A kind of method that utilization yak hair prepares nanofiberTechnical field
The present invention relates to nanofiber preparing technical field, particularly a kind of utilization yak hair prepares the side of nanofiberMethod.
Background technology
Animal origin is also known as protein fibre, because their main comprise material is protein.Animal origin is divided into threeClass：The scared and fine hair of animal, the eider down of birds and feather, silk, main source is the animal of artificial feeding.
The species of animal wool is a lot, most importantly sheep's wool, abbreviation wool.Wool is widely used for manufacturing various weavingsProduct, also to felt.In addition to wool, also cashmere, the rabbit hair, camel hair, yak hair etc..Animal wool beyond wool, sometimesBe referred to as special animal hair fibers, also for manufacturing textile, can it is pure spinning or with other fiber blends.It is special using them in blendingSome gloss, fineness and flexibility, can improve the warmth retention property and feel of fabric.The eider down and feather of birds can be with weavingOther fiber blends, can also do packing material, such as duck's down, goose down.Silk is the glandular secretion thing of silkworm, have mulberry silk, tussah silk,Ricinus silk and art potato silk etc..
By taking wool as an example, wool is a kind of higher natural fiber of value.Wool is import in China's livestock productsMeasure one of maximum product, current import volume has accounted for the 2/3 of domestic production of wool, as wool importer maximum in the world itOne, and domestic wool is in a disadvantageous position in quality compared with import wool, wool is short and thick, in the international market without competitiveness.This causes the processing of domestic wool in use, producing many abbs, if these waste wools lost, and is undoubtedly one kindThe wasting of resources, can also be polluted to environment.If not only these waste resource regenerations can be alleviated into wool resource shortScarce present situation, and reference can be provided to the regeneration of other poultry hairs.
For a long time, correlative study be mostly around wool expansion, and all in all can be with the research that wool is recycledIt is divided into two aspects：On the one hand make full use of technological means to lift the value of wool；On the other hand research renewal theory, is realizedThe fibrosis regeneration of wool keratin, obtains desired wool keratin modified viscose fiber.For wool keratin againBiochemical technology have been carried out at present it is widely studied, most of technologies all be using chemistry method by waste wool dissolve be made sheepFeather keratin solution, and select suitable solvent and dissolution conditions to be the key for preparing wool keratin solution.At present with animal woolThe mode for preparing raw liquid of ceratin is to use urea/sulphur sodium/SDS techniques mostly, i.e., with sodium sulfide, urea, dodecyl sulphateThe mixed system of sodium is solvent, and pending animal wool is put into this mixed solution, is made certain density after dissolution filterKeratin solution.
Yak is the peculiar ox kind of extremely frigid zones, phytophage ruminant domestic animal.It is main to originate in Chinese Qinghai-Tibet height above sea level 3000More than rice area, the diameter of yak hair is more than 25 microns, and length can be more than 20 centimetres, and profile is straight, and surface is smooth, and what is had hasContinuous medula, strong and unyielding and glossy, felting property is low.Yak wool fibre is largely made up of scale layer and cortical layer, comprises only poleFew medullary substance layer, due to the special living environment of yak, is compared to the loose arrangement of wool scale layer, the scale layer of yak hairMore close compared to wool, scale is close to hair shaft, and its scale layer has and relatively strong resists enzyme and the work of chemical agent etchWith the recovery rate of minimal amount of keratin, i.e. keratin can only be dissolved very using the technique of wool is handled to handle yak hairIt is low, and then the cost of acquisition yak hair nanofiber is higher, yak hair wastage of material is than a kind of more serious, spy for yak hairDetermine nanofiber preparation technology and need badly to be developed.
The content of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of method that utilization yak hair prepares nanofiber,The problem of solving in the prior art not specifically designed for yak hair nanofiber preparation technology.
The technical solution adopted for the present invention to solve the technical problems is：A kind of utilization yak hair prepares the side of nanofiberMethod, comprises the following steps：
Step [1]：Yak hair is cleaned for several times with water, the removal of impurity is gone, is then dried using centrifuge, standby is driedWith；
Step [2]：Above-mentioned dried yak hair is crushed through hair pulverizer；
Step [3]：Yak hair after crushing is put into acidification liquid, soaked 20~30 minutes at 30~35 DEG C,Dehydrate；
Step [4]：By it is acidified processing and dried yak hair be put into pretreatment liquid, stir 8 at 30~35 DEG C~10 minutes, filtering, it is neutrality to be washed to yak hair pH value；
Step [5]：Yak hair after step [4] processing will be put into reduction treatment liquid, 40~50 are stirred at 35 DEG CMinute, 100 DEG C are warming up to, immersion dissolving 1.2~2 hours is filtered, and fully washes undissolved yak hair with distilled water, is receivedCollect filtrate and water lotion, be put into bag filter and dialysed, it is then freeze-dried after obtain keratin powder；
Step [6]：Keratin powder is dissolved in hexafluoroisopropanol, a certain amount of polyurethane is then added and stirs, is stirred20~25 DEG C of temperature, stirs 10~15 minutes, then adds a certain amount of epoxy acrylate, is well mixed, it is warming up to 60~Continue to stir 1 hour after 80 DEG C, obtain spinning solution；
Step [7]：Electrostatic spinning is carried out using gained spinning solution, and nano wire is received with aluminium foil, blending Nanowire is producedDimension；
Further, the component composition of the following concentration of acidification liquid：5~8g/L of sulfuric acid, potassium citrate 12~16g/L, 23~29g/L of benzoic acid, 140~150g of ethanol, remaining is water.
Further, the weight ratio between the acidification liquid and yak hair is 5~6:1.
Further, the pretreatment liquid is made up of the component of following concentration：60~90g/L of potassium hydrogen peroxymonosulfate, hydrogen-oxygenChange 10~15g/L of potassium, 34~45g/L of polyethylene glycol, 5~7g/L of sodium lignin sulfonate, remaining is water.
Further, the weight ratio between the pretreatment liquid and yak hair is 5~8:1~3.
Further, the reduction treatment liquid is made up of the component of following concentration：Sodium sulfide 30~38g g/L, urea 280~320g/L, 12~15g/L of lauryl sodium sulfate, 12~18g/L of Potassium Adipate, 18~23g/L of butanol, remaining is water.
Further, the weight ratio between the reduction treatment liquid and yak hair is 20~30:1.
Further, the quality in step [5] between keratin powder, hexafluoroisopropanol, polyurethane and epoxy acrylateThan for 1:2~3:1~1.5:0.17~0.19.
Further, the length of the yak hair after being crushed through hair pulverizer is 1~3mm.
The positive effect of the present invention：
1. the present invention acidification has been carried out to yak hair first, its use sulfuric acid, potassium citrate, benzoic acid, ethanol withThe mixed system of water, can carry out appropriate erosion to the surface scale layer of yak wool fibre, effectively reduce the tight ness rating of scale layer,Make its it is loose be easily stripped, while do not carry out excessive erosion to it, in order to avoid produce damage to the structure below scale layer, this acidifyingProcess step is peeled off to the appropriateness of scale layer for next step and provides favourable basis.
2. the present invention adds pre-treatment step before reduction treatment handling process, potassium hydrogen peroxymonosulfate/hydrogen is employedThe combined system of potassium oxide/polyethylene glycol/sodium lignin sulfonate, and crushed yak hair before pre-treatment, in order toMore preferable oxidation processes are carried out to yak hair, wherein compared to the independent conventional situation using potassium hydrogen peroxymonosulfate, present treatment liquid addsPolyhydroxy structure type compound polyethylene glycol is entered, while being also added into sodium lignin sulfonate.We have found initial stage in research, adoptDuring with single potassium hydrogen peroxymonosulfate because the strong oxidizing property of potassium hydrogen peroxymonosulfate, yak hair add initial stage its first pair withContact yak hair carry out oxidation processes, now easily to yak hair fiber surface scale layer produce transition peel off damage, afterAnd keratin is aoxidized, and this can finally influence the recovery rate of keratin and extract quality, therefore, and the present invention is crossing a sulphurAdded on the basis of potassium hydrogen phthalate belong to polymerization species have highly viscous polyethylene glycol, because it is in oxidation processesGenerate stronger complexing effect and its high viscosity having is easily in yak hair fiber surface one layer of mucous layer of formation, preferably resistanceThe damage of the transition to yak hair surface is stopped so that potassium hydrogen peroxymonosulfate is gentleer to the oxidizing process of yak hair, effectivePeel off the also strong oxidation for reducing keratin while yak hair fiber surface scale layer, for improve keratin recovery rate andExtract quality and provide strong basis.
3. the reduction treatment liquid of the present invention uses the group of sodium sulfide/urea/lauryl sodium sulfate/Potassium Adipate/butanolZoarium system, i.e., add Potassium Adipate and butanol, and employ high level on the basis of traditional sodium sulfide/urea/SDSReducing agent sodium hydrogensulfite, wherein Potassium Adipate as few hydroxyl structure (compare polyethylene glycol in pretreatment liquid) complexingCorrosion inhibiter, butanol is as a kind of inhibition conditioning agent, and both combine to fetter the sulfurous acid hydrogen radical ion in solution jointly, so thatTotal recovery rate of keratin is improved while dissolving keratin.
4. the present invention using the combined system of keratin powder/polyurethane/epoxy acrylate as spinning solution, especiallyThe addition of epoxy acrylate so that the lateral crosslinking points between macromolecular are effectively reduced, while so that keratin molecule structureAnd molecular conformation changes, together with polyurethane, the active force between molecular machinery is effectively increased, molecular structure is improvedHeat endurance, and then cause into the uniformity of silk and effectively lifted, effectively improve keratin into fine quality.
Embodiment
Below to a preferred embodiment of the present invention will be described in detail.
Embodiment 1
The preferred embodiment of the present invention 1 provides a kind of method that utilization yak hair prepares nanofiber, comprises the following steps：
Step [1]：Yak hair is cleaned for several times with water, the removal of impurity is gone, is then dried using centrifuge, standby is driedWith；
Step [2]：Above-mentioned dried yak hair is crushed to 2mm through hair pulverizer；
Step [3]：Yak hair after crushing is put into acidification liquid, soaked 20~30 minutes at 30~35 DEG C,Dehydrate；
Wherein, the component composition of the following concentration of acidification liquid：Sulfuric acid 7g/L, potassium citrate 14g/L, benzoic acid25g/L, ethanol 145g, remaining is water；Weight ratio between the acidification liquid and yak hair is 6:1.
Step [4]：By it is acidified processing and dried yak hair be put into pretreatment liquid, at 35 DEG C stir 10 pointsClock, filtering, it is neutrality to be washed to yak hair pH value；
Wherein, the pretreatment liquid is made up of the component of following concentration：Potassium hydrogen peroxymonosulfate 750g/L, potassium hydroxide 12g/L, polyethylene glycol 37g/L, sodium lignin sulfonate 6g/L, remaining is water；
Weight ratio between the pretreatment liquid and yak hair is 8:1.
Step [5]：Yak hair after step [4] processing will be put into (wherein, the reduction treatment liquid in reduction treatment liquidIt is made up of the component of following concentration：Sodium sulfide 33g g/L, urea 289g/L, lauryl sodium sulfate 13.5g/L, Potassium Adipate13.4g/L, butanol 20g/L, the weight ratio between the reduction treatment liquid and yak hair are 30:1) 45 points, are stirred at 35 DEG CClock, is warming up to 100 DEG C, immersion dissolving 1.5 hours is filtered, and fully washes undissolved yak hair with distilled water, collects filtrateWeighed with water lotion and mixing, be put into bag filter and dialysed, it is then freeze-dried after keratin powder and weigh, calculatingThe mass fraction for obtaining keratin in mixed liquor (filtrate and water lotion) is 3.67%.
Step [6]：Keratin powder is dissolved in hexafluoroisopropanol, a certain amount of polyurethane is then added and stirs, is stirred20 DEG C of temperature, stirs 15 minutes, then adds a certain amount of epoxy acrylate, is well mixed, is warming up to after 80 DEG C and continues to stirMix 1 hour, obtain spinning solution；Mass ratio wherein between keratin powder, hexafluoroisopropanol, polyurethane and epoxy acrylate is 1:3:1:0.18。
Step [7]：Electrostatic spinning is carried out using gained spinning solution, and nano wire is received with aluminium foil, blending Nanowire is producedDimension.100 gained nanofibers are randomly selected, and electron microscope observation is scanned to it, taken nanofiber is calculatedMiddle minimum diameter is 158nm, and maximum gauge is 438nm, and average diameter is 231nm.
Embodiment 2
The preferred embodiment of the present invention 2 provides a kind of method that utilization yak hair prepares nanofiber, comprises the following steps：
Step [1]：Yak hair is cleaned for several times with water, the removal of impurity is gone, is then dried using centrifuge, standby is driedWith；
Step [2]：Above-mentioned dried yak hair is crushed to 2mm through hair pulverizer；
Step [3]：Yak hair after crushing is put into pretreatment liquid, stirred 10 minutes at 35 DEG C, filtering is washed toYak hair pH value is neutrality；
Wherein, the pretreatment liquid is made up of the component of following concentration：Potassium hydrogen peroxymonosulfate 750g/L, potassium hydroxide 12g/L, polyethylene glycol 37g/L, sodium lignin sulfonate 6g/L, remaining is water；
Weight ratio between the pretreatment liquid and yak hair is 8:1.
Step [4]：Yak hair after step [3] processing will be put into (wherein, the reduction treatment liquid in reduction treatment liquidIt is made up of the component of following concentration：Sodium sulfide 33g g/L, urea 289g/L, lauryl sodium sulfate 13.5g/L, Potassium Adipate13.4g/L, butanol 20g/L, the weight ratio between the reduction treatment liquid and yak hair are 30:1) 45 points, are stirred at 35 DEG CClock, is warming up to 100 DEG C, immersion dissolving 1.5 hours is filtered, and fully washes undissolved yak hair with distilled water, collects filtrateWeighed with water lotion and mixing, be put into bag filter and dialysed, it is then freeze-dried after keratin powder and weigh, calculatingThe mass fraction for obtaining keratin in mixed liquor (filtrate and water lotion) is 2.17%.
Step [5]：Keratin powder is dissolved in hexafluoroisopropanol, a certain amount of polyurethane is then added and stirs, is stirred20 DEG C of temperature, stirs 15 minutes, then adds a certain amount of epoxy acrylate, is well mixed, is warming up to after 80 DEG C and continues to stirMix 1 hour, obtain spinning solution；Mass ratio wherein between keratin powder, hexafluoroisopropanol, polyurethane and epoxy acrylate is 1:3:1:0.18。
Step [6]：Electrostatic spinning is carried out using gained spinning solution, and nano wire is received with aluminium foil, blending Nanowire is producedDimension.100 gained nanofibers are randomly selected, and electron microscope observation is scanned to it, taken nanofiber is calculatedMiddle minimum diameter is 168nm, and maximum gauge is 480nm, and average diameter is 259nm.
Embodiment 3
The preferred embodiment of the present invention 3 provides a kind of method that utilization yak hair prepares nanofiber, comprises the following steps：
Step [1]：Yak hair is cleaned for several times with water, the removal of impurity is gone, is then dried using centrifuge, standby is driedWith；
Step [2]：Above-mentioned dried yak hair is crushed to 2mm through hair pulverizer；
Step [3]：Yak hair after crushing is put into acidification liquid, soaked 20~30 minutes at 30~35 DEG C,Dehydrate；
Wherein, the component composition of the following concentration of acidification liquid：Sulfuric acid 7g/L, potassium citrate 14g/L, benzoic acid25g/L, ethanol 145g, remaining is water；Weight ratio between the acidification liquid and yak hair is 6:1.
Step [4]：By it is acidified processing and dried yak hair be put into pretreatment liquid, at 35 DEG C stir 10 pointsClock, filtering, it is neutrality to be washed to yak hair pH value；
Wherein, the pretreatment liquid is made up of the component of following concentration：Potassium hydrogen peroxymonosulfate 750g/L, potassium hydroxide 12g/L, remaining is water；
Weight ratio between the pretreatment liquid and yak hair is 8:1.
Step [5]：Yak hair after being handled through step [4] puts into (wherein, the reduction treatment liquid in reduction treatment liquidIt is made up of the component of following concentration：Sodium sulfide 33g g/L, urea 289g/L, lauryl sodium sulfate 13.5g/L, Potassium Adipate13.4g/L, butanol 20g/L, the weight ratio between the reduction treatment liquid and yak hair are 30:1) 45 points, are stirred at 35 DEG CClock, is warming up to 100 DEG C, immersion dissolving 1.5 hours is filtered, and fully washes undissolved yak hair with distilled water, collects filtrateWeighed with water lotion and mixing, be put into bag filter and dialysed, it is then freeze-dried after keratin powder and weigh, calculatingThe mass fraction for obtaining keratin in mixed liquor (filtrate and water lotion) is 2.26%.
Step [6]：Keratin powder is dissolved in hexafluoroisopropanol, a certain amount of polyurethane is then added and stirs, is stirred20 DEG C of temperature, stirs 15 minutes, then adds a certain amount of epoxy acrylate, is well mixed, is warming up to after 80 DEG C and continues to stirMix 1 hour, obtain spinning solution；Mass ratio wherein between keratin powder, hexafluoroisopropanol, polyurethane and epoxy acrylate is 1:3:1:0.18。
Step [7]：Electrostatic spinning is carried out using gained spinning solution, and nano wire is received with aluminium foil, blending Nanowire is producedDimension.100 gained nanofibers are randomly selected, and electron microscope observation is scanned to it, taken nanofiber is calculatedMiddle minimum diameter is 118nm, and maximum gauge is 409nm, and average diameter is 252nm.
Embodiment 4
The preferred embodiment of the present invention 4 provides a kind of method that utilization yak hair prepares nanofiber, comprises the following steps：
Step [1]：Yak hair is cleaned for several times with water, the removal of impurity is gone, is then dried using centrifuge, standby is driedWith；
Step [2]：Above-mentioned dried yak hair is crushed to 2mm through hair pulverizer；
Step [3]：Yak hair after crushing is put into acidification liquid, soaked 20~30 minutes at 30~35 DEG C,Dehydrate；
Wherein, the component composition of the following concentration of acidification liquid：Sulfuric acid 7g/L, potassium citrate 14g/L, benzoic acid25g/L, ethanol 145g, remaining is water；Weight ratio between the acidification liquid and yak hair is 6:1.
Step [4]：By it is acidified processing and dried yak hair be put into pretreatment liquid, at 35 DEG C stir 10 pointsClock, filtering, it is neutrality to be washed to yak hair pH value；
Wherein, the pretreatment liquid is made up of the component of following concentration：Potassium hydrogen peroxymonosulfate 750g/L, potassium hydroxide 12g/L, polyethylene glycol 37g/L, sodium lignin sulfonate 6g/L, remaining is water；
Weight ratio between the pretreatment liquid and yak hair is 8:1.
Step [5]：Yak hair after being handled through step [4] puts into (wherein, the reduction treatment liquid in reduction treatment liquidIt is made up of the component of following concentration：Sodium sulfide 33g g/L, urea 289g/L, lauryl sodium sulfate 13.5g/L, the reductionWeight ratio between treatment fluid and yak hair is 30:1), stirred 45 minutes at 35 DEG C, be warming up to 100 DEG C, immersion dissolving 1.5Hour, filtering, and undissolved yak hair is fully washed with distilled water, collect filtrate and water lotion and mix and weigh, be put intoAnalysis bag is dialysed, it is then freeze-dried after obtain keratin powder and weigh, calculate in mixed liquor (filtrate and water lotion)The mass fraction of keratin is 2.41%.
Step [6]：Keratin powder is dissolved in hexafluoroisopropanol, a certain amount of polyurethane is then added and stirs, is stirred20 DEG C of temperature, stirs 15 minutes, then adds a certain amount of epoxy acrylate, is well mixed, is warming up to after 80 DEG C and continues to stirMix 1 hour, obtain spinning solution；Mass ratio wherein between keratin powder, hexafluoroisopropanol, polyurethane and epoxy acrylate is 1:3:1:0.18
Step [7]：Electrostatic spinning is carried out using gained spinning solution, and nano wire is received with aluminium foil, blending Nanowire is producedDimension.100 gained nanofibers are randomly selected, and electron microscope observation is scanned to it, taken nanofiber is calculatedMiddle minimum diameter is 143nm, and maximum gauge is 534nm, and average diameter is 229nm.
Embodiment 5
The preferred embodiment of the present invention 5 provides a kind of method that utilization yak hair prepares nanofiber, comprises the following steps：
Step [1]：Yak hair is cleaned for several times with water, the removal of impurity is gone, is then dried using centrifuge, standby is driedWith；
Step [2]：Above-mentioned dried yak hair is crushed to 2mm through hair pulverizer；
Step [3]：Yak hair after crushing is put into acidification liquid, soaked 20~30 minutes at 30~35 DEG C,Dehydrate；
Wherein, the component composition of the following concentration of acidification liquid：Sulfuric acid 7g/L, potassium citrate 14g/L, benzoic acid25g/L, ethanol 145g, remaining is water；Weight ratio between the acidification liquid and yak hair is 6:1.
Step [4]：By it is acidified processing and dried yak hair be put into pretreatment liquid, at 35 DEG C stir 10 pointsClock, filtering, it is neutrality to be washed to yak hair pH value；
Wherein, the pretreatment liquid is made up of the component of following concentration：Potassium hydrogen peroxymonosulfate 750g/L, potassium hydroxide 12g/L, polyethylene glycol 37g/L, sodium lignin sulfonate 6g/L, remaining is water；
Weight ratio between the pretreatment liquid and yak hair is 8:1.
Step [5]：Yak hair after step [4] processing will be put into (wherein, the reduction treatment liquid in reduction treatment liquidIt is made up of the component of following concentration：Sodium sulfide 33g g/L, urea 289g/L, lauryl sodium sulfate 13.5g/L, Potassium Adipate13.4g/L, butanol 20g/L, the weight ratio between the reduction treatment liquid and yak hair are 30:1) 45 points, are stirred at 35 DEG CClock, is warming up to 100 DEG C, immersion dissolving 1.5 hours is filtered, and fully washes undissolved yak hair with distilled water, collects filtrateWeighed with water lotion and mixing, be put into bag filter and dialysed, it is then freeze-dried after keratin powder and weigh, calculatingThe mass fraction for obtaining keratin in mixed liquor (filtrate and water lotion) is 3.63%.
Step [6]：Keratin powder is dissolved in hexafluoroisopropanol, a certain amount of polyurethane is then added and stirs, is stirred20 DEG C of temperature, stirs 1.5 hours, obtains spinning solution；Wherein, the mass ratio between keratin powder, hexafluoroisopropanol, polyurethane is 1:3:1。
Step [7]：Electrostatic spinning is carried out using gained spinning solution, and nano wire is received with aluminium foil, blending Nanowire is producedDimension.100 gained nanofibers are randomly selected, and electron microscope observation is scanned to it, taken nanofiber is calculatedMiddle minimum diameter is 222nm, and maximum gauge is 693nm, and average diameter is 408nm.
Embodiment 6
The preferred embodiment of the present invention 6 provides a kind of method that utilization yak hair prepares nanofiber, comprises the following steps：
Step [1]：Yak hair is cleaned for several times with water, the removal of impurity is gone, is then dried using centrifuge, standby is driedWith；
Step [2]：Above-mentioned dried yak hair is crushed to 2mm through hair pulverizer；
Step [3]：By (wherein, the reduction treatment liquid is by following dense in the yak hair input reduction treatment liquid after crushingThe component composition of degree：Sodium sulfide 33g g/L, urea 289g/L, lauryl sodium sulfate 13.5g/L, the reduction treatment liquid withWeight ratio between yak hair is 30:1), stirred 45 minutes at 35 DEG C, be warming up to 100 DEG C, immersion dissolving 1.5 hours, mistakeFilter, and undissolved yak hair is fully washed with distilled water, collect filtrate and water lotion and mix and weigh, be put into bag filter progressDialysis, it is then freeze-dried after keratin powder and weigh, calculate keratin in mixed liquor (filtrate and water lotion)Mass fraction is 1.01%.
Step [4]：Keratin powder is dissolved in hexafluoroisopropanol, 20 DEG C of whipping temp stirs 1.5 hours, obtains spinning solution；Mass ratio wherein between keratin powder, hexafluoroisopropanol is 1:3.
Step [5]：Electrostatic spinning is carried out using gained spinning solution, and nano wire is received with aluminium foil, blending Nanowire is producedDimension.100 gained nanofibers are randomly selected, and electron microscope observation is scanned to it, taken nanofiber is calculatedMiddle minimum diameter is 356nm, and maximum gauge is 1025nm, and average diameter is 764nm.
Above-described is only the preferred embodiments of the present invention, and the explanation that should be understood that above example is to useUnderstand the method and its core concept of the present invention in help, the protection domain being not intended to limit the present invention is all the present invention'sAny modification for being made within thought and principle, equivalent substitution etc., should be included in the scope of the protection.