) to pass through a normal-temperature nitrogen air gap with the length of 80mm, and cooling with chilled water at the temperature of 15 ℃ to prepare gel fiber;
(10) and (3) drying the gel fiber prepared in the step (9), then, entering a three-stage hot oven to carry out hot stretching in three stages, wherein the first-stage hot stretching temperature is 108 ℃, and the multiple is 4, the second-stage hot stretching temperature is 117 ℃, and the multiple is 5, the third-stage hot stretching temperature is 123 ℃, and the multiple is 6, and after the third-stage hot stretching, the high molecular weight polyethylene fiber is prepared.
Experimental example:
the breaking strength, initial modulus and breaking strength variation coefficient of the high molecular weight polyethylene fibers prepared in the first example, the second example and the third example are measured according to GB/T19975-.
TABLE 1
And (4) judging the standard: GB/T29554-2013 tensile property test method for high-strength fiber filaments stipulates that the physical properties of the ultrahigh molecular weight polyethylene fibers meet the regulations in Table 2.
TABLE 2 physical Properties of ultra high molecular weight polyethylene fibers
The invention has the beneficial effects that: the breaking strength of the high molecular weight polyethylene fibers prepared in the first embodiment, the second embodiment and the third embodiment is 3441MPa, 3481MPa and 3412MPa in sequence, and is all larger than 3395MPa, and the breaking strength index requirements of the ultrahigh molecular weight polyethylene fibers in the GB/T29554-;
the initial moduli of the high molecular weight polyethylene fibers prepared in the first embodiment, the second embodiment and the third embodiment are 117GPa, 121GPa and 118GPa in sequence, which are all larger than 112GPa, and both meet the initial modulus index requirement of the ultrahigh molecular weight polyethylene fibers in the specification of GB/T29554-2013 'test method for tensile property of high strength fiber filaments';
the breaking strength variation coefficients of the high molecular weight polyethylene fibers prepared in the first embodiment, the second embodiment and the third embodiment are respectively 2.67%, 2.54% and 2.43%, and are less than 8.0%, and both meet the breaking strength variation coefficient index requirement of the ultrahigh molecular weight polyethylene fibers in the GB/T29554-;
the oil content of the oil-free agent fiber of the high molecular weight polyethylene fiber prepared in the first embodiment, the second embodiment and the third embodiment is 0.011%, 0.009% and 0.014% in sequence, and is less than 0.5%, which all meet the oil content index requirement of the oil-free agent fiber of the ultra-high molecular weight polyethylene fiber in the GB/T29554-.
Typical cases are as follows: (1) adding 8 parts by mass of kaolin crude ore and 150 parts by mass of deionized water into a stirring barrel, fully stirring, standing for 20min, siphoning out suspension liquid with the upper part of 75mm, adding deionized water with the same volume as the sucked suspension liquid into the stirring barrel, stirring, settling and extracting for many times, repeating the steps until the suspension liquid with the upper part of 75mm in the stirring barrel is not turbid after adding the deionized water and stirring for 20min, and filtering and drying the obtained kaolin pulp to obtain purified kaolin;
(2) adding 5 parts by mass of the purified kaolin prepared in the step (1) and 30 parts by mass of deionized water into an electric stirrer, stirring and dispersing for 4 hours by using the electric stirrer at room temperature, adding 8 parts by mass of a sodium hydroxide solution with the mass fraction of 4% into the electric stirrer, continuously stirring for 3 hours at room temperature, centrifuging and washing until the upper layer centrifugate is neutral, drying at 80 ℃, and grinding to 200 meshes after drying to prepare micron-sized modified kaolin;
(3) adding 1.5 parts by mass of the modified kaolin prepared in the step (2) into 30 parts by mass of deionized water, and stirring and mixing at a high speed to prepare a high-dispersion modified kaolin suspension;
(4) adding 6 parts by mass of methacryloyloxyethyl trimethyl ammonium chloride into 60 parts by mass of deionized water, and fully stirring and mixing to prepare a DMC aqueous solution;
(5) mixing the modified kaolin suspension prepared in the step (3) and the DMC aqueous solution prepared in the step (4), adding the mixture into an electric stirrer, stirring at a high speed for 14 hours at the temperature of 60 ℃, naturally cooling to room temperature, carrying out suction filtration on the reaction solution to obtain a white precipitate, washing the white precipitate with deionized water until no chloride ion exists, then placing the white precipitate in a vacuum drying oven, drying the white precipitate for 21 hours at the temperature of 80 ℃, grinding the white precipitate, sieving the white precipitate with a 200-mesh sieve, and carrying out sealed storage to obtain a modifier;
(6) adding 6 parts by mass of the modifier prepared in the step (5) and 0.4 part by mass of dibenzoyl peroxide into 8 parts by mass of absolute ethyl alcohol, and stirring for 20min to prepare a mixed solution;
(7) adding the mixed solution prepared in the step (6) and 50 parts by mass of high molecular weight polyethylene into an electric stirrer, stirring and mixing at a high speed for 2 hours, and granulating by adopting a granulation auxiliary machine to prepare modified high molecular weight polyethylene particles;
(8) placing the modified high molecular weight polyethylene particles prepared in the step (7) in a vacuum drying oven, drying for 6h at 102 ℃, taking out, adding into a screw extruder, wherein the temperature of a first zone of the extruder is 168 ℃, the temperature of a second zone of the extruder is 200 ℃, the temperature of a third zone of the extruder is 245 ℃, the temperature of a fourth zone of the extruder is 250 ℃, the rotating speed of a screw of the extruder is 3.5r/min, the high molecular weight polyethylene particles are melted in the screw extruder and extruded from a monofilament machine head with the diameter of 2mm, and simultaneously, pre-drawing by a tractor at 80r/min to prepare nascent fibers;
(9) allowing the nascent fiber prepared in the step (8) to pass through a normal-temperature nitrogen air gap with the length of 60mm, and cooling with chilled water at the temperature of 12 ℃ to prepare gel fiber;
(10) and (3) drying the jelly glue fiber prepared in the step (9), putting the jelly glue fiber into a three-stage hot oven, and carrying out hot stretching in three stages, wherein the first-stage hot stretching temperature is 106 ℃, the multiple is 3, the second-stage hot stretching temperature is 115 ℃, the multiple is 4, the third-stage hot stretching temperature is 121 ℃, the multiple is 5, and after the three-stage hot stretching, carrying out hot setting, curling and false twisting to obtain the high molecular weight polyethylene fiber, wherein the breaking strength of the high molecular weight polyethylene fiber is 3481MPa, the initial modulus of the high molecular weight polyethylene fiber is 121GPa, the breaking strength variation coefficient of the high molecular weight polyethylene fiber is 2.54%, and the oil content of the oil-free agent.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.