CN101781847A - Sol-gel technology based activation process before chemical plating on fabric - Google Patents
Sol-gel technology based activation process before chemical plating on fabric Download PDFInfo
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- CN101781847A CN101781847A CN201010107620A CN201010107620A CN101781847A CN 101781847 A CN101781847 A CN 101781847A CN 201010107620 A CN201010107620 A CN 201010107620A CN 201010107620 A CN201010107620 A CN 201010107620A CN 101781847 A CN101781847 A CN 101781847A
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Abstract
The invention relates to a sol-gel technology based activation process before chemical plating on fabric. The invention provides an activation process before chemical plating on fabric, solving the problems of poor binding force of active center and flexible substrate while the fabric is activated, uneven distribution of the active center and large noble metal consumption. The technical scheme of the invention is as follows: preparing a coating solution from ethyl orthosilicate, 3-glycidoxypropyltrimethoxysilane (GPTMS), acetylacetone, hydrochloric acid or ammonia water, ethanol and deionized water; and coating the solution on the fabric surface as the carrier of palladium after adding beta-cyclodextrin to the coating solution, or directly soaking the fabric in a beta-cyclodextrin aqueous solution and then soaking in the coating solution, and finally combining with the noble metal palladium. The invention can be applied to the metallization process of textile fabrics.
Description
Technical field
The present invention relates to a kind of fabric activation process before chemical plating based on sol-gel technique.Be applicable to metallization process of textile fabrics.
Background technology
Along with the develop rapidly of electronic industry, the electronic product in the productive life is used widely, and when bringing convenience to the human lives, also becomes the pollution sources of electromagnetic radiation.Electromagnetic energy has the expert to foretell with the speed increment in every year 7～14%, can increase by 700 times after 50 years, and the electromagnetic pollution problem has become the fifth-largest public hazards after " three wastes " and noise.A large amount of research report show both at home and abroad: electromagnetic radiation can cause serious injury the systemic-functions such as nervous system, immune system, the circulatory system and reproduction of human body.
Present this material mainly is to form metal composite layer by chemical plating or sputter technology at fiber surface.Wherein chemical plating method is because major technique applied widely, plurality of advantages becomes this material of preparation such as technology is simple.Domestic representative manufacturer Zhejiang ternary electronics adopts patented technology ZL200410053403.9, ZL200410089513.0, and its product quality is higher, just gradually imported product outside the subrogate country; The new material Tao Wei of power unit is just waiting the people to adopt electroless copper nickel plating technology development electromagnetic shielding material and is applying for patent; People, East China University of Science, Shanghai University of Science and Technologys such as the Chen Wen of Institutes Of Technology Of Zhejiang is emerging, Wang Lan are also all in the research of carrying out electromagnetic shielding material.
Activation method in the past mainly contains following several: stannous chloride and palladium bichloride (or silver nitrate) activation two-step method, colloid palladium activation method, ionic palladium activation method.Do not have the combining of chemical bond between the activated centre that these methods produce and the substrate, adhesive force is weak, easily come off and lost efficacy, and the amount of the precious metal palladium that consumes is very big, the cost costliness.In addition with in the traditional handicraft owing to contain Sn
2+Materials such as ion and be unfavorable for environmental protection.
The basic principle of sol-gel technique is to form colloidal sol (less than 10nm) after adopting inorganic or organically-modified compound (metal alkoxide) hydrolysis of nonmetal or metal or alcoholysis, is coated on matrix then and is transformed into gel through condensation and polycondensation from colloidal sol by evaporation drying or ultra-violet radiation.
At present, be mainly used in preparing on glass, superfine powder and the film, adopt 300-800 ℃ high-temperature roasting, when the system film, adopt smooth surfaces such as glass, metal, plastics to carry out coating as matrix, form continuous film in stromal surface, combine by Van der Waals force between film and the carrier, do not have chemical bond.It is unpractical that above-mentioned then technology is used on the textiles, because textiles can't bear high-temperature roasting.
Application number is that to disclose a kind of be the activation method of main raw material with the shitosan to the patent application of 200810040170.7 " a kind of activation method before flexible backing material chemical plating based on numerator self-assembly technique ", be relatively leading at present technology, but this scheme rely on reactive group amino and hydroxyl on the shitosan directly to realize Pd
2+Grappling, but this mode capture rate is low, and the reunion of inevitable noble metal, cause the waste of noble metal.
To be a class pass through a-1 by D-(+)-glucopyranose of some to cyclodextrin (cyclodextrin), the cyclic polysaccharide compound that the 4-glycosidic bond joins end to end and forms, acting on starch by cyclodextrin glycosyltransferase and produce, is the second generation host compound of supramolecular chemistry research after crown ether.Three kinds of comparatively common cyclodextrin contain 6,7,8 glucose units respectively, be referred to as α-, β-, gamma-cyclodextrin.Wherein, (β-CD) is most widely used beta-schardinger dextrin-.The profile of cyclodextrin molecular is frustum-like shape, and each glucose unit in the molecule is taked unwrung chair conformation, wards off unit 4C as adjoining the grape of muttering
1The result of conformation, all primary hydroxyls all are located in a side of ring in the cyclodextrin molecular, it is the interarea (narrow end) that 6 hydroxyls of glucose unit have constituted cyclodextrin frustum-like shape structure, and all secondary hydroxyls are located in the opposite side of ring, and promptly 2 and 3 hydroxyls have constituted the inferior face (than platyopia) of cyclodextrin frustum-like shape structure.The inwall of cyclodextrin is made of the C3 that points to cavity and the hydrogen atom on the C5 and sugared general key oxygen atom, makes its cavity inside that higher cloud density be arranged, and shows certain hydrophobicity.The Zhong Jingji of cyclodextrin time face then makes its big opening end and outer wall show as hydrophily.The circular ring structure that β-CD is slightly tapered.Wherein, the primary hydroxyl of cyclodextrin has surrounded the osculum of taper, and its secondary hydroxyl has surrounded big mouthful of taper.
Because β-CD has bigger molecular volume and special hydroxyl distributes, thereby can be used as a kind of main body and match, can form the support type complex compound, and β-CD has advantage free from environmental pollution with multiple group or metal.
Summary of the invention
The technical problem to be solved in the present invention is: based on sol-gel technique, design feature and character in conjunction with beta-schardinger dextrin-, and a kind of fabric activation process before chemical plating based on sol-gel technique is proposed, poor, activated centre skewness of the adhesion of activated centre and flexible parent metal and the big problem of noble metal consumption when being intended to solve the fabric activation.
The technical solution adopted in the present invention is: a kind of fabric activation process before chemical plating based on sol-gel technique is characterized in that comprising following operation:
1, preparation lotion I,
Take by weighing the raw material of following corresponding weight portion:
8～12 parts of ethyl orthosilicates,
9～13 parts of 3-glycidyl ether trimethoxy silanes,
0.001～0.003 part of acetylacetone,2,4-pentanedione,
10～20 parts of hydrochloric acid or ammoniacal liquor,
20～40 parts of ethanol,
All the other are deionized water, and above-mentioned raw materials is totally 100 weight portions,
The mixture of this raw material is being shaken under the normal temperature on the isothermal vibration device, it is mixed, obtaining lotion I;
2, at fabric face deposition beta-schardinger dextrin-, two kinds of methods are arranged:
Method one: the beta-schardinger dextrin-of 0.3～0.6 weight portion is joined among the described lotion I, obtain lotion II, afterwards textile impregnation is taken out after 20～40 minutes in lotion II, it is cleaned one time with deionized water, stand-by with 80～120 ℃ of oven dry;
Method two: is in the beta-schardinger dextrin-aqueous solution of 0.007～0.008mg/L 5～10 minutes with textile impregnation in concentration, is 2～4kg/cm at padding machine pressure
2Situation under, two soak two rolls; With textile impregnation in described lotion I 5～10 minutes, be 1～4kg/cm again at padding machine pressure
2Situation under, two soak two rolls; Then with fabric with 80 ℃ of preliminary dryings 5 minutes, baked 30 minutes with 120 ℃;
3, fabric is placed the palladium chloride solution of 35～45mg/L, electromagnetic agitation was taken out after 20～40 minutes under 20～80 ℃ of temperature, after twice of washed with de-ionized water, with this fabric drying.
The invention has the beneficial effects as follows: 1) utilize the beta-schardinger dextrin-distinctive molecular structure, adopt sol-gal process that it is anchored at fabric face, utilize its " nest is dwelt " effect afterwards, make the palladium ion original position be created on fabric face, with fabric adhesion height.2) utilize the cavity structure and the ring-shaped distributed polyhydroxy of beta-schardinger dextrin-, to the absorption of Metal Palladium ion location, the reunion of restriction precious metal palladium makes to be difficult for the palladium high degree of dispersion reuniting, so the palladium particle size of the Catalytic Layer that obtains is very little, can reach Nano grade, nano level palladium film surface has produced very big specific area, has greatly increased its surface-activity, reduced the consumption of precious metal palladium simultaneously, cost is obviously reduced.Comparing application number is 200810040170.7 " a kind of activation method before flexible backing material chemical plating based on numerator self-assembly technique " disclosed state-of-the-art technology of patent application, and the present invention is higher to the capture rate of palladium, and is difficult for reuniting, and obvious improvement is arranged.
Description of drawings
Fig. 1 is the molecular structural formula of beta-schardinger dextrin-.
Fig. 2 is the stereoscan photograph of fabric before colloidal sol is handled.
Fig. 3 is the stereoscan photograph of activation back fabric.
Fig. 4 is the stereoscan photograph of fabric after the chemical plating.
Fig. 5 is Pd-β-CD colloid and H
2PdCl
4Ultraviolet-visible spectrum test result figure.
The specific embodiment
Embodiment one:
1, preparation lotion I,
Take by weighing 3-glycidyl ether trimethoxy silane (GPTMS), 0.0001kg acetylacetone,2,4-pentanedione, the 1kg of 0.8kg ethyl orthosilicate, 0.9kg hydrochloric acid, 2kg ethanol, all the other are deionized water, above-mentioned raw materials is 10kg altogether.This raw material is mixed the back shaking under the normal temperature on the isothermal vibration device, mix, obtain lotion I.
2, at fabric face deposition beta-schardinger dextrin-,
The beta-schardinger dextrin-of 0.03kg is joined among the described lotion I, obtain lotion II, afterwards textile impregnation is taken out after 20 minutes in lotion II, it is cleaned one time with deionized water, stand-by with 80 ℃ of oven dry.
3, fabric is placed the palladium chloride solution of 35mg/L, 20 ℃ of following electromagnetic agitation were taken out after 20 minutes, clean twice at least with deionized water after, with this fabric drying.
So far, activation work is finished, and the fabric after activated can better carry out chemical plating.
Embodiment two:
1, preparation lotion I,
Take by weighing 3-glycidyl ether trimethoxy silane, 0.0002kg acetylacetone,2,4-pentanedione, the 1.5kg of 1kg ethyl orthosilicate, 1.1kg ammoniacal liquor, 3.5kg ethanol, all the other are deionized water, above-mentioned raw materials is 10kg altogether.Said mixture shaking under the normal temperature on the isothermal vibration device, is mixed, obtain lotion I.
2, at fabric face deposition beta-schardinger dextrin-,
The beta-schardinger dextrin-of 0.06kg is joined among the described lotion I, obtain lotion II, afterwards textile impregnation is taken out after 40 minutes in lotion II, it is cleaned one time with deionized water, stand-by with 120 ℃ of oven dry.
3, fabric is placed the palladium chloride solution of 40mg/L, 60 ℃ of following electromagnetic agitation were taken out after 30 minutes, clean twice at least with deionized water after, with this fabric drying.
Embodiment three:
1, preparation lotion I,
Take by weighing 3-glycidyl ether trimethoxy silane, 0.0002kg acetylacetone,2,4-pentanedione, the 1.5kg of 1kg ethyl orthosilicate, 1.1kg hydrochloric acid, 3kg ethanol, all the other are deionized water, above-mentioned raw materials is 10kg altogether.Above-mentioned raw materials is mixed the back shaking under the normal temperature on the isothermal vibration device, mix, obtain lotion I.
2, at fabric face deposition beta-schardinger dextrin-,
With textile impregnation in the beta-schardinger dextrin-aqueous solution of 0.007mg/L 5 minutes, be 2～4kg/cm at padding machine pressure
2Situation under, two soak two rolls; With textile impregnation in described lotion I 5 minutes, be 1～4kg/cm again at padding machine pressure
2Situation under, two soak two rolls; Then with fabric with 80 ℃ of preliminary dryings 5 minutes, baked 30 minutes with 120 ℃.
3, fabric is placed the palladium chloride solution of 40mg/L, 60 ℃ of following electromagnetic agitation were taken out after 30 minutes, clean twice at least with deionized water after, with this fabric drying.
Embodiment four:
1, preparation lotion I,
Take by weighing 3-glycidyl ether trimethoxy silane, 0.0003kg acetylacetone,2,4-pentanedione, the 2kg of 1.2kg ethyl orthosilicate, 1.3kg ammoniacal liquor, 4kg ethanol, all the other are deionized water, above-mentioned raw materials is 10kg altogether.Above-mentioned raw materials is mixed the back shaking under the normal temperature on the isothermal vibration device, mix, obtain lotion I.
2, at fabric face deposition beta-schardinger dextrin-,
With textile impregnation in the beta-schardinger dextrin-aqueous solution of 0.008mg/L 5～10 minutes, be 2～4kg/cm at padding machine pressure
2Situation under, two soak two rolls; With textile impregnation in described lotion I 5～10 minutes, be 1～4kg/cm again at padding machine pressure
2Situation under, two soak two rolls; Then with fabric with 80 ℃ of preliminary dryings 5 minutes, baked 30 minutes with 120 ℃.
3, fabric is placed the palladium chloride solution of 45mg/L, 80 ℃ of following electromagnetic agitation were taken out after 40 minutes, clean twice at least with deionized water after, with this fabric drying.
In the above-described embodiments, Fig. 1 is the molecular structural formula of beta-schardinger dextrin-; Fig. 2 is the stereoscan photograph of fabric before colloidal sol is handled; Fig. 3 is the stereoscan photograph of activation back fabric.After testing: after the fabric after the above activation processing was handled through chemical plating nickel-phosphorus alloy, product surface side's resistance reached 0.2-0.3 Ω/, 4～5 grades of crocking resistances, and its stereoscan photograph is as shown in Figure 4.
Fig. 5 demonstrates Pd-β-CD colloid and H
2PdCl
4The ultraviolet-visible spectrum test result, as can be seen, two kinds of solution lotus all occurs at 210nm and 240nm place and moves spectrum.Because Pd-β-CD colloid and H
2PdCl
4Be the complex compound of two kinds of different ligands of transition metal palladium ion, and part charge density distribution and polarizability all can influence the position of complex compound absorption band.For β-CD and Cl
-Two kinds of parts, the former is because owing to be the cavity structure that is the approximate circle tubular, molecular volume is bigger, and charge density is higher on every side, and its degree of polarization should high Cl
-, therefore, β-CD part and transition metal Pd
2+Break-up energy after the complexing compares Cl
-Big.Thereby in UV-Vis spectrum, the absworption peak wavelength of Pd-β-CD colloid should be less than H
2PdCl
4The absworption peak wavelength. as seen from the figure, near 275nm, the absworption peak wavelength of colloidal solution is lower than H
2PdCl
4The absworption peak wavelength, and absorption signal strengthens, and β-CD and Pd are described
2+Complexing has generated the complex compound of certain structure, and promptly palladium has obtained conceivable in theory dispersion, exposes more catalytic active center, thereby causes chemical plating with higher activity.
Claims (1)
1. fabric activation process before chemical plating based on sol-gel technique is characterized in that comprising following operation:
1.1, preparation lotion I,
Take by weighing the raw material of following corresponding weight portion:
8～12 parts of ethyl orthosilicates,
9～13 parts of 3-glycidyl ether trimethoxy silanes,
0.001～0.003 part of acetylacetone,2,4-pentanedione,
10～20 parts of hydrochloric acid or ammoniacal liquor,
20～40 parts of ethanol,
All the other are deionized water, and above-mentioned raw materials is totally 100 weight portions,
The mixture of described raw material is being shaken under the normal temperature on the isothermal vibration device, it is mixed, obtaining lotion I;
1.2, at fabric face deposition beta-schardinger dextrin-, two kinds of methods are arranged:
Method one: the beta-schardinger dextrin-of 0.3～0.6 weight portion is joined among the described lotion I, obtain lotion II, afterwards textile impregnation is taken out after 20～40 minutes in lotion II, it is cleaned one time with deionized water, stand-by with 80～120 ℃ of oven dry;
Method two: is in the beta-schardinger dextrin-aqueous solution of 0.007～0.008mg/L 5～10 minutes with textile impregnation in concentration, is 2～4kg/cm at padding machine pressure
2Situation under, two soak two rolls; With textile impregnation in described lotion I 5～10 minutes, be 1～4kg/cm again at padding machine pressure
2Situation under, two soak two rolls; Then with fabric with 80 ℃ of preliminary dryings 5 minutes, baked 30 minutes with 120 ℃;
1.3, fabric is placed the palladium chloride solution of 35～45mg/L, electromagnetic agitation was taken out after 20～40 minutes under 20～80 ℃ of temperature, clean twice at least with deionized water after, with this fabric drying.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103132059A (en) * | 2013-01-29 | 2013-06-05 | 上海工程技术大学 | Fabric chemical plating method using HBP-NH2/ Ag+ coordination compound as activate fluid |
| CN111420624A (en) * | 2020-03-20 | 2020-07-17 | 安徽大学 | Parallel synthesis device for sol-gel |
| CN115478432A (en) * | 2022-08-30 | 2022-12-16 | 江南大学 | Preparation method of flame-retardant conductive fabric |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208513C (en) * | 2003-01-14 | 2005-06-29 | 东华大学 | Textile product with effects of bird's nest and its preparing method |
| DE102004008942A1 (en) * | 2004-02-24 | 2005-09-08 | Henkel Kgaa | Use of cyclodextrin derivatives with optionally quaternised polyalkyleneimine, e.g. in textile washing- or cleaning mediums, cosmetic skin care medium such as deodorants, soaps, body lotions and perfumes |
| CN100451166C (en) * | 2005-09-09 | 2009-01-14 | 清华大学 | Chemical plating activating process and metal depositing process therewith |
| CN1966765B (en) * | 2005-11-17 | 2012-07-18 | 中国科学院金属研究所 | Activation method for chemical plating of non-metallic material and chemical plating therefor |
| CN101302080B (en) * | 2007-05-10 | 2011-06-15 | 西北工业大学 | Pretreatment method of chemical plating conductive magneto-conductive glass fibre |
| DE102007034724A1 (en) * | 2007-07-23 | 2009-01-29 | Stiftung Nano Innovations, Olten | Preparing a composition, useful to coat e.g. textile materials, shoes, diapers, airplanes and plastics, comprises dispersing a gel-forming material in an aqueous solution and adding cyclodextrin derivative to the dispersion |
| CN101319315A (en) * | 2008-07-03 | 2008-12-10 | 东华大学 | Activation method before flexible backing material chemical plating based on numerator self-assembly technique |
-
2010
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103132059A (en) * | 2013-01-29 | 2013-06-05 | 上海工程技术大学 | Fabric chemical plating method using HBP-NH2/ Ag+ coordination compound as activate fluid |
| CN103132059B (en) * | 2013-01-29 | 2015-05-20 | 上海工程技术大学 | Fabric chemical plating method using HBP-NH2/ Ag+ coordination compound as activate fluid |
| CN111420624A (en) * | 2020-03-20 | 2020-07-17 | 安徽大学 | Parallel synthesis device for sol-gel |
| CN115478432A (en) * | 2022-08-30 | 2022-12-16 | 江南大学 | Preparation method of flame-retardant conductive fabric |
| CN115478432B (en) * | 2022-08-30 | 2024-01-05 | 江南大学 | Preparation method of flame-retardant conductive fabric |
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