Hydraulic Sulfur Concrete(HSC)

Summary VersionSummary Version

Green Green ConTechConTech., Inc.., Inc.Hydraulic Sulfur ConcreteHydraulic Sulfur Concrete

GCT SPC

2011

JinseongJinseong ChoiChoi

Ph.D. & PESEPh.D. & PESE

Green Green ConTechConTech., Inc.., Inc.

2011

JinseongJinseong ChoiChoi

Ph.D. & PESEPh.D. & PESE

Green Green ConTechConTech., Inc.., Inc.

=== Table of Contents ===

1. Terminology

2. Sulfur2.1 Periodic Table

2.2 Phase Change of Sulfur with Temperature

2.3 Viscosity Change of Sulfur with Temperature

2.4 Characteristic Material Properties of Sulfur

3. SPC(Sulfur Polymer Cement)3.1 Type of Modifiers

3.2 Material Property-controlling Factors

3.3 Polymerization Termination Criteria

3.4 Types of SPC

3.5 GCT SPC Manufacturing Pilot Plant

3.6 GCT SPC Modification Process

GCT SPC

=== Table of Contents ===

1. Terminology


2.2 Phase Change of Sulfur with Temperature

2.3 Viscosity Change of Sulfur with Temperature


3. SPC(Sulfur Polymer Cement)3.1 Type of Modifiers



3.4 Types of SPC

3.5 GCT SPC Manufacturing Pilot Plant

3.6 GCT SPC Modification Process

3.7 GCT SPC Polymerization Reaction 3.8 GCT SPC Manufacturing Criteria3.9 GCT SPC Proportioning

4. HSC(Hydraulic Sulfur Concrete)4.1 Comparison between HSC and SC4.2 Manufacturing of HSC4.3 Characteristic Material Properties of HSC 4.4 Application Fields of HSC

5. Example; HSC Bridge Deck Overlay Pavement5.1 Mixture Proportioning5.2 Strength Test

6. HPC(High Performance Concrete)6.1 Definition6.2 Advantages6.3 Design Criteria(SHRP)6.4 Performance Grade(FHWA)

GCT SPC

3.7 GCT SPC Polymerization Reaction 3.8 GCT SPC Manufacturing Criteria3.9 GCT SPC Proportioning

4. HSC(Hydraulic Sulfur Concrete)4.1 Comparison between HSC and SC4.2 Manufacturing of HSC4.3 Characteristic Material Properties of HSC 4.4 Application Fields of HSC

5. Example; HSC Bridge Deck Overlay Pavement5.1 Mixture Proportioning5.2 Strength Test

6. HPC(High Performance Concrete)6.1 Definition6.2 Advantages6.3 Design Criteria(SHRP)6.4 Performance Grade(FHWA)

7. SPC Asphalt(Sulfur Polymer Cement Asphalt)

8. SC(Sulfur Concrete) & SA(Sulfur Asphalt)8.1 GRC Inc.(Chempruf Sulfur Concrete)

8.2 STARcrete Technologies Inc.(STARcrete™)

8.3 Shell Group(Thiocrete® & Thiopave®)

8.4 JX Nippon Oil & Energy(RECOSUL)

8.5 SK(Micropowder)

8.6 GS Caltex

GCT SPC


8. SC(Sulfur Concrete) & SA(Sulfur Asphalt)8.1 GRC Inc.(Chempruf Sulfur Concrete)

8.2 STARcrete Technologies Inc.(STARcrete™)

8.3 Shell Group(Thiocrete® & Thiopave®)


8.5 SK(Micropowder)

8.6 GS Caltex

1. Terminology

* SM is a material or mixture of materials which modifies the properties of sulfur.

i.e., SM is a material or mixture of materials which lowers the Melting Point(M.P.)

and increases the Flowability by reducing the Crystallinity of sulfur.

GCT SPC

① SM(Sulfur Modifier)

② SP(Sulfur Plasticizer)

* SP is a material or mixture of materials which plasticizes the properties of sulfur.

i.e., SP is a material or mixture of materials which increases the Plasticity or

the Fluidity, when added in the sulfur.

* SP is a material or mixture of materials which plasticizes the properties of sulfur.

i.e., SP is a material or mixture of materials which increases the Plasticity or

the Fluidity, when added in the sulfur.

③ SPC(Sulfur Polymer Cement)

* SPC, termed as a general Sulfur Polymer Cement, can not be mixed with water,

i.e., Non-hydraulic, and is conventionally named as SPC.

* For SPC to be hydraulic, SPC should be remelted at temperature lower than

100℃, that is, SPC must be SPC-LM.

à For the SPC to have hydration reaction with hydraulic Portland cement.

GCT SPC

④ HSPC(Hydraulic Sulfur Polymer Cement)

* Sulfur Concrete is often called as Sulfur Polymer Cement Concrete, or Sulfur

Polymer Concrete. It is usually abbreviated as SC.

* Only SPC itself can be functioned as binder to make SC.

⑤ SC(Sulfur Concrete)

⑥ HSC(Hydraulic Sulfur Concrete)

* Hydraulic Sulfur Concrete is often called as Hydraulic Sulfur Polymer Cement

Concrete, or Hydraulic Sulfur Polymer Concrete. It is usually abbreviated

as HSC.

* HSPC and HC(Hydraulic Cement) can be functioned as binders to make HSC.

* Sulfur Concrete is often called as Sulfur Polymer Cement Concrete, or Sulfur

Polymer Concrete. It is usually abbreviated as SC.

* Only SPC itself can be functioned as binder to make SC.

* MS is a modified sulfur to improve the material properties of sulfur, and

MS has the same meaning with SPC, and can be interchanged each other.

GCT SPC

⑦ MS(Modified Sulfur)

⑧ PS(Plasticized Sulfur)

* PS is a plasticized sulfur to plasticize the material properties of sulfur.

⑨ SA(Sulfur Asphalt)

* Sulfur Asphalt is Asphalt which Sulfur and/or SPC is added into as Modifier,

Additive or Extender. It is usually abbreviated as SA.

* Sulfur Asphalt is Asphalt which Sulfur and/or SPC is added into as Modifier,

Additive or Extender. It is usually abbreviated as SA.

⑩ SPC Asphalt(Sulfur Polymer Cement Asphalt)

* Sulfur Polymer Cement Asphalt is Asphalt which SPC is added into as Modifier,

Additive or Extender. It is usually abbreviated as SPC Asphalt.


Group 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

Period IA IIA IIIB IVB VB VIB VIIB VIIIB VIIIB VIIIB IB IIB IIIA IVA VA VIA VIIA VIIIA

1

Hydrogen1H

1.0079

Name of elementAtomic numberChemical symbolRelative atomic mass

Helium2

He4.0026

2

Lithium3Li

6.941(2)

Beryllium4Be

9.0122

Boron5B

10.811(7)

Carbon6C

12.011

Nitrogen7N

14.0067

Oxygen8O

15.9994

Fluorine9F

18.998

Neon10Ne

20.180

3

Sodium11Na

22.990

Magnesium12Mg

24.305

Aluminium13Al

26.982

Silicon14Si

28.086

Phosphorus15P

30.974

Sulfur16S

32.066(6)

Chlorine17Cl

35.453

Argon18Ar

39.948(1)

4

Potassium19K

39.098

Calcium20Ca

40.078(4)

Scandium21Sc

44.956

Titanium22Ti

47.867(1)

Vanadium23V

50.942(1)

Chromium24Cr

51.996

Manganese25Mn

54.938

Iron26Fe

55.845(2)

Cobalt27Co

58.933

Nickel28Ni

58.693

Copper29Cu

63.546(3)

Zinc30Zn

65.39(2)

Gallium31Ga

69.723(1)

Germanium32Ge

72.61(2)

Arsenic33As

74.922

Selenium34Se

78.96(3)

Bromine35Br

79.904(1)

Krypton36Kr

83.80(1)

5

Rubidium37Rb

85.468

Strontium38Sr

87.62(1)

Yttrium39Y

88.906

Zirconium40Zr

91.224(2)

Niobium41Nb

92.906

Molybdenum42Mo

95.94(1)

Technetium43Tc

[97.907]

Ruthenium44Ru

101.07(2)

Rhodium45Rh

102.906

Palladium46Pd

106.42(1)

Silver47Ag

107.868

Cadmium48Cd

112.411(8)

Indium49In

114.818(3)

Tin50Sn

118.710(7)

Antimony51Sb

121.760(1)

Tellurium52Te

127.60(3)

Iodine53I

126.904

Xenon54Xe

131.29(2)

GCT SPC

Element categories in the periodic table

Metals

Metalloids

NonmetalsUnknownchemical

propertiesAlkali metals Alkaline earth metals

Inner transition elementsTransition elements Other metals Other nonmetals Halogens Noble gases

Lanthanides Actinides

State at Standard Temperature and Pressure (0°C and Earth´s Atmosphere Pressure)

Gas Liquid Solid Unknown

Natural Occurrence

Primordial Trace Radioisotope Synthetic

5

Rubidium37Rb

85.468

Strontium38Sr

87.62(1)

Yttrium39Y

88.906

Zirconium40Zr

91.224(2)

Niobium41Nb

92.906

Molybdenum42Mo

95.94(1)

Technetium43Tc

[97.907]

Ruthenium44Ru

101.07(2)

Rhodium45Rh

102.906

Palladium46Pd

106.42(1)

Silver47Ag

107.868

Cadmium48Cd

112.411(8)

Indium49In

114.818(3)

Tin50Sn

118.710(7)

Antimony51Sb

121.760(1)

Tellurium52Te

127.60(3)

Iodine53I

126.904

Xenon54Xe

131.29(2)

6

Caesium55Cs

132.905

Barium56Ba

137.327(7)

Lanthanides57-71

*

Hafnium72Hf

178.49(2)

Tantalum73Ta

180.948

Tungsten74W

183.84(1)

Rhenium75Re

186.207(1)

Osmium76Os

190.23(3)

Iridium77Ir

192.217(3)

Platinum78Pt

195.084(9)

Gold79Au

196.967

Mercury80Hg

200.59(2)

Thallium81Tl

204.383

Lead82Pb

207.2(1)

Bismuth83Bi

208.980

Polonium84Po

[208.982]

Astatine85At

[209.987]

Radon86Rn

[222.018]

7

Francium87Fr

[223.020]

Radium88Ra

[226.0254]

Actinides89-103

**

Rutherfordium104Rf

[263.113]

Dubnium105Db

[262.114]

Seaborgium106Sg

[266.122]

Bohrium107Bh

[264.1247]

Hassium108Hs

[269.134]

Meitnerium109Mt

[268.139]

Darmstadtium110Ds

[272.146]

Roentgenium111Rg

[272.154]

Copernicium112Cn

[277]

Ununtrium113Uut

[284]

Ununquadium114Uuq

[289]

Ununpentium115Uup

[288]

Ununhexium116Uuh

[292]

Ununseptium117Uus

[294]

Ununoctium118Uuo

[294]

* Lanthanides

Lanthanum57La

138.905

Cerium58Ce

140.116(1)

Praseodymium59Pr

140.908

Neodymium60Nd

144.242(3)

Promethium61Pm

[144.913]

Samarium62Sm

150.36(2)

Europium63Eu

151.964(1)

Gadolinium64Gd

157.25(3)

Terbium65Tb

158.925

Dysprosium66Dy

162.500(1)

Holmium67Ho

164.930

Erbium68Er

167.259(3)

Thulium69Tm

168.934

Ytterbium70Yb

173.04(3)

Lutetium71Lu

174.967(1)

** Actinides

Actinium89Ac

[227.027]

Thorium90Th

232.038

Protactinium91Pa

231.036

Uranium92U

238.029

Neptunium93Np

[237.048]

Plutonium94Pu

[244.064]

Americium95Am

[243.061]

Curium96Cm

[247.070]

Berkelium97Bk

[247.070]

Californium98Cf

[251.080]

Einsteinium99Es

[252.083]

Fermium100Fm

[257.095]

Mendelevium101Md

[258.098]

Nobelium102No

[259.101]

Lawrencium103Lr

[262.110]

2.2 Phase Change of Sulfur with Temperature Phase Temp. ℃ Allotrope Structure Crystallinity Arrangement Remark

Solid

Ambient-------------

95.5~

114.5(112.8)(M.P.)

Sα

ρα= 2.07

S8 Ring

OrthorhombicCrystalline

Cyclo-S8

Ring Packed

Puckered Ring

(Crown)

Pale YellowPale Yellow~~

Light Light YellowYellow

114.5(112.8)

~119.3(M.P.)

Sβ

ρβ= 1.96

((SSγγ))ρργγ=1.92=1.92

Cyclo-S8

Ring Packed

Puckered Ring

(Crown)

AmberAmber

GCT SPC

114.5(112.8)

~119.3(M.P.)

Sβ

ρβ= 1.96

((SSγγ))ρργγ=1.92=1.92 Monoclinic

Crystalline

Cyclo-S8

Ring Packed

Puckered Ring

(Crown)

Solid +

Liquid119.3(M.P.)

Sλà

Sμà

Amorphous

Viscosity Transition

Ring Separation

à

Ring Opening

à

Free Radicalà

Initiation à

Dark RedDark Red~~

Dark BrownDark Brownà

(Curing)

Liquid

119.3 ~157

157~160

Bi-Radical

Phase Temp. ℃ Allotrope Structure Crystallinity Arrangement Remark

Liquid

157~160Sπ

ρρ= 1.78= 1.78~~1.801.80

Dependent Dependent on on

TempTemp..

Amorphous Cyclizationà

Catenation(Short à Long)

àCross-linking(Entanglement) (Intertwining)

àNetworking

àChain Scission

Propagation à

Dark BlackDark Black

Termination

Depolymerization

Reduction in Viscosity

160~188

188~444.6(B.P.)

GCT SPC

Cyclizationà

Catenation(Short à Long)

àCross-linking(Entanglement) (Intertwining)

àNetworking

àChain Scission

Cooling at Ambient Temp.

from444.6(B.P.)

PlasticSulfur

Plastic

Plastification

Gas

444.6 S3

S2, S3, S4530 S3, S2

720 S2

* 1 cP = 1 mPa·s

1 P = 100 cP

1 Pa·s = 1,000 mPaᆞs

<N.B.>

cP; centi-Poise

P; Poise

Pa·s; Pascal·second

mPa·s; milli-Pascal·second

GCT SPC

2.3 Viscosity Change of Sulfur with TemperaturecP P

SPC

Viscosity

Viscoelasticity

Elasticity

* 1 cP = 1 mPa·s

1 P = 100 cP

1 Pa·s = 1,000 mPaᆞs

<N.B.>

cP; centi-Poise

P; Poise

Pa·s; Pascal·second

mPa·s; milli-Pascal·second

Temp , ℃ cP P Log P Remark119 11 0.110 -0.959157 7 0.070 -1.155 Min. Viscosity159 Viscosity Transition Transition Temp.160 30 0.300 -0.523188 93,200 932 2.969 Max. Viscosity306 2,000 20 1.301444 Boiling Point N/A

SulfurElasticity

(1) High Strength

(2) Acid–resistant,

Chemical-resistant,

Chloride-resistant

(3) Rapid Setting,

Early Strength

(4) Corrosion –resistant,

Abrasion-resistant

(5) Water-tight, Air-tight

(6) Resistant to Freeze/Thaw

(7) Low Shrinkage Deformation

(8) Fatigue-resistant

GCT SPC


(1) High Strength

(2) Acid–resistant,

Chemical-resistant,

Chloride-resistant

(3) Rapid Setting,

Early Strength

(4) Corrosion –resistant,

Abrasion-resistant

(5) Water-tight, Air-tight

(6) Resistant to Freeze/Thaw

(7) Low Shrinkage Deformation

(8) Fatigue-resistant Strength Development of Sulfur Concrete and Cement Concrete as Function of Concrete Age and Moisture Supply(Adapted from Gregor and Hackl, 1977)

Where, Other Modifiers in this case are as follows;

(1) Not Used à The first SPC(USBM) in 1972

(2) CPD(Cyclopentadiene) Oligomer

(3) Olefin Oligomer à SK(Micropowder) in Korea, JX Nippon O& E, etc.

(4) Amine(Heterocyclic Amine or Alkyl Amine) à Hanmi in Korea

(5) Ammonium Salt or Urea

(6) Amino Acid

(7) Amide à GCT in Korea

(8) Aromatic Compounds à GS Caltex in Korea

GCT SPC

3.1 Type of Modifiers

1) Sulfur + DCPD(dicyclopentadiene) + Other Modifiers

3. SPC(Sulfur Polymer Cement)

Where, Other Modifiers in this case are as follows;

(1) Not Used à The first SPC(USBM) in 1972

(2) CPD(Cyclopentadiene) Oligomer

(3) Olefin Oligomer à SK(Micropowder) in Korea, JX Nippon O& E, etc.

(4) Amine(Heterocyclic Amine or Alkyl Amine) à Hanmi in Korea

(5) Ammonium Salt or Urea

(6) Amino Acid

(7) Amide à GCT in Korea

(8) Aromatic Compounds à GS Caltex in Korea

Where, Modifiers in this case are basically the derivatives of DCPD.

(1) THI(Tetrahydroindene) à JX Nippon O&E

(2) ENB(Ethylidenenorbornene) or VNB(Vinylnorbornene)

à Shell, JX Nippon O& E

(3) ENB + DCPD and/or THI 또는 THI + DCPD and/or ENB

à JX Nippon O& E

(4) Polysulfide with Organosilane à JX Nippon O& E

(5) Polycyclic Aromatic Hydrocarbon Compounds(Bitumen)

à UAE

GCT SPC

2)Sulfur + Modifiers

Where, Modifiers in this case are basically the derivatives of DCPD.

(1) THI(Tetrahydroindene) à JX Nippon O&E

(2) ENB(Ethylidenenorbornene) or VNB(Vinylnorbornene)

à Shell, JX Nippon O& E

(3) ENB + DCPD and/or THI 또는 THI + DCPD and/or ENB

à JX Nippon O& E

(4) Polysulfide with Organosilane à JX Nippon O& E

(5) Polycyclic Aromatic Hydrocarbon Compounds(Bitumen)

à UAE

(1)Type of Modifiers

(2) Purity of Components

(3) Proportion of Components

(4) Mixing Method & Mixing Sequence

(5) Mixing Speed of Polymerization Reactor

(6) Thermal History of Polymerization Process

Mixing Temperature, Polymerization Temperature,

Curing Temperature, Curing Time, Cooling Rate,

Storage Method(LLiquid, Powder, Flake, Granule & Pellet etc)iquid, Powder, Flake, Granule & Pellet etc)

GCT SPC


(1)Type of Modifiers

(2) Purity of Components

(3) Proportion of Components

(4) Mixing Method & Mixing Sequence

(5) Mixing Speed of Polymerization Reactor

(6) Thermal History of Polymerization Process

Mixing Temperature, Polymerization Temperature,

Curing Temperature, Curing Time, Cooling Rate,

Storage Method(LLiquid, Powder, Flake, Granule & Pellet etc)iquid, Powder, Flake, Granule & Pellet etc)

When measured by GPC(Gel Permeation Chromatograpy),

the weight average molecular weight is as follows;

In general,

320~1,500 in Mw .

GCT SPC


(1) Weight-average Molecular Weight

(2) Melt Viscosity(2) Melt Viscosity

When measured by type B viscometer,

the viscosity of manufactured GCT SPC is as follows;

Excluded intentionally

GCT SPC

3.4 Types of SPC

(1)SPC-LM(SPC with Lower Than 100℃ Remelting Temperature)

To mix SPC-LM with PCC properly, the temperature of final mixture should be

kept around 30 ~ 40℃(Even if the remelting temperature of SPC-LM is about 60℃,

the melting temperature before pouring to the concrete mixture is usually maintained

around 100℃ to incorporate the successful mixing that SPC with PCC.

GCT, Inc. in Korea has developed the new kind of SPC, which is the sulfur modified

with DCPD and Amide functional group. That SPC has shown the excellent material

properties and also can be mixed with the conventional PCC to make HSC.

The remelting temperature of this SPC-LM(HSPC) is far below than that of usual

SPC-HM(SPC). The remelting temperature difference between the two SPC’s

reaches about 50 ~ 60℃. Therefore, GHG(Green House Gas) can be reduced

in a sufficient amount, since the Less Energy Consumption can be expected to

manufacture that kind of SPC-LM.

This technology is a good example of Sustainable Green Technology.

To mix SPC-LM with PCC properly, the temperature of final mixture should be

kept around 30 ~ 40℃(Even if the remelting temperature of SPC-LM is about 60℃,

the melting temperature before pouring to the concrete mixture is usually maintained

around 100℃ to incorporate the successful mixing that SPC with PCC.

GCT, Inc. in Korea has developed the new kind of SPC, which is the sulfur modified

with DCPD and Amide functional group. That SPC has shown the excellent material

properties and also can be mixed with the conventional PCC to make HSC.

The remelting temperature of this SPC-LM(HSPC) is far below than that of usual

SPC-HM(SPC). The remelting temperature difference between the two SPC’s

reaches about 50 ~ 60℃. Therefore, GHG(Green House Gas) can be reduced

in a sufficient amount, since the Less Energy Consumption can be expected to

manufacture that kind of SPC-LM.

This technology is a good example of Sustainable Green Technology.

To mix SPC-HM with aggregates properly, the temperature of final mixture

before placing and hardening should be kept over 130 ~ 140℃.

Almost all SPC’s are included in this category, such as SPC’s of U.S.A, Japan,

Canada, Russia, Europe, UAE, SK(Micropowder) & GS Caltex and so on.

The biggest and weakest problem of using this kind of SPC is that the sulfur

concrete structures cannot be supported by themselves at temperature over 120℃,

whose temperature is the melting temperature of SPC-HM(SPC).

That means the sulfur concrete structures can be collapsed over that temperature

if there does not exist liquid or water.

GCT SPC

(2) SPC-HM(SPC with Higher Than 100℃ Remelting Temperature)

To mix SPC-HM with aggregates properly, the temperature of final mixture

before placing and hardening should be kept over 130 ~ 140℃.

Almost all SPC’s are included in this category, such as SPC’s of U.S.A, Japan,

Canada, Russia, Europe, UAE, SK(Micropowder) & GS Caltex and so on.

The biggest and weakest problem of using this kind of SPC is that the sulfur

concrete structures cannot be supported by themselves at temperature over 120℃,

whose temperature is the melting temperature of SPC-HM(SPC).

That means the sulfur concrete structures can be collapsed over that temperature

if there does not exist liquid or water.

Table. HSPC(SPC-LM) vs. SPC(SPC-HM)

Type

Item

HSPC(SPC-LM) SPC(SPC-HM) Remark

GCT(HSC)

Hanmi(HMSC)

JX Nippon O&E (RECOSUL)

Chempruf STARcreteSK

(Micropowder)GS Caltex Sulfur Concrete

Modifier

DCPD/Amide or

DCPD/SAE

DCPD/Amine

DCPD(/Modifiers)

DCPD DCPD DCPDDCPD

/AromaticSulfur + Modifiers

Anti-spalling/Fire-

resistant

Anti-spalling/Fire-

resistant

Anti-spalling/Fire-

resistant

Melting At 120℃

Over

Melting At 120℃

Over

Melting At 120℃

Over

Melting At 120℃

Over

Melting At 120℃

Over

Dependent onMiscibility w/ PCC

Applied Area

Anywhere AnywhereArea

w/ Liquid Area

w/ Liquid Area

w/ Liquid Area

w/ Liquid Area

w/ Liquid Dependent on

Miscibility w/ PCCRemelting

Temp.

GCT SPC

--------------------------------------------------------------------------------------------

RemeltingTemp.

≥60℃ ≥80℃ ≥120℃ ≥120℃ ≥120℃ ≥120℃ ≥120℃ SPC

Working Temp.

30~40℃ 40~50℃ 130~140℃ 130~140℃ 130~140℃ 130~140℃ 130~140℃Mixture Temp.

after Pouring SPC

SettingTime

30 Min.~5 Hr.

30 Min.~5 Hr.

≤30 Min. ≤30 Min. ≤30 Min. ≤30 Min. ≤30 Min. SPC Setting Time

SPC Continuous Batch Batch Batch Batch Batch BatchManufacturing

Method

Cost High High Low Low Low Low Low SPC Unit Price

Quantity0.2~1.5%

(Additives)0.3~2.0%(Additives)

10~20%(Binder)

10~20%(Binder)

10~20%(Binder)

10~20%(Binder)

10~20%(Binder)

SPC/Sulfur Concrete

Miscibility w/ PCC

Possible(HSC)

Possible(HSC)

Impossible(SC)

Impossible(SC)

Impossible(SC)

Impossible(SC)

Impossible(SC)

Dependent on Remelting Temp. of

SPC

3.6 GCT SPC Modification Process 1 2 3 4

5 6 7 8

GCT SPC

9 10 11 12

13 14 15 16

1 2

5 6

3 4

7 8

3.7 GCT SPC Polymerization Reaction

GCT SPC

9 10

13 14

11 12

15 16

[[Sulfur Polymer Cement and Method for Making SameSulfur Polymer Cement and Method for Making Same]]

Publication Patent(KR10-2011-0037825)

GCT SPC

3.8 GCT SPC Manufacturing Criteria

1)GCT SPC Patent

2)GCT SPC Manufacturing Criteria

(1) For Strength à General Purpose

(2) For Durability

(3) For Adhesion/Cohesion

(4) For Special Purpose

(1) For Strength à General Purpose

(2) For Durability

(3) For Adhesion/Cohesion

(4) For Special Purpose

3.9 GCT SPC Proportioning


GCT SPC

Polymers in Concrete

PIC PPCC PC

--------------------╋┏ ┓--------------------

<Note> PIC(Polymer Impregnated Concrete); PCC + Polymer((ImpregnatorImpregnator)). .

PPCC (Polymer Portland Cement Concrete ); PCC + Polymer((AdditiveAdditive)),

Sometimes called as PMC(Polymer Modified Concrete)

or LMC(Latex Modified Concrete)

PC(Polymer Concrete); Polymer((BinderBinder))

Where, PCC means Portland Cement Concrete.

HSC SC

4. HSC(Hydraulic Sulfur Concrete)

<Note> PIC(Polymer Impregnated Concrete); PCC + Polymer((ImpregnatorImpregnator)). .

PPCC (Polymer Portland Cement Concrete ); PCC + Polymer((AdditiveAdditive)),

Sometimes called as PMC(Polymer Modified Concrete)

or LMC(Latex Modified Concrete)

PC(Polymer Concrete); Polymer((BinderBinder))

Where, PCC means Portland Cement Concrete.

Figure. Classification of Polymers in Concrete

GCT SPC

4.1 Comparison between HSC and SC

(1)HSC(Hydraulic Sulfur Polymer Cement Concrete)HSC is a newly developed concrete, which is a mixture of remelted HSPC(Hydraulic

Sulfur Polymer Cement, i.e., GCT SPC-LM) with Porland Cement Concrete. It is

hardened at ambient temperature. This HSC is equivalent to PPCC(Polymer Portland

Cement Concrete), which uses latex or resin as polymers in concrete. Instead of

these polymers in concrete, HSC uses HSPC. HSPC is included in the concrete

mixture as additivesadditives, HSPCHSPC functions as functions as Hydraulic Binder Hydraulic Binder with Portland Cementwith Portland Cement.

HSC is a newly developed concrete, which is a mixture of remelted HSPC(Hydraulic

Sulfur Polymer Cement, i.e., GCT SPC-LM) with Porland Cement Concrete. It is

hardened at ambient temperature. This HSC is equivalent to PPCC(Polymer Portland

Cement Concrete), which uses latex or resin as polymers in concrete. Instead of

these polymers in concrete, HSC uses HSPC. HSPC is included in the concrete

mixture as additivesadditives, HSPCHSPC functions as functions as Hydraulic Binder Hydraulic Binder with Portland Cementwith Portland Cement.

(2)SC(Sulfur Polymer Cement Concrete)SC is a conventionally used concrete, which is a mixture of remelted SPC(Sulfur

Polymer Cement, i.e., SPC-HM) with aggregates. It also hardened at ambient

temperature. This SC is equivalent to PC(Polymer Concrete), which uses the latex

or resin as polymers in concrete, too. Instead of these polymers, SC uses the SPC.

SPC is included in the concrete mixture as bindersbinders, SPC SPC functions by itself as functions by itself as

BinderBinder.

GCT SPC

SC

HSC

PCC

Com

pre

ssiv

e S

trength

(kgf/

cm2)

Compressive Strength vs. AgeC

om

pre

ssiv

e S

trength

(kgf/

cm2)

Figure. Comparative Compressive Strength vs. Age Curves

<Note> SC: Sulfur Concrete, HSC: Hydraulic Sulfur Concrete, PCC: Portland Cement Concrete

Age (Days)

GCT SPC

4.2 Manufacturing of HSC

HSC can be prepared by using mobile mixer or existing ready-mixed plant.

The followings are the general recommended HSC manufacturing procedures general recommended HSC manufacturing procedures

to make best HSC mixtures at the existing ready-mixed concrete plant.

(1) Aggregates(fine, coarse), Portland cement are stored at places

where some levels of temperature can be maintained.

(2) Remelted HSPC is prepared using SPC melting facilities and is maintained

at about 100℃, not more than 120℃.

(3) Heated water at about 60℃ is also prepared(if needed).

(4) Fine aggregates, some portion of heated water & remelted HSPC are poured

into the mixer, and pre-mixed before pouring the Portland cement.

HSC can be prepared by using mobile mixer or existing ready-mixed plant.

The followings are the general recommended HSC manufacturing procedures general recommended HSC manufacturing procedures

to make best HSC mixtures at the existing ready-mixed concrete plant.

(1) Aggregates(fine, coarse), Portland cement are stored at places

where some levels of temperature can be maintained.

(2) Remelted HSPC is prepared using SPC melting facilities and is maintained

at about 100℃, not more than 120℃.

(3) Heated water at about 60℃ is also prepared(if needed).

(4) Fine aggregates, some portion of heated water & remelted HSPC are poured

into the mixer, and pre-mixed before pouring the Portland cement.

GCT SPC

(5) Next, coarse aggregates, Portland cement, remained heated water & proper

admixtures(i.e., HRWRA etc.) are included to the pre-mixed mixtures, and then

mix again to disperse the remelted HSPC completely, homogeneously into HSC

mixtures.

(6) Discharge the completely mixed HSC mixtures, and transport the HSC mixtures

using the ready-mixed truck or other suitable transportation means to the

construction site.

<N.B.>

To make best HSC mixtures, mixing method mixing method and mixing sequence mixing sequence are important

to disperse the remelted HSPC effectively within the HSC mixtures.

(5) Next, coarse aggregates, Portland cement, remained heated water & proper

admixtures(i.e., HRWRA etc.) are included to the pre-mixed mixtures, and then

mix again to disperse the remelted HSPC completely, homogeneously into HSC

mixtures.

(6) Discharge the completely mixed HSC mixtures, and transport the HSC mixtures

using the ready-mixed truck or other suitable transportation means to the

construction site.

<N.B.>

To make best HSC mixtures, mixing method mixing method and mixing sequence mixing sequence are important

to disperse the remelted HSPC effectively within the HSC mixtures.

(1) Increased Strength(Compressive, Flexural, Splitting, and Bond)

(2) Excellent Acid-resistance, Chemical-resistance & Chloride-resistance

(3) Increased Corrosion-resistance & Abrasion-resistance

(4) Good Water-tightness & Air-tightness due to Low Permeability

(5) Increased Resistance to Freeze/Thaw

(6) Reduced Shrinkage Crack due to Low Volumetric Deformation

(7) Increased Resistance to Fatigue

(8) Increased Toughness(Impact, and Fracture)

(9) Anti-spalling/Fire-resistance

GCT SPC

4.3 Characteristic Material Properties of HSC

(1) Increased Strength(Compressive, Flexural, Splitting, and Bond)

(2) Excellent Acid-resistance, Chemical-resistance & Chloride-resistance

(3) Increased Corrosion-resistance & Abrasion-resistance

(4) Good Water-tightness & Air-tightness due to Low Permeability

(5) Increased Resistance to Freeze/Thaw

(6) Reduced Shrinkage Crack due to Low Volumetric Deformation

(7) Increased Resistance to Fatigue

(8) Increased Toughness(Impact, and Fracture)

(9) Anti-spalling/Fire-resistance

(1) Permeable Concrete Paver

(2) Precast Concrete Products

(3) Barrier, Median Strip, Gutter(Type-U, L etc) and Parapet

(4) Underwater Concrete or Seawater Concrete

(5) Stabilization and Solidification of Waste

(6) HPC Structures

(7) Shrinkage-compensating HSPC Mortar

(8) HSC Pavement(New or Rehabilitation)

(9) Anti-spalling/Fire-resistant HSC Structures

(10) Others

GCT SPC

4.4 Application Fields of HSC

(1) Permeable Concrete Paver

(2) Precast Concrete Products

(3) Barrier, Median Strip, Gutter(Type-U, L etc) and Parapet

(4) Underwater Concrete or Seawater Concrete

(5) Stabilization and Solidification of Waste

(6) HPC Structures

(7) Shrinkage-compensating HSPC Mortar

(8) HSC Pavement(New or Rehabilitation)

(9) Anti-spalling/Fire-resistant HSC Structures

(10) Others

Mixture Design: (fbk = 4.5 MPa Pavement Concrete + HSPC 7.5%) 1 m3

Mixture: (fbk = 4.5 MPa Pavement Concrete + HSPC 7.5 %) 1 m3


Gmax

Design Strength Slump

Air Content F. M. HSPC HRWRCompressive

fck

Flexuralfbk

mm MPa MPa mm % % % %

13 27 4.5 180 4.5 2.97 7.5 0.5~2.5

GCT SPC

5. Example; HSC Bridge Deck Overlay Pavement

5.1 Mixture ProportioningMixture Design: (fbk = 4.5 MPa Pavement Concrete + HSPC 7.5%) 1 m3

Mixture: (fbk = 4.5 MPa Pavement Concrete + HSPC 7.5 %) 1 m3


GCT SPC

à à à à

à à à à

à

àà

à à

à à

Photo. Mixing and Strength Test Procedure in Lab.

(1) Compressive Strength

(2) Flexural Strength

GCTSPC

HSPC Slump Air Content

Compressive Strength

Remark

cP % mm %MPa

fc,7 fc,28

115 7.5 190 6.0 32.6 42.9

132 7.5 210 4.0 29.9 38.7 Reference

251 7.5 200 5.0 35.0 38.1

GCT SPC

5.2 Strength Test

(1) Compressive Strength

(2) Flexural Strength

251 7.5 200 5.0 35.0 38.1

GCT SPC

HSPC Slump Air Content

Flexural Strength

Remark

cP % mm %MPa

fb,7 fb,28

115 7.5 190 6.0 6.3 5.8

132 7.5 210 4.0 6.2 6.0 Reference

251 7.5 200 5.0 N/A 5.8

Photo. Fractured Area of Compressive Test

FracturedArea ofCompressiveTest at 7th

Age Day

Front View

Fractured

Area of

Compressive

Test at 7th

Age Day

Side View

GCT SPC


Age Day

Front View


Age Day

Side View

GCT SPC

Photo. Fractured Section of Flexural Test

FracturedSection ofFlexural Strength Test at 7th

Age Day

Over View

FracturedSection ofFlexural StrengthTest at 7th

Age Day

Detail View


Age Day

Over View


Age Day

Detail View

(1) Maximum Water-Cementitious Materials RatioàMaximum W/B, 0.35

(2) Minimum Durability Factor, 80%àASTM C666 Procedure A

(3) Minimum Strength Criteria, After Concrete Placement

GCT SPC

6. HPC(High Performance Concrete)

6.1 Definition

(1) Maximum Water-Cementitious Materials RatioàMaximum W/B, 0.35

(2) Minimum Durability Factor, 80%àASTM C666 Procedure A

(3) Minimum Strength Criteria, After Concrete Placement

Type of HPC Minimum Strength Criteria Remark

VES(Very Early Strength) 3,000 psi/4 hours 21 MPa/4hours

HES(High Early Strength) 5,000 psi/24 hours 34 MPa/24hours

VHS(Very High Strength) 10,000 psi/28 days 69 MPa/28days

FR(Fiber Reinforced) HES + (Steel /Polymer)

à Easy Concrete Placement

à Compaction without Segregation

à Excellent Long-term Mechanical Properties

à High Strength

à High Toughness

à Low Permeability

à Volume Stability

à Long Life under Severe Environments

GCT SPC

6.2 Advantages

(1)Performance Benefits

à Easy Concrete Placement

à Compaction without Segregation

à Excellent Long-term Mechanical Properties

à High Strength

à High Toughness

à Low Permeability

à Volume Stability

à Long Life under Severe Environments

à Less Material

à Fewer Beams

à Reduced Maintenance

à Extended Life Cycle Cost

à Aesthetics

GCT SPC

(2) Cost & Other Benefits

à Less Material

à Fewer Beams

à Reduced Maintenance

à Extended Life Cycle Cost

à Aesthetics

Strength Criteria Durability Criteria Remarks

Compressive Strength Freeze/Thaw

Modulus of Elasticity Scaling

GCT SPC

6.3 Design Criteria(SHRP)

Shrinkage Abrasion

Creep Chloride Permeability

6.4 Performance Grade(FHWA)

GCT SPC

(1) SPC Asphalt Pavement

(2) RAP(Reclaimed Asphalt Pavement)

(3) FDR(Full Depth Reclamation) Pavement

(4) WMA(Warm Mix Asphalt) Pavement

(5) CMA(Cold Mix Asphalt) Pavement


GCT SPC

(1) SPC Asphalt Pavement

(2) RAP(Reclaimed Asphalt Pavement)

(3) FDR(Full Depth Reclamation) Pavement

(4) WMA(Warm Mix Asphalt) Pavement

(5) CMA(Cold Mix Asphalt) Pavement

8.1 GRC Inc(8.1 GRC Inc(ChemprufChempruf sulfur concrete)* Used McBee modifier à SSβ β crystalscrystals (monoclinic phase) + (monoclinic phase) + CPDCPD

GCT SPC

8. SC(Sulfur Concrete) & SA(Sulfur Asphalt)

Tank system for Chempruf sulfur concrete Chemical plant for Chempruf sulfur concrete

GRC's concrete mixer truck for Chempruf sulfur concrete

What is STARcrete™ ?

STARcrete™, a STable Acid Resistant, sulfur-based concrete, has extreme corrosion resistance, high physical strength, high fatigue resistance and low water permeability. It is well suited for specific applications where its unique properties are needed. Both the properties and extreme durability of STARcrete™ result from the incorporation of a small quantity of a proprietary sulfur modifier called STX™. This ingredient prevents the formation of macro sulfur crystals. The result is a concrete based on stable, orthorhombic sulfur with greatly enhanced durability. For a dramatic comparison between STARcrete™ and Portland cement concrete, view the deterioration photo in the Properties section. STARcrete™, and its predecessor, Sulfurcrete is the original commercial sulfur concrete, developed by Dr. Alan H. Vroom of Sulphur Innovations Ltd., and was first marketed in Canada in 1976.

GCT SPC

8.2 8.2 STARcrete Technologies Inc(STARcrete™) * Used Used Vroom Vroom modifier(STXmodifier(STX™) ) àà smallersmaller SSαα crystals(orthorhombic phase)crystals(orthorhombic phase)

What is STARcrete™ ?

STARcrete™, a STable Acid Resistant, sulfur-based concrete, has extreme corrosion resistance, high physical strength, high fatigue resistance and low water permeability. It is well suited for specific applications where its unique properties are needed. Both the properties and extreme durability of STARcrete™ result from the incorporation of a small quantity of a proprietary sulfur modifier called STX™. This ingredient prevents the formation of macro sulfur crystals. The result is a concrete based on stable, orthorhombic sulfur with greatly enhanced durability. For a dramatic comparison between STARcrete™ and Portland cement concrete, view the deterioration photo in the Properties section. STARcrete™, and its predecessor, Sulfurcrete is the original commercial sulfur concrete, developed by Dr. Alan H. Vroom of Sulphur Innovations Ltd., and was first marketed in Canada in 1976.

PropertyComparison with 34.5 MPa (5,000 psi)

Portland cement concrete

Compressive Strength greater

Flexural Strength greater

Splitting Tensile Strength greater

Modulus of Elasticity greater

Compressive Creep less

Bond Strength to Reinforcing Steel greater

Properties of STARcrete™Data from independent laboratories

GCT SPC

Bond Strength to Reinforcing Steel greater

Bond Strength to Concrete much greater

Coefficient of Linear Expansion equivalent

Thermal Conductivity less

Durability under Thermal Cycling equivalent or higher

Corrosion Resistance much greater

Fire Resistance slightly less

Fatigue Resistance much greater

Water Permeability much less

Abrasion Resistance much greater

DescriptionSTARcrete™

MPa (psi)Portland cement concrete

MPa (psi)

Compressive Strength 62.0 (9,000) 34.5 (5,000)

Tensile Strength 7.4 (1,080) 2.6 (380)

Modulus of Rupture 12.7 (1,850) 3.65 (530)

Modulus of Elasticity 3 ~ 4 x 104 (4 ~ 6 x 106) 2.8 ~ 3.7 x 104 (3 ~ 4 x 106)

The table below gives test results as compared to a typical Portland cement concrete using a 19 mm (3/4") washed gravel with approximately 60% fractured face. Note that the relationship of compressive strength to modulus of elasticity can, if desired, be varied with special additives.

GCT SPC

Modulus of Elasticity 3 ~ 4 x 104 (4 ~ 6 x 106) 2.8 ~ 3.7 x 104 (3 ~ 4 x 106)

Coefficient of Linear Expansion8.3 x 10-6 /°F

(4.6 x 10-6 /°C)8.3 x 10-6 /°F

(4.6 x 10-6 /°C)

Density2,400 kg/m3

150 lb/ft32,400 kg/m3

150 lb/ft3

Amount of Binder297 kg/m3

500 lb/yd3371 kg/m3

625 lb/yd3

1) ThiocreteSulfur concrete(Shell Thiocrete®)

Shell Thiocrete-Benefits• High strength• Rapid curing• Resistance to water and acid• Tolerant of wide range of aggregate properties–> Can use lesser-quality aggregates than possible with conventional PCC• Enabling a wide range of colors, textures and finishes• Easy to recycle• Requires no water• Significantly lower carbon footprint than Portland cement

GCT SPC

8. 3 Shell Group(Thiocrete® & Thiopave®)

Shell Thiocrete-Benefits• High strength• Rapid curing• Resistance to water and acid• Tolerant of wide range of aggregate properties–> Can use lesser-quality aggregates than possible with conventional PCC• Enabling a wide range of colors, textures and finishes• Easy to recycle• Requires no water• Significantly lower carbon footprint than Portland cement

Shell Thiocrete-How it is used?• Product to be supplied in liquid or pellet form• Mixed with aggregate @ 275 °F (135 °C) –> HMA plant• Poured into molds• When cooled to ambient temperature, it is ready for use–> No chemical reaction, curing is when the molten sulfur “freezes” into a solid• To recycle, simply heat to melt sulfur then recast

Solid pellets, ~ 97% sulfur• Includes plasticizers, compaction agent and fume suppressants• Can be stored on the ground or in silos• No concern with moisture during storage• Blended with the mixture, not directly with asphalt binder• Melts in hot-mix plant, disperses into mixture• Keep temperature below 285 °F

GCT SPC

2) Thiopave, formerly known as SEAM(Sulfur Extended Asphalt Modifier)Sulfur-enhanced asphalt(Shell Thiopave®)

Effects of Thiopave Modification• Partial replacement of asphalt binder –> 20 ~25% reduction in bitumen demand– >Increased stiffness at high service temperatures,

reduced temperature susceptibility– >Improved resistance to rutting/permanent deformation• No significant effect on cracking– >Ability to increase total binder content

and use softer binders may prove to improve resistance to thermal and fatigue cracking


GCT SPC

GCT SPC

GCT SPC

8.5 SK(Micropowder)

Element Sulfur와 특수 Chemical을 반응시켜 Modified Sulfur Polymer Cement(SPC)를 제조함 .

SPC는 골재의 결합물질(Binder)로 사용할 수 있음.

+

Modifiers

Modified Sulfur Polymer Cement Concrete

PolymerizationPolymerization

GCT SPC

일반일반 콘크리트콘크리트(PCC)(PCC)

SPC SPC 콘크리트콘크리트(SC)(SC)

자갈자갈 36%36% 모래모래 40%40% 시멘트시멘트 15%15% 물물 9%9%

모래모래 37%37% Filler Filler 88%%자갈자갈 39%39% SPC 16%

SPC를 Binder로 사용하는 SPC 콘크리트(SC)는 기존 포틀랜드 시멘트 콘크리트와 전혀

다른 Curing Mechanism을 갖고 있는 Organic, Dry & Thermoplastic Concrete임.

Elemental Sulfur SPCSPCHydrocarbon

특징 비교 SPC 콘크리트(SC)

Curing Mechanism Phase Transformation

일반 콘크리트(PCC)

Chemical Reaction

Curing Time 2~3시간 후, 최고 강도의 80% 발현 7~28일 소요

물 사용 여부 물이 필요 없어 겨울에도 시공가능 겨울 시공 불가능

재생 사용 여부 재생 사용 가능 재생 사용 불가능

SPC를 사용한 SPC 콘크리트는 내화학성, 초속경성 및 고강도 등에서 기존 포틀랜드 시멘트

콘크리트보다 우수한 성능을 보유함.

GCT SPC

SPC를 사용한 SPC 콘크리트는 내화학성, 초속경성 및 고강도 등에서 기존 포틀랜드 시멘트

콘크리트보다 우수한 성능을 보유함.

u초속경성 및 고강도SPC 콘크리트(SC)

일반 콘크리트(PCC)

§별도의 양생기간 불필요.

§시공 24시간 후 강도 90% 이상 발현.

§인장강도 및 휨강도 우수.

§ 시험기관 ; 수원대학교 산업기술연구소(시험기간 -> 6개월)

§ 각종 Acid Solution에서 6개월간 침지 시 Weight Loss 0.5%이하

u내화학성

GCT SPC

SC PCC

300 Cycle 후 시편

SPC 콘크리트(SC)는 일반 콘크리트 대비 큰 압축강도와 탄성계수 및 최대응력 시 변형능력이크며, 뛰어난 내산성능, 염소이온 차단성 및 장기 내구성을 가짐.

◆ Freeze /Thaw Durability(한국건설기술연구원)

구 분상대동탄성계수(초기 100 기준)

300 Cycle 후중량 변화율

300 Cycle후(시편 3개 평균)

96.5 0.18

GCT SPC

300 Cycle 후 시편

항 목 SC

최대응력 시 변형도** 2.5~3 x 10-8

PCC

1.5~2 x 10-8

압축강도 * (3시간) 267 kgf/cm2

휨강도 * (3시간) 80.2 kgf/cm2

사선전단강도 * (3시간) 153.1 kgf/cm2

138 kgf/cm2

35 kgf/cm2

-

염소이온투과성** 10~35 Coulombs 2,300~4,800 Coulombs

* 도로교통연구원 수행, ** 수원대 수행

Modified Sulfur Polymer Cement Asphalt

GCT SPC

GCT SPC

GCT SPC

8.6 GS Caltex

GCT SPC

[Sulfur Polymer and Its Concrete Compositions] (KR10-1020519)

Sulfur Polymer Manufacturing, Fabrication and Sale of Sulfur Polymer Pipe

by Joint Venture with Samsung Industrial.

Documents

Hydraulic Sulfur Concrete(HSC)