A kind of antiseptic sanitary glaze and preparation method
Technical field
The invention belongs to ceramic technology field, more particularly to a kind of antiseptic sanitary glaze and preparation method.
Background technology
With the improvement of people's living standards and the enhancing of environmental consciousness, people increasingly pay close attention to daily necessities pair at one's side
The impact of own health.And family kitchen, toilet, particularly hospital, the easy breed bacteria of the sanitary ceramic product of public place,
Affect the health of people.Antiseptic sanitary is a kind of new function material of environmental protection, and it is by antimicrobial technology and ceramic material
Material combines, while both having maintained the original use function of ceramic, decorative effect and physical and chemical performance, increased again antibacterial,
Sterilized and self-cleaning function, in can be widely used for the environment such as health, medical treatment, family room.
Open in hospital, dining room, high-end residential etc. early in developed countries such as late 1980s, Japan, the U.S., European Union
Begin using the construction sanitary ceramic product with antibacterial functions, recent year average family also gradually begins to use anti-bacteria ceramic
Product.Simultaneously at present antiseptic sanitary there are problems that production cost is high, Durability of antimicrobial effect is poor, anti-microbial property not.
The content of the invention
The technical problem to be solved is to provide a kind of low cost, the antiseptic sanitary glaze of excellent antibacterial performance
And preparation method.
The technical scheme that the present invention solves above-mentioned technical problem is as follows:
A kind of antiseptic sanitary glaze, including following raw material:23~24 parts of potassium feldspar, 34~35 parts of sandstone, in vain
3~4 parts of marble, 11~12 parts of lime stone, 9~11 parts of zirconium English powder, 4~6 parts of frit, 2~3 parts of aluminum oxide, 2~3 parts of zinc oxide,
4~5 parts of Suzhou soil, 0.01~0.03 part of zirconium iron pink, spectrum is yellow 0.06~0.08 part, 0.1~0.2 part of cellulose, compound antibacterial powder
2~3 parts of body;
The compound antibacterial powder includes the raw material of following weight/mass percentage composition:Silver molybdate 15~20%, zinc molybdate 60~
65%, titanium dioxide 20~25%.
Further, a kind of antiseptic sanitary glaze, including following raw material:23.5 parts of potassium feldspar, sandstone
34.5 parts, 3.5 parts of dolomite, 11.5 parts of lime stone, 10 parts of zirconium English powder, 5 parts of frit, 2.5 parts of aluminum oxide, 2.5 parts of zinc oxide, Soviet Union
4.5 parts of state soil, 0.02 part of zirconium iron pink, spectrum is yellow 0.07 part, 0.15 part of cellulose, 2.5 parts of compound antibacterial powder;
The compound antibacterial powder includes the raw material of following weight/mass percentage composition:Silver molybdate 18%, zinc molybdate 62%, dioxy
Change titanium 20%.
A kind of preparation method of antiseptic sanitary glaze, comprises the following steps:
The preparation of A, compound antibacterial powder
The preparation of molybdic acid aluminium powder:By silver nitrate and ammonium molybdate in molar ratio 2:1~1.2 is added separately in deionized water
Silver nitrate solution and ammonium molybdate solution are prepared, by both the above solution as mixing 10~15min, Ran Houzhi in reactor
3~5min of heating response in the micro-wave oven that power is 800~1000W, gained light yellow precipitate distillation water washing, mistake
Filter, is dried 10~12h under 60~70 DEG C of constant temperatures, obtains the molybdic acid aluminium powder that particle diameter is 2~4 μm;
The preparation of zinc molybdate powder:By zinc nitrate and ammonium molybdate in molar ratio 1:1.2 are added separately to match somebody with somebody in deionized water
Zinc nitrate solution processed and ammonium molybdate solution, are then slowly dropped to zinc nitrate solution in ammonium molybdate solution, and stirring 20~
30min, gained white depositions distillation water washing, filtration, is dried 10~12h under 80~100 DEG C of constant temperatures, obtains grain
Footpath is 3~5 μm of zinc molybdate powder;
Titanium dioxide powder that particle diameter is 2~3 μm, molybdic acid aluminium powder, zinc molybdate powder are mixed by proportioning, is combined
Antimicrobial powder;
The preparation of B, glaze slip
The raw material of the compound antibacterial powder in step A and other proportionings is added in ball mill, wet ball grinding is carried out to glaze
It is 2~4% that slurry fineness is 325 mesh 10000-hole sieve screen over-sizes, obtains glaze slip;
The preparation of C, antiseptic sanitary glaze
Glaze slip in step B is imposed on sanitary ceramic body surface, using tunnel cave, is aoxidized at 1200~1250 DEG C
Fire in atmosphere, its heating rate is 2.5~3 DEG C/min, firing period is 16~18h, is incubated 2~3h, i.e., in sanitary ceramics
Antiseptic sanitary glaze is obtained in billet surface.
The invention has the beneficial effects as follows:
1) present invention is using chemical synthesis synthesis silver molybdate, zinc molybdate antimicrobial powder, and preparation method is simple to operation, former
Material low cost.
2) silver molybdate, zinc molybdate and titanium dioxide powder are constituted into proportion compound antibacterial powder, by it as additive
In being introduced into ceramic glaze, with reliable antibiotic property, glaze nondiscolouring during high temperature.
Its Antibacterial Mechanism of antiseptic sanitary glaze of the present invention:One is the presence due to moisture, the silver molybdate of glaze, zinc molybdate
The silver-colored zinc ion being sustained out is entered in bacterium body, destroys the respiratory system and electric transmission system of microbial cell, causes enzyme
Damage;Two is that silver ion and optically catalytic TiO 2 form the very strong hydroxyl of activity certainly with the water and oxygen for being adsorbed in its surface
By base and active oxygen, can react with most organic matters (including the organic matter in bacterium), carbon dioxide and water be generated, so as to short
Bacterium is killed in time, stench and greasy dirt is eliminated, so as to ensure glaze antibiotic property.
Description of the drawings
Fig. 1 is non-antibacterial Ceramic glaze electromicroscopic photograph figure;
Fig. 2 is anti-bacteria ceramic glaze electromicroscopic photograph figure of the present invention;
Fig. 3 is non-antibacterial ceramic blank glaze faying face scanning electron microscope (SEM) photograph;
Fig. 4 is anti-bacteria ceramic glaze-body bonding Surface scan electron microscope of the present invention.
Specific embodiment
The principle and feature of the present invention are described below in conjunction with accompanying drawing, example is served only for explaining the present invention, and
It is non-for limiting the scope of the present invention.
Fig. 1 is non-antibacterial Ceramic glaze electromicroscopic photograph figure
Fig. 2 is anti-bacteria ceramic glaze electromicroscopic photograph figure of the present invention, it can be seen that antiseptic sanitary glaze exists cubic
Crystal, due to add compound antibacterial powder, and glaze color with for add compound antibacterial powder it is consistent.
Fig. 3 is non-antibacterial ceramic blank glaze faying face scanning electron microscope (SEM) photograph
Fig. 4 is anti-bacteria ceramic glaze-body bonding Surface scan electron microscope of the present invention, it can be seen that after adding compound antibacterial powder, base
Glaze junction quality has not significant impact.
Embodiment 1
The preparation of A, compound antibacterial powder
The preparation of molybdic acid aluminium powder:By silver nitrate and ammonium molybdate in molar ratio 2:1 is added separately to be prepared in deionized water
Silver nitrate solution and ammonium molybdate solution, by both the above solution as 10min is mixed in reactor, be then as power
Heating response 3min in the micro-wave oven of 800W, gained light yellow precipitate distillation water washing, filtration, under 60 DEG C of constant temperatures
10h is dried, the molybdic acid aluminium powder that particle diameter is 2 μm is obtained;
The preparation of zinc molybdate powder:By zinc nitrate and ammonium molybdate in molar ratio 1:1.2 are added separately to match somebody with somebody in deionized water
Zinc nitrate solution processed and ammonium molybdate solution, are then slowly dropped to zinc nitrate solution in ammonium molybdate solution, stir 20min, institute
Obtain white depositions distillation water washing, filter, under 80 DEG C of constant temperatures 10h is dried, obtain the molybdic acid zinc powder that particle diameter is 3 μm
Body;
Titanium dioxide powder that particle diameter is 2 μm, molybdic acid aluminium powder, zinc molybdate powder are mixed by proportioning, obtains compound anti-
Bacterium powder body.
The preparation of B, glaze slip
By 23 parts of potassium feldspar, 34 parts of sandstone, 3 parts of dolomite, 11 parts of lime stone, 9 parts of zirconium English powder, 4 parts of frit, aluminum oxide 2
Part, 2 parts of zinc oxide, 4 parts of Suzhou soil, 0.01 part of zirconium iron pink, spectrum is yellow 0.06 part, 0.1 part of cellulose, 2 parts of compound antibacterial powder;Institute
State raw material of the compound antibacterial powder including following weight/mass percentage composition:Silver molybdate 15%, zinc molybdate 60%, titanium dioxide 25%,
In adding ball mill, it is that 325 mesh 10000-hole sieve screen over-sizes are 2% to carry out wet ball grinding to glaze slip fineness, obtains glaze slip;
The preparation of C, antiseptic sanitary glaze
Glaze slip in step B is imposed on sanitary ceramic body surface, using tunnel cave, in oxidizing atmosphere at 1200 DEG C
Fire, its heating rate is 2.5 DEG C/min, and firing period is 16h, be incubated 2h, i.e., resisted on sanitary ceramic body surface
Bacterium sanitary ceramics glaze.
Embodiment 2
The preparation of A, compound antibacterial powder
The preparation of molybdic acid aluminium powder:By silver nitrate and ammonium molybdate in molar ratio 2:1.1 are added separately to match somebody with somebody in deionized water
Silver nitrate solution processed and ammonium molybdate solution, by both the above solution as 13min is mixed in reactor, then as power
For heating response 4min in the micro-wave oven of 900W, gained light yellow precipitate distillation water washing, filtration, in 65 DEG C of constant temperatures
Under be dried 11h, obtain the molybdic acid aluminium powder that particle diameter is 3 μm;
The preparation of zinc molybdate powder:By zinc nitrate and ammonium molybdate in molar ratio 1:1.2 are added separately to match somebody with somebody in deionized water
Zinc nitrate solution processed and ammonium molybdate solution, are then slowly dropped to zinc nitrate solution in ammonium molybdate solution, stir 25min, institute
Obtain white depositions distillation water washing, filter, under 90 DEG C of constant temperatures 11h is dried, obtain the molybdic acid zinc powder that particle diameter is 4 μm
Body;
Titanium dioxide powder that particle diameter is 2.5 μm, molybdic acid aluminium powder, zinc molybdate powder are mixed by proportioning, is combined
Antimicrobial powder.
The preparation of B, glaze slip
By 23.5 parts of potassium feldspar, 34.5 parts of sandstone, 3.5 parts of dolomite, 11.5 parts of lime stone, 10 parts of zirconium English powder, frit 5
Part, 2.5 parts of aluminum oxide, 2.5 parts of zinc oxide, 4.5 parts of Suzhou soil, 0.02 part of zirconium iron pink, spectrum is yellow 0.07 part, 0.15 part of cellulose,
2.5 parts of compound antibacterial powder;The compound antibacterial powder includes the raw material of following weight/mass percentage composition:Silver molybdate 18%, molybdic acid
Zinc 62%, titanium dioxide 20%, in adding ball mill, carry out wet ball grinding is for 325 mesh 10000-hole sieve screen over-sizes to glaze slip fineness
3%, obtain glaze slip;
The preparation of C, antiseptic sanitary glaze
Glaze slip in step B is imposed on sanitary ceramic body surface, using tunnel cave, in oxidizing atmosphere at 1230 DEG C
Fire, its heating rate is 2.8 DEG C/min, and firing period is 17h, be incubated 2.5h, i.e., obtain on sanitary ceramic body surface
Antiseptic sanitary glaze.
Embodiment 3
The preparation of A, compound antibacterial powder
The preparation of molybdic acid aluminium powder:By silver nitrate and ammonium molybdate in molar ratio 2:1.2 are added separately to match somebody with somebody in deionized water
Silver nitrate solution processed and ammonium molybdate solution, by both the above solution as 15min is mixed in reactor, then as power
For heating response 5min in the micro-wave oven of 1000W, gained light yellow precipitate distillation water washing, filtration, in 70 DEG C of constant temperature bars
12h is dried under part, the molybdic acid aluminium powder that particle diameter is 4 μm is obtained;
The preparation of zinc molybdate powder:By zinc nitrate and ammonium molybdate in molar ratio 1:1.2 are added separately to match somebody with somebody in deionized water
Zinc nitrate solution processed and ammonium molybdate solution, are then slowly dropped to zinc nitrate solution in ammonium molybdate solution, stir 30min, institute
Obtain white depositions distillation water washing, filter, under 100 DEG C of constant temperatures 12h is dried, obtain the zinc molybdate that particle diameter is 5 μm
Powder;
Titanium dioxide powder that particle diameter is 3 μm, molybdic acid aluminium powder, zinc molybdate powder are mixed by proportioning, obtains compound anti-
Bacterium powder body.
The preparation of B, glaze slip
By 24 parts of potassium feldspar, 35 parts of sandstone, 4 parts of dolomite, 12 parts of lime stone, 11 parts of zirconium English powder, 6 parts of frit, aluminum oxide 3
Part, 3 parts of zinc oxide, 5 parts of Suzhou soil, 0.03 part of zirconium iron pink, spectrum is yellow 0.08 part, 0.2 part of cellulose, 3 parts of compound antibacterial powder;Institute
State raw material of the compound antibacterial powder including following weight/mass percentage composition:Silver molybdate 15%, zinc molybdate 65%, titanium dioxide 20%,
In adding ball mill, it is that 325 mesh 10000-hole sieve screen over-sizes are 4% to carry out wet ball grinding to glaze slip fineness, obtains glaze slip;
The preparation of C, antiseptic sanitary glaze
Glaze slip in step B is imposed on sanitary ceramic body surface, using tunnel cave, in oxidizing atmosphere at 1250 DEG C
Fire, its heating rate is 3 DEG C/min, and firing period is 18h, be incubated 3h, i.e., obtain antibacterial on sanitary ceramic body surface
Sanitary ceramics glaze.
Comparative example 1
The preparation of A, compound antibacterial powder
The preparation of molybdic acid aluminium powder:By silver nitrate and ammonium molybdate in molar ratio 2:1.1 are added separately to match somebody with somebody in deionized water
Silver nitrate solution processed and ammonium molybdate solution, by both the above solution as 13min is mixed in reactor, then as power
For heating response 4min in the micro-wave oven of 900W, gained light yellow precipitate distillation water washing, filtration, in 65 DEG C of constant temperatures
Under be dried 11h, obtain the molybdic acid aluminium powder that particle diameter is 3 μm;
The preparation of zinc molybdate powder:By zinc nitrate and ammonium molybdate in molar ratio 1:1.2 are added separately to match somebody with somebody in deionized water
Zinc nitrate solution processed and ammonium molybdate solution, are then slowly dropped to zinc nitrate solution in ammonium molybdate solution, stir 25min, institute
Obtain white depositions distillation water washing, filter, under 90 DEG C of constant temperatures 11h is dried, obtain the molybdic acid zinc powder that particle diameter is 4 μm
Body;
Titanium dioxide powder that particle diameter is 2.5 μm, molybdic acid aluminium powder, zinc molybdate powder are mixed by proportioning, is combined
Antimicrobial powder.
The preparation of B, glaze slip
By 23.5 parts of potassium feldspar, 34.5 parts of sandstone, 3.5 parts of dolomite, 11.5 parts of lime stone, 10 parts of zirconium English powder, frit 5
Part, 2.5 parts of aluminum oxide, 2.5 parts of zinc oxide, 4.5 parts of Suzhou soil, 0.02 part of zirconium iron pink, spectrum is yellow 0.07 part, 0.15 part of cellulose,
8 parts of compound antibacterial powder;The compound antibacterial powder includes the raw material of following weight/mass percentage composition:Silver molybdate 18%, zinc molybdate
62%, titanium dioxide 20%, in adding ball mill, carry out wet ball grinding is for 325 mesh 10000-hole sieve screen over-sizes to glaze slip fineness
3%, obtain glaze slip;
The preparation of C, antiseptic sanitary glaze
Glaze slip in step B is imposed on sanitary ceramic body surface, using tunnel cave, in oxidizing atmosphere at 1230 DEG C
Fire, its heating rate is 2.8 DEG C/min, and firing period is 17h, be incubated 2.5h, i.e., obtain on sanitary ceramic body surface
Antiseptic sanitary glaze.
Comparative example 2
The preparation of A, compound antibacterial powder
The preparation of molybdic acid aluminium powder:By silver nitrate and ammonium molybdate in molar ratio 2:1.1 are added separately to match somebody with somebody in deionized water
Silver nitrate solution processed and ammonium molybdate solution, by both the above solution as 13min is mixed in reactor, then as power
For heating response 4min in the micro-wave oven of 900W, gained light yellow precipitate distillation water washing, filtration, in 65 DEG C of constant temperatures
Under be dried 11h, obtain the molybdic acid aluminium powder that particle diameter is 3 μm;
The preparation of zinc molybdate powder:By zinc nitrate and ammonium molybdate in molar ratio 1:1.2 are added separately to match somebody with somebody in deionized water
Zinc nitrate solution processed and ammonium molybdate solution, are then slowly dropped to zinc nitrate solution in ammonium molybdate solution, stir 25min, institute
Obtain white depositions distillation water washing, filter, under 90 DEG C of constant temperatures 11h is dried, obtain the molybdic acid zinc powder that particle diameter is 4 μm
Body;
Titanium dioxide powder that particle diameter is 2.5 μm, molybdic acid aluminium powder, zinc molybdate powder are mixed by proportioning, is combined
Antimicrobial powder.
The preparation of B, glaze slip
By 23.5 parts of potassium feldspar, 34.5 parts of sandstone, 3.5 parts of dolomite, 11.5 parts of lime stone, 10 parts of zirconium English powder, frit 5
Part, 2.5 parts of aluminum oxide, 2.5 parts of zinc oxide, 4.5 parts of Suzhou soil, 0.02 part of zirconium iron pink, spectrum is yellow 0.07 part, 0.15 part of cellulose,
1 part of compound antibacterial powder;The compound antibacterial powder includes the raw material of following weight/mass percentage composition:Silver molybdate 18%, zinc molybdate
62%, titanium dioxide 20%, in adding ball mill, carry out wet ball grinding is for 325 mesh 10000-hole sieve screen over-sizes to glaze slip fineness
3%, obtain glaze slip;
The preparation of C, antiseptic sanitary glaze
Glaze slip in step B is imposed on sanitary ceramic body surface, using tunnel cave, in oxidizing atmosphere at 1230 DEG C
Fire, its heating rate is 2.8 DEG C/min, and firing period is 17h, be incubated 2.5h, i.e., obtain on sanitary ceramic body surface
Antiseptic sanitary glaze.
Non- antiseptic sanitary glaze control sample example
The preparation of A, glaze slip
By 23.5 parts of potassium feldspar, 34.5 parts of sandstone, 3.5 parts of dolomite, 11.5 parts of lime stone, 10 parts of zirconium English powder, frit 5
Part, 2.5 parts of aluminum oxide, 2.5 parts of zinc oxide, 4.5 parts of Suzhou soil, 0.02 part of zirconium iron pink, spectrum is yellow 0.07 part, 0.15 part of cellulose,
0 part of compound antibacterial powder, in adding ball mill, it is that 325 mesh 10000-hole sieve screen over-sizes are 3% to carry out wet ball grinding to glaze slip fineness,
Obtain glaze slip;
The preparation of B, sanitary ceramics glaze
Glaze slip in step A is imposed on sanitary ceramic body surface, using tunnel cave, in oxidizing atmosphere at 1230 DEG C
Fire, its heating rate is 2.8 DEG C/min, and firing period is 17h, be incubated 2.5h, i.e., obtain on sanitary ceramic body surface
Antiseptic sanitary glaze.
1st, antiseptic sanitary glaze anti-microbial property test
Using colony counting method, by determining comparative example with embodiment antimicrobial sample and bacterial number increase and decrease in control sample
Method evaluating the anti-anti-microbial property of material.
Specific experiment step:
A. will by coupons l.0cm × 3.0cm and control print (with by coupons homogeneous material, equal size, but do not contain
Anti-biotic material, and sterilized process) each 3, it is divided into 3 groups and is placed in the PBS solution of sterilizing.Add tested bacterial liquid culture
It is placed in 36 DEG C of insulating boxs after dilution, fully vibration and cultivates 6h.
B. bacterium solution 0.5ml after culture is taken with pipette, is instilled containing (attention in 4.5ml sterilizing PBSs along tube wall
Pipette tip should not touch in-line dilution liquid), tube shaken is well mixed, and is made 1:10 dilution.
C. 1ml sterilizing pipettes are separately taken, by aforesaid operations order, make 10 times of incremental thin liquids, be so often incremented by dilution once,
Use 1 1ml sterilizing pipette instead.
D. will cool down in the culture dish of the nutrient agar injection sterilizing of proper temperature standby.
E. 3 acceptable diluent degree are selected, respectively while making 10 times and being incremented by dilution, i.e., drawing the dilution liquid relief
Pipe moves 0.1ml in culture dish, and is coated with uniform.Each dilution factor makees two culture dishes.
F. culture dish is put into 36 DEG C of constant incubator, takes out after 18~24h of culture and count.
G. method for counting colonies.Flat board of the clump count between 30~300 is chosen as total plate count bioassay standard.One
Dilution factor uses two flat boards, should adopt two flat board averages, when its middle plateform has larger sheet colony growth, does not then adopt
With, and using the flat board without sheet colony growth as the dilution clump count, if sheet falls less than the half of flat board, and remaining
Bacterium colony distribution is again very uniform in half, you can calculates and take advantage of 2 to represent full ware clump count after half flat board.
H. calculate in bacteriostasis rate (part)=(A-B)/A × 100 formula:A represents non-anti-bacteria ceramic control sample and averagely reclaims bacterium
Number;B represents the average bacterial count recovered of test specimen (comparative example and embodiment).
Antiseptic sanitary glaze (comparative example and embodiment) and non-anti-bacteria ceramic control sample are put into by the above process
In being diluted to certain density colibacillary cushioning liquid, after immersion 24h their antibiotic rate is tested.As a result such as table 1.
The anti-microbial property of the antibacterial ceramic glaze of table 1
Embodiment |
Clump count before sterilized |
Clump count after sterilization |
Antibiotic rate (%) |
Embodiment 1 |
2650 |
133 |
95.0 |
Embodiment 2 |
2650 |
90 |
96.6 |
Embodiment 3 |
2650 |
95 |
96.4 |
Comparative example 1 |
2650 |
81 |
96.9 |
Comparative example 2 |
2650 |
1315 |
50.4 |
Control sample example |
2650 |
2650 |
0 |
It can be seen from Table 1 that, antiseptic sanitary glaze of the present invention, antibiotic rate is up to 95~96%.When antimicrobial powder exists
When the solubility of glaze reaches saturation, increase its content, the ion that glaze superficial dissolution goes out will not change, such as comparative example 1, resist
Bacterium powder content has increased to 8 parts, compared with 2.5 parts of antimicrobial powder content in embodiment 2, the two other preparation condition all same,
But antibacterial effect essentially unchangedization.
2nd, antiseptic sanitary physicochemical property test
Comparative example and embodiment antimicrobial sample and non-anti-bacteria ceramic control sample are done by physical and chemical quality according to GB6952-2015
Testing result such as table 2.It can be seen from the test results that, no matter outward appearance is detected or physical and chemical performance detection anti-bacteria ceramic, is met
Standard.
The antiseptic sanitary glaze physical and chemical quality testing result of table 2
Embodiment |
Aberration |
Water absorption rate (%) |
Crack resistance |
Open defect |
Antibiotic rate (%) |
Embodiment 1 |
It is unobvious |
0.3 |
Flawless |
Nothing |
95.0 |
Embodiment 2 |
It is unobvious |
0.3 |
Flawless |
Nothing |
96.6 |
Embodiment 3 |
It is unobvious |
0.2 |
Flawless |
Nothing |
96.4 |
Comparative example 1 |
It is more apparent |
0.7 |
Flawless |
Low in glossiness |
96.9 |
Comparative example 2 |
It is unobvious |
0.8 |
Flawless |
Nothing |
50.4 |
Control sample example |
It is unobvious |
0.3 |
Flawless |
Nothing |
0 |
The foregoing is only presently preferred embodiments of the present invention, not to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.