Method for recovering carbon fibers from composite waste
10851308 ยท 2020-12-01
Assignee
Inventors
- Gang Sui (Beijing, CN)
- Xiaoping Yang (Beijing, CN)
- Xin Jin (Beijing, CH)
- Zhu Ming (Beijing, CN)
- Tianyu Wu (Beijing, CN)
Cpc classification
B08B3/12
PERFORMING OPERATIONS; TRANSPORTING
Y02W30/62
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B01J35/50
PERFORMING OPERATIONS; TRANSPORTING
C01B32/05
CHEMISTRY; METALLURGY
B01J27/125
PERFORMING OPERATIONS; TRANSPORTING
C10B53/07
CHEMISTRY; METALLURGY
D01F9/12
TEXTILES; PAPER
B01J27/138
PERFORMING OPERATIONS; TRANSPORTING
Y02P20/143
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
D01F9/12
TEXTILES; PAPER
B08B3/12
PERFORMING OPERATIONS; TRANSPORTING
B01J27/138
PERFORMING OPERATIONS; TRANSPORTING
B01J27/125
PERFORMING OPERATIONS; TRANSPORTING
C10B53/07
CHEMISTRY; METALLURGY
C01B32/05
CHEMISTRY; METALLURGY
Abstract
A method for recovering carbon fibers from composite waste includes coating a water-soluble catalyst powder on a surface of composite waste having carbon fibers and a resin matrix and pyrolyzing the resin matrix of the coated composite waste.
Claims
1. A method for recovering carbon fibers from composite waste, the method comprising: coating a water-soluble catalyst powder on a surface of composite waste having carbon fibers and a resin matrix; and pyrolyzing the resin matrix of the coated composite waste.
2. The method of claim 1 wherein the step of coating includes spraying the water-soluble catalyst powder on the surface of the composite waste with an amount of 0.1-0.5 g/cm.sup.2.
3. The method of claim 1 wherein the step of pyrolyzing includes putting the coated composite waste into a pyrolysis device.
4. The method of claim 1 wherein the step of pyrolyzing includes heating to 250 to 450 C. for 10 to 30 minutes.
5. The method of claim 4 further comprising stopping the heating and naturally cooling to room temperature.
6. The method of claim 1 wherein the catalyst is a solid powder at room temperature, has a melting point between 250 C. and 400 C., and has stable chemical properties.
7. The method of claim 1 wherein the catalyst includes a main catalyst and sodium bicarbonate.
8. The method of claim 7 wherein the main catalyst includes zinc chloride, sodium tetrachloroaluminate, zinc sulfate, or a mixture thereof.
9. The method of claim 1 wherein the resin matrix includes a thermosetting resin.
10. The method of claim 9 wherein the thermosetting resin includes at least one of epoxy resin, unsaturated polyester, and phenolic resin.
11. The method of claim 1 wherein the resin matrix includes a thermoplastic resin.
12. The method of claim 11 wherein the thermoplastic resin includes at least one of polyolefin, nylon, and polyester.
13. The method of claim 1 wherein the carbon fibers include at least one of polyacrylonitrile-based carbon fibers and asphalt-based carbon fibers.
14. The method of claim 1 wherein a morphology of the carbon fibers includes at least one of continuous fibers, long fibers, short fibers, powdered fibers and carbon fiber fabrics.
15. The method of claim 1 wherein the catalyst becomes a molten state as liquid film adhering to a surface of the composite waste, thereby facilitating a degradation of the resin matrix.
16. The method of claim 1 further comprising subjecting recovered carbon fibers to ultrasonic cleaning in water to obtain carbon fibers with a clean surface.
17. A method for recovering carbon fibers from composite waste, the method comprising: spraying a water-soluble catalyst powder on a surface of composite waste having carbon fibers and a resin matrix with an amount of 0.1-0.5 g/cm.sup.2; and putting the catalyst covered composite waste into a pyrolysis device and heating the catalyst covered composite waste to 250 to 450 C. for 10 to 30 minutes.
18. The method of claim 17 further comprising stopping the heating and naturally cooling to room temperature.
19. The method of claim 18 further comprising taking the carbon fibers out of the pyrolysis device and ultrasonic cleaning the carbon fibers in water to obtain carbon fibers with a clean surface.
20. The method of claim 17 wherein the catalyst is a solid powder at room temperature, has a melting point between 250 C. and 400 C., and has stable chemical properties.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
(8) As shown in
(9) In an aspect, the method includes the following steps: (1) evenly spraying the water-soluble catalyst powder on the surface of the composite material waste with an amount of 0.1-0.5 g/cm.sup.2; and (2) putting the catalyst covered composite material waste into a pyrolysis device and heat the materials to 270-450 C. for 10-30 minutes. A pyrolysis reaction occurs in the resin matrix of the composite during this time. Then, the heating is stopped and the pyrolyzed waste is naturally cooled to room temperature, and the recovered fibers are taken out of the pyrolysis device and cleaned with deionized water using ultrasonic.
(10) Compared with existing technologies, the method of the present description decreases the pyrolytic temperature by 50-100 C. and reduces the degradation time by no less than 10 min due to the addition of catalyst. Therefore, the energy consumption is reduced during the pyrolysis process. Additionally, the catalyst dissolved in water after ultrasonic cleaning can be recycled. The recycling efficiency of the carbon fibers in the present description is very high and the retention ratio of monofilament tensile strength can reach 95%. The operation process is simple, so it is suitable for industrial production.
(11) In an aspect, the catalyst is a solid powder at room temperature, the melting point is between 250 and 400 C., and the chemical properties are stable. The catalyst may consist of a main catalyst and sodium bicarbonate, wherein the main catalyst is preferably zinc chloride, sodium tetrachloroaluminate, zinc sulfate, or a mixture thereof composed in a certain ratio, and wherein the sodium bicarbonate as an auxiliary reagent is decomposed to produce carbon dioxide and water during the heating process, which facilitates the catalysis effect of the main catalyst on the pyrolysis reaction occurring in the resin matrix of the composite waste.
(12) In an aspect, the matrix resin in said composite material waste is epoxy resin, or the epoxy resin may be replaced with a thermosetting resin such as unsaturated polyester, phenolic resin or thermoplastic resin such as polyolefin, nylon, or polyester.
(13) In an aspect, the carbon fibers in the composite material waste are polyacrylonitrile-based carbon fibers, or the polyacrylonitrile-based carbon fibers may be replaced with asphalt-based carbon fibers.
(14) In an aspect, the carbon fibers in the composite material waste have a morphology of continuous fibers, or the continuous fibers may be replaced with long fibers, short fibers, powdered fibers, or carbon fiber fabrics.
(15) In an aspect, the catalyst becomes a molten state as liquid film adhering to the surface of the carbon fiber composite at a certain temperature, facilitating the degradation of the resin matrix.
(16) In an aspect, the recovered carbon fibers are subjected to ultrasonic cleaning in water to obtain carbon fibers with a clean surface and a structural integrity
(17) In an aspect, the catalyst can be recycled from the aqueous solution, and the recovered carbon fibers are not oxidized, which has a high retention ratio of mechanical properties, and is good for future applications.
(18) The objective of the present description is to provide a method capable of achieving the effective separation and recovery of high-performance carbon fibers from carbon fiber-reinforced resin composite waste, so as to increase the recovery efficiency, reduce the energy consumption and cost in the recovery process, and achieve resource savings and low impact on environment.
(19) The essence of the present description lies in reducing the temperature and time of the pyrolysis of the resin matrix in waste carbon fiber composites by catalyst addition. The catalyst forms a liquid film on the surface of the waste composites and permeates into the material, so that the temperature and time of the decomposition of the resin matrix are reduced. A small amount of the resin matrix degradation product is combined with the catalyst and cooled to form a solid, and after ultrasonic cleaning with deionized water, carbon fibers with a clean surface and a structural integrity can be obtained. The mass recovery rate of the obtained carbon fibers in the present description is very high and the retention ratio of monofilament tensile strength can reach 95%, which is advantageous for various subsequent applications.
(20) Preferably, the catalyst is solid powder at room temperature, the melting point is between 250 and 400 C., and the chemical properties are stable. The catalyst consists of main catalyst and sodium bicarbonate. The main catalyst is preferably zinc chloride, sodium tetrachloroaluminate, zinc sulfate, or a mixture thereof in a certain ratio. The sodium bicarbonate as an auxiliary reagent is decomposed to produce carbon dioxide and water in the temperature increase process, which can facilitate the catalysis effect of the main catalyst on the pyrolysis reaction occurring to the resin matrix of the composite. The mixture of the main catalyst and the sodium bicarbonate is evenly sprayed on the surface of the material in an amount of 0.1-0.5 g/cm.sup.2.
(21) Preferably, said pyrolysis reaction temperature is 250-450 C. According to TGA test, the resin matrix can be fully degraded at 450 C. in air atmosphere, and the carbon fibers can hardly be oxidized, so that the properties of the recycled carbon fibers can be retained very well. If the temperature is higher than 450 C., the carbon fibers surface will be oxidized which leads to bad performance. When the temperature is lower than 250 C., the rate of the resin degradation is low, even the degradation of resin could be incomplete, which will increase the treatment time and cost, or cannot get clean recycled fibers.
(22) As compared to the prior art, the method in the present description has the following advantages: firstly, the equipment is simple, the technological process is facile, and the treatment cost is low. And secondly, the present description not only can achieve fully decomposition of the resin matrix in the composite waste (SEM photographs of carbon fibers recovered by pyrolysis with addition of catalyst, carbon fibers recovered by pyrolysis without addition of the catalyst, and virgin commercial carbon fiber shown in
(23) The present description is described in further detail in conjunction with particular embodiments below.
Example 1
(24) In a chosen carbon fiber composite waste, the carbon fibers are Toray T700, the resin matrix is 4,4-diaminodiphenylmethane epoxy resin, and the curing agent is diaminodiphenyl sulfone, wherein the carbon fibers have a mass fraction of 65%, a 2 mm thick carbon fiber composite plate is cut into about 25 cm.sup.2, placed in a square crucible, then placed in a pyrolysis furnace and heated to 450 C., so that the resin matrix in the composite undergoes a pyrolysis reaction at this temperature, the heating is stopped after 20 min, the material is naturally cooled to room temperature, a product is taken out, and then the product is placed in deionized water, subjected to ultrasonic cleaning for 10 min, and dried to obtain recovered carbon fibers. According to standard ASTM-D 3379, the carbon fibers are subjected to a monofilament tensile test, and the monofilament tensile strength is 4.05 GPa. The tensile strength retention rate is 82.7% with respect to that of the commercial T700 carbon fiber monofilaments.
(25) For the same carbon fiber composite sample, the catalyst is evenly sprayed on the surface thereof, the mass ratio of zinc chloride to sodium tetrachloroaluminate to zinc sulfate to sodium bicarbonate in the catalyst being 75:5:10:10, the amount of the catalyst being 0.1 g/cm.sup.2. Then, the sample is placed in a pyrolysis furnace and heated to 270 C., so that the resin matrix in the carbon fiber composite undergoes a pyrolysis reaction at this temperature for 30 min, the material is naturally cooled to room temperature, a product is taken out, and then the product is placed in deionized water, subjected to ultrasonic cleaning, and dried to obtain recovered carbon fibers. According to standard ASTM-D 3379, the carbon fibers are subjected to a monofilament tensile test, and the monofilament tensile strength is 4.11 GPa. The tensile strength retention rate is 83.9% with respect to that of the commercial T700 carbon fiber monofilaments.
(26) For the same carbon fiber composite sample, the catalyst is evenly sprayed on the surface thereof, the mass ratio of zinc chloride to sodium tetrachloroaluminate to zinc sulfate to sodium bicarbonate being 75:5:10:10, the amount of the catalyst being 0.1 g/cm.sup.2, then, the sample is placed in a pyrolysis furnace and heated to 350 C., so that the resin matrix in the carbon fiber composite undergoes a pyrolysis reaction at this temperature for 20 min, the material is naturally cooled to room temperature, a product is taken out, and then the product is placed in deionized water, subjected to ultrasonic cleaning for 10 min, and dried to obtain recovered carbon fibers. According to standard ASTM-D 3379, the carbon fibers are subjected to a monofilament tensile test, and the monofilament tensile strength is 4.19 GPa. The tensile strength retention rate is 85.5% with respect to that of the commercial T700 carbon fiber monofilaments.
(27) For the same carbon fiber composite sample, a catalyst is evenly sprayed on the surface thereof, the mass ratio of zinc chloride to sodium tetrachloroaluminate to zinc sulfate to sodium bicarbonate being 75:5:10:10, the amount of the catalyst being 0.1 g/cm.sup.2, then, the sample is placed in a pyrolysis furnace and heated to 400 C., so that the resin matrix in the carbon fiber composite undergoes a pyrolysis reaction at this temperature for 10 min, the material is naturally cooled to room temperature, a product is taken out, and then the product is placed in deionized water, subjected to ultrasonic cleaning for 10 min, and dried to obtain recovered carbon fibers. According to standard ASTM-D 3379, the carbon fibers are subjected to a monofilament tensile test, and the monofilament tensile strength is 4.39 GPa. The tensile strength retention rate is 89.6% with respect to that of the commercial T700 carbon fiber monofilaments.
(28) For the same carbon fiber composite sample, a catalyst is evenly sprayed on the surface thereof, the mass ratio of zinc chloride to sodium tetrachloroaluminate to zinc sulfate to sodium bicarbonate being 75:5:10:10, the amount of the catalyst being 0.1 g/cm.sup.2, then, the sample is placed in a pyrolysis furnace and heated to 450 C., so that the resin matrix in the carbon fiber composite undergoes a pyrolysis reaction at this temperature for 10 min, the material is naturally cooled to room temperature, a product is taken out, and then the product is placed in deionized water, subjected to ultrasonic cleaning for 10 min, and dried to obtain recovered carbon fibers. According to standard ASTM-D 3379, the carbon fibers are subjected to a monofilament tensile test, and the monofilament tensile strength is 4.27 GPa. The tensile strength retention rate is 87.1% with respect to that of the commercial T700 carbon fiber monofilaments.
Example 2
(29) In a chosen carbon fiber composite waste, the carbon fibers are Toray T700, the resin matrix is a 4,4-diaminodiphenylmethane epoxy resin, and the curing agent is diaminodiphenyl sulfone, wherein the carbon fibers have a mass fraction of 65%, a 2 mm thick carbon fiber composite plate is cut into about 25 cm.sup.2, placed in a square crucible, then placed in a pyrolysis furnace and heated to 400 C., so that the resin matrix in the carbon fiber resin composite undergoes a pyrolysis reaction, the heating is stopped after 30 min, the material is naturally cooled to room temperature, a product is taken out, and then the product is placed in deionized water, subjected to ultrasonic cleaning for 10 min, and dried to obtain recovered carbon fibers. According to standard ASTM-D 3379, the carbon fibers are subjected to a monofilament tensile test, and the monofilament tensile strength is 4.10 GPa. The tensile strength retention rate is 83.7% with respect to that of the commercial T700 carbon fiber monofilaments.
(30) For the same carbon fiber composite sample, a catalyst is evenly sprayed on the surface thereof, the mass ratio of zinc chloride to sodium tetrachloroaluminate to zinc sulfate to sodium bicarbonate being 75:5:10:10, the amount of zinc chloride being 0.1 g/cm.sup.2, then, the sample is placed in a pyrolysis furnace and heated to 400 C., so that the resin in the carbon fiber resin composite undergoes a pyrolysis reaction at this temperature for 20 min, the material is naturally cooled to room temperature, a product is taken out, and then the product is placed in deionized water, subjected to ultrasonic cleaning for 10 min, and dried to obtain recovered carbon fibers. According to standard ASTM-D 3379, the carbon fibers are subjected to a monofilament tensile test, and the monofilament tensile strength is 4.45 GPa. The tensile strength retention rate is 90.8% with respect to that of the commercial T700 carbon fiber monofilaments.
Example 3
(31) In a chosen carbon fiber composite waste, the carbon fibers are Toray T700, the resin matrix is a 4,4-diaminodiphenylmethane epoxy resin, and the curing agent is diaminodiphenyl sulfone, wherein the carbon fibers have a mass fraction of 65%, a 2 mm thick carbon fiber composite plate is cut into about 25 cm.sup.2, placed in a square crucible of which the surface is layered with a catalyst with a mass ratio of zinc chloride to sodium tetrachloroaluminate to zinc sulfate to sodium bicarbonate of 75:5:10:10 and a catalyst amount of 0.1 g/cm.sup.2, then placed in a pyrolysis furnace and heated to 400 C., so that the resin matrix in the carbon fiber resin composite undergoes a pyrolysis reaction, the heating is stopped after 10 min, the material is naturally cooled to room temperature, a product is taken out, and then the product is placed in deionized water, subjected to ultrasonic cleaning for 10 min, and dried to obtain recovered carbon fibers. According to standard ASTM-D 3379, the carbon fibers are subjected to a monofilament tensile test, and the monofilament tensile strength is 4.17 GPa. The tensile strength retention rate is 85.1% with respect to that of the commercial T700 carbon fiber monofilaments.
(32) For the same carbon fiber composite sample, a catalyst is evenly sprayed on the surface thereof, the mass ratio of zinc chloride to sodium tetrachloroaluminate to zinc sulfate to sodium bicarbonate in the catalyst being 75:5:10:10, the amount of the catalyst being 0.3 g/cm.sup.2, then, the sample is placed in a pyrolysis furnace and heated to 400 C., so that the resin in the carbon fiber resin composite undergoes a pyrolysis reaction at this temperature for 10 min, the heating is stopped, the material is naturally cooled to room temperature, thereafter a product is taken out, and then the product is placed in water, subjected to ultrasonic cleaning for 10 min, and dried to obtain recovered carbon fibers. According to standard ASTM-D 3379, the carbon fibers are subjected to a monofilament tensile test, and the monofilament tensile strength is 4.49 GPa. The tensile strength retention rate is 91.6% with respect to that of the commercial T700 carbon fiber monofilaments.
Example 4
(33) In a chosen carbon fiber composite waste, the carbon fibers are Toray T700, the resin matrix is a 4,4-diaminodiphenylmethane epoxy resin, and the curing agent is diaminodiphenyl sulfone, wherein the carbon fibers have a mass fraction of 65%, a 2 mm thick carbon fiber composite plate is cut into about 25 cm.sup.2, placed in a square crucible of which the surface is evenly sprayed with a catalyst with a mass ratio of zinc chloride to sodium tetrachloroaluminate to zinc sulfate to sodium bicarbonate of 80:20:0:0 and a catalyst amount of 0.5 g/cm.sup.2, then placed in a pyrolysis furnace and heated to 400 C., so that the resin in the carbon fiber resin composite undergoes a pyrolysis reaction at this temperature for 10 min, the heating is stopped, the material is naturally cooled to room temperature, thereafter a product is taken out, and then the product is placed in water, subjected to ultrasonic cleaning for 10 min, and dried to obtain recovered carbon fibers. According to standard ASTM-D 3379, the carbon fibers are subjected to a monofilament tensile test, and the monofilament tensile strength is 4.50 GPa. The tensile strength retention rate is 91.8% with respect to that of the commercial T700 carbon fiber monofilaments.
Example 5
(34) In a chosen carbon fiber composite waste, the carbon fibers are Toray T700, the resin matrix is a 4,4-diaminodiphenylmethane epoxy resin, and the curing agent is diaminodiphenyl sulfone, wherein the carbon fibers have a mass fraction of 65%, a 2 mm thick carbon fiber composite plate is cut into about 25 cm.sup.2, placed in a square crucible of which the surface is evenly sprayed with a catalyst with a mass ratio of zinc chloride to sodium tetrachloroaluminate to zinc sulfate to sodium bicarbonate of 100:0:0:0 and a catalyst amount of 0.3 g/cm.sup.2, then placed in a pyrolysis furnace and heated to 400 C., so that the resin in the carbon fiber resin composite undergoes a pyrolysis reaction at this temperature for 20 min, the heating is stopped, the material is naturally cooled to room temperature, thereafter a product is taken out, and then the product is placed in water, subjected to ultrasonic cleaning for 10 min, and dried to obtain recovered carbon fibers. According to standard ASTM-D 3379, the carbon fibers are subjected to a monofilament tensile test, and the monofilament tensile strength is 4.36 GPa. The tensile strength retention rate is 89.0% with respect to that of the commercial T700 carbon fiber monofilaments.
Example 6
(35) In a chosen carbon fiber composite waste, the carbon fibers are Toray T700, the resin matrix is a 4,4-diaminodiphenylmethane epoxy resin, and the curing agent is diaminodiphenyl sulfone, wherein the carbon fibers have a mass fraction of 65%, a 2 mm thick carbon fiber composite plate is cut into about 25 cm.sup.2, placed in a square crucible of which the surface is evenly sprayed with a catalyst with a mass ratio of zinc chloride to sodium tetrachloroaluminate to zinc sulfate to sodium bicarbonate of 75:5:10:10 and a catalyst amount of 0.3 g/cm.sup.2, then placed in a pyrolysis furnace and heated to 400 C., so that the resin in the carbon fiber resin composite undergoes a pyrolysis reaction at this temperature for 20 min, the heating is stopped, the material is naturally cooled to room temperature, thereafter a product is taken out, and then the product is placed in water, subjected to ultrasonic cleaning for 10 min, and dried to obtain recovered carbon fibers. According to standard ASTM-D 3379, the carbon fibers are subjected to a monofilament tensile test, and the monofilament tensile strength is 4.56 GPa. The tensile strength retention rate is 93.1% with respect to that of the commercial T700 carbon fiber monofilaments.
Example 7
(36) In a chosen carbon fiber composite waste, the carbon fibers are Toray T700, the resin matrix is a 4,4-diaminodiphenylmethane epoxy resin, and the curing agent is diaminodiphenyl sulfone, wherein the carbon fibers have a mass fraction of 65%, a 2 mm thick carbon fiber composite plate is cut into about 25 cm.sup.2, placed in a square crucible of which the surface is evenly sprayed with a catalyst with a mass ratio of zinc chloride to sodium tetrachloroaluminate to zinc sulfate to sodium bicarbonate of 75:5:10:10 and a catalyst amount of 0.3 g/cm.sup.2, then placed in a pyrolysis furnace and heated to 400 C., so that the resin in the carbon fiber resin composite undergoes a pyrolysis reaction at this temperature for 30 min, the heating is stopped, the material is naturally cooled to room temperature, thereafter a product is taken out, and then the product is placed in water, subjected to ultrasonic cleaning for 10 min, and dried to obtain recovered carbon fibers. According to standard ASTM-D 3379, the carbon fibers are subjected to a monofilament tensile test, and the monofilament tensile strength is 4.66 GPa. The tensile strength retention rate is 95.1% with respect to that of the commercial T700 carbon fiber monofilaments.
(37) Examples of the present description may be described in the context of an aircraft manufacturing and service method 100, as shown in
(38) Each of the processes of method 100 may be performed or carried out by a system integrator, a third party, and/or an operator (e.g., a customer). For the purposes of this description, a system integrator may include without limitation any number of aircraft manufacturers and major-system subcontractors; a third party may include without limitation any number of venders, subcontractors, and suppliers; and an operator may be an airline, leasing company, military entity, service organization, and so on.
(39) The disclosed methods may be employed during any one or more of the stages of the aircraft manufacturing and service method 100, particular during material procurement 106, component/subassembly manufacturing 108, system integration 110, and routine maintenance and service 116.
(40) As shown in
(41) The disclosed methods are described in the context of an aircraft; however, one of ordinary skill in the art will readily recognize that the disclosed methods may be utilized for a variety of vehicles and non-vehicles. For example, implementations of the embodiments described herein may be implemented in any type of vehicle including, e.g., helicopters, passenger ships, and automobiles or in any type of non-vehicle, e.g., sporting goods, construction goods and communication products.
(42) Although various embodiments of the disclosed methods have been shown and described, modifications may occur to those skilled in the art upon reading the specification. The present application includes such modifications and is limited only by the scope of the claims.