CN1014049B - Underglaze color reinforced porcelain and production method thereof - Google Patents
Underglaze color reinforced porcelain and production method thereofInfo
- Publication number
- CN1014049B CN1014049B CN 89105753 CN89105753A CN1014049B CN 1014049 B CN1014049 B CN 1014049B CN 89105753 CN89105753 CN 89105753 CN 89105753 A CN89105753 A CN 89105753A CN 1014049 B CN1014049 B CN 1014049B
- Authority
- CN
- China
- Prior art keywords
- glaze
- porcelain
- crystal
- mullite
- admixtion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 91
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 48
- 229910052863 mullite Inorganic materials 0.000 claims abstract description 45
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 28
- 239000010431 corundum Substances 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011521 glass Substances 0.000 claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 12
- 239000010453 quartz Substances 0.000 claims abstract description 9
- 238000010304 firing Methods 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 238000005728 strengthening Methods 0.000 claims description 17
- 239000010433 feldspar Substances 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 230000002787 reinforcement Effects 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 239000000454 talc Substances 0.000 claims description 14
- 235000012222 talc Nutrition 0.000 claims description 14
- 229910052623 talc Inorganic materials 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000000049 pigment Substances 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- 239000004576 sand Substances 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 9
- 239000004615 ingredient Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 4
- 210000003298 dental enamel Anatomy 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 229940075397 calomel Drugs 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 238000009432 framing Methods 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000009827 uniform distribution Methods 0.000 claims 1
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 abstract 1
- 239000013081 microcrystal Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 13
- 230000035939 shock Effects 0.000 description 13
- 239000004927 clay Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000011440 grout Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 235000006491 Acacia senegal Nutrition 0.000 description 1
- 241001408630 Chloroclystis Species 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000002742 anti-folding effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- DZUDZSQDKOESQQ-UHFFFAOYSA-N cobalt hydrogen peroxide Chemical compound [Co].OO DZUDZSQDKOESQQ-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000011226 reinforced ceramic Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention belongs to the technical field of ceramics, and relates to a reinforced porcelain and a manufacturing method thereof, wherein the reinforced porcelain body comprises 30-45% of crystal phase, 20-30% of mullite, 5-15% of corundum and 1-6% of quartz, and the balance of amorphous phase (weight ratio), the mullite crystal is a fine acicular crystal which is mutually interwoven and uniformly distributed in a porcelain body like a felt to be used as a main crystal phase framework, the corundum crystal is a granular microcrystal which is uniformly distributed and embedded among the mullite acicular crystals, and the mullite acicular crystals are obviously grown in a glaze layer glass phase, and the impact strength of the porcelain is greatly improved by the microstructure of the porcelain. The main raw materials used in the production are industrial alumina, potassium feldspar and kaolin.
Description
The present invention relates to a kind of reinforcement porcelain and manufacture method thereof, more particularly, the present invention relates to a kind of colour-in-glaze strengthening ceramics, be applicable to daily ceramic product and concrete manufacture method thereof.
The physical strength that improves ceramic is an important development direction of household china, and is along with in dining room, the hotel tableware for daily use being washed the raising of adopting mechanization degree, particularly also more and more higher to the requirement of resistance to impact shock to the household china physical strength.The higher porcelain of physical strength mainly is a hard-paste at present, typical hard-paste is representative with kaolin-quartz-feldspar three-part system in prescription, firing temperature can reach more than 1400 ℃, the porcelain body microstructure is for distributing mullite crystal brokenly in the successive glass matrix, residual quartz crystal, parent rock remains, and sealed porosity, the glass phasor can be up to 70% in the higher porcelain body of transparence.In the mechanical property of hard-paste, ultimate compression strength is quite high, but anti-folding and tensile strength approximately have only the 1/7-1/10 of ultimate compression strength, and especially resistance to impact shock is the poorest, generally has only 1.7-2.2kgf/cm
2Mechanical property is presented as typical brittleness material, the porcelain body microstructure of this and it is closely related, in feldspar hard-paste microstructure, and the one, mullite content is few, there is not the corundum crystalline phase again, and it is more to contain quartzy brilliant bits, the glassy phase height, and the fragility that therefore wants to change hard-paste is the comparison difficulty, the resistance to impact shock that improves porcelain mainly is the microstructure that changes porcelain, and a kind of new porcelain structure porcelain-reinforcement porcelain is being developed and developed in countries in the world at present.According to No. 1656 reports of Japanese pottery ten days report, Japan is developing energetically and is strengthening porcelain, during Japan's reinforcement porcelain is raw materials used, contains the artificial raw material of aluminum oxide about 30%, and firing temperature is more than 1420 ℃.The artificial raw materials cost height of aluminum oxide, and the firing temperature height of goods (surpassing hard-paste), energy consumption is big, in addition by the existing porcelain sample microstructure analysis of strengthening is shown, in the microstructure, corundum is that principal crystalline phase accounts for 20-24%, mullite is a paracrystalline phase, accounts for 5-10%, and microstructure is to the improve of the resistance to impact shock of porcelain like this, be subjected to certain influence (because the corundum crystal Young's modulus is big, anti-impact elasticity is little).And be difficult to realize strengthening the under glazed of porcelain.
The objective of the invention is to improve the resistance to impact shock of strengthening porcelain, reduce and produce raw materials used cost, reduce firing temperature, save energy, and produce colour-in-glaze strengthening ceramics.
Another object of the present invention provides a kind of method of strengthening porcelain of producing.
Realize that the object of the invention technical scheme is: make and strengthen microstructural 30%-45%(that porcelain porcelain body crystalline phase amount accounts for porcelain body by weight), crystalline phase is a mullite, corundum, quartz crystal, with the mullite is principal crystalline phase, even corundum is that the content of paracrystalline phase mullite is greater than corundum, the microstructure compositing range of porcelain is (by weight), mullite 20-30%, corundum 5-20%, quartzy 1-6%, all the other equate to be amorphous phase for glass, mullite crystal is that fine needle-like crystal (most particles＜30 μ m) resembles be interweaved as the felt (reticulating staggered) and is evenly distributed in the porcelain base as the crystalline phase main framing, corundum crystal is uniformly distributed between the mullite needle-like crystal as granular crystallite (＜1 μ m), and make in the carcass surface mullite needle-like crystal extend glaze layer bottom glass mutually in.Adopt the reason of this technical scheme to be: in the crystalline phase of porcelain body, the folding strength of corundum, hardness all is maximum, and elasticity little (being that Young's modulus is big) causes the porcelain resistance to impact shock relatively poor.The mullite crystal folding strength, hardness is only second to corundum more greatly, and its elasticity big (Young's modulus is big), has higher resistance to impact shock, if with mullite crystal as the principal crystalline phase in the porcelain body microstructure, corundum is as paracrystalline phase, the growth of control mullite crystal is not thick excessively, and (mullite crystal is grown up and the quantity minimizing, and distribute and be difficult for evenly, reduce physical strength on the contrary), mullite crystal is grown to the netted needle-like crystal that is interweaved, and corundum crystal makes it be grown to granular crystallite, evenly iron chains are embedded between the mullite needle-like crystal mesh, making the porcelain body structure like this, firm but gentle (to be embedded with folding strength big for iron chains between the mullite crystal of good springiness, the corundum crystallite that hardness is big), make porcelain body be presented as that in macroscopic view resistance to impact shock improves greatly, and because the needle-like crystal that mullite is interweaved grows the porcelain body surface, go deep in the enamel, make the combination very securely of porcelain body and enamel, be formed with the buffering tire, the physical strength and the shock resistance of whole porcelain have been improved in glaze ply stress strained middle layer.
Realize technique scheme, key is stable content, shape, size and the distribution of strengthening mullite in the porcelain microstructure, corundum, quartz, amorphous phase (glass equates), come to determine the chemical ingredients of porcelain thus, therefore production technique, requirement and processing parameter must have the Al of enough content in porcelain body
2O
3(aluminum oxide) chemical ingredients, with the mullite crystal that guarantees that generation is enough, corundum crystal, and to control quartz (particularly cristobalite) crystal, suppress because the stress-strain that quartzy crystal conversion produces, the chemical ingredients scope of definite porcelain body thus:
SiO
245-55% Al
2O
340-50%
K
2O+Na
2O 4.5-5.2%（Na
2O≤1.2%）
CaO 0.5%-1% Fe
2O
3≤0.4% MgO≤1%
When formulating this chemical ingredients, also consider factors such as firing range, thermostability, technology controlling and process, Al
2O
3Content determine will to consider to generate mullite (3Al
2O
32SiO
2) t and corundum (2-Al
2O
3) crystal is required, intrinsic energy is too not high again, otherwise raw materials cost rises, and firing temperature raises, (Al in the porcelain body
2O
3Content surpasses 40%, and sintering temperature is generally with Al
2O
3Content increase and improve) expend fuel, introduce K
2O+Na
2O is in order to introduce the feldspar raw material in raw material, as flux, reduces firing temperature, and the feldspar raw material can be introduced a certain amount of Al again
2O
3Reduce raw materials cost, in chemical ingredients, introduce a spot of MgO as fusing assistant, further reduce firing temperature, the introducing of MgO helps mullite crystal to generate at high temperature in addition, and (glassy phase physical strength in the porcelain body microstructure is the poorest to reduce the glass phasor, reducing glass phasor in the porcelain body relatively, is the favourable approach that improves the porcelain physical strength).
The glaze layer of colour-in-glaze strengthening ceramics must with porcelain body in mechanical property, aspect of performances such as thermal expansivity are complementary, used glaze chemical ingredients neither influences the stable color development of under glazed pigment, can further improve the physical strength of strengthening porcelain again, it is considered herein that in the microstructure of glaze layer on the porcelain body surface and the glaze bottom generates equally distributed 1-5%(weight ratio) thermal expansivity little, a spot of trichroite crystallite can make glaze obtain higher glaze intensity, improve the physical strength that the present invention strengthens porcelain, for this reason, the chemical ingredients scope of determining enamel of the present invention is SiO
270-72%, Al
2O
314-15%, MgO3.5-4%, K
2O+Na
2O≤6.5%, Fe
2O
3＜0.1%, CaO 1-5%.
When making colour-in-glaze strengthening ceramics, in the raw material of glaze, must not contain Li
+, Ba
++, Zn
++, Sn
++Plasma is in order to avoid influence the stable color development of under glazed pigment.When selecting under glazed pigment for use, the admixtion of used pigment should with the thermal expansivity basically identical of base glaze, tinting strength is stronger, non-foaming, sintering range and base glaze basically identical, generally at 1300-1420 ℃, viscosity is suitable in the porcelain firing range, does not flow, bank does not fall.
Production method of the present invention is produced this reinforcement porcelain by following described mode.The technical process of producing, need through raw material processing, batching, ball milling, take out and starch the sieve press filtration of suction iron, pugging, blank forming, body drying, biscuiting, glazing, glaze firing, inspection after construction, packing warehouse-in etc., the characteristics of the inventive method are that (1) blank raw material selects kaolin, potassium felspar sand, commercial alumina material for use, fineness requirement 250 mesh screen residues≤0.2% of raw material, and the blank composition of raw materials is (by weight): kaolin 40-60%; Potassium felspar sand 25-30%; Commercial alumina 10-30%; In order to reduce firing temperature, can in the blank composition of raw materials, add fusing assistant raw material such as the calcination of talc of 1-5%, talcum can be introduced the composition MgO that fluxes.(2) the glaze raw material is selected fineness requirement 300 mesh screen residues≤0.2% of potassium felspar sand, quartz, kaolin, commercial alumina, talc materials, raw material for use, and the glaze composition of raw materials is (by weight): potassium felspar sand 42-45%, quartzy 25-30%, kaolin 8-14%, commercial alumina 3-7%, talcum 10-15%.When (3) blank prepares, vacuum pugging number of times 〉=4 time, vacuum tightness 720-740mmHg.Find by detecting, increase the vacuum pugging number of times, can improve the physical strength (it is as follows to detect data) of porcelain body:
Vacuum pugging number of times porcelain body folding strength (kgf/cm
2)
One time 680
Secondary 705
Three times 720
Four times 836
(4) calcining system: oxydizing flame biscuiting, temperature 700-800 ℃, during glaze firing, the initial oxidation flame, back reducing flame, temperature was controlled at 1050-1100 ℃ when oxydizing flame changeed reducing flame, during little fire, contain O in the weak oxide atmosphere
2Amount is 2-5%, contains CO amount 3-5% during big fire in the reducing atmosphere, 1350 ℃-1420 ℃ of glaze firing firing temperatures.
When manufacturing colour-in-glaze strengthening ceramics, after the base substrate biscuiting, carry out under glazed and decorate glazing more afterwards, glaze firing.The technical process of under glazed pigment prepared is: batching → mixing (dry ground) → high-temperature calcination → dry method coarse crushing → wet ball grinding → drying → porphyrize, full mistake 200 mesh sieves of dry ground fineness, 1350-1400 ℃ of high-temperature calcination temperature, 20 mesh sieves are crossed in the dry method coarse crushing, and wet ball grinding is crossed 200 mesh sieves, drying temperature 100-105 ℃.Porphyrize is crossed 300 mesh sieves.The prescription of under glazed pigment admixtion mainly contains following several prescription: (weight percent) according to different colors
(1) pink admixtion compositing range under the glaze:
Aluminium sesquioxide 75-79%
Manganous carbonate 11-13%
Lime carbonate 1-2%
Burn borax 8-10%
(2) careless blue or green admixtion compositing range under the glaze:
Chromic oxide 22-23%
Cobalt oxide 2-3%
Quartzy 20-23%
Feldspar 28-31%
Kaolin 14-20%
Talcum 3-5%
(3) the glaze green admixtion compositing range of plunging into the commercial sea:
Aluminum oxide 30-33%
Zinc oxide 20-22%
Cobalt oxide 4-6%
Burn borax 24-27%
Feldspar in powder 16-18%
(4) white admixtion compositing range under the glaze:
Burn talcum 7-8%
Potassium felspar sand 26-28%
Zinc oxide 3-4%
Silica powder 22-24%
Cobalt dioxide 35-37%
(5) the glaze blue admixtion compositing range of plunging into the commercial sea:
Cobalt oxide 7-8%
Chromic oxide 15-16%
Aluminum oxide 30-31%
Zinc oxide 15-16%
Calomel mercurous chloride 30-31%
(6) yellow admixtion compositing range under the glaze:
Vanadium oxide 4-5%
Zirconium white 95-96%
(7) the bright down black admixtion compositing range of glaze:
Vanadium Pentoxide in FLAKES 40-41%
Quartzy 40-41%
Lime carbonate 1-2%
Oxalic acid 15-18%
(8) the gorgeous black admixtion compositing range of under glazed:
Cobalt oxide 10-12%
Chromic oxide 43-44%
Ferric oxide 6-7%
Do blue or green all 38-40%
Utilization the present invention makes colour-in-glaze strengthening ceramics such as daily used reinforced ceramic such as square position, fish dish, bowl, cup, and resistance to impact shock mean value reaches 2.9-3.65kgfcm/cm after tested
2, maximum can reach 732kgfcm/cm
2, hardness of glaze surface mean value reaches
6.7kgf/mm
2, be up to 1088.2kgf/mm
2, and the resistance to impact shock mean value of Datong District, Taiwan reinforcement porcelain is 2.51kgf/cm
2, hardness of glaze surface mean value 699.1kgf/cm
2, and the resistance to impact shock of ordinary rigid porcelain has only 1.7-22kgfcm/cm
2, therefore reinforcement porcelain resistance to impact shock of the present invention improves closely 70% than hard-paste, strengthens porcelain than Taiwan Datong District and improves 16-45%, and hardness of glaze surface is strengthened porcelain than Taiwan Datong District and is improved 28%.
The present invention will be described in more detail in conjunction with the embodiments above.
Embodiment, the glaze blue production of strengthening the porcelain tableware of plunging into the commercial sea
(1) determines blank formulation: (by weight)
Potassium felspar sand 30%
Commercial alumina 22%
(Jiepai clay) kaolin 46% calcination of talc 2%
Various material chemical components see Table 1
(2) glaze composition of raw materials: (by weight)
Potassium felspar sand 43%
Silica powder 25%
Calcination of talc 14%
Commercial alumina powder 4%
(Jiepai clay) kaolin 14%
Various material chemical components see Table the 1(table and see below)
(3) raw material processing: by product the requirement of raw material is selected materials will reject as Jiepai clay (kaolin) and remove sandwich impurity after pork liver mud, yellow mud, black mud, free quartzy, bulk smash and select the bulk white clay and make to join glaze; Talcum: calcine the back, smash yellow mud, black mud, the sandwich impurity of bulk; Return the processing of wheel mud: strengthen that porcelain pug is inaccurate to be obscured with other any pugs, strengthen porcelain and return that wheel mud is inaccurate directly to advance pug mill, return in the wheel mud and remove the surplus mud of moulding, the biscuit bits are outside ball milling processing can be used, and all the other mud that cancel are without exception handled.
(4) mud making process flow process:
Plastic molding pug: the slurry of selecting materials → prepare burden → ball milling → the mistake vibratory screening apparatus → take out → suction iron → mistake vibratory screening apparatus → stir → take out slurry → press filtration → thick white silk → old → Zhao's sky pugging.
Grout material: clear water+water glass+Sudan Gum-arabic
Wash mill (stirring 24 hours) → sieve → suction pit (standby) is gone in the weighing of plastic pug → vacuum pugging → accurately
Glaze:
Dry mixing → ball milling → suction iron → sieve → glaze stock tank (standby)
(5) milling parameters
1. the blank ball milling adds labor and materials: ball: water=1: 1.8: 0.9
The glaze ball milling adds labor and materials: ball: water=1: 1.8: 0.4
The large, medium and small ratio 20%, 50%, 30% of ballstone
2. ball milling time: about 25 hours of blank
About 80 hours of glaze;
(all being as the criterion) with the actual fineness that records
3. fineness control: blank 250 mesh screen residues≤0.2%
Glaze 300 mesh screen residues≤0.2%
4. the reverse-flow suction iron in pug secondary upfield machine is inhaled iron, crosses secondary 200 order vibratory screening apparatuss
5. the reverse-flow suction iron in upfield of glaze is once crossed 200 order vibratory screening apparatuss
6. blank processing performance
Water ratio 23.4%
Plastic index 5.3%
Linear shrinkage drying 2.1%
Burn 14.5%
Total 17%
Body drying folding strength 25kgf/cm
2
(7) moulding: except that fish dish, in more wait with the pressure grout method, all the other dishes, dish, cup, bowl are all used rolling forming, mouth to the dish product adds a circle webbing along non-easy meeting, and rounding off is to normal wall thickness, so both can increase the ability of opposing collision, and not thicken wall again and influence attractive in appearance.
(8) biscuiting: the base substrate after the moulding carries out biscuiting through after the drying treatment, adopts oxydizing flame, and temperature is controlled at about 750 ℃.
(9) glaze is decorated down: the glaze blue pigment admixtion prescription of plunging into the commercial sea is: cobalt oxide 7.69%, chromic oxide 15.33%, zinc oxide 15.33%, calomel mercurous chloride 30.70%, aluminum oxide 30.77%(weight percent), after the prescription batching, mix grinding is even, after the dry ball milling 24 hours at 1360 ℃ of temperature lower calcinations, 20 mesh sieves are crossed in coarse crushing, claim 55 parts with above-mentioned calcining colorant then, other adds 45 parts of the glaze powders of being joined, be mixed into the ball mill wet-milling 150 hours, cross 200 mesh sieves, dry under 100 ℃ of temperature, porphyrize gets final product, with this under-glaze pigment by the known method grain pattern of on the base substrate after the biscuiting, painting.
(10) glazing: the glaze for preparing is imposed under the glaze on the base substrate after decorating.
(11) glaze firing: in the long tunnel kiln of 70M, burn till, the initial oxidation flame, back reducing flame, when oxydizing flame changeed reducing flame, temperature was controlled at about 1080 ℃, contains O in the little fiery weak oxide atmosphere
2Amount is 4%, and containing the CO amount during big fire in the reducing atmosphere is 3%, 1390 ℃ of firing temperatures, high fiery soaking time 40 minutes.
(12) inspection after construction, packing.
Be product sample microstructure analysis of the present invention below, and compare with common feldspar porcelain microstructure.
Figure 1A strengthens the porcelain dish cross section microstructure photograph (amplifying 400 times, single polarisation) of vertically trying to get to the heart of a matter for the present invention.
Figure 1B is porcelain body layer cross section microstructure photograph among Figure 1A (amplifying 400 times, single polarisation).
Fig. 2 A is the common feldspar porcelain dish cross section microstructure photograph (single polarisation, amplify 400 times) of vertically trying to get to the heart of a matter.
Fig. 2 B is porcelain body layer cross section microstructure photograph among Fig. 2 A (400 times of single polarisation, amplification).
Among the figure: M-mullite crystallite, the brilliant bits of F-feldspar illusion (glass and mullite aggregate), the quartzy brilliant bits of Q-, C-corundum, G-glass, Fm pore.
In Figure 1A, figure top is the glaze layer, the figure bottom is plies, the plies of porcelain and glaze layer contact that the division is clearly demarcated, straight, the mineral composition of plies is: mullite 20-25%, corundum 5-7%, cristobalite＜1%, quartzy 4%, glass 62-70%, pore 1-2%, Figure 1B are presented at the components such as the mullite that distributes more equably in the glass matrix, and mullite crystalline phase amount is more, be needle-like and fibrous agrregate, in addition granular, long 6-70 μ m reaches individually 84 μ m, length-width ratio is about 2-10: 1, the corundum crystallite is irregular granular, and crystal grain is very little, is uniformly distributed between the mullite crystal, be difficult under the mirror differentiating, pore is circle, ellipse, minority are irregular, and diameter is 3-28 μ m. Figure 1A shows the glaze layer place that contacts with plies, and the acicular mullite crystal in the visible plies generally extends in the glaze layer glass (the mullite needle is in the seedlings of cereal crops are grown into the glaze layer) significantly. Be formed with the intermediate layer of cushioning tire, glaze ply stress effects of strain at plies and glaze interlayer, strengthen the adhesion of plies and glaze interlayer, greatly improve the dirty impact strength of porcelain.
Be the glaze layer on Fig. 2 A(figure top, the figure bottom is plies) show in the microstructure there is not corundum in the mineral composition among the 2B, only have mullite, quartz, glass. Consist of: mullite 14%, quartzy 7%, glass are about 78%, pore about 1%. The crystalline phase amount is less in the common feldspar porcelain body layer, and glaze layer and plies boundary line are clear, straight, does not have grow into phenomenon in the glaze layer of the crystal of plies.
Therefore reinforcement porcelain of the present invention is mutually more with the crystalloid of distribution uniform, wherein mullite crystal content is higher, corundum has again some, and its crystal grain is again very little, especially the acicular mullite in the plies surface extends to wait in the glaze layer bottom glass and is feature, these features all are that the mechanical strength that helps to increase porcelain, particularly impact strength are higher than the feldspar hard-paste far away
With the reinforcement porcelain that the present invention manufactures, can manufacture under the glaze do not have color, overglaze color with underglaze colour, this reinforcement porcelain both can have been produced and be household china, also can be used as architectural ceramics, chemical industry porcelain etc.
Each material chemical component
Table 1
SiO AlO FeO CaO MgO KO NaO burns and loses
Jiepai clay (%) 71.15 20.40 0.37 0.34 0.06 12.98
Potassic feldspar (%) 65.22 19.25 0.14 0.65 0.18 1,070 2.97 0.51
Quartzy (%) 99.0 0.10
Talcum (%) 62.26 0.38 0.05 1.14 31.65 0.12 0.12 4.50
Commercial alumina
（%） 98.0
In sum, the invention has the advantages that the blank that (1) adopts commercial alumina, potassic feldspar, three kinds of primary raw material systems of kaolin to form increases the Al in the porcelain body chemical composition by a relatively large margin2O
3Content, tiny mullite needle and the corundum crystallite of distributing that interweave in glass matrix improved the impact strength of porcelain greatly. (2) cost of material is low, with lower cost of material, produces high-grade porcelain. (3) production technology can be utilized the feldspar porcelain production technology and equipments, and firing temperature is saved the energy below 1420 ℃. (4) developed the traditional art of underglaze colour porcelain, the high temperature under-glaze pigment has been strengthened in the present invention stablized color development in the porcelain.
Claims (7)
1, a kind of reinforcement porcelain, its porcelain body crystalline phase amount accounts for microstructural 30～45% (by weight) of porcelain, crystalline phase comprises mullite, corundum, quartz crystal, all the other equate amorphous phase for glass, wherein mullite crystal 20～30%, corundum crystal 5～20%, quartz crystal 1～6% (by weight), mullite crystal content is greater than corundum crystal content, and the chemical ingredients scope of porcelain body is (weight ratio) SiO
240～55%, Al
2O
338～50%, K
2O+Na
2O4.0～5.2% (Na
2O≤1.2%), CaO0.5-1%, Fe
2O
3≤ 0.4%, MgO≤1%, mullite crystal is fine needle-like, long 6-70 μ m, reach 84 μ m, long-width ratio individually and be (2-10): 1, they resemble to be interweaved as the felt and reticulate, as the main framing of crystalline phase, corundum crystal is granular crystallite in the uniform distribution porcelain body, and particle diameter is less than 1 μ m, evenly be embedded between the mullite needle-like crystal, the mullite needle-like crystal on carcass surface extend glaze layer bottom glass mutually in.
2, reinforcement porcelain according to claim 1 is characterized in that the chemical ingredients scope of said enamel is (weight ratio):
SiO
270～72%、Al
2O
314-15%、MgO3.5-4% K
2O+Na
2O＜6.5%
Fe
2O
3＜0.1% CaO 1-5%
3, reinforcement porcelain according to claim 2 is characterized in that reaching the glaze bottom and generates the little trichroite crystallite of equally distributed thermal expansivity on the porcelain body surface in the microstructure of glaze layer.
4, reinforcement porcelain according to claim 3 is characterized in that carrying out decorating under the glaze to this porcelain becoming colour-in-glaze strengthening ceramics.
5, a kind of production method of strengthening porcelain needs through raw material processing, batching, ball milling, takes out slurry, sieves, inhales iron, press filtration, old, pugging, blank forming, body drying, biscuiting, glazing, glaze firing, the invention is characterized in:
(1) blank composition of raw materials scope (by weight): potassium felspar sand 25-30%, commercial alumina 10-30%, kaolin 40-60%, calcination of talc 1-5%, fineness requirement 250 mesh screen residue rate≤0.2% of raw material
(2) glaze composition of raw materials scope (by weight) is: potassium felspar sand 42-45%, quartzy 25-30%, kaolin 8-14%, commercial alumina 3-7%, talcum 10-15%, fineness requirement 300 mesh screen residue rate≤0.2% of raw material
When (3) blank prepares, vacuum pugging number of times 〉=4 time, vacuum tightness 720-740mmHg
(4) calcining system: 700-800 ℃ of oxydizing flame temperature adopted in biscuiting, glaze firing initial oxidation flame, back reducing flame, and temperature range was 1050-1100 ℃ when oxydizing flame changeed reducing flame, O in the little fiery weak oxide atmosphere
2Content 2-5%, CO content 3-5% in reducing atmosphere during big fire, temperature of glaze firing 1350-1420 ℃.
6, according to the described reinforcement porcelain of claim 5 production method, it is characterized in that carrying out under glazed and decorate after the base substrate biscuiting, under glazed pigment admixtion preparation technology flow process is: batching → mixing (dry ground) → high-temperature calcination → dry method coarse crushing → wet ball grinding → drying → porphyrize.
7, reinforcement porcelain production method according to claim 6 is characterized in that the formula range of under glazed pigment admixtion is (weight percent):
(1) pink admixtion compositing range under the glaze:
Aluminium sesquioxide 75-79%
Manganous carbonate 11-13%
Lime carbonate 1-2%
Burn borax 8-10%
(2) careless blue or green admixtion compositing range under the glaze:
Chromic oxide 22-23%
Cobalt oxide 2-3%
Quartzy 20-30%
Feldspar 28-30%
Kaolin 14-20%
Talcum 3-5%
(3) the glaze green admixtion compositing range of plunging into the commercial sea:
Aluminum oxide 30-33%
Zinc oxide 20-22%
Cobalt oxide 4-6%
Burn borax 24-27%
Feldspar in powder 16-18%
(4) white admixtion compositing range under the glaze:
Burn talcum 7-8%
Potassium felspar sand 26-28%
Zinc oxide 3-4%
Silica powder 22-24%
Zirconium dioxide 35-37%
The glaze blue admixtion compositing range of plunging into the commercial sea:
Cobalt oxide 7-8%
Chromic oxide 15-16%
Aluminum oxide 30-31%
Zinc oxide 15-16%
Calomel mercurous chloride 30-31%
(6) yellow admixtion compositing range under the glaze:
Vanadium oxide 4-5%
Zirconium white 95-96%
(7) the bright down black admixtion compositing range of glaze:
Vanadium Pentoxide in FLAKES 40-41%
Quartzy 40-41%
Lime carbonate 1-2%
Oxalic acid 15-18%
(8) gorgeous black admixtion compositing range under the glaze:
Cobalt oxide 10-12%
Chromic oxide 43-44%
Ferric oxide 6-7%
Do blue or green all 38-40%
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89105753 CN1014049B (en) | 1989-08-26 | 1989-08-26 | Underglaze color reinforced porcelain and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89105753 CN1014049B (en) | 1989-08-26 | 1989-08-26 | Underglaze color reinforced porcelain and production method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1050175A CN1050175A (en) | 1991-03-27 |
| CN1014049B true CN1014049B (en) | 1991-09-25 |
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|---|---|---|---|
| CN 89105753 Expired CN1014049B (en) | 1989-08-26 | 1989-08-26 | Underglaze color reinforced porcelain and production method thereof |
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-
1989
- 1989-08-26 CN CN 89105753 patent/CN1014049B/en not_active Expired
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|---|---|
| CN1050175A (en) | 1991-03-27 |
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