Disclosure of Invention
The invention aims to provide a preparation method of a high-efficiency air filter material, the air filter material prepared by the invention comprises three layers, the first layer is PET spun-bonded non-woven fabric, the second layer is PET melt-blown non-woven fabric, the third layer is a composite filter cloth layer, the three layers are bonded by an adhesive, a point bonding mode is adopted between the filter material layers, in the point bonding mode, except bonding points, other parts of the filter material layer are not covered by the adhesive, more gaps still exist, and the air permeability of the whole filter material can be ensured; the PET spunbonded nonwoven fabric has large fiber diameter and pore diameter, the PET meltblown nonwoven fabric has the characteristics of fine fibers, multiple pores and small pore size, the fiber diameter and the pore diameter of the composite filter cloth layer are also large, and the filter material forms a multi-layer structure with different porosities in the thickness direction to construct a good dust holding gradient, so that the PET spunbonded nonwoven fabric has high filter efficiency and dust holding capacity, and can achieve ideal protection effect under various polluted weather conditions.
The purpose of the invention can be realized by the following technical scheme:
the preparation method of the high-efficiency air filter material comprises the following steps:
firstly, pretreating PET spun-bonded non-woven fabric and PET melt-blown non-woven fabric, specifically, immersing the PET spun-bonded non-woven fabric and the PET melt-blown non-woven fabric into a mixed solution of NaOH and a penetrating agent JFC with the mass concentration of 25g/L and 5g/L respectively, immersing in water bath at 100 ℃ for 1h, wherein the bath ratio is 20:1, taking out after the immersion, washing with deionized water to be neutral, and drying for later use;
wherein the thickness of the PET spunbonded nonwoven fabric is 0.34-0.4mm, and the thickness of the PET meltblown nonwoven fabric is 0.3-0.35 mm;
step two, carrying out interlayer bonding compounding on the pretreated PET spun-bonded non-woven fabric and the PET melt-blown non-woven fabric, specifically, compounding in a point bonding mode, uniformly spreading point coating adhesive on the PET spun-bonded non-woven fabric at intervals of 3cm in the longitudinal direction and the transverse direction, covering the PET melt-blown non-woven fabric, drying the PET spun-bonded non-woven fabric in a 45 ℃ oven for 70-80min, and taking out to complete the compounding of the PET spun-bonded non-woven fabric and the PET melt-blown non-woven fabric;
spreading the modified carbon fibers on a polyester needled felt, continuously and uniformly spraying catalytic active particles on a modified carbon fiber material, then coating a layer of modified carbon fibers, placing a layer of polyester fabric, and performing hydraulic pressing, wherein the temperature of a hydraulic press is set to be 50 ℃, and the pressure is 2MPa, so as to prepare a composite filter cloth layer; wherein the spraying amount of the catalytic active particles is 10 percent of the mass of the modified carbon fiber, and the thickness of the obtained composite filter cloth layer is 0.12-0.15 mm;
and step four, compounding the composite filter cloth layer on the other surface of the PET melt-blown non-woven fabric in a point bonding mode, specifically, uniformly spreading a point coating adhesive on the PET melt-blown non-woven fabric at intervals of 3cm in the longitudinal direction and the transverse direction, covering the composite filter cloth layer, drying the composite filter cloth layer in a 50 ℃ oven for 60-70min, and taking out the dried composite filter cloth layer to obtain the high-efficiency air filter material.
Furthermore, the high-efficiency air filter material comprises three layers, wherein the first layer is PET spun-bonded non-woven fabric, the second layer is PET melt-blown non-woven fabric, the third layer is a composite filter cloth layer, and the three layers are bonded through an adhesive.
Further, the adhesive is prepared by the following method:
weighing guar gum, adding the guar gum into distilled water, heating and stirring the guar gum in a water bath condition at 70-80 ℃, adding carboxymethyl cellulose after gelatin is completely dissolved, and continuously stirring the mixture until the carboxymethyl cellulose is dissolved to obtain an adhesive;
wherein the mass ratio of the guar gum to the carboxymethyl cellulose to the distilled water is 2:1: 30.
Further, the modified carbon fiber in the third step is prepared by the following method:
1) according to the feed-liquid ratio of 1 g: adding 15-20mL of pre-oxidized fiber into concentrated nitric acid with the mass fraction of 30%, soaking for 10min, performing ultrasonic treatment for 30min, cooling to room temperature, filtering, washing the pre-oxidized fiber to be neutral by using a large amount of deionized water, and drying in a vacuum drying oven at 130 ℃ for 4 h;
2) placing the dried preculture filaments in a tube furnace at 80cm3CO at a flow rate of/min2Heating to 1100 ℃ at the heating rate of 10-15 ℃/min under gas, carrying out heat preservation and activation for 100-130min, and cooling to room temperature to obtain the activated carbon fiber;
3) washing activated carbon fiber with acetone and deionized water for 3-4 times, respectively, and drying in a vacuum drying oven at 120 deg.C for 5-6 h;
4) soaking the dried activated carbon fiber in NaOH solution with the mass fraction of 20%, performing ultrasonic treatment for 10min, taking out, drying, placing the dried activated carbon fiber in a quartz tube at the length of 100cm3N of flow rate/min2Heating to 750-850 ℃ at the heating rate of 10 ℃/min in the atmosphere, preserving the heat for 3h, taking out, repeatedly washing to neutrality by using deionized water, and drying;
5) putting the dried activated carbon fiber into a quartz tube again at 150cm3NH flow/min3Raising the temperature to 780-820 ℃ at the temperature rise rate of 5 ℃/min in the atmosphere, preserving the temperature for 90min, and stopping introducing NH3In N at2And cooling to room temperature in the atmosphere, and taking out to obtain the modified carbon fiber.
Further, the catalytically active particles described in step three are prepared by the following method:
carrying silver TiO according to the mass ratio of 1:192Mixing the powder into P25 type TiO2Drying the nano particles for 3 hours in vacuum at 90 ℃, and then grinding and sieving the nano particles with a 100-mesh sieve to obtain catalytic active particles;
wherein, the silver-carrying TiO2The particle size of the powder was 30 nm.
The invention has the beneficial effects that:
the composite filter cloth layer adopts the modified carbon fiber as a main body, and the surface of the activated carbon fiber subjected to NaOH heat treatment generates a large number of micropores, so that the specific surface area and the pore volume of the activated carbon fiber are increased, the average pore diameter of the activated carbon fiber is reduced, and the adsorption performance (physical adsorption) of the activated carbon fiber is remarkably improved; after ammonia heat treatment, the surface of the activated carbon fiber can react to form a nitrogen-containing functional group which takes pyridine type nitrogen as a main component, the surface of the activated carbon fiber can not be broken and the surface structure can not be damaged, the pyridine type nitrogen is a six-membered ring and contains a heterocyclic nitrogen atom, and a pair of non-bonded lone pair electrons on the nitrogen atom are positioned in SP2The hybrid orbit is not involved in conjugation, so that the hybrid orbit can be combined with H on volatile polar gas molecules to form a hydrogen bond for adsorbing polar molecular gas, and therefore, the increase of the number of pyridine type nitrogen-containing functional groups on the surface of the activated carbon fiber can enhance the adsorption capacity (chemical adsorption) of the active carbon fiber on the polar molecular gas; the activated carbon fiber subjected to alkali heat treatment and ammonia heat treatment can remarkably improve physical adsorption and chemical adsorption, and obtain a modified carbon fiber with excellent adsorption performance;
in the composite filter cloth layer, catalytic active particles, namely P25 type TiO are sprayed between the modified carbon fiber layers2The nanometer particle has great specific surface area, can generate superoxide radical and hydroxyl radical with strong activity when receiving light, can catalyze and oxidize volatile organic compounds, thereby achieving the effect of degrading pollutants, and in addition, the TiO has the advantages of high activity, high stability and the like2Meet withWhen bacteria are used, the organic matters in cells can be catalyzed and oxidized to achieve the effect of killing the bacteria, but the catalytic and bacteriostatic activity exists only under ultraviolet light, and the silver-loaded TiO with the particle size of 30nm2(Ag/TiO2) is mixed into P25 type TiO at a certain ratio2In, TiO can be greatly improved2The antibacterial property of the powder enables the catalytic active particles to have high-efficiency photocatalytic property and antibacterial property;
the air filter material prepared by the invention comprises three layers, wherein the first layer is PET spun-bonded non-woven fabric, the second layer is PET melt-blown non-woven fabric, the third layer is a composite filter cloth layer, the three layers are bonded through an adhesive, a point bonding mode is adopted between the filter material layers, other parts of the filter material layer are not covered by the adhesive except bonding points in the point bonding mode, more gaps still exist, and the air permeability of the whole filter material can be ensured; the PET spunbonded nonwoven fabric has large fiber diameter and pore diameter, the PET meltblown nonwoven fabric has the characteristics of fine fibers, multiple pores and small pore size, the fiber diameter and the pore diameter of the composite filter cloth layer are also large, and the filter material forms a multi-layer structure with different porosities in the thickness direction to construct a good dust holding gradient, so that the PET spunbonded nonwoven fabric has high filter efficiency and dust holding capacity, and can achieve ideal protection effect under various polluted weather conditions.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood 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 preparation method of the high-efficiency air filter material comprises three layers, wherein the first layer is PET spun-bonded non-woven fabric, the second layer is PET melt-blown non-woven fabric, the third layer is a composite filter cloth layer, and the three layers are bonded through an adhesive;
the adhesive is prepared by the following method:
weighing guar gum, adding the guar gum into distilled water, heating and stirring the guar gum in a water bath condition at 70-80 ℃, adding carboxymethyl cellulose after gelatin is completely dissolved, and continuously stirring the mixture until the carboxymethyl cellulose is dissolved to obtain an adhesive;
wherein the mass ratio of the guar gum to the carboxymethyl cellulose to the distilled water is 2:1: 30;
when the guar gum is used as the bonding material, the requirement of high strength can be met, but the filtering material layer is hard, otherwise, when the carboxymethyl cellulose is used alone, the filtering material layer is soft, but the bonding strength is not enough, and when the guar gum and the carboxymethyl cellulose are mixed according to the proportion and used, the bonding strength and the bonding strength are matched with each other, so that the required bonding strength can be achieved, and the flexibility of the filtering material layer can be improved;
the preparation method of the high-efficiency air filter material comprises the following steps:
firstly, pretreating PET spun-bonded non-woven fabric and PET melt-blown non-woven fabric, specifically, immersing the PET spun-bonded non-woven fabric and the PET melt-blown non-woven fabric into a mixed solution of NaOH and a penetrating agent JFC with the mass concentration of 25g/L and 5g/L respectively, immersing in water bath at 100 ℃ for 1h, wherein the bath ratio is 20:1, taking out after the immersion, washing with deionized water to be neutral, and drying for later use;
wherein the thickness of the PET spunbonded non-woven fabric is 0.34-0.4mm, and the thickness of the PET melt-blown non-woven fabric is 0.3-0.35 mm;
step two, carrying out interlayer bonding compounding on the pretreated PET spun-bonded non-woven fabric (first layer) and the PET melt-blown non-woven fabric (second layer), specifically, compounding in a point bonding mode, uniformly spreading point coating adhesive on the PET spun-bonded non-woven fabric at the longitudinal and transverse intervals of 3cm, coating the PET melt-blown non-woven fabric, drying the PET melt-blown non-woven fabric in a drying oven at the temperature of 45 ℃ for 70-80min, and taking out to complete the compounding of the first layer and the second layer;
spreading the modified carbon fibers on a polyester needled felt, wherein the polyester needled felt plays a role in stress buffering to prevent the structure of the material from being damaged due to overlarge material pressure, continuously and uniformly spraying catalytic active particles on the modified carbon fiber material, then covering a layer of modified carbon fibers, placing a layer of polyester fabric, and performing hydraulic pressing, wherein the temperature of a hydraulic press is set to be 50 ℃, and the pressure is 2MPa, so as to prepare a composite filter cloth layer (a third layer); wherein the spraying amount of the catalytic active particles is 10 percent of the mass of the modified carbon fiber, and the thickness of the obtained composite filter cloth layer is 0.12-0.15 mm;
step four, compounding the composite filter cloth layer on the other surface of the PET melt-blown non-woven fabric (second layer) in a point bonding mode, specifically, uniformly scattering point coating adhesive on the PET melt-blown non-woven fabric at intervals of 3cm in the longitudinal direction and the transverse direction, covering the composite filter cloth layer, drying the composite filter cloth layer in a 50 ℃ oven for 60-70min, and taking out to obtain the high-efficiency air filter material;
the filter material layers adopt a point bonding mode, other parts of the filter material layers are not covered by the adhesive except for the bonding points in the point bonding mode, more gaps still exist, the air permeability of the whole filter material can be ensured, the surface of the composite filter material is covered by the adhesive in the surface bonding mode, and the gaps between fibers are filled with the adhesive, so that the resistance pressure drop is large and the air permeability is poor;
the PET spun-bonded non-woven fabric in the air filtering material has larger fiber diameter and pore diameter, the PET melt-blown non-woven fabric has the characteristics of fine fiber, more pores and small pore size, the fiber diameter and pore diameter of the composite filtering cloth layer are also larger, and the filtering material forms a multi-layer structure with different porosities in the thickness direction to construct a good dust holding gradient, so that the air filtering material has higher filtering efficiency and dust holding capacity and can achieve ideal protection effect under various polluted weather conditions;
wherein, the modified carbon fiber in the third step is prepared by the following method:
1) according to the feed-liquid ratio of 1 g: adding 15-20mL of pre-oxidized fiber into concentrated nitric acid with the mass fraction of 30%, soaking for 10min, performing ultrasonic treatment for 30min, cooling to room temperature, filtering, washing the pre-oxidized fiber to be neutral by using a large amount of deionized water, and drying in a vacuum drying oven at 130 ℃ for 4 h;
2) placing the dried precured filaments in a tube furnace in CO2Gas (80 cm)3Min) heating to 1100 ℃ at the heating rate of 10-15 ℃/min, keeping the temperature and activating for 100-;
3) washing activated carbon fiber with acetone and deionized water for 3-4 times, respectively, and drying in a vacuum drying oven at 120 deg.C for 5-6 h;
4) soaking the dried activated carbon fiber in NaOH solution with the mass fraction of 20%, carrying out ultrasonic treatment for 10min, taking out and drying, putting the dried activated carbon fiber into a quartz tube, and adding N2Atmosphere (100 cm)3Min) heating to 750-;
5) putting the activated carbon fiber dried in the step into a quartz tube again, and putting the activated carbon fiber into NH3Atmosphere (150 cm)3Min) is increased to 780-820 ℃ at the temperature rise rate of 5 ℃/min, and NH is stopped to be introduced after the temperature is kept for 90min3In N at2Cooling to room temperature in the atmosphere, and taking out to obtain modified carbon fiber;
the surface of the activated carbon fiber subjected to NaOH heat treatment generates a large number of micropores, the generation of the micropores increases the specific surface area and the pore volume of the activated carbon fiber, reduces the average pore diameter of the activated carbon fiber, and remarkably improves the adsorption performance (physical adsorption) of the activated carbon fiber; after ammonia heat treatment, the surface of the activated carbon fiber can react to form a nitrogen-containing functional group which takes pyridine type nitrogen as a main component, the surface of the activated carbon fiber can not be broken and the surface structure can not be damaged, the pyridine type nitrogen is a six-membered ring and contains a heterocyclic nitrogen atom, and a pair of non-bonded lone pair electrons on the nitrogen atom are positioned in SP2The hybrid orbit is not involved in conjugation, so that the hybrid orbit can be combined with H on volatile polar gas molecules to form a hydrogen bond for adsorbing polar molecular gas, and therefore, the increase of the number of pyridine type nitrogen-containing functional groups on the surface of the activated carbon fiber can enhance the adsorption capacity (chemical adsorption) of the active carbon fiber on the polar molecular gas; the activated carbon fiber subjected to alkali heat treatment and ammonia heat treatment can remarkably improve physical adsorption and chemical adsorption, and obtain a modified carbon fiber with excellent adsorption performance;
the catalytically active particles described in step three are prepared by the following method:
carrying silver TiO according to the mass ratio of 1:192Mixing the powder into P25 type TiO2In nanoparticles, then at 90 ℃Drying for 3h under vacuum, grinding and sieving with a 100-mesh sieve to obtain catalytic active particles;
wherein, the silver-carrying TiO2The particle size of the powder is 30nm, and the powder is produced by Guangzhou Yanrui chemical company Limited;
TiO type P252The nanometer particle has great specific surface area, can generate superoxide radical and hydroxyl radical with strong activity when receiving light, can catalyze and oxidize volatile organic compounds, thereby achieving the effect of degrading pollutants, and in addition, the TiO has the advantages of high activity, high stability and the like2When meeting bacteria, the photocatalyst can catalyze and oxidize organic matters in cells to achieve the effect of killing the bacteria, but the photocatalyst has catalysis and bacteriostasis activity only under ultraviolet light, and silver-loaded TiO with the particle size of 30nm2(Ag/TiO2) is mixed into P25 type TiO at a certain ratio2In, TiO can be greatly improved2The antibacterial property of the powder enables the catalytic active particles to have high-efficiency photocatalytic property and antibacterial property.
Example 1
The preparation method of the high-efficiency air filter material comprises the following steps:
firstly, pretreating PET spun-bonded non-woven fabric and PET melt-blown non-woven fabric, specifically, immersing the PET spun-bonded non-woven fabric and the PET melt-blown non-woven fabric into a mixed solution of NaOH and a penetrating agent JFC with the mass concentration of 25g/L and 5g/L respectively, immersing in water bath at 100 ℃ for 1h, wherein the bath ratio is 20:1, taking out after the immersion, washing with deionized water to be neutral, and drying for later use;
step two, carrying out interlayer bonding compounding on the pretreated PET spun-bonded non-woven fabric and the PET melt-blown non-woven fabric, specifically, compounding in a point bonding mode, uniformly spreading point coating adhesive on the PET spun-bonded non-woven fabric at intervals of 3cm in the longitudinal direction and the transverse direction, covering the PET melt-blown non-woven fabric, drying the PET melt-blown non-woven fabric in a 45 ℃ oven for 70min, and taking out the PET melt-blown non-woven fabric to complete the compounding of the first layer and the second layer;
laying the modified carbon fibers on a polyester needled felt, wherein the polyester needled felt plays a role in stress buffering to prevent the structure of the material from being damaged due to overlarge material pressure, continuously and uniformly spraying catalytic active particles on the modified carbon fiber material, then coating a layer of modified carbon fibers, placing a layer of polyester fabric, and performing hydraulic pressing, wherein the temperature of a hydraulic press is set to be 50 ℃, and the pressure is 2MPa, so as to prepare a composite filter cloth layer; wherein the spraying amount of the catalytic active particles is 10% of the mass of the modified carbon fiber, and the thickness of the obtained composite filter cloth layer is 0.12 mm;
and step four, compounding the composite filter cloth layer on the other surface of the PET melt-blown non-woven fabric (the second layer) in a point bonding mode, specifically, uniformly scattering point coating adhesive on the PET melt-blown non-woven fabric at intervals of 3cm in the longitudinal direction and the transverse direction, covering the composite filter cloth layer, drying the composite filter cloth layer in an oven at the temperature of 50 ℃ for 60min, and taking out the dried composite filter cloth layer to obtain the high-efficiency air filter material.
Example 2
The preparation method of the high-efficiency air filter material comprises the following steps:
firstly, pretreating PET spun-bonded non-woven fabric and PET melt-blown non-woven fabric, specifically, immersing the PET spun-bonded non-woven fabric and the PET melt-blown non-woven fabric into a mixed solution of NaOH and a penetrating agent JFC with the mass concentration of 25g/L and 5g/L respectively, immersing in water bath at 100 ℃ for 1h, wherein the bath ratio is 20:1, taking out after the immersion, washing with deionized water to be neutral, and drying for later use;
step two, carrying out interlayer bonding compounding on the pretreated PET spun-bonded non-woven fabric (first layer) and the PET melt-blown non-woven fabric (second layer), specifically, compounding in a point bonding mode, uniformly spreading point coating adhesive on the PET spun-bonded non-woven fabric at the longitudinal and transverse intervals of 3cm, coating the PET melt-blown non-woven fabric, drying the PET melt-blown non-woven fabric in a 45 ℃ oven for 75min, and taking out to complete the compounding of the first layer and the second layer;
spreading the modified carbon fibers on a polyester needled felt, wherein the polyester needled felt plays a role in stress buffering to prevent the structure of the material from being damaged due to overlarge material pressure, continuously and uniformly spraying catalytic active particles on the modified carbon fiber material, then covering a layer of modified carbon fibers, placing a layer of polyester fabric, and performing hydraulic pressing, wherein the temperature of a hydraulic press is set to be 50 ℃, and the pressure is 2MPa, so as to prepare a composite filter cloth layer (a third layer); wherein the spraying amount of the catalytic active particles is 10% of the mass of the modified carbon fiber, and the thickness of the obtained composite filter cloth layer is 0.14 mm;
and step four, compounding the composite filter cloth layer on the other surface of the PET melt-blown non-woven fabric (the second layer) in a point bonding mode, specifically, uniformly scattering point coating adhesive on the PET melt-blown non-woven fabric at intervals of 3cm in the longitudinal direction and the transverse direction, covering the composite filter cloth layer, drying the composite filter cloth layer in an oven at the temperature of 50 ℃ for 65min, and taking out the dried composite filter cloth layer to obtain the high-efficiency air filter material.
Example 3
The preparation method of the high-efficiency air filter material comprises the following steps:
firstly, pretreating PET spun-bonded non-woven fabric and PET melt-blown non-woven fabric, specifically, immersing the PET spun-bonded non-woven fabric and the PET melt-blown non-woven fabric into a mixed solution of NaOH and a penetrating agent JFC with the mass concentration of 25g/L and 5g/L respectively, immersing in water bath at 100 ℃ for 1h, wherein the bath ratio is 20:1, taking out after the immersion, washing with deionized water to be neutral, and drying for later use;
step two, carrying out interlayer bonding compounding on the pretreated PET spun-bonded non-woven fabric (first layer) and the PET melt-blown non-woven fabric (second layer), specifically, compounding in a point bonding mode, uniformly spreading point coating adhesive on the PET spun-bonded non-woven fabric at the longitudinal and transverse intervals of 3cm, coating the PET melt-blown non-woven fabric, drying the PET melt-blown non-woven fabric in a 45 ℃ oven for 80min, and taking out to complete the compounding of the first layer and the second layer;
spreading the modified carbon fibers on a polyester needled felt, wherein the polyester needled felt plays a role in stress buffering to prevent the structure of the material from being damaged due to overlarge material pressure, continuously and uniformly spraying catalytic active particles on the modified carbon fiber material, then covering a layer of modified carbon fibers, placing a layer of polyester fabric, and performing hydraulic pressing, wherein the temperature of a hydraulic press is set to be 50 ℃, and the pressure is 2MPa, so as to prepare a composite filter cloth layer (a third layer); wherein the spraying amount of the catalytic active particles is 10% of the mass of the modified carbon fiber, and the thickness of the obtained composite filter cloth layer is 0.15 mm;
and step four, compounding the composite filter cloth layer on the other surface of the PET melt-blown non-woven fabric (the second layer) in a point bonding mode, specifically, uniformly scattering point coating adhesive on the PET melt-blown non-woven fabric at intervals of 3cm in the longitudinal direction and the transverse direction, covering the composite filter cloth layer, drying the composite filter cloth layer in an oven at the temperature of 50 ℃ for 70min, and taking out the dried composite filter cloth layer to obtain the high-efficiency air filter material.
The air filter materials prepared in examples 1 to 3 and a common disposable mask were subjected to the following filtration performance tests:
method for testing filtration efficiency the filtration efficiency test was carried out using the most penetrating particle size Method (MPPS) of the European Standard (EN1882-1:1998) using particles of 0.3um diameter, and then by varying the flow rate and particle diameter, the filtration efficiency of the test material for particles of different diameters, and the relationship between flow rate and filtration resistance, the test results are given in the following table:
it can be seen that the air filter material prepared by the invention has the filtering efficiency of more than 68.6 percent on 0.3um particles, the filtering resistance of less than 138Pa and high filtering efficiency.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.