CN101602575B

CN101602575B - Glass fiber formula

Info

Publication number: CN101602575B
Application number: CN2009100168478A
Authority: CN
Inventors: 张志法; 徐言超; 宋晓; 孟宪明
Original assignee: Taishan Fiberglass Inc
Current assignee: Taishan Fiberglass Inc
Priority date: 2009-07-17
Filing date: 2009-07-17
Publication date: 2011-04-20
Anticipated expiration: 2029-07-17
Also published as: CN101602575A

Abstract

A glass fiber formula relates to the production formula of glass fibers, in particular to the glass fiber formula with excellent acid resistance property. The formula is characterized in that the composition comprises SiO2, Al2O3, B2O3, F, CaO, MgO, K2O, Na2O and ZnO. Compared with the E glass formula which is widely applied at present, in the formula of the invention, the acid resistance property of the glass fiber is greatly improved, and the electrical property, mechanical property and operational property are improved as the content of B2O3 is greatly lowered and ZnO is introduced, therefore, the formula is suitable for large scale production under the production process conditions of the E glass tanks at present.

Description

A kind of glass fiber formula

Technical field

The present invention relates to a kind of production formula of continuous glass fibre, relate in particular to a kind of glass fiber formula with good acid attack resistance, this fiber is applicable in the sour environment.

Background technology

Be used to make the most frequently used glass composition of continuous glass fibre precursor and be " E glass ".The liquidus temperature of E glass is 1050 ℃ or lower, and E glass is alkali metal oxide content less than 1% aluminium, boron, silicate glass.Because of containing higher boron content, structural framework is loose, is not sufficiently complete, and acid attack resistance is relatively poor, and glass reinforced plastic prepared therefrom is very easy under sour environment to be peeled off with resin matrix by acid attack, loses intensity rapidly.

At this shortcoming, scientific research institution of many enterprises has carried out big quantity research.As the glass fibre of glass ingredient production as described in the patent of number of patent application 200710069773.5 and E glassy phase than the acid attack resistance that has improved glass greatly.But because it does not contain boron and fluorine etc. fully and fluxes, reduces capillary composition, viscosity is very big under its high temperature, being difficult to clarify, being easy to during wire-drawing shape to occur defectives such as calculus, striped at present technology condition causes the fiber quality produced poor, and the product cost height is difficult to large-scale promotion application.

The present invention is directed to these characteristics of traditional E glass and existing acidproof erosion glass, seek the factor that influences the glass acid resistance in the glass ingredient by a large amount of experiments, adjust prescription and seek best composition blend proportion,, guaranteed its good working performance improving the acidproof rodent while.

Summary of the invention

For solving the shortcoming of traditional E glass acid resistance difference, the invention provides the glass formula that a kind of acid resistance is extremely superior, operation is more stable.

The fibre property of glass composition of the present invention comprises: fiberization temperature, liquidus temperature and Δ T.Fiberization temperature is defined as the temperature that viscosity is 1000 pools; Reduce fiberization temperature, increase operation annex work-ing life, be easy to produce, reduce production costs greatly.Liquidus temperature is defined as glass liquid state equilibrated top temperature between the matrix cystal phase with it, is easy to form crystal when being lower than this temperature, and fiberizing is interrupted.Another fibrosis performance is Δ T, is defined as the poor of fiberization temperature and liquidus temperature, and bigger Δ T helps fiberizing, has reduced the control requirement to process facility, reduces production costs.

The present invention partly is a kind of glass composition, and this glass composition is fit to make acidproof erosive continuous glass fibre.This glass composition is adapted at large tank furnace used middle production of existing E glass, agalmatolite, living lime stone, borocalcite, silica powder, fluorite, magnesium oxide and the soda ash etc. that use present E glass generally to adopt are main raw material, adopt the direct fusion method to make glass fibre at an easy rate.

Composition of the present invention each composition by weight percentage comprises SiO ₂57.5%, Al ₂O ₃13.8%, B ₂O ₃0.5%, CaO 21.0%, and MgO 4.0%, and F 0.3%, R ₂O (K ₂O+Na ₂O) 0.7%, with SiO ₂Get about 57.5% Al ₂O ₃Get about 13.8%, for guaranteeing melting properties that glass is good and lower fiberization temperature B ₂O ₃Get 0.5%, F gets 0.3%, for improving the acid resistance of glass, introduces 2.0% ZnO, and ZnO is that glass forms intermediate, in the glass forming process, with ZnO ₄Form enters in the network structure, can improve the chemical stability and the acidproof aggressiveness of glass; R ₂O gets the electrical insulation capability of 0.7% assurance glass fibre.

Glass formula of the present invention has kept 0.5% B ₂O ₃, therefore 0.3% F has guaranteed temperature of fusion and the viscosity that glass is lower.In addition, with E glassy phase ratio, because B ₂O ₃, F reduces greatly, so its volatilization in kiln significantly reduces, alleviated environmental pollution.

Acid-resistant glass prescription of the present invention is characterized in that: this glass formula in 10% sulphuric acid soln, to set acid liquor temperature be digestion 4h, 24h, 48h, 96h respectively under 99 ℃ the condition, weight residual rate K value representation, K _(96h)〉=90%, and the weight residual rate of traditional E glass under similarity condition, K _(96h)Value is about 60%.

Among the present invention, glass is formed the reasons are as follows of being defined as above:

SiO ₂, Al ₂O ₃And B ₂O ₃Be both the composition that forms the glass skeleton, so SiO ₂Be defined as at 57.5% o'clock, can provide enough skeleton structures to be unlikely to improve greatly the fusing difficulty again.

Al ₂O ₃Can effectively stop the glass phase-splitting at 13.8% o'clock, the stabilized glass skeleton structure is unlikely to improve greatly glass viscosity again well, guarantees transaction capabilities.

B ₂O ₃Not only guarantee glass excellent acid aggressiveness at 0.5% o'clock, also effectively reduced the temperature of fusion and the glass viscosity of glass.

CaO, MgO can reduce the viscosity of glass metal, are beneficial to glass melting, make the fibrosis difficulty but CaO, MgO and amount the crystallization noted phase separation phenomena can occur greater than 25% o'clock glass, and particularly MgO content was greater than 5% o'clock, and the crystallization noted phase separation phenomena can increase the weight of.Therefore CaO is defined as 21%, and MgO is defined as 4.0%.

Na ₂O, K ₂O has the fusing assistant effect, and these compositions total at 1.0% o'clock, acidproof, the water resistance variation of glass, and influence the insulating property of product.Therefore with Na ₂O+K ₂O is defined as 0.7%.

Among the present invention, except that mentioned component, introduce by ore inevitably, at the most 1.5% TiO ₂, SrO, Fe ₂O ₃, P ₂O ₅, ZrO ₂, Cr ₂O ₃Deng composition.

Following the present invention is described in detail according to case study on implementation, and glass is formed the composition that is based on claim 2 of the present invention in the table 1.Be mixed with batch of material by the composition of the glass shown in the table 1, in the platinum crucible of packing into, place in the electric furnace, found into glass under 1420～1480 ℃ condition, be incubated 2 hours, take out the cooling back.

The acid resistance of tested glass:

1, the glass in the platinum crucible is taken out, grind.Use sample sifter to choose 65 orders～70 purpose samples, and take by weighing about 2.0g, be designated as M with electronic balance ₀

2, the compound method of 10% sulphuric acid soln:

For the collimation of guaranteeing to test as far as possible, the disposable required acid solution of all experiments of foot of joining.Be example with preparation 10000ml acid solution below.

Take the 10000ml wide-necked bottle, the deionized water of packing into is placed in the pond, opens water pipe, guarantees that wide-necked bottle can both obtain cooling constantly.

By calculating the requirement that can get 98% vitriol oil is 580ml.Measure the vitriol oil with graduated cylinder and slowly inject wide-necked bottle, injection speed is as the criterion with bottle wall non-scald on hand.

Treat solution cold fully but after, re-use stirrer and continue to stir 16 hours.

3, heating in water bath

Set 99 ℃ of water bath with thermostatic control temperature.The sample that takes by weighing is poured in the plastic beaker, in beaker, injected 150～200ml acid solution again, with rubber hose and plastics film sealing, beaker is put into water-bath again, behind 4h, 24h, 48h, 96h, take a sample respectively.To note in the experimentation allowing water level be lower than 2/3 of beaker.

4, sample washing

Beaker is taken out, while hot acid solution is poured out, it is slow that action is wanted, and prevents that glass sample runs off.Wash plastic beaker with wash bottle.Glass is transferred in the specified glass beaker, used a large amount of deionized water rinsings more than three times again.

5, suction filtration sample

This step need use vacuum pump, filter flask and sand hopper to finish jointly.The sand hopper quality is designated as M ₁

Connect filter flask and vacuum pump, the sand hopper that will clean oven dry again is installed on the filter flask, opens switch, washes beaker bottom with wash bottle, and glass powder is transferred to funnel.Use deionized water rinsing hopper walls and bottom again after shifting fully, guarantee that glass is tiled in funnel bottom.

6, oven dry weighing

Baking oven is transferred to 100 ℃, put into the sand hopper drying more than three hours, take out after the constant weight, be cooled to room temperature.Weigh and be designated as M ₂

7. calculate:

K＝(M ₂-M ₁)/M ₀×100％

Table 1

	Comparative example	Comparative example	Glass ingredient of the present invention
				Composition	E glass	Patent 200710069773.5	1
SiO ₂	54	60.2	57.5
				Al ₂O ₃	14	13.0	13.8
CaO	22.8	22.0	21.0
				MgO	0.46	3.0	4.0
B ₂O ₃	7.3	0	0.5
				Li ₂O	0	0	0.1
Na ₂O	0.50	0.5	0.2
				K ₂O	0.25	0.3	0.5
ZnO	0	0	2.0

F	0.7	0	0.3
				TiO ₂	0.23	0.36	0
K％(96h)	60％	87％	93％
				Filament strength/MPa	3058	3080	3100
Volume specific resistance/(Ω cm)	1.2×10 ¹⁵	1.17×10 ¹⁵	1.18×10 ¹⁵
				Liquidus temperature/℃	1050	1170	1128
Fiberization temperature/℃	1150	1258	1238
				ΔT/℃	100	?88	?110

In weight part mix according to 68 parts silica powder, 702 parts agalmatolite, 221 parts of unslaked limes, 12 parts of borocalcites, 7 parts of fluorites, 44 parts magnesium oxide, 20 parts of zinc oxide and 7 parts of soda ash and the glass ingredient of case study on implementation as shown in table 1.This glass acid resistance is superior, and K (96h) value is more than 90%, than E glass remarkable advantages is arranged.

Glass fibre of the present invention has very superior acid resistance, is made into matrix material, can keep its intensity in certain sour environment muchly.And its can be under the manufacturing condition of present E glass fibre well clarification, homogenizing, can stablize operation, have cheaper cost, be fit to scale operation.

Claims

1. acidproof erosive glass fibre, it is characterized in that: described glass fiber formula each composition by weight percentage comprises SiO ₂57.5%, Al ₂O ₃13.8%, B ₂O ₃0.5%, CaO 21.0%, and MgO 4.0%, and ZnO 2.0%, fluorine 0.3%, R ₂O (K ₂O+Na ₂O) 0.7%; It is to use silica powder, agalmatolite, unslaked lime, borocalcite, fluorite, zinc oxide, magnesium oxide and soda ash, mixes the back fusion draw in weight part according to 68 parts silica powder, 702 parts agalmatolite, 221 parts of unslaked limes, 12 parts of borocalcites, 7 parts of fluorites, 44 parts magnesium oxide, 20 parts of zinc oxide and 7 parts of soda ash and forms.

2. the prepared fiber reinforced articles of glass fiber formula as claimed in claim 1.