CN101805987B - Method for preparing silver fibers by penetration-immersion method - Google Patents
Method for preparing silver fibers by penetration-immersion method Download PDFInfo
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- CN101805987B CN101805987B CN2010101375514A CN201010137551A CN101805987B CN 101805987 B CN101805987 B CN 101805987B CN 2010101375514 A CN2010101375514 A CN 2010101375514A CN 201010137551 A CN201010137551 A CN 201010137551A CN 101805987 B CN101805987 B CN 101805987B
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Abstract
The invention discloses a method for preparing silver fibers by a penetration-immersion method. The method comprises: a de-oiling step, a purifying and expanding step, a surface expanding step, a rinsing step and a silver covering step. The space structure of fiber molecules is rearranged and silver is dissolved in the fibers by the penetration-immersion method and fully covers a fiber surface to prepare silver fibers, wherein the penetration-immersion method comprises the following steps: refining, washing and drying chemical fibers; soaking the refined, washed and dried chemical fibers in an organic solvent, pressurizing and permeating the chemical fibers to enlarge fiber molecule intervals; removing the organic solvent and adding silver nitrate and an assistant to perform a silver reaction; and partially embedding the silver into the fibers and fully covering the remaining silver on the fiber surface and all intervals, wherein no pollutant is produced in an entire processing process; produced waste water has no polluting effect on the environment after being chemically treated; and the silver fibers have high firmness and silver content of the silver fibers can be up to over 40 percent.
Description
Technical field
The invention belongs to the fiber production field, be specifically related to a kind of preparation method of new function fibrous material.
Background technology
21 century is the New Times that high-tech develops rapidly, and the International Textile market competition has also entered a brand-new period.People are also more and more higher to taking the dress material demand, developed into and not only required physiological comfort (frivolous, warming, nice and cool) but also will possess psychosensorial comfortable (visual color light modulation pool, sense of touch feel, flexibility, bulkiness, drapability), more need certain specific functionality (antibiotic, antistatic, fire-retardant, antiultraviolet, anti-electromagnetic radiation), promptly require comprehensively have comfortableness, the characteristics of functionalization, high-quality, fitnessization.Functional textile is one of current textile garment, family expenses and fabrics for industrial use development in future trend.It will constitute seven big tendencies of following textiles jointly with fine count fiber textiles, nonwoven fabric, composite, ep-type material etc., become the development main flow of textiles.At present, the acquisition of functional textile is except the back arrangement by textiles realizes, more important is to reach requirement by developing various functional fibres.
Functional fibre is meant the physical and mechanical properties that has except that general fiber also have the tencel of certain specific function.Such as: fiber has health care function (antibiotic, kill mite, physiotherapy and eliminate the unusual smell etc.); Safeguard function (radiation proof, antistatic, uvioresistant etc.); The wet comfortable function (heat absorption, heat release, moisture absorption, moisture releasing etc.) of heat; Medical treatment and environment-friendly function (biocompatibility and biological degradability).The development of functional fibre is the symbol of modern fibre science progress.The technological innovation that develops into traditional textile industry of functional fibre, fibre in differentiation and high-performance fiber, created advantage to the conversion of high-tech industry, for human growth in the living standard contributes.
The silver fiber more and more is subjected to people's attention because of possessing multiple specific functions such as powerful antibacterial and deodouring, durability, antistatic anti-shielding, heat conduction, health care simultaneously, become contemporary functional fibre research and used new focus, gather around and have broad application prospects, can be widely used in every field such as family is spun, physical culture, military affairs, health care, also can drive the development of related industries such as mineral reserve, metallurgy, chemical industry, weaving.
At present, the main method by chemical silvering (also being surface absorption silver impregnation method) of the acquisition of silver-colored fiber: promptly obtain plating (being coated with) silver-colored fiber at polymer surfaces plating one deck fine silver.Can produce heavy metal ion sewage in the chemical plating production process in the past, environmental pollution is serious.Because the fiber of placing is many and technology, can cause firmness not enough, institute's silver coating became uneven is even, the uniformity is poor, poor performance, silver-colored fiber appearance poor, low in glossiness, fastness is poor, shortcoming such as easily come off, therefore the product washability made of the silver-colored fiber of method preparation at present is poor, and washing once back silver layer comes off or ruptures, it is infinitely great that resistance value becomes, and loses the function of silver-colored fiber.Although external having silver-colored fiber product commercialization, this product adopts continuous rapid chemical silver impregnation method, and only silver-plated at fiber surface, fastness is poor, and its washable number of times does not reach 50 times.
Summary of the invention
The objective of the invention is deficiency, the silver-colored fiber preparation method that a kind of fastness is good, silver layer is even, performance is good is provided at the prior art existence.
Purpose of the present invention can reach by following measure:
A kind ofly permeate the method that infusion method prepares silver-colored fiber, comprise the steps:
A, deoil: the polyamide fiber processing of in alkaline solution and under the heating, pressure 0.1～0.8MPa, deoiling.
Wherein alkaline solution is a NaOH solution, and its concentration is 2～10g/L.Bath raio when deoiling (solid-liquid mass ratio) is 1: 8～1: 20.Being heated to temperature is 80～100 ℃.
B, purification are expanded: adopt organic solvent to soak the polyamide fiber of handling through deoiling under pressure 0.1～0.8MPa and liquid flow.At this moment, the organic matter of fibrous inside and remained on surface is thoroughly removed by the volatile dry of organic solvent, makes fiber purify expansion fully.
Wherein organic solvent is tetrachloro-ethylene, ether, hydrocarbon class (as benzinum, hexane, heptane, octane) etc.Flow velocity during liquid flow is 5～20L/min, the bath raio during immersion 1: 5～1: 20, and soaking temperature is a normal temperature, and soak time is 1～2 hour, and inert gas is adopted in pressurization.
C, surface spreading: adopt acid under the condition of pressure 0.1～0.8Mpa, heating and liquid flow, fiber to be carried out the surface area divergence process.This processing can make fiber surface area expansion several times, affinity, fiber surface plating amount and fibrous inside plating amount when increasing follow-up plating step.
Wherein said acid solution is phosphoric acid or sulfuric acid (aqueous solution), its concentration 10～20ml/L.This step need be heated to 60～80 ℃.The flow velocity of liquid flow is 5～10L/min.
D, rinsing: the polyamide fiber washing after will handling is also dry.Concrete adopt distilled water clean and take off dried, be dried to solvent and volatilize fully totally.
E, cover silver: with liquor argenti nitratis ophthalmicus and ammonia spirit is mixed to transparent and evenly after, add buffer and reductant and make and cover silver-colored solution, add the polyamide fiber after the rinsing again, under pressure 0.1～0.8MPa and liquid flow, cover silver to silver and adsorb fully.
Cover in the silver-colored step, reductant is a formaldehyde, and described buffer is a dodecanol, and the concentration of covering each material in the silver-colored solution is: silver nitrate 5～20g/L, ammoniacal liquor 8～40g/L, formaldehyde 2～8ml/L, dodecanol 2～5ml/L.Covering the density that adds polyamide fiber in the silver-colored solution is 0.1～0.8g/cm
3, the flow velocity during liquid flow is 5～20L/min.Silver ion in the solution all is adsorbed in fiber and generally needs 1～2 hour, can not have precipitation and separate out with the concentration of watery hydrochloric acid titration test reaction liquid silver ion, shows that reaction finishes.
Again fiber is carried out rinsing, oils and baking step after covering silver and finishing, wherein also comprise oil, detect, concrete steps such as packing.A kind of detailed steps comprises: take out fiber, and discharge opeing, rinsing oils, and oven dry detects.Short fiber detects the back and beats compressed package; Long filament is packed through rolling up rich moulding again.
Deoil, purify expansion, surface spreading among the present invention and cover silver-colored step and all preferably under the pressurization situation, carry out, so the preferred pressure when each step is carried out is: 0.2～0.8MPa deoils, purify 0.2～0.8MPa when expanding, surface spreading 0.2～0.8MPa covers silver 0.2～0.8MPa.
The present invention (particularly deoils under 0.2～0.8MPa) the pressure, can make the deoil effect of rapid and rapid swelling of fiber at 0.1～0.8MPa.In purifying expansion process, make liquid flow can make the fiber immersion expand full and uniform, (particularly 0.2～0.8MPa) with mobile and the employing organic solvent soaks and cooperation is pressurizeed, not only make the abundant swelling in space of fiber, the fiber molecule gap increases, also make the fibrous inside Impurity removal clean, rearrange the interior molecules space structure.Subsequently, use sour agent 0.1～0.8
MPa (particularly handles fiber under 0.2～0.8MPa) the pressure, enlarges its surface area, make silver and fiber that more binding sites closely be arranged.When covering silver-colored step, adopt the condition of pressurization and liquid flow, overcome the shortcoming that existing method only is plated on the surface, under the cooperation of step before (particularly deoil and expand), under the situation in increased fiber internal structure and gap, all carry out even plating from the inside of fiber until the surface, pressurization (particularly under 0.2～0.8MPa) simultaneously increases the adhesive fastness of silver layer and fiber.Therefore silver-colored fiber fastness of the present invention is good, silver layer is even, performance good, difficult drop-off, silver content height (silver content can reach more than 40%).
What existing silver-coating method adopted is that successive replenishment is silver-plated, recycles by constantly replenishing silver in the reactant liquor.So there is silver ion in its solution forever.The metering inaccuracy has added AgNO in activation
3, this moment AgNO
3Easily oxidation, non-oxidizability is poor.The present invention accurately feeds intake by the reaction prescription, accurately detects concentration of silver ions in the solution with titration during end, detects just to finish reaction when not having silver ion.So this method can once be utilized the silver in the silver nitrate fully.
The present invention is by rearranging spatial configuration of molecules, and also covering fiber surface fully prepares silver-colored fiber with the infiltration infusion method silver to be dissolved in fibrous inside.Zhi Bei silver-colored fiber is silver-colored firm with combining of fiber by this method, excellent performance.And complete reaction of reactant liquor of the present invention (promptly covering silver-colored solution), can not produce waste or heavy metal pollution, the waste water that is produced does not have any contamination to environment after chemical treatment.Prepared product silver content is stable, the fastness of silver is strong, constant after washing 100 times, maximum performance undamaged washing times can reach more than 250 times, and silver layer is even, filament covers silver evenly, so the end properties excellence, good conductivity, resistance value is little, resistance value more can reach 3～6 ohm/cm below 20 ohm/cm.
The specific embodiment
Embodiment 1: polyamide fibre silver short fiber
The polyamide fibre short fiber of polyamide fibre short fiber specification: 1.5D/38mm (that is: fibre diameter is 1.5D, and length is 38mm).Concrete plating step is as follows:
1. the pre-treatment of deoiling: use 5 grams per liter caustic soda (NaOH) to the processing of deoiling of raw material polyamide fibre staple fiber material, bath raio (solid-to-liquid ratio) is 1: 12,, temperature: 90 ℃, plus-pressure is to 0.3-0.4MPa.
2. purify, expand: use tetrachloro-ethylene under mobility status, fully to soak above-mentioned raw material, flow velocity be controlled at the 10-15 liter/minute, normal temperature soaked 1-2 hour down.Must be during immersion with the inert gas plus-pressure to 0.3-0.4MPa, fiber addition and quantity of solvent bath raio are 1: 10-1: 12.
3. surface spreading: adopt phosphoric acid (10-15ml/L) under pressure 0.2～0.3Mpa, 60～70 ℃ of temperature and liquid flow conditions such as (6-8L/min), fiber to be handled, make fiber surface area expansion several times.
4. rinsing: from solvent, take out fiber, clean, take off to do to solvent with distilled water and bring into play fully totally, standby.
5. cover silver: use agitator that salpeter solution and ammonia spirit are stirred well to water white transparency, and mix, this moment, the pH value of solution was an alkalescent, slowly add buffer (dodecanol) and formalin, stir while adding to even matter, must cover silver-colored solution, wherein AgNO
3Concentration is the 10-12 grams per liter, NH
3H
2O is the 20-25 grams per liter, formaldehyde (reductant) 4-5 milliliter/liter, dodecanol (buffer): the 3-4 milliliter/liter; The fiber that will purify all adds in the container then, continues to stir, and makes fiber and solution full and uniform, and fibre density is controlled at 0.2-0.3 gram/cubic centimetre, and solution temperature is a normal temperature.Covered container is forced into 0.3-0.4MPa, allows reactant liquor circulate, flow velocity be controlled at the 10-12 liter/minute.Through reaction in 1-2 hour, treat that the silver ion in the solution all is adsorbed in fiber.With the concentration of watery hydrochloric acid titration test reaction liquid silver ion, do not have precipitation and separate out, show that reaction finishes.
6. rinsing, oven dry: take out fiber, discharge opeing, rinsing oils, and oven dry detects.Short fiber detects the back and beats compressed package; Long filament is packed through rolling up rich moulding again.Factory effluent does not have any pollution to environment after simple chemical treatment, can directly discharge or reuse.
Silver fiber electromicroscopic photograph shows that each filament covers silver evenly, and the silver layer on the fiber is even.Silver content and coating are constant after the silver fiber wash 100 times, and maximum washing times can reach 250 times, and the average electrical resistance is 6 ohm/cm.
With the silver-colored fiber of this example preparation and the silver-colored fiber contrast of technology in the past, the result is as follows:
| Index name | Embodiment 1 silver medal fiber | The silver-colored fiber of technology in the past |
| 1CM resistance | 6 ohm (＜20 ohm) | ＜200 ohm |
| Washability | 250 times | ＜50 times |
| The silver layer outward appearance | Evenly, continuously | Inhomogeneous, fracture arranged |
| Other performance indications (as discharging of pollutant etc.) | Pollution-free | Pollution is arranged |
Embodiment 2: polyamide fibre silver long filament
The chinlon filament of chinlon filament specification: 70D/24F; The tow diameter is 70D, wherein comprises 24 monofilament.Twisting: 120 sth. made by twisting/rice, Z to.The chinlon filament of ring-type.Concrete plating step is as follows:
1. the pre-treatment of deoiling: use 8 grams per liter caustic soda (NaOH) to the processing of deoiling of chinlon filament material, bath raio (solid-to-liquid ratio) is 1: 15,, temperature: 92 ℃, plus-pressure is to 0.2-0.3MPa.
2. purify, expand: use ether under mobility status, fully to soak above-mentioned raw material, flow velocity be controlled at the 10-15 liter/minute, normal temperature soaked 1-2 hour down.Must be during immersion with the inert gas plus-pressure to 0.4-0.5MPa, fiber addition and quantity of solvent bath raio are 1: 10-1: 12.
3. surface spreading: adopt sulfuric acid (14-17ml/L) at pressure 0.3～0.4Mpa, under 70～80 ℃ of temperature and the liquid flow conditions such as (6-8L/min) fiber is handled, make fiber surface area expansion several times.
4. rinsing: from solvent, take out fiber, clean, take off to do to solvent with distilled water and bring into play fully totally, standby.
5. cover silver: use agitator that salpeter solution and ammonia spirit are stirred well to water white transparency, and mix, this moment, the pH value of solution was an alkalescent, slowly add buffer (dodecanol) and formalin, stir while adding to even matter, must cover silver-colored solution, wherein AgNO
3Concentration is the 11-12 grams per liter, NH
3H
2O is the 20-22 grams per liter, formaldehyde (reductant) 4-5 milliliter/liter, dodecanol (buffer): the 3-4 milliliter/liter; The fiber that will purify all adds in the container then, continues to stir, and makes fiber and solution full and uniform, and fibre density is controlled at 0.2-0.3 gram/square centimeter, and solution temperature is a normal temperature.Covered container is forced into 0.4-0.5MPa, allows reactant liquor circulate, flow velocity be controlled at the 10-12 liter/minute.Through reaction in 1-2 hour, treat that the silver ion in the solution all is adsorbed in fiber.With the concentration of watery hydrochloric acid titration test reaction liquid silver ion, do not have precipitation and separate out, show that reaction finishes.
6. rinsing, oven dry: take out fiber, discharge opeing, rinsing oils, and oven dry detects.Short fiber detects the back and beats compressed package; Long filament is packed through rolling up rich moulding again.Factory effluent does not have any pollution to environment after simple chemical treatment, can directly discharge or reuse.
Silver fiber electromicroscopic photograph shows that each filament covers silver evenly, and the silver layer on the fiber is even.Silver content and coating are constant after the silver fiber wash 100 times, and maximum washing times can reach more than 250 times, and the average electrical resistance is 5 ohm/cm.
The present invention is not specifically limited the specification of fiber, and those skilled in the art can be covered silver to the polyamide fiber of other any specifications according to said method and handle.
Claims (9)
1. one kind is permeated the method that infusion method prepares silver-colored fiber, it is characterized in that comprising the steps:
A, deoil: the polyamide fiber processing of in alkaline solution and under the heating, pressure 0.1～0.8MPa, deoiling;
B, purification are expanded: adopt organic solvent to soak the polyamide fiber of handling through deoiling under pressure 0.1～0.8MPa, heating and liquid flow; Described organic solvent is tetrachloro-ethylene, ether or hydrocarbon kind solvent;
C, surface spreading: adopt acid solution under the condition of pressure 0.1～0.8MPa, heating and liquid flow, fiber to be carried out the surface area divergence process;
D, rinsing: the polyamide fiber washing after will handling is also dry;
E, cover silver: with liquor argenti nitratis ophthalmicus and ammonia spirit is mixed to transparent and evenly after, add buffer and reductant and make and cover silver-colored solution, add the polyamide fiber after the rinsing again, under pressure 0.1～0.8MPa and liquid flow, cover silver to silver and adsorb fully.
2. infiltration infusion method according to claim 1 prepares the method for silver-colored fiber, it is characterized in that in the step of deoiling, and described alkaline solution is a NaOH solution, and its concentration is 2～10g/L; Being heated to temperature is 80～100 ℃, and the bath raio when deoiling is 1: 8～1: 20.
3. infiltration infusion method according to claim 1 prepares the method for silver-colored fiber, it is characterized in that the flow velocity during liquid flow is 5～20L/min, the bath raio during immersion 1: 5～1: 20 in purifying expansion step.
4. infiltration infusion method according to claim 1 prepares the method for silver-colored fiber, it is characterized in that in the surface spreading step, and described acid solution is phosphoric acid or sulfuric acid, and its concentration is 10～20ml/L; Being heated to temperature is 60～80 ℃, and the flow velocity of liquid flow is 5～10L/min.
5. infiltration infusion method according to claim 1 prepares the method for silver-colored fiber, it is characterized in that covering in the silver-colored step, and described reductant is a formaldehyde, and described buffer is a dodecanol.
6. infiltration infusion method according to claim 5 prepares the method for silver-colored fiber, it is characterized in that the concentration of covering each material in the silver-colored solution is: silver nitrate 5～20g/L, ammoniacal liquor 8～40g/L, formaldehyde 2～8ml/L, dodecanol 2～5ml/L.
7. infiltration infusion method according to claim 1 prepares the method for silver-colored fiber, and it is characterized in that covering the density that adds polyamide fiber in the silver-colored solution is 0.1～0.8g/cm
3, the flow velocity during liquid flow is 5～20L/min.
8. infiltration infusion method according to claim 1 prepares the method for silver-colored fiber, pressure when it is characterized in that deoiling is 0.2～0.8MPa, the pressure that purifies when expanding is 0.2～0.8MPa, and the pressure during surface spreading is 0.2～0.8MPa, and the pressure when covering silver is 0.2～0.8MPa.
9. infiltration infusion method according to claim 1 prepares the method for silver-colored fiber, again fiber is carried out rinsing, oils and dries after it is characterized in that covering silver.
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| CN2010101375514A CN101805987B (en) | 2010-04-01 | 2010-04-01 | Method for preparing silver fibers by penetration-immersion method |
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| CN2010101375514A CN101805987B (en) | 2010-04-01 | 2010-04-01 | Method for preparing silver fibers by penetration-immersion method |
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| CN101805987B true CN101805987B (en) | 2011-10-12 |
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| CN103088663A (en) * | 2012-12-12 | 2013-05-08 | 吴江麦道纺织有限公司 | Radiation-resistant cloth |
| CN107268214A (en) * | 2017-06-20 | 2017-10-20 | 丹阳市斯鲍特体育用品有限公司 | A kind of method that infusion process prepares conductive fencing metallic plastron fabric |
| CN109811540B (en) * | 2019-01-21 | 2021-11-19 | 新奥石墨烯技术有限公司 | Graphene conductive fiber, preparation method thereof and flexible electronic device |
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| CN87104346A (en) * | 1987-06-18 | 1988-02-24 | 江苏省纺织研究所 | The manufacture method of durable and conductive fibre |
| DE69212597T2 (en) * | 1991-03-25 | 1997-01-02 | Du Pont | ELECTRIC METALLIZATION OF ARAMID SURFACES |
| CN101016692A (en) * | 2007-01-26 | 2007-08-15 | 北京工业大学 | Organic fiber conductive powder and preparing method thereof |
| CN101446037B (en) * | 2008-12-29 | 2011-07-20 | 中国科学院长春应用化学研究所 | Preparation method of electric-conducting polyimide fiber |
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